JPH03116140A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To form an image without impairing gloss and coating film strength even at the time of processing with a color developing solution in a temperature of >= 40 deg.C by regulating the coating amount of the hydrophilic colloidal layer of a photosensitive material to <= 75 mg/dm<2> and using a hardener for the hydrophilic colloid, capable of reacting with a gelatin and releasing an organic or inorganic acid. CONSTITUTION:At least one of the silver halide emulsion layer and the nonphotosensitive layers are formed on a support, and the total coating amount of the hydrophilic colloidal layers on the emulsion layer side of the support is regulated to <= 75 mg/dm<2> and the emulsion layer and/or the nonphotosensitive layer contains the hardener capable of reacting with a gelatin and releasing an organic or inorganic acid. This photosensitive material is processed with the color developing solution. It is preferred to use a pig skin calcium-treated gelatin for the hydrophilic colloidal layer farthest from the support from the viewpoint of a gloss-improving effect, thus permitting qualitis superior in gloss and strength of the hardened film to be obtained even at the time of using a processing solution as high as >= 40 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide photographic materials, and particularly to a processing method that can shorten processing time.

[Background of the invention]

Normally, in the method of forming dye images using silver halide color photographic light-sensitive materials, a subtractive color reproduction method is applied.
Cyan, magenta, and yellow dye images corresponding to green and blue are formed on the respective photosensitive layers. In recent years, in order to shorten the development process when forming such dye images, high-temperature development and the abbreviation of the processing process have generally been carried out. In particular, increasing the development speed in color development is extremely important for shortening the development processing time by high-temperature development.

The development speed in color development is influenced by two aspects. One is a silver halide color photographic material,
The other one is a color developer.

In the former, in particular, the shape, size and composition of the grains of the photosensitive silver halide emulsion used greatly affect the development speed;
Furthermore, the latter is easily influenced by the conditions of the color developing solution, especially the type of development inhibitor, and it has been found that silver chloride particles in particular exhibit a significantly high development rate under certain conditions.

For this reason, a silver halide color photographic light-sensitive material (hereinafter referred to as a silver chloride color photographic light-sensitive material) has a silver halide emulsion layer containing silver halide grains consisting essentially of silver chloride.

) can be processed much faster than conventional photosensitive materials using silver chlorobromide, resulting in shorter processing times, smaller automatic processors, less developer replenishers, and less pollution. Minilabs and the like, which have been attracting attention in recent years, have great merits, so their practical application is progressing and becoming widespread.

On the other hand, in light-sensitive materials using silver chlorobromide, processing speed is increased exclusively by increasing the temperature of the color developing solution. Although this method does not speed up processing as much as that of silver chloride-based light-sensitive materials, it has the advantage of easily speeding up processing because it does not require changing the processing solution.

However, speeding up processing using this method causes deterioration of the gloss of the surface of the finished photosensitive material and deterioration of film strength, so if conventional photosensitive materials are used as is, the texture will be poor and the film will be easily damaged. The quality will be poor.

Up to now, several techniques have been disclosed for rapid processing using processing liquids at 40° C. or higher. For example, JP-A-1-10605
No. 0 discloses a method for reducing the loss of color balance that occurs with processing liquids at temperatures of 45° C. or higher.

In addition, in 1972, from Eastman Kodak Company,
Processing of Kodachrome 160 at 52°C is disclosed. However, none of the high-temperature rapid processing technologies to date have questioned the quality of the finished film surface, and this is an issue that should be improved, especially when used as a processing method for photosensitive materials for direct viewing (such as color paper). It was left as.

As a result of intensive studies to improve this problem, the present inventors have determined that the coating amount of the hydrophilic colloid layer of the photosensitive material is 75mg/
dm" or less, and by using a hardening agent for the hydrophilic colloid that reacts with gelatin and releases an organic or inorganic acid, even when processed with a color developing solution of 40'O or more, it will not have gloss or shine. It has been found that images can be formed without impairing film strength.

Until now, it has been known that among hardeners that react with gelatin and release organic or inorganic acids, gloss can be improved by using chlorotriazine-based hardeners, but the present inventors According to the study, the effect of high-temperature treatment at 40° C. or higher was small and at an insufficient level. On the other hand, it was found that with the combination of the present invention, the deterioration in gloss caused by high-temperature treatment was extremely small, and furthermore, even with high-temperature treatment, almost no visible increase in fog occurred. This fact was unexpected and surprising based on conventional knowledge.

[Purpose of the invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material, which provides excellent gloss and film hardness even when a high-temperature processing solution is used.

[Structure of the invention]

The above object of the present invention is to have at least one silver halide emulsion layer and a non-photosensitive layer on a support, and a total coating amount of hydrophilic colloid on the emulsion layer coating side of the support is 75 mg/ dm
``A silver halide photographic light-sensitive material that is as follows and contains a hardening agent in the emulsion layer and/or non-light-sensitive layer that reacts with gelatin to release an organic or inorganic acid is processed with a color developing solution at 40°C or higher. This was achieved by

[Specific structure of the invention]

In the silver halide photosensitive material according to the processing method of the present invention, the total amount of hydrophilic colloid coated on the side of the support on which the emulsion layer is coated is 75 mg/do+'' or less.Support Depending on the type of emulsion layer, a hydrophilic colloid may be coated on the uncoated side of the emulsion layer to prevent curling, etc., but these are not related to the present invention.
Not included in the coating amount above. When a transparent support or the like is used and emulsion layers are coated on both sides of the support, the wood-philic colloid must be 75 mg/dm'' or less on each side.

The hydrophilic colloids used in the present invention include natural gelatin such as ossein gelatin, bixkin gelatin, and hydrogelatin; cellulose derivatives such as casein, colloidal albumin, and carboxymethyl cellulose; and synthetic highly hydrophilic colloids such as polyvinyl alcohol and polyacrylamide. Examples include molecules. Alternatively, a gelatin derivative obtained by partially treating natural gelatin with a reactive reagent may be used.

Furthermore, two or more of these hydrophilic colloids may be used in combination.

Particularly, among these, it is preferable to use pigskin lime-treated gelatin in the wood-philic colloid layer furthest from the support because it has a large gloss-improving effect.

Examples of hardeners that react with gelatin and release organic or inorganic acids used in the present invention include JP-A No. 49-51945, JP-A No. 50-38540, JP-A No. 51-126125, JP-A No. 51-59625; No. 52-48311, No. 52-
No. 93470, No. 56-43353, No. 58-113
No. 929, No. 60-237445, Special Publication No. 51-96
No. 09, U.S. Patent No. 2,080.019, U.S. Patent No. 3.186
．． No. 848, No. 3,321.313, No. 3,325,
287, No. 3,362.827, British Patent No. 974.7
No. 23, No. 990.275, No. 1,004,658, No. 1,192.775, No. 1,193,290, etc.

Typical examples of hardeners that react with gelatin and release organic or inorganic acids used in the present invention are shown below, but are not limited to these, of course.

B r CH! C: ON HCHz CH2N H
COCHx B rIn order to grind the hydrophilic colloid layer in the present invention, the following general formula [HDA] or (HDB
) It is preferable to use a chlorotriazine-based hardening agent.

General formula [HDA] In the formula, R1 and R2 are each a chlorine atom, a hydroxyl group, an alkyl group, an alkoxy group, or a -0M group (M represents a monovalent metal atom). -NR3R, group (R3 and R4 are each,
(represents a hydrogen atom, alkyl group, aryl group) or -NH
CORs (Rs represents a hydrogen atom, an alkyl group, or an aryl group). However, R+ and R8 do not become chlorine atoms at the same time.

General Formula (HDB) In the formula, R6 and R2 each represent a chlorine atom, a hydroxyl group, an alkyl group, an alkoxy group, or a -0M group (M represents a monovalent metal atom). Q and Q' are respectively -o-,
It represents a linking group representing -s- or -NH-, and L represents an alkylene group or an arylene group.

p and q each represent 0 or l.

Next, typical specific examples of hardeners represented by the above general formulas (HD A) and ()IDB) will be given. To add it, it may be dissolved in water or a water-miscible solvent (for example, methanol, ethanol, etc.) and added to the coating liquid of the above-mentioned constituent layer. The addition method may be either a batch method or an in-line method. The timing of addition is not particularly limited, but it is preferably added immediately before coating.

These hardeners have a concentration of 0.5 to 100 per gram of gelatin.
mg5, preferably 2.0 to 50 mg.

As the hardening agent for the hydrophilic colloid layer used in the silver halide photosensitive material according to the present invention, in addition to the hardening agent that reacts with gelatin to release an organic or inorganic acid, other hardeners known in the art may be used. agent (for example, German Patent No. 1.100.942, Japanese Patent Publication No. 44-29622, German Patent Publication No. 47.25373, German Patent No. 47
-8736, JP-A No. 49-24435, JP-A No. 51-4
4164 etc.) can be used in combination with other hydrophilic colloid layers, or mixed and used in the same hydrophilic colloid layer. In this case, the amount of the hardening agent that reacts with the gelatin according to the present invention to release an organic or inorganic acid and other hardening agents is optional, but the total weight of the hardening agent of the silver halide photosensitive material is 30
% or more, preferably 40% or more is the hardening agent according to the present invention.

In the color development process, it is usually necessary to incorporate a color developing agent into the color developing solution, but a color developing agent containing a color developing agent or It also includes treatment with an alkaline solution (activator solution).

The color developing agent contained in the color developing solution is an aromatic primary amine color developing agent, and includes amine phenol derivatives and p-phenyl diamine derivatives, with p-7 polynylene diamine derivatives being particularly preferred. . These color developing agents can be used as salts of organic and inorganic acids;
For example, hydrochloride, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate, etc. can be used.

These compounds generally have a color developer IQ of about 0.
A concentration of 1 to 30 g is used, more preferably a concentration of about 1 to 15 g for color developer IQ.

Further, the processing solution temperature of the color developing solution in the present invention is 40°C or higher, more preferably 45°C or higher.

Examples of the above amine phenol developer include 0-aminophenol, p-aminophenol, 5-aminophenol,
These include 2-hydroxytoluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene, and the like.

Particularly useful primary aromatic amine color developers include N, N-
A dialkyl-p-phinidine diamine compound,
Alkyl groups and phenyl groups may be substituted or unsubstituted.

Among them, examples of particularly useful compounds include N,N-diethyl-p-7 22-diamine hydrochloride, N-methyl-p-7
-Funidiamine hydrochloride, N,N-dimethyl-p-
Phenyldiamine hydrochloride, 2-amino-5-(N-ethyl-N~dotecylamino)toluene, N-ethyl-N
-β-methanesulfonamidoethyl-3-methyl-4~
Aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N
, N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

For example, a method of incorporating a color developing agent in the form of a metal salt as described in U.S. Pat. No. 3,719.492, and U.S. Pat. No. 3.34
2.559 and Research Disclosure (Res.
earah Disclosure) 1976, N
15159, a method of incorporating a color developing agent as a dye precursor as shown in JP-A-58-65429 and JP-A-58-24137, and US Pat. , 342.
A method of incorporating the color developing agent as a precursor as shown in No. 597 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 the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention includes alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium carbonate,
It may contain sodium phosphate, potassium hydroxide, ammonium hydroxide, sodium carbonate, sodium metaborate or boric acid, etc., and may further contain various additives such as benzyl alcohol, alkali metal halides, such as potassium bromide or potassium chloride. , or as a development regulator such as citradinic acid, or as a preservative such as hydroxylamine,
It may also contain polyethyleneimine, glucose, sulfite, etc. Furthermore, various antifoaming agents and surfactants, and organic solvents such as methanol, N,N-dimethylformamide, ethylene glycol, diethylene glycol, or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developer is usually 7 or higher, preferably about 9.
~13.

After color development, silver halide color photosensitive materials are usually bleached. The bleaching treatment may be performed simultaneously with the fixing treatment (bleaching and fixing) or separately, but it is preferable to use a bleach-fixing bath that processes bleaching and fixing in one bath.

The pH of the bleach-fix solution used in the present invention is preferably in the range of 4.5 to 6.8.

A metal complex salt of an organic acid is used as a bleaching agent that can be used in the bleach-fix solution. It has the effect of coloring parts, and its composition is that metal ions such as iron, cobalt, copper, etc. are coordinated with aminopolycarboxylic acid or organic acids such as oxalic acid and citric acid. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The following can be mentioned as specific representative examples of these organic acids.

(1) Ethylenediaminetetraacetic acid [2] Nitrilotriacetic acid [3] Iminoniacetic acid [4] Ethylenediaminetetraacetic acid disodium salt [5] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [6] Ethylenediaminetetraacetic acid tetrasodium salt [7] The bleaching agent used in the sodium nitrilotriacetic acid salt contains a metal complex salt of an organic acid as described above as a bleaching agent, and may also contain various additives. As additives, it is particularly desirable to include rehalogenating agents, metal salts, and chelating agents such as alkali halides or ammonium halides, such as potassium bromide, sodium bromide, sodium chloride, and ammonium bromide. In addition, pH buffering agents such as borates, oxalates, acetates, carbonates, and phosphates, alkylamines, polyethylene oxides, and other substances known to be added to ordinary bleaching solutions may be added as appropriate. can.

Furthermore, the fixer and bleach-fixer contain ammonium sulfite,
Sulfites such as potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, potassium metabisulfite, sodium metabisulfite, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, carbonic acid It may contain one or more pH buffers consisting of various salts such as potassium, sodium bisulfite, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide.

When carrying out the process of the present invention while replenishing the bleach-fix solution (bath) with a bleach-fix replenisher, the bleach-fix solution (bath) may contain thiosulfate, thiocyanate, sulfite, etc. These salts may be added to the bleach-fixing replenisher to replenish the processing bath.

In the present invention, in order to increase the activity of the bleach-fix solution, air or oxygen may be blown into the bleach-fix bath and the bleach-fix replenisher storage tank, if desired, or an appropriate oxidizing agent, For example, hydrogen peroxide, bromate, persulfate, etc. may be added as appropriate.

The processing steps of the present invention essentially consist of steps such as color development, bleach-fixing, washing with water, or stabilization treatment in place of it (stabilization instead of washing with water).

〔Example〕

Specific examples of the present invention will be described below, but the aspects of the present invention are not limited thereto.

Example 1 Each layer of the structure shown in Table 1 was coated on a paper support laminated with polyethylene on one side and polyethylene containing titanium oxide on the first layer side of the other side, and a multilayer halogen A silver oxide photographic light-sensitive material was prepared.

Furthermore, samples 101-112 were obtained by changing the type and amount of gelatin applied and the type and amount of hardening agent.

Table 1 (l) Table 1 (2) 5u-2 and 5U-3 were used as coating aids, and H-1 and H-2 were used as hardeners.

Each color-sensitive emulsion was prepared as follows.

[Blue-sensitive silver chlorobromide emulsion 1 Average grain size 0.7 μm 1 A silver chlorobromide emulsion with a silver bromide content of 90 mol% was optimally sensitized at 57°C using sodium thiosulfate. Dye (S-1) and Z-1 as a stabilizer were added.

[Green-sensitive silver chlorobromide emulsion 1 Average grain size 0.5 μm 1 A silver chlorobromide emulsion with a silver bromide content of 70 mol % was optimally sensitized at 59°C using sodium thiosulfate. Z-1 as a sensitive dye (S-2) and stabilizer
was added.

[Red-sensitive silver chlorobromide emulsion] Sodium thiosulfate, sensitizing dye (S-3) and phenol resin were used in a silver chlorobromide emulsion with an average grain size of 0.4 μm and a silver bromide content of 60 mol%. The sample was optimally sensitized at 60° C. and Z-1 was added as a stabilizer.

-t 0 -2 T-1 T-3 T-4 DOP (dioctyl 7 tallate) D N P' (dinonyl 7 tallate) DIDP (diisodecyl 7 tallate) HQ-1 AI-1 I-2 A-1 HQ-2 U -1 -3 U-2 -2 -1 -2 -3 -1 Twelve types of silver halide photosensitive materials shown in Table 2 were evaluated as follows.

■ Glossiness Each sample was left unexposed and processed through the development process A shown below, and then gloss meter (manufactured by Tokyo Denshoku Co., Ltd.) was used to determine glossiness (% ) was measured.

Print image quality is insufficient unless it is 85% or more, preferably 90% or more.

Processing step A Time Temperature Light color development
Table 3 Description Table 3 Bleach fixing 1 minute 30 seconds Washing with water at 33°C 3 minutes
33°C Color developer N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.9g Hydroxylamine sulfate 2.0g Potassium carbonate 25.0g Sodium bromide 0.6g Anhydrous sodium sulfite 2.0g benzyl alcohol
13m (2 diethylenetriaminepentaacetic acid 3.0g triethanolamine
IO, 0g diethylene glycol
Add 1O, 0g water to make the solution 112, and adjust the pH to 1O10 with sodium hydroxide.

Bleach-fix solution Ethylenediaminetetraacetic acid iron (I [I) sodium salt 60g Ammonium thiosulfate 100g Sodium bisulfite log Sodium metabisulfite 3g Add water to make 112, and adjust to pH 7.0 with aqueous ammonia.

■ Film strength After each sample was subjected to standard color development processing, the scratch strength (g) at which scratches occur on the sample surface was measured using a scratch meter (manufactured by HEYDON) with a 0.3 mm needle, and the film strength was determined. .

If it is not 40 g or more, it will be easily scratched, which is a practical problem.

■Fog After processing each sample in the above-mentioned development process A without exposing it to light, use a reflection photographic densitometer (manufactured by Xrite) to measure the lowest density of Y, where capri is most likely to occur, and calculate the fog density. did.

The obtained results are shown in Tables 3-1 to 3-3.

Table-3-1 Glossiness evaluation> Table 3-2 <During film strength evaluation> Table-3-3 Fog density evaluation> From the results in Tables-3-1 to 3, when color development processing was performed at 33°C There is no big difference in gloss, film strength, fog, etc.
As the temperature of the color developing solution was increased to 40°C, 145°C, and 150°C, Samples 103, 104, and 109 outside the present invention
Samples 101, 102, and 105 to 10 of the present invention deteriorated in terms of gloss, film strength, and fog.
8,111°112 shows that the deterioration is small, and the higher the temperature of the color developing solution, the greater the effect.

Furthermore, among the present invention, the one in which pigskin lime-treated Zeftin is used in the seventh layer located farthest from the support,
It can be seen that the gloss and film strength are particularly excellent.

Furthermore, among these, those using chlorotriazine hardeners as hardeners are found to be of extremely excellent quality.

Example 2 A silver halide photosensitive material having the following configuration was produced in the same manner as in Example 1.

Note that Samples 201 to 205 were obtained by changing the total gelatin amount and hardening agent as shown in Table 4.

2-3 BS- VP (Polyvinylpyrrolidone) -3 -4 Table-4 "-]- Images 201 to 205 were subjected to imaging according to the processing step B below, and the gloss and gloss were evaluated in the same manner as in Example-1. Evaluate the film strength.

The results are shown in Tables 5-1 and 5-2 t6 Oniri process Bli degree Time Development color development 35.0:I:0.3℃ 45 seconds bleach fixing 35.0±0.5°0 45 seconds washing
30-34℃ 90 seconds developer water
800mQ reethanolamine
legN, N-diethylhydroxylamine
5g potassium bromide 0.02g
Potassium chloride 2g Potassium sulfite 0.3g 1-Hydroxyethylidene-1-1-diphosphonic acid 1.0g Ethylenediaminetetraacetic acid 1.0g Disodium catechol-3,5-disulfonate 1.0g N-
Ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 aminoaniline sulfate 4.5g optical brightener (4,4'-diaminostilbendisulfonic acid derivative) l, 0g potassium carbonate
Add 27g water to bring the total volume to 1I2, and adjust the pH to 10.10.

Bleach-fix solution Ethylene diamine tetraacetic acid ferric ammonium dihydrate 60 g Ethylene diamine tetra acetate Ammonium thiosulfate (70% aqueous solution) Ammonium sulfite (40% aqueous solution) Add water to bring the total volume to Iff, and adjust pH with potassium carbonate glacial acetic acid.
Adjust to 5,7.

3g 100+nQ 27.5m (2 ram or zero The inside of the loco is the present invention The inside of the loco is the present invention From the results in Tables 5-1 and 2, the purpose is for rapid processing using an emulsion with a high silver chloride content. It has been found that the effects of the present invention can be obtained even with a treatment system in which:

Claims (3)

[Claims] (1) It has at least one silver halide emulsion layer and a non-photosensitive layer on a support, and the total coating amount of hydrophilic colloid on the emulsion layer coating side of the support is 75 mg/dm^2 or less and processing a silver halide photographic light-sensitive material containing a hardening agent in the emulsion layer and/or non-light-sensitive layer that reacts with gelatin to release an organic or inorganic acid with a color developing solution at 40°C or higher. A method for processing a silver halide photographic material, characterized by: (2) The method for processing a silver halide photographic material according to claim 1, wherein the hardening agent which reacts with gelatin to release an organic or inorganic acid is represented by the following general formula [HDA] and/or [HDB]. General formula [HDA] ▲ Numerical formulas, chemical formulas, tables, etc.
(represents a valent metal atom). -NR_3R_4 group (R_3 and R_4 each represent a hydrogen atom, an alkyl group, or an aryl group) or -NHCOR_5 (R_5 represents a hydrogen atom, an alkyl group, or an aryl group). However, R_1 and R_2 do not become chlorine atoms at the same time. 〕General formula〔
HDB] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_6 and R_7 each represent a chlorine atom, hydroxyl group, alkyl group, alkoxy group, or -OM group (M represents a monovalent metal atom) . Q and Q' are each -
It represents a linking group representing O-, -S- or -NH-, and L represents an alkylene group or an arylene group. p and q each represent 0 or 1. ] (3) The method for processing a silver halide photographic material according to claim 1, wherein the layer furthest from the support among the non-light-sensitive layers of the silver halide photographic material contains pigskin lime-treated gelatin.