JPS6117143A - Method for processing color photographic sensitive silver halide material - Google Patents

Abstract

PURPOSE:To prevent color stain, to bleach well silver and to obtain high image quality with high sensitivity by imagewise exposing a color photographic sensitive silver halide material, processing it with a color developing soln. contg. a phenylenediamine type color developing agent, and processing the material with a bleach-fix bath contg. iron (III) ethylenediaminetetraacetate. CONSTITUTION:Silver halide particles whose diameter is >= times, preferably 5- 100 times, especially preferably 7-30 times the thickness are used so as to produce effects on color stain and image quality, and the preferred diameter is >=0.5mum, especially 0.6-6mum. A color developing agent used as a p-phenylenediamine type color developing agent having at least one water soluble group and amino groups, and the concn. of the color developing agent is about 1-15g per 1l developing soln. The amount of iron (III) ethylenediaminetetraacetate in a bleach-fix bath is >=0.05mol, and the bath is adjusted to 6.5-8.5 pH before processing.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, to a method for processing silver halide color photographic materials, which improves color staining occurring in bleach-fix clears and improves bleaching performance. The present invention relates to a method for processing silver halide color photographic materials.

[Prior art]

Generally, in silver halide color photographic materials, after image exposure, a dye image is formed through a series of photographic processes whose basic steps are a color development step and a desilvering step.

In the above-mentioned color development step, the oxidized form of the color developing agent undergoes a force/sampling reaction with the coexisting color coupler to form a dye image corresponding to the imagewise exposure, and at the same time, reduced silver is produced. The silver produced here is subsequently oxidized by a whitening agent in the desilvering step, transformed into a soluble silver complex under the action of a fixing agent, dissolved and removed, and cleaned by washing with water.

In the actual development process, the basic steps for the purpose of color development and desilvering are as follows: a stop bath, a black and white development bath,
Auxiliary treatment baths such as a capri bath, hardening bath, stabilization bath, intensification bath, and backing removal tower are provided.

On the other hand, in recent years, there has been a trend toward bleaching or bleach-fixing directly linked to color development in order to speed up and simplify processing, and to make automatic processors more compact.

However, if bleaching or bleaching treatment is performed directly after color development, color staining occurs in the bleach or bleach-fix solution due to the color developing agent in the color developer. For this reason, JP-A-50-136031, JP-A-51-
It has been known that color staining can be improved by adding amine compounds or mercapto compounds, such as those described in Japanese Patent Publication No. 102640 and Japanese Patent Publication No. 12222/1983, to bleach solutions or bleach-fix solutions. The reality is that the effect is still insufficient for highly active treatments such as high-temperature treatments in recent years. In particular, when using iron ethylenediaminetetraacetate (side complex salt), which has been commonly used as a bleaching agent in recent years due to pollution and economic reasons, the generation of color stain is more pronounced and the silver bleaching ability is also low. Rapid processing is becoming a major problem.

Furthermore, in recent years there has been a need for color paper to shorten the exposure time on printers, and for color negatives to be able to take pictures even in the dark, and to have a deeper depth of field and better focus. Therefore, it is desired to increase the sensitivity of silver halide color photographic light-sensitive materials.

The following techniques have been used to increase the sensitivity of silver halide emulsions. Generally, when silver halide grains in an emulsion are uniformly exposed to light, the grains with larger projected areas receive more light, and the thicker the grains, the better they absorb the heated light. Therefore, if the number of incident light quanta per unit area is the same for the silver halide grains in the emulsion layer to be developable, the larger grains will have higher sensitivity.

However, the use of these large silver halide grains has the disadvantage that the amount of silver used increases and that the image quality is also poor. In order to improve these drawbacks, JP-A-58-113930 and JP-A-58-113934
No. 58-127921 and No. 58-108532
Techniques using tabular (silver tetragenide) grains such as those described in No. 1, etc. have been developed.

Due to this tabular grain technology, even if the number of photons captured by the halogenated grains increases, the amount of silver used does not increase, and image quality does not deteriorate. However, these tabular grains have the disadvantage that developed silver formed by development with a p-phenylenediamine color developing agent has poor silver bleaching properties.

Therefore, there has been a strong desire for a processing system that does not cause color staining, has good silver bleaching properties, and can provide high sensitivity and high image quality in rapid processing in which bleach-fixing is performed immediately after color development.

[Purpose of the invention]

It is an object of the present invention to provide a quick processing method in which color development processing is followed by bleach-fixing processing, which does not cause color staining in the bleach-fixing solution, has improved silver bleaching properties, and has high sensitivity and high image quality. An object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which yields the following.

[Structure of the invention]

As a result of intensive research, the present inventors found that the particle diameter was 5% of the particle thickness.
After imagewise exposure of a silver halide color photographic material having at least one silver halide emulsion layer containing tabular silver halide grains on a support, an amine group having at least one water-soluble group. The objective of the present invention can be achieved under the conditions of processing with a color developing solution containing a p-phenylenediamine color developing agent having It has been found that this can be achieved.

The tabular silver halide grains having a grain size of 5 times or more the grain thickness according to the present invention are disclosed in JP-A-58-113930 and JP-A-58-113930;
B-113934, No. 58-127921 and No. 5
8-108-532, etc., and in the present invention, from the viewpoint of effects on color staining and image quality, the particle diameter is 5 times or more the particle thickness, preferably 5 times or more. ~100 times, particularly preferably 7 to 30 times, is used. Further, the particle size is preferably 0.5p or more, and 0.
．． Particularly preferably used is one having a diameter of 6 to 6μ. The grain diameter here refers to the diameter of the projection plane when observed perpendicularly to the flat surface of a tabular silver halide grain. Assuming that, this diameter is used. When these tabular silver halide grains are contained in the silver halide emulsion layer at least in a print weight %, the desired effects of the present invention are more preferably exhibited, and when most of them are the tabular grains of the present invention, especially This has particularly favorable effects.

The color developing agent according to the present invention is a p-phenylenediamine type color developing agent having an amino group having at least one water-soluble group, and is particularly preferably a p-phenylenediamine color developing agent having the following general formula [1
] This is a compound represented by

General formula (11) In the formula, R represents a hydrogen atom, a halogen atom, or an alkyl group, and this alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and may have a substituent. R2 and R3 represent a hydrogen atom, an alkyl group, or an aryl group, but these groups may have a substituent, and in the case of an alkyl group, an alkyl group substituted with an aryl group is preferable. At least one of R3 is a hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amine group,
It is an alkyl group substituted with a water-soluble group such as a sulfonamide group or 1+-+CH2t-〇nihanR4. This alkyl group may further have a substituent.

Incidentally, R4 represents a hydrogen atom or an alkyl group, the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and n and m represent integers of 1 to 5.

Next, typical examples of the compound represented by the general formula [T1] will be listed, but the invention is not limited thereto.

N.H.

N.H.

NH2 NH2 N.H.

NH2 N.H.

N.H.

N.H.

N.H.

N.H.

N.H.

These p-phenylenediamine derivatives represented by general formula (1) can be used as salts of organic acids and inorganic acids, such as hydrochloride, sulfate, phosphate, p-)luenesulfonate, sulfite, Oxalates, benzenedisulfonates, etc. can be used.

In the present invention, among these p-7x nylenediamine derivatives not represented by the general formula (1), R2 and/or R3 is 1+−+−cH3+rl〇9, R, (n+
m and R4 have the same meanings as above. ), the desired effects of the present invention are particularly well achieved.

Kowara's color developing agent is generally about 0 for development h1i.
．． 1.9 to about 309, more preferably a developer solution of 11
at a concentration of about 1 g to about 15 F.

Further, the above color developing agents may be used alone or in combination of two or more. Moreover, the above-mentioned color developing agent may be incorporated into a color photosensitive material. For example, a method of incorporating a color developing agent in the form of a metal salt as in U.S. Pat. No. 3,719,492, U.S. Pat. No. 3,342, No. 559 and Research Disclosure Y - (Re5earch
Disclosure) 1976/141151
59, a method of incorporating a color developing agent into a Schiff salt, JP-A-58-65429 and JP-A-58-65429;
-24137, etc., and the method of incorporating it as a dye precursor, as shown in US Pat. No. 3,342,597.
A method of incorporating the color developing agent as a precursor as shown in No. J can be used. In this case, it is also possible to process the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and after the alkali IJ ii, it is immediately subjected to a bleach-fixing process.

The color developing solution according to the present invention contains an alkaline agent commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium fmate, sodium metaborate, or borax. may further contain various additives, f! Ill
For example, it may contain benzyl alcohol, an alkali metal halide such as potassium bromide or potassium chloride, a development regulator such as citradinic acid, and a preservative such as hydroxylamine or sulfite.

Furthermore, various antifoaming agents, surfactants, and organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide can be appropriately contained.

Further, the field of the developer according to the present invention is usually 7 or more,
Preferably it is about 9-13.

In addition, the color developer used in the present invention may optionally contain antioxidants such as hydroxylamine, 'tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, and benthose. Sumataha hexose, pyrogallol-1,
3-dimethyl ether and the like may also be contained.

Further, various chelating agents can be used in combination as metal ion sequestering agents in the developer according to the present invention.

For example, as the chelating agent, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid,
Organic phosphonic acids such as 1-hydroxyethylitine-1,1-diphosphonic acid, aminotri(methylenephosphonic acid) 1
or aminopolyphosphonic acids such as ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4-)licarboxylic acid, tripolyphosphoric acid, and hexametaphosphoric acid. Polyphosphoric acid etc. are based.

The ethylenediaminetetraacetic acid iron (I) complex salt contained in the bleach-fix solution of the present invention can be used as an alkali metal salt such as sodium salt, potassium salt, or lithium salt, or as an ammonium salt, or as a water-soluble amine salt, such as a triethanolamine salt. used. It is necessary to use at least one type of iron (1) #salt, but two or more types can also be used in combination. The amount used can be selected according to the amount of silver and silver halide composition of the e1 optical material to be processed, but in general, the amount used is i1? It can be used in an amount of 0.02 mol or more, preferably 0.05 mol or more.

In addition, it is desirable to use the replenisher after increasing its solubility in order to make the replenisher more concentrated and less replenishable.

The bleach-fix solution of the present invention is used at a pH of 4.0 or more, but is generally used at a pH of 5.0 or more and a pH of 9.0 or less,
It is preferably used at pI (6.0 or higher and pI (8,5 or lower); more specifically, the most preferable pH is 6.5 or higher and 8.5 or higher.
Processed below. The processing temperature is used at 55°C or lower, preferably 55°C or lower to suppress evaporation and the like.

The bleach-fix solution according to the present invention has a composition containing the above-mentioned iron(I) complex salt of ethylenediaminetetraacetate as a bleaching agent, a silver halide fixing agent, and, if necessary, a sulfite as a preservative. liquid is applied. In addition, a bleach-fix solution consisting of a lead salt bleach (iron ethylenediaminetetraacetate < W) and a small amount of a halide such as potassium bromide in addition to the above-mentioned silver halide fixing agent, or conversely, potassium bromide Bleach-fix solutions containing a large amount of halides, such as iron ethylenediaminetetraacetate, and special bleach-fix solutions containing a combination of iron ethylenediaminetetraacetate (I-complex bleach) and a large amount of halides, such as potassium bromide. etc. can also be used.

In addition to potassium bromide, the halides include hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide,
Ammonium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used.

The silver halide fixing agent to be included in the bleach-fixing solution includes compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. Typical examples thereof include thiosulfates such as potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thioureas, thioethers, and the like. These fixed adhesives can be used in an amount of 59/1 or higher, within the range that can be dissolved.

Bleach-fixing traps include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate,
pH buffering agents consisting of various salts such as ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, methanol, dimethylsulfonamide, dimethylsulfonate, etc. Organic solvents such as oxides can be contained as appropriate.

The bleach-fixing solution according to the present invention includes Japanese Patent Publication No. 46-280, Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 46-556, Belky Patent No. 770,910, Japanese Patent Publication No. 45-8836, Japanese Patent Publication No. 53-9854. , JP-A No. 54-71634 and No. 4
Although various bleaching accelerators described in No. 9-42349 etc. can be added, in the present invention, from the viewpoint of bleaching performance and color staining, a bleaching accelerator represented by the following general formula (It) is used. is particularly preferred.

General formula [■] In the formula, Q is a compound necessary to form a petro ring containing one or more nitrogen atoms (including those fused to at least one 5- to 6-membered unsaturated ring). or represents an alkyl group, where the alkyl group is linear or branched and has 1 to 4 carbon atoms.
The alkyl group is preferred. However, Q' has the same meaning as Q above.

Next, typical examples of the bleaching accelerator represented by the general formula [1] will be listed, but the invention is not limited thereto.

t-2 -N S, HSH +1-6 -N 1-7 Hf-8 N□N II II C! ,H.

■-10 These bleach accelerators may be used alone or in combination of two or more, and the amount added to the bleach-fixing solution is 1/M O, 0.1 to 50 g of the processing solution. and especially 0.1
~30g is preferably used, most preferably 0.1~
The range is 1.59.

The silver halide color photographic light-sensitive material of the present invention is produced by an internal development method (U.S. Pat.
, 376.679, 2,801,171), and an external development method in which a coupler is contained in the liquid solution (U.S. Pat. No. 2,252,718, 2,592,243).
No. 2.590, No. 970). Further, as the coupler, any type of coupler generally known in the art can be used. For example, cyan couplers are based on naphthol or phenol structures and form indoaniline dyes upon coupling, magenta couplers have a 5-pyrazolone ring with an active methylene group as their backbone structure, and yellow couplers are active. Those having a benzoylacedoanilide, pivalyl acetanilide, or acylacedoanilide structure having a methylene chain, with or without a substituent at the coupling position can be used. Thus, as the coupler, both the so-called 2-equivalent type coupler and the 4-equivalent type coupler can be applied.

However, in the present invention, among the above magenta couplers, a coupler represented by the following general formula m is particularly preferably used because it produces less magentastin when bleach-fixing is carried out directly after color development.

General formula El) In the formula, %R6 and R7 represent an alkyl group or an aryl group, which may have a substituent, and 2 can be separated by coupling with a hydrogen atom or an oxidized product of a color developing agent. represents a group. Also, R3 is (Σoco-, 〇-Co--Cool-1-NO2,-ON, R
,ooao or R,. -0[')- represents "I"
! represents. RIo is an alkyl group, preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and RII represents a hydrogen atom, -COOH or 100 OR, o.

R8 and Ro may each be the same group or different groups.Next, specific examples of the compound represented by the above general formula [R] will be described, but the present invention is not limited thereto. -1 nc, o) (2゜no, OH,.

[-4 tC呵HII K-6 tC,H,.

These magenta couplers can be synthesized by the general synthesis methods described in Japanese Patent Publication No. 48-30895, Japanese Patent Application Laid-open No. 56-133734, and the like.

Silver halide emulsions that can be used in the present invention include any silver halide emulsion such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, and silver chloroiodobromide. It may also be one using silver oxide. Furthermore, as protective colloids for these silver halides, in addition to natural products such as gelatin, various products obtained by synthesis can be used. The silver halogenide emulsion may contain conventional photographic additives such as stabilizers, sensitizers 1, hardeners, sensitizing dyes, and surfactants.

In the processing method of the present invention, it is necessary to carry out bleach-fixing after color development, but washing with water may be performed after bleach-fixing, or stabilizing processing may be performed without washing with water. It may be washed with water and then stabilized.

Further, it is optional to use a commonly used processing solution such as a black and white developer, a fogging solution, a stop solution, and a water washing solution before the color developer of the present invention.

The silver halide color photographic light-sensitive materials used in the present invention include color negative films, color vapors, color reversal films, color reversal papers, etc. to which a processing process including a color development process (including an activator) and a bleach-fixing process is applied. Any photosensitive material can be used.

〔Example〕

The present invention will be described in detail below using Example f91], but the present invention is not limited thereto.

Implementation 1. An antihalation layer and a gelatin layer are provided on a triacetate film base, and on top of this, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a filter layer containing yellow colloidal silver, and a blue-sensitive halide emulsion layer. The silver emulsion layer was coated such that the total amount of silver was 88 η/100 d.

The green-sensitive silver halide emulsion used was JP-A-58-1
Tabular silver halide grains having a grain size 9 times the grain thickness and a grain size of 4.5ρ were prepared and used according to the method described in No. 13934. For emulsions other than the green-sensitive silver halide emulsion, spherical silver halide grains having an average grain size of 1.2 .mu.m were prepared according to the method described in JP-A-58-4'9938.

At this time, the following coupler (Y-1''l) was used as a yellow coupler in the blue-sensitive silver halide emulsion layer, and the exemplified compound (IN-1''l) was used as a magenta coupler in the green-sensitive silver halide emulsion layer.
4), and the following coupler (C-1) was used as a cyan coupler in the red-sensitive silver halide emulsion layer, and each emulsion layer contained a high boiling point solvent, a sensitizing dye, a hardening agent, and a generally extended ring. additives were used. The color negative film thus produced was used as a sample.

Yellow coupler (Y-1) Cyan coupler (C-1) This film sample was exposed to light in a conventional manner and subjected to the following treatments.

Processing process Processing temperature ('C') Processing time 1, color development: 3 minutes 15 seconds 2 Bleach fixing
38 8 minutes 3 Water wash 30-34 2 minutes 4
Stable 30-34 1 minute 5,
Drying 40-60 The following color developing solutions, bleach-fixing, and stabilization were used.

[Color developer]

[Bleach-fixing solution] [Stabilizing solution] The color developing agent and organic acid iron (carbonate) complex salt shown in Table 1 below were used.

After processing, the sample was measured for magentastin in the minimum density area using a Sakura photoelectric densitometer PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.), and the amount of residual silver in the maximum density area was measured using a fluorescent X-ray method. It was measured.

In addition, in the table, KDTA bone Fe is ethylenediaminetetraacetate iron (I) ammonium, GEDTA-Fe is glycol ether diamine tetraacetate iron (I) ammonium, C
yDTA@Fe represents iron (1') ammonium 1,2-cyclohexanediaminetetraacetate, and HEDTA@Fe represents hydroxyethylethylenediamine iron (CI) ammonium triacetate.

From the table above, when a color developing agent other than the present invention was added to the color developing solution as in Comparative Example Samples 4 and 5, magentastin was produced significantly, and Comparative Example Sample A
When a bleaching agent other than the ethylenediaminetetraacetic acid iron (I) complex salt according to the present invention is used as the bleaching agent in the bleach-fix solution as shown in Nos. 6 to 8, the amount of residual silver is so large that it cannot be put to practical use. Furthermore, as in Comparative Example Sample Flat 9, when a color developing agent and an organic acid iron (I) complex salt other than those of the present invention are used, both the amount of magentastin and the amount of residual silver are significantly large.

However, when the color developing agent and the organic acid iron(I) complex salt are both related to the present invention, as in the present invention examples of Samples A1 to A1 to A3, surprisingly, magentastin is also good and there is no residue. It can be seen that the amount of silver is also significantly small.

Example 2 The green-sensitive silver halide emulsion and red-sensitive silver halide emulsion used in Example 1 were replaced with spherical halogen emulsions having an average grain size of 1.2 pm prepared according to the method described in JP-A-58-49938. A color negative film for comparison was prepared in the same manner as in Example 1 except that the emulsion containing chemically modified steel particles was used.

Using the processing solution of sample A1 (using exemplified compound 1-1 sulfate as a color developing agent and further using EDTA Fe as an organic acid iron complex salt) according to the processing steps of Example 1, The film was processed in the same manner as in Example 1, and the amount of magentastin in the minimum density area and the amount of residual silver in the maximum density area of the processed film were measured.

Table 2 From this table, it can be seen that when the tabular silver halide grains according to the present invention are not used, the occurrence of magentastin is large, but when the treatment of the present invention and the silver halide color photographic light-sensitive materials using tabular grains are used, the occurrence of magentastin is large. Surprisingly, it has been found that both magentastin and desilvering properties are improved when these are used in combination.

Example 3 A film was prepared in the same manner as in Example 1 except that the magenta coupler used in Example 1 was replaced with the magenta coupler exemplified compound (1-4) according to the present invention. Example 2
Performed using the same processing solution used in F! The treatment was carried out according to the treatment steps of AI 1.

After processing, the amount of magenta tin in the minimum density area and the amount of residual silver in the maximum density area of the film sample was measured.

The results are shown in Table 3 below.

Table 3 This shows that when the magenta coupler according to the present invention is used, both the occurrence of magentastin and the amount of residual silver become even better. Similar results were also obtained when exemplified compounds (1-1) and (1-7) were used as magenta couplers.Therefore, in the present invention, by using couplers represented by the general formula [sub. , it can be seen that more favorable effects can be achieved.

Claims (1)

[Claims] After imagewise exposure of a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer containing tabular silver halide grains with a grain size of 5 times or more the grain thickness on a support, at least one water-soluble The process is characterized by processing with a color developing solution containing a p-phenylenediamine color developing agent having an amino group substituted with a functional group, and subsequently processing with a bleach-fix solution containing an ethylenediaminetetraacetic acid iron (III) complex salt. A method for processing silver halide color photographic materials.