JPS5857736B2 - Halogen Kagin Color - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to silver halide color photographic materials, especially multilayer...
This invention relates to a silver halide color photographic material that solves the unique problems that arise when the silver halide color photographic material is automatically processed by a machine, such as developing, bleaching and fixing, washing with water, and stabilizing.

It is well known that roll-shaped silver halide color photographic materials, especially multilayer silver halide color photographic materials, are processed automatically after exposure by a processor, such as development, bleach-fixing, and water-washing stability. Processing is performed.

In recent years, as rapid processing of silver halide color photographic materials has been required, efforts have been made to shorten the washing process and reduce the amount of water used for washing.

In addition, due to the need for rapid processing and additional pollution control measures, the conventional processing method using red blood salt has been replaced with a one-bath bleach-fixing process using a ferric complex salt of ethylenediaminetetraacetic acid as an oxidizing agent after development.

However, it has been found that serious problems occur when silver halide color photographic materials are subjected to such a short washing step, particularly a one-bath bleach-fixing process, in a processor.

That is, it has been found that a large number of spot-like unevenness occurs in silver halide color photographic materials regardless of exposure.

This spot-like unevenness is particularly noticeable in the uppermost layer of a multilayer silver halide color photographic material, and is the color developed by the coupler in the uppermost layer.

However, surprisingly, it was found that when color development processing using a one-bath bleach-fix solution with a short water washing process was performed, such spot-like unevenness did not occur at all if tank processing was performed without processor processing. .

The mechanism by which this spot-like unevenness occurs is not clear, but in any case, this spot-like unevenness is a serious quality defect. It is important to provide silver color photographic materials.

As a result of various studies, the present inventors found that )・Silver halogenide formation・
A silver halide emulsion layer containing at least one water-soluble iridium compound in the presence of 10-7 mol to 10-5 mol per 1 mol of silver halide during dispersion or physical ripening, and a silver halide color. It has been found that a silver halide color photographic material containing at least one non-diffusible dihydroxybenzene compound, preferably 2.5 m9/m or more, in the constituent elements of the photographic material significantly suppresses spot-like unevenness. .

More specifically, in the present invention...a water-soluble iridium compound is added during the production and dispersion of silver halide or during physical ripening, and a non-diffusible dihydroxybenzene compound is added to the constituent elements of the silver halide color photographic material. In silver halide color photographic materials containing additives, during processing, especially in one-bath bleach-fixing processing in processor processing,
In the present invention, we have discovered a completely new fact that the spot-like unevenness that frequently occurs during the processing of silver halogenide color photographic materials using or not adding the compounds added in combination is significantly suppressed.

The present invention is based on the above-mentioned new facts, and as is clear from the descriptions so far, the purpose of the present invention is to reduce the tendency for spot-like unevenness to occur in single-bath bleach-fixing processing during processor processing. The object of the present invention is to provide a silver halide color photographic material with significantly suppressed silver halide.

Typical water-soluble iridium compounds used in the practice of the present invention include hexahalogen complex salts [for example, hexahalogen iridium (m) salts, hexahalogen iridium (IV) salts, etc.], iridium chloride (m), Examples include iridium (IV) chloride, iridium (m) bromide, and iridium (IV) bromide.

It is already known to use these water-soluble iridium compounds by adding them to silver halide photographic emulsions.

For example, British Patent No. 602,158 describes the stabilizing effect of silver halide photographic holes and agents using ruthenium salts, palladium salts or iridium salts.

Further, U.S. Patent No. 2,448,060 describes water-soluble ruthenium, rhodium, palladium, osmium, iridium [
There is a description of sensitizing a silver halide photographic emulsion by adding at least one compound (platinum) to the emulsion during the production and dispersion of silver halide grains, during physical ripening, during chemical ripening, or before coating.

Further, Japanese Patent Publication No. 4935/1983 describes a photographic material for flash exposure in which a water-soluble iridium compound is added during precipitation or ripening of a silver halide photographic emulsion with low sensitivity and high contrast.

Also, Japanese Patent Publication No. 4933781 and Japanese Patent Publication No. 48-672
In No. 5, a water-soluble iridium compound and a water-soluble rhodium compound are added together at the time of emulsification or physical ripening to improve the flash exposure characteristics and latent image stability of a silver halide photographic light-sensitive material for flash exposure. is proposed.

On the other hand, dialkylhydroquinone (
Alkyl is preferably from butyl to cetyl.

It is already known to use non-diffusible dihydroxybenzene compounds . . . in the constituent elements of silver halide color photographic materials.

For example, the hydroquinone compounds described in U.S. Pat. No. 2,675,314 are added to multilayer color photographic emulsion layers containing color couplers, and the hydroquinone compounds described in U.S. Pat.
The dialkylhydroquinone compounds described in U.S. Pat.
The compounds described in No. 7, the pihydroquinone compounds described in U.S. Pat. No. 2,735,765, and the hydroquinone compounds described or exemplified in U.S. Pat. It is used.

Further, higher alkylhydroquinone compounds having a soluble group as described in US Pat. No. 891,158 are also used as stain inhibitors or antioxidants.

However, in the literature known so far, there is a feature that a specific compound in the present invention, namely, a combination of at least one water-soluble iridium compound and at least one non-diffusible dihydroxybenzene compound is added. There is no description whatsoever regarding silver halide color photographic materials.

More specifically, during the production and dispersion of silver halide or during physical ripening, a small amount of water-soluble iridium compounds (both 1
10-7 mol or more of seeds per 1 mol of silver halide 10-5
Particularly preferably, at least one non-diffusible dihydroxybenzene compound is present in an amount of 2.5 m? By containing more than /m,
Until now, there has been no mention in the known literature of a practical silver halide color photographic material that has the extremely excellent effect of significantly suppressing the tendency for frequent spot-like unevenness to occur during single-bath bleach-fixing processing in processor processing. Not yet.

As for the amount of water-soluble iridium compound used in carrying out the present invention, as a result of various studies, silver halide 1
If it is less than 10-7 mol per mole, the effect of significantly suppressing spot-like unevenness by the treatment is weak (but if it is more than 10-5 mol, the treatment will desensitize and cause fogging, which is not preferable, but the above-mentioned 10- per mole of silver halide as
Extremely excellent effects can be obtained when the amount is in the range of 7 mol or more and 10' mol or less.

On the other hand, as a result of various studies, the amount of the non-diffusible dihydroxybenzene compound used together with water-soluble iridium in carrying out the present invention was determined to be 2.5/.If it is 1 or more, spot-like unevenness will occur in the treatment. It tends to be difficult or not to occur, and it has an extremely good effect, but at 25 m9/
If the amount added is less than m, spot-like unevenness will occur frequently.

Also, there is no particular limit on the upper limit (addition amount), but it is 100
/d is a practically acceptable range.

In addition, the optimum amounts of the water-soluble iridium compound and the non-diffusible dihydroxybenzene compound in the present invention can significantly suppress spot-like unevenness, which is the objective of the present invention required for silver halide color photographic materials. First, it is determined, and then it is determined based on photographic characteristics such as sensitivity tone and fog, as well as its storage stability.

Type of compound used, silver halide composition, particle size,
Crystal habit, production conditions such as production and dispersion of silver halide, physical ripening, washing with water, and chemical ripening, type and amount of sensitizing dye (conditions for spectral sensitization), chemical sensitizer, binder color coupler, and hardness. Silver halide color photographic materials are manufactured by taking into consideration the types and amounts of various additives such as film agents, development accelerators, desilvering accelerators, etc., but the present invention is not limited by these various conditions. .

The water-soluble iridium compound used in the practice of the present invention is
Although it is effective when added at any stage before the completion of physical ripening, it is particularly preferable to add it by incorporating it into the halogen solution during the production and dispersion of silver halide, or to add it immediately after the production and dispersion of silver halide. It is best to add it in portions or at different times.

On the other hand, the non-diffusible dihydroxybenzene compound used in the practice of the present invention is included in the constituent elements of silver halide color photographic materials (emulsion layer, subbing layer, protective layer, ultraviolet absorbing layer, etc.).
It may be added at any stage after ripening, and it is particularly preferable to add it to the gelatin liquid together with known additives, and add a dispersion prepared by adding color couplers and the like to the ripened emulsion.

The silver halide color photographic material according to the present invention may contain various additives during the production and dispersion of silver halide grains, during or after physical ripening.

For example, a water-soluble rhodium compound is used to make the tone deeper, a mercapto heterocyclic compound is used to control crystal habit, and a general formula R2MX6 (where R is an alkali metal atom) is used to increase sensitivity and make the tone more intense. or an ammonium radical, X represents a halogen atom, and M represents ruthenium, palladium, osmium, or platinum.

) and silver halide grains [
Water-soluble inorganic and organic metal salts such as zinc, lithium, and cadmium for the purpose of forming fine particles U.S. Pat. No. 244,853
Ethylenediamine described in No. 4 may be contained alone or in combination.

Further, various sensitizers can be contained in the emulsion layer of the silver halide color photographic material of the present invention.

For example, sulfur sensitizers (e.g., sodium thiosulfate, thiourea, gelatin containing unstable sulfur, etc.), noble metal sensitizers (e.g., gold chloride, gold rhodan, ammonium chloroplatinate, silver nitrate, etc.), U.S. Pat. 2,448,060, polyalkylene polyamine compounds as described in US Pat. No. 2,518,698, German Patent No. 102
Chemical sensitizers such as iminoamino-methantophic acid described in No. 0864, alone or in combination, can be included.

Furthermore, the emulsion layer of the silver halide color photographic material of the present invention can also contain various color couplers, particularly DIR couplers (development inhibitor releasing couplers).
can advantageously be contained.

For example, U.S. Patent No. 2991177,
No. 30933, No. 48-43938, No. 48-668
Yellow, magenta, and cyan couplers described or exemplified in No. 36 and No. 49-42345, U.S. Pat.
-66834, 48-66835, 48-73
No. 147, No. 48-94432, No. 47-37423
Yellow coupler Special Publication Showa 4 described or exemplified in the issue, etc.
Magenta couplers described or exemplified in JP-A No. 3-16187, JP-A-49-11331, etc., JP-A-47-44
．． Cyan couplers described or exemplified in No. 30, No. 4727024, No. 48-42732, etc. may be contained alone or in combination.

Furthermore, the emulsion layer of the silver halide color photographic material of the present invention may also contain various sensitizing dyes that can very advantageously spectral sensitize the red-, green-, or blue-sensitive layers.

For example, Special Publication No. 43-4930, No. 48-42974
Red-sensitizing dyes described in JP-A-49-106322, JP-A-49-111629, JP-A-48-56426, etc., JP-A-46-549, JP-A-47-2
No. 6126, No. 48-28224, No. 48-2472
No. 6, No. 48-33817, No. 48-41733,
48-59828, etc., the green-sensitizing dye described in
Blue-sensitizing dyes described in Japanese Patent Publication No. 4519034, Japanese Patent Application Laid-Open No. 46-1630, US Pat. No. 3,752,670, etc. may be contained alone or in combination.

Furthermore, among the constituent elements of the silver halide color photographic material of the present invention, ultraviolet absorbers or light stabilizers (for example, German Patent No. 1182066, JP-A-47-102
No. 6, etc.), development accelerators (e.g., guanidine compounds described in JP-A No. 48-41739), surfactants (e.g., saponins, alkylbenzene sulfonates, sulfosuccinates, etc.) salts, etc.), desilvering accelerators (for example, JP-A-4
8-74832),
Organic hardeners [for example, active halogen compounds described in JP-A-4831937, vinyl sulfone compounds described in JP-A-48-74832, JP-A-48-71639
Epoxy and aziridine compounds described or exemplified in No.
The Theory of the Photographic Process by Mees
of thePhotographic Pro
aldehydes, halogencarboxylic acids, vinyl sulfones, aziridines, epoxies, active halogen compounds, etc. described or exemplified in
For example, chrome alum, potash alum), sharpness-enhancing pigments [for example, Amaranth
, acid dyes as exemplified in JP-A-4717421 and the like].

Examples of the dispersion medium for silver halide in the silver halide color photographic material of the present invention include gelatin (alkaline method gelatin, acid method gelatin, etc.), modified gelatin (for example, Japanese Patent Publication No. 38-4854, No. 40-122)
A variety of dispersion media may be used, such as modified gelatins such as those described in US Pat. No. 37, US Pat.

Further, in order to incorporate a color coupler together with an ultraviolet absorber, a light stabilizer, etc. into the constituent elements of the silver halide color photographic material of the present invention, in the case where these compounds have a water-soluble group, 1. Advantageously, it is dissolved in an aqueous alcoholic alkali solution and then incorporated into the constituent elements of a silver halide color photographic material.

On the other hand, when these compounds are oil-soluble, they can be treated with high boiling point solvents (e.g., phthalate esters, succinate esters, etc.), as described in U.S. Pat. etc.), it is advantageously dispersed in a dispersion medium such as an aqueous gelatin solution and incorporated into the constituent elements of a silver halide color photographic material.

: Furthermore, the production, dispersion, and physical ripening of silver halide in the present invention can be carried out by various methods and conditions.

For example, forward mixing method, back mixing method, combination of forward and back mixing methods, double jet method, 1 silver method, 2 silver method, converted silver halide method, total ammonia method, partial ammonia method,
This can be carried out by various methods such as acid method, neutral method, and alkaline method.

After exposure, the silver halide color photographic material having the novel effects of the present invention produced by adding a combination of a water-soluble iridium compound and a non-diffusible dihydroxybenzene compound is subjected to color development treatment in a processor, When performing bleach-fixing processing, CD-m, CD
-IV (the above two compounds are trade names of Kodak Co.), droxychrome (trade name of May and Baker Co.), and any other color developer can be used for processing.

A developer containing such a main agent may also contain a development accelerator such as phenidone, hydroxyquinoline, or thallium salt.

A useful one-bath bleach-fix solution is a solution of a metal salt of an aminopolycarboxylic acid (for example, a ferric complex salt or a cupric complex salt such as ethylenediaminetetraacetic acid, aminotriacetic acid, propylenediaminetetraacetic acid, etc.), and is used as a fixing agent. Ammonium thiosulfate, sodium thiosulfate, ammonium rhodan, and the like are useful.

In addition, such single-bath bleach-fix solutions contain various combinations of various compounds such as desilvering accelerators, anti-staining agents, PH regulators or PH buffering agents, hardeners, fluorescent brighteners, and surfactants. It can be contained in

After one-bath bleach-fixing, washing with water and stabilization are performed.

The emulsion layer and other protective colloid layers of the silver halide color photographic material in the present invention can be formed by various coating methods [
For example, dip (Dip), meniscus (Me
Niscus), Ebar coating method, etc.] on any commonly used supports such as paper, synthetic films such as triacetate cellulose polyethylene terephthalate, polystyrene, and polypropylene, paper and their laminates. Good too.

Next, Examples will be described to further specifically explain the present invention, but the present invention is not limited to these examples and can be applied in various ways within the scope of the claims.

Example 1 30 grams of gelatin is added to 11 grams of water, swollen, and then heated to obtain a gelatin solution. 50 grams of silver nitrate is added to 150 cc of water, and a solution of 40 cc of 28% ammonia water is added to the gelatin solution.

Further, 37.5P of potassium bromide and 2.51P of potassium chloride were dissolved in 130cc of water, and 1.5% potassium hexachloroiridate(IV) aqueous solution was added. A solution containing Qcc is added to the silver nitrate solution and aged at 40°C.

The emulsion that has undergone physical ripening is called Milk MIJ A.
In addition, an emulsion prepared in the same manner without using the 0.05% potassium hexachloroiridate (IV) aqueous solution was used as emulsion B, and 0.05% potassium hexachloroiridate (IV) was used instead of the 0.05% potassium hexachloroiridate (IV) aqueous solution. 1. chlororuthenium compound. The emulsion using OCC is called emulsion C.

After physical ripening, each emulsion has a pH of 4.0,
After cooling to 30°C, magnesium sulfate is added to precipitate and dehydrate the emulsion.

After washing with water, the emulsion is subjected to chemical ripening.

Each emulsion thus prepared was added and dissolved in 120 OCC of an active gelatin aqueous solution with a gelatin concentration of 4%, and the pH of the emulsion was
Chemical ripening was carried out at 55°C with a temperature of 6.5.

After ripening, the temperature of each emulsion was cooled to 55°C, and a 0.01% solution 12c of red sensitizing dye (I) represented by the following formula was added.
c, while 10% gelatin aqueous solution 180CCK5
% sodium dotecylbenzenesulfonate aqueous solution 30
cc and 0.15S' of 2,5-di-n-octyl-hydroquinone as a non-diffusible dihydroxybenzene compound in the present invention and 6. (1) is dissolved in high-boiling point oil, then added to the gelatin solution and a dispersion prepared by dispersing is added.

Furthermore, 10% of the hardening agent (III) represented by the following formula
Methanol solution7. Qcc, 7.0 cc of a 10% methanol solution of hardener (IV) represented by the following formula, 25 cc of a 2% chromium alum aqueous solution, and 30 cc of a 1% aqueous solution of sharpness-enhancing dye (V) represented by the following formula. Add.

After that, the pH of each emulsion was adjusted to 6.4, and the total amount was 1000.
Add water to make P.

These emulsions are coated together with a protective layer of a red-sensitive emulsion layer on photographic polyethylene resin laminated paper in a multilayer manner.

The numbers of emulsions in the practice of the present invention and emulsions for comparison are shown below.

Emulsion A-1: Contains a water-soluble iridium compound and a non-diffusible dihydroxybenzene compound.

Emulsion A-2: Contains only a water-soluble iridium compound.

(Contains no non-diffusible dihydroxybenzene compounds.

) Emulsion B-1: Contains only a non-diffusible dihydrochimibenzene compound.

(Contains no water-soluble iridium compounds.

) Emulsion B-2: Contains neither water-soluble iridium compounds nor non-diffusible dihydroxybenzene compounds.

Emulsion C-1 = Contains a water-soluble ruthenium compound and a non-diffusible dihydroxybenzene compound.

Emulsion C-2: Contains only a water-soluble ruthenium compound.

(Contains no non-diffusible dihydroxybenzene compounds.

) After drying and cutting the coated sample, it was heated at 35°C for 2 days, exposed to light, and subjected to color development, one-bath bleach-fixing, washing with water, and stabilization in sequence using a processor.The sample was then dried and photographic properties were measured. .

Tank processing was also carried out for comparison, and the photographic properties were measured. Even in the sample coated with the emulsion that did not contain the compound used in the practice of the present invention, no spot-like unevenness occurred.

For processing such as color development and one-bath bleach-fixing using a processor, first perform color development at 33°C for 4 minutes using each processing solution with the following formulation, then bleach-fix with a ferric complex salt of ethylenediaminetetraacetic acid. After this was carried out for 2 minutes, water washing was carried out for 2 minutes, stabilization treatment was carried out for 1 minute, and further water washing was carried out for 10 seconds.

Color developer Sodium hydroxide Sodium metaborate Anhydrous sodium sulfite Potassium bromide D-m Sodium hexametaphosphate Hydrochloride Hydroxylamine Benzyl alcohol Diethylene gelicol Total amount with water 1.71 0 P 1.81 0.51 4.4 g 0.51 1.0g 2CC Qcc l Ferric complex salt of ethylenediaminetetraacetic acid Bleach-fix solution Ferric complex salt of ethylenediaminetetraacetic acid Disodium salt of ethylenediaminetetraacetic acid 56g 2g* Ammonium thiosulfate Anhydrous sodium sulfite Sodium acid sulfite Disodium phosphate Salt Total amount with water 01 0P 1 21 1 N Stabilized liquid Fluorescent brightener 0.5f Potassium alum 20g Anhydrous sodium acetate
51 Sodium acid sulfite
10 P36% formalin 10c
c Total amount of water 11 When the red-sensitive emulsion of the present invention and the red-sensitive emulsion for comparison were used in the red-sensitive layer of a silver halide color photographic material, the results after processor processing were compared in [Table 1]. It should be noted that the characteristics in the table are those of the cyan image after color development and desilvering.

As can be seen from this table, the silver halide color photographic material using the red-sensitive emulsion (emulsion A-1) of the present invention, which uses a water-soluble iridium compound and a non-diffusible dihydroxybenzene compound in combination, is Significantly suppresses spot-like unevenness that occurs during bleach-fixing processing.

It can be seen that in other comparative emulsions, spot-like unevenness occurs significantly.

Example 2 The same procedure as in Example 1 (emulsion A-1) was carried out except that only the type of non-spreadable dihydroxybenzene compound added was changed.

The non-diffusible dihydroxybenzene compound used in this example is 2,5-di-tert-octyl-hydroquinone and 2,5-di-tert-butyl-hydroquinone.

The results after processor processing are shown in Table 2 for comparison.
The characteristics in the table are those of the cyan image after color development and desilvering.

As can be seen from this table, even if the non-diffusible dihydroxybenzene compound used together with the water-soluble iridium compound in the present invention is changed as shown in Table 2, almost no spot-like unevenness occurs.

Among them, the one with the least electrophilic unevenness was 2.5-
Di-tert-butyl-hydroquinone.

*
*Example 3 The amount of the water-soluble iridium compound used in Example 1 (emulsion A-1) was varied, and an emulsion prepared in the same manner as in Example 1 was given the following formula in place of formula (I). A green sensitizing dye represented by formula (IV) was added, and a magenta coupler represented by formula (■) was used in place of formula (n).

Also, in place of formula (V), 20 c of a 1% aqueous solution of food red No. 2
Add c.

After that, adjust the pH to 6.4 and add water so that the total amount is 100 OP.

This emulsion is coated together with a protective layer of a green-sensitive emulsion layer on a photographic polyethylene resin laminated paper.

Thereafter, the treatment was carried out in the same manner as in Example 1, and the results after treatment are shown in Table 1-2, when the amount of water-soluble iridium compound added until the end of physical ripening of silver halide was varied.
Shown in 3.

The characteristics in the table are those of the magenta image after color development and desilvering.

Table 3 Trend of occurrence of spot-like unevenness when the amount of water-soluble iridium compound is changed As can be seen from this table, the amount of water-soluble iridium compound added until the end of physical ripening of silver halide is It can be seen that when used in combination with a dihydroxybenzene compound, 10@-7 mol or more per mol of silver halide is effective.

On the other hand, if the amount is more than 10-5 mol per mol of silver halide, the desensitization will be extremely inappropriate. Therefore, in order to significantly suppress the tendency to generate spot-like unevenness, the amount of water-soluble iridium compound must be 1 mol of silver halide. 10-7 mole or more per mole 10-5
It can be seen that less than a molar amount is effective.

Example 4 In Example 1 (emulsion A-1), the amount of the water-soluble iridium compound added was a constant amount (0.05% potassium hexachloroiridate (IV) aqueous solution ICC), and 2 was added as a non-diffusible dihydroxybenzene compound. - The same procedure as in Example 1 was carried out except that 5-di-tert-butyl-hydroquinone was used and the amount added was varied.

The results after processing are shown in Table 4 for comparison, and the characteristics in the table are those of the cyan image after color development and desilvering.

Table 4. Occurrence trend of spot-like unevenness when the amount of non-diffusible dihydroxybenzene compound is changed. As seen from Table-4, if the amount of non-diffusible dihydroxybenzene added is 2.51n97 m or more, spots will appear. The tendency for unevenness to occur is significantly reduced and good results are obtained.

Example 5 In Example 1 (emulsion A-1), only the water-soluble iridium compound was mixed with 0.05% hexachloroiridium (IV
), 1 cc of 0.05% iridium chloride (■) aqueous solution, and 1 cc of 0.05% iridium bromide aqueous solution were added to Example 1 (emulsion A-
A sample was prepared in the same manner as in 1).

The processing was carried out in the same manner as in Example 1, and the results after processing are compared and described in Table 5. The characteristics in the table are those of the cyan image after color development and desilvering.

Table 5 Trend of occurrence of spot-like unevenness when changing the type of water-soluble iridium compound As shown in this table, the water-soluble iridium compounds are
Even if it is changed as in step 5, spot-like unevenness hardly occurs.

Claims (1)

[Claims] 1 During the generation/dispersion or physical ripening of silver halide,
An emulsion containing at least one water-soluble iridium compound in an amount of 10-7 mol to 10-5 mol per mol of silver halide, and then at least one non-diffusible dihydroxybenzene compound mixed into the emulsion. Silver halogenide color photographic material formed by coating layers.