JPH02168246A - Silver halide photographic sensitive material prevented from causing fluctuation of performance - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material wherein fluctuation of photographic performance for every lot is inhibited by incorporating a tetrazolium compd. into a silver halide emulsion after flocculating and desalting the sivler halide emulsion with an inorganic precipitant. CONSTITUTION:A silver halide emulsion is flocculated and desalted with an inorganic precipitant, and a tetrazolium compd. is incorporated into the emulsion. The amt. of the tetrazolium compd. is about 1 - 10mg preferably about 10mg - 2g per 1 mole silver halide to be contained in a photosensitive material. The tetrazolium compd. may be used as a single compd. or as a mixture of >=2 kinds in an appropriate proportion. The fluctuation of photographic performance between lots is inhibited.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a desalting process.

[Background of the invention]

There are various methods for desalting in the manufacturing process of silver halide photographic materials, but in recent years, the coagulation-precipitation method has become common. The coagulation-sedimentation method has less gelatin and finer precipitated particles than the conventional terdel water-washing method, so the water-washing efficiency is better. It is also easy to manage, and the degree of water washing is stable.

It has the advantage that the emulsion is concentrated after desalting.

Initially, inorganic precipitants such as sodium sulfate and magnesium sulfate were used as precipitants in such desalination, but in recent years, organic precipitants have been mainly used because of their superior water washing efficiency and workability. It became so. Organic precipitants are well known in the art.

On the other hand, in recent years, demands for the stable performance of silver halide photographic materials have become extremely strict, and as a result of studies by the present inventors, we have found that, for example, polymarine condensates of naphthalene sulfonic acid, p-styrene sulfonic acid It has been found that the use of organic precipitants such as low condensates of salts causes performance fluctuations.

It has been found that this variation, particularly in silver halide photographic materials containing a tetrazolium compound, shows that variations in the residual amount of these organic precipitants from loft to loft have a large effect on performance variations.

Incidentally, recent examples of using inorganic precipitants include JP-A-6
No. 2-232645, which is a technology related to tailing failure in slide hopper coating,
This technique is different from the present invention, which is a technique for suppressing fluctuations in performance, particularly in photosensitive materials containing a tetrazolium compound.

[Purpose of the invention]

In order to solve the above-mentioned problem, an object of the present invention is to provide a silver halide photographic light-sensitive material whose performance does not vary due to the coagulation and precipitant used in the desalting step.

[Structure of the invention]

The above object of the present invention is to produce a silver halide emulsion in which coagulation desalting is carried out using an inorganic precipitant, and the silver halide emulsion contains at least one type of tetrazolium compound. This can be achieved using silver oxide photographic materials.

The present invention will be explained in detail below.

As the tetrazolium compound used in the present invention, a compound represented by the following general formula [11] can be used.

The above general formula [! ], preferable examples of the substituent represented by R1 or R1 include an alkyl group (e.g., methyl, ethyl, cyclopropyl, propyl, inglovil, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), an amino group, an acylamide group (e.g., acetyl (amino), hydroxyl group, alkoxy group (e.g. methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.)
, acyloxy groups (e.g. acetyloxy), halogen atoms (e.g. fluorine, chlorine, bromine, etc.), carbamoyl groups, acylthio groups (e.g. acetylthio), alkoxycarbonyl groups (e.g. ethoxycarbonyl), carboxyl groups, acyl groups (e.g. acetyl), Examples include groups such as a cyano group, a nitro group, a mercapto group, a sulfoxy group, and an aminosulfoxy group.

Examples of the anion represented by Xe include halogen ions such as chloride ion, bromide ion, and iodide ion, acid groups of inorganic acids such as nitric acid, sulfuric acid, and perchloric acid, and acid groups of organic acids such as sulfonic acid and carboxylic acid. , anionic activators, specifically lower alkylbenzenesulfonic acid anions such as p-toluenesulfonic acid anions, p-dotecylbenzenesulfonic acid anions, higher alkyl sulfate ester anions such as lauryl sulfate anions, and tetraphenylpolone. boric acid anions such as di-2-ethylhexyl sulfosuccinate anions, polyether alcohol sulfate anions such as cetyl polyethenoxy sulfate anions, higher aliphatic anions such as stearate anions, Examples include polymers such as acrylic acid anions with acid groups attached.

Hereinafter, specific examples of the compound represented by the general formula [T] used in the present invention are listed in Table 1, but the metal compound of the present invention is not limited thereto.

The tetrazolium compound used in the present invention is described in, for example, Chemical Review (Chemical Rev.
iews), Vol. 55, pp. 335-483.

The tetrazolium compound represented by the general formula [I] used in the present invention is about 1 mg or more and about 10 g per mole of silver halide contained in the silver halide photographic material of the present invention.
up to about 1 (1 mg or more) to about 2 g.

The tetrazolium compound represented by the general formula [1F] used in the present invention may be used alone or in combination of two or more in an appropriate ratio. Furthermore, the tetrazolium compound of the present invention and the tetrazolium compound outside the present invention may be used in combination in an appropriate ratio.

In the present invention, particularly favorable results can be obtained when an anion that binds to the tetrazolium compound of the present invention and lowers the hydrophilicity of the tetrazolium compound of the present invention is used in combination. Examples of such anions include acid groups of inorganic acids such as perchloric acid, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, and specifically lower alkylbenzene sulfones such as p-toluenesulfonic acid anions. acid anion,
Dialkyl sulfosuccinate anions such as p-dodecylbenzenesulfonate anions, alkylnaphthalenesulfonate anions, lauryl sulfate anions, tetraphenylpolones, di-2-ethylhexylsulfosuccinate anions, cetyl polyethenoxysal 7ate Examples include polyether alcohol sulfate anions such as anions, stearate anions, and polyacrylate anions.

Such anions may be added to the hydrophilic colloid layer after being premixed with the tetrazolium compound of the present invention, or may be added alone to the silver halide emulsion layer containing or not containing the tetrazolium of the present invention or the water-based Can be added to the colloid layer.

The silver halide composition used in the silver halide photographic material of the present invention is not particularly limited, but silver chloride and silver chlorobromide are preferred, and silver chlorobromide containing 80 to 30% silver chloride is particularly preferred. . The average grain size of silver halide grains is 0.0
5 to 0.7 μm is preferable, particularly preferably 0.05 to 0.7 μm.
It is 0.4 μm. Also, at least 75% of the total number of particles
The size is 0.7 to 1.3 times the average particle size, particularly preferably 80x or more.

As the inorganic precipitant used in the present invention, those known in the art can be used. Specific examples include sodium sulfate, magnesium sulfate, ammonium i-acid, and ammonium nitrate.

The gelatin concentration during coagulation and precipitation was 0.3 to 2.0%, and
The ratio of silver and gelatin in terms of i2 silver is 4:l~15
:1 is preferable. pl( during aggregation is 1.(1~5.0,
pl at the time of water washing is preferably 5.0 to 7.0. p at the time of aggregation
When H is lower than 1°0, when the gelatin concentration is higher than 2%, and when the ratio of silver and gelatin is lower than 4:1, the precipitated particles become too large and the washing efficiency is reduced. In the opposite case, precipitation becomes difficult.

Various additives can be used in the photosensitive material of the present invention depending on the purpose. These additives are, in more detail,
Research Disclosure Volume 176 1tea17
643 (December 1978) Village and Volume 187 Ite
m18716 (November 1979), and the relevant parts are summarized in Table 2 below.

Furthermore, there are no particular limitations regarding the exposure and development processing conditions for the photosensitive material of the present invention, and reference may be made to, for example, the description in the aforementioned Research Disclosure, Vol. 176, pages 28-30.

Table 2 2. Sensitivity enhancers 3, spectral sensitizers, supersensitizers pages 23-24 4. Brighteners page 24 5. Antifoggants and stabilizers pages 24-25 7. Anti-stinting agents 8, dyes Image stabilizer 9, hardener 10, binder 11, plasticizer, lubricant 12, coating aid, surfactant 25 page right column 25 page 26 page 26 page 27 page 26-27 Same as above page 648 right column - 649 Pages right column 649 pages right column 650 pages left to right page 651 pages left column same as above page 650 right column same as above Examples of supports used in the present invention include baryta paper, polyethylene coated paper, polypropylene synthetic paper, glass plate,
Representative examples include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

After exposure, the silver halide photographic material according to the present invention can be developed by various commonly used methods.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Preparation of Emulsion A A silver chlorobromide emulsion was prepared using the following solutions A, B and C.

<Solution A> Ossein gelatin 85g polyisopropylene-polyethylene oxydisuccinate sodium salt 10% ethanol solution 25 Kasumi Q distilled water 6400m2 <Solution B> Silver nitrate 850g distilled water
2050+aff〈Solution C〉 Sodium chloride 2259 Potassium bromide 1379 Polyisopropylene oxydisuccinic acid ester sodium salt 10% ethanol solution 15+I+Q Ossein gelatin-1559 Distilled water 2035 mQ After keeping solution A at 40°C, the EAg value is Sodium chloride was added to make the volume 160 mv.

Next, solutions B and C were added by a double jet method using the mixing agitator described in JP-A-57-92523 and JP-A-57-92524.

The addition flow rate was gradually increased over the total addition time of 80 minutes as shown in Figure 3 below, and addition was carried out while keeping the EAg constant.

EAg value is 3 mol/Q 5 minutes after starting addition from 160 mv.
The EAg value was changed to 120 mv using an aqueous sodium chloride solution, and this value was maintained thereafter until the completion of mixing.

In order to keep the EAg value constant, the EAg value was controlled using a 3 mol/Q aqueous sodium chloride solution.

For the measurement of EAg, a metal electrode and a double junk/thin type saturated Ag/AgCQ reference electrode were used. As for the structure of the electrode, a double juncture disclosed in Japanese Patent Application Laid-Open No. 57-197534 was used. Further, a variable flow rate roller tube metering pump was used to add solutions B and C.

Further, during the addition, sampling of the emulsion confirmed that no new particles were observed in the system using electron microscopy W1. Parents are inspecting and confirming in the mirror.

Also, during the addition, the pH value of the system was kept constant at 3.0.
% nitric acid aqueous solution.

After the addition of solutions B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, divided into five equal parts, and each part was precipitated by adding a 2:1 solution of magnesium sulfate and water.

The pH of all emulsions at this time was 3.0. After draining the supernatant liquid so that 1270cc remains in each case,
2300 cc of distilled water was added, the pH was adjusted to 6.0 using a 10% aqueous potassium hydroxide solution, and water washing was performed with stirring for 10 minutes. Thereafter, the pH was lowered to 4.5 using a 56% acetic acid aqueous solution, and the pH was again reduced to 2 = 2 = magnesium sulfate and water.
1 solution was added to cause precipitation. After repeating water washing and precipitation once again in the same manner, 600 ml of an aqueous solution of ossein gelatin (1 (containing 30 g of ossein gelatin)) was added to each emulsion, and the pH was adjusted to 5 using a 10% aqueous potassium hydroxide solution. After dispersing by stirring for 30 minutes at 55°, the emulsion was adjusted to 750 cc.The resulting emulsion was
1, A-2, A-3, A-4, and A-5.

Preparation of emulsion B After adding liquids B and C in the same manner as emulsion A, the emulsion is
After Ostwald ripening for 0 minutes, the pH was adjusted to 5.8 using a 3% aqueous sodium carbonate solution. Thereafter, the emulsion was divided into five equal parts, and each part was precipitated by adding a 5% aqueous solution of a formalin condensate of sodium naphthalene sulfonate. After draining the supernatant liquid so that the remaining amount was 270 cc, 2300 cc of distilled water was added, and water washing with stirring was performed for 10 minutes. Next, a 1=4 solution of magnesium sulfate and water was added to cause precipitation.

In the same manner, after repeating water washing and precipitation once more, 600 fflQ of an aqueous solution of ossein gelatin was added to each emulsion.
(containing 30 g of ossein gelatin) was added, and the pH was adjusted to 5.8 using a 10% aqueous potassium hydroxide solution.
After dispersion by stirring for 5° and 30 minutes, the volume was adjusted to 750 cc. The obtained emulsions were B-1, B-2, B-3, B
-4, B-5.

Preparation of Emulsion C Samples C-1, C-2, C-3,
Obtained C-4 and C-5.

Next, all emulsions A-1-C-5 were subjected to total sulfur sensitization, and 6-methyl-4-hydroxy-1°3 was added as a stabilizer.
．． 1 g of 3a,7-titrazaindene was added per mole of silver halide, and l-(#-hydroxyethyl)-3-phenyl-5-[(3-#-sulfobropyru-penzoxazolidene) was added as a sensitizing dye. )-ethylidene]thiohydantoin in an amount of 150 m5 per mole of silver halide contained in the emulsion. Then 1- of general formula CI)
Emulsion A-1-A-5 contained 600 mg of the tetrazolium compound represented by 6 per mole of silver halide, and Emulsion B-
Add 750 mg to 1-B-5 to form emulsion C-1-C-5.
I didn't add it to. Furthermore, p-dodecylbenzenesulfone maleic acid copolymer polymer 2K styrene-butyl acrylate-acrylic acid copolymer latex (average grain convention 0.25μ11) 159 was added to all emulsions to give an Agi of 3.59/2.
A coating solution for the emulsion layer was prepared so that the amount of gelatin was 2.0 g/m''.At that time, l-decyl-2-(3-inpentyl)succinate-2- was added as a spreading agent to the aqueous gelatin solution. Sodium sulfonate at 30 mg/m'', 5-nitroindazole at 35+o per mole of silver halide.
g/+” and formalin 2 5 ra as a hardening agent.
g/rx! A coating solution for a protective layer was prepared.

The coating solution for the emulsion layer and protective layer was coated with
Simultaneously coated at 1 iM onto a polyethylene terephthalate film base coated with the subbing described in Example (1) of No. 41.
;. These samples were exposed using an optical wedge.

The above test sample was processed in an automatic developing machine using a phenomenon liquid and a fixing liquid according to the following formulation.

[Developer processing element P]

(Process) Development and fixation Water landing Washing and drying Drying Developer formulation (composition A) Pure water (ion-exchanged water) 150m (2 (hours) 30 seconds Approximately 20 seconds Approximately 20 seconds 15 seconds (Temperature) 28°C 28°C Room temperature 50°C Ethylenediaminetetraacetic acid disodium salt 29 Diethylene glycol 509 Potassium sulfite (55% W/V aqueous solution) 100m (Potassium dicarbonate 50g Hydroquinone 1595-Methylbenzotri, azole 200mgl-Phenyl-5
-Mercaptotetrazole 30111g Potassium hydroxide Adjust the pH of the working solution to 10. Total potassium bromide to 4
4.59 (composition) Pure water (ion exchange water) 3+aQ
Diethylene glycol 509 Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90
% aqueous solution) 0.3mQ5-nitroindazole 1101191-phenyl-3-pyrazolidone 500mg When using a developer, the above compositions A and B were dissolved in 500ml of water and finished to If.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% Vl/V aqueous solution) 2
40f1112 sodium sulfite
179 Sodium acetate trihydrate 6
．． 59 Boric acid 6g Sodium citrate dihydrate 2g Acetic acid (9
0% W/W aqueous solution) 13.6 Peng Q (
Composition) Pure water (ion exchange water) 17fiIQ Sulfuric acid (50% W/W aqueous solution) 4.
7g aluminum sulfate (A12.03 equivalent content 8.1%W/stomach aqueous solution)
26.59 When using the fixer, dissolve it in 500 mQ of water in the order of the above composition A1, and! It was finished into Q and used.

The pH of this fixer was about 4.3.

Photographic characteristic curves were drawn for the developed samples, and the Huntlast was expressed as a gamma value with respect to the exposure amount giving optical densities of 0.2 and 1.5. Moreover, the sensitivity is optical density 2-2.
Sample A-
It is expressed as relative sensitivity when 1 is set as 100. These results are shown in Table 4.

Table 4 Sample A is inventive and Samples B and C are comparative.

As is clear from Table 4, samples A-1 to A-5 of the present invention
The stability of sensitivity is extremely high compared to comparative samples B-1 to B-5. Also, the general formula [1]! -Sample C not containing 6
-1-C-5 has good sensitivity stability, but low contrast and high capri, making it unsuitable for use as a photosensitive material for printing.

〔Effect of the invention〕

According to the present invention, it has been possible to provide a silver halide photographic material in which variation in photographic performance between lofts is suppressed.

Claims (1)

[Claims] A silver halide photographic light-sensitive material characterized in that a silver halide emulsion is coagulated and desalted using an inorganic precipitant in the production of the silver halide emulsion, and the silver halide emulsion contains at least one kind of tetrazolium compound.