JPH04287038A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a high-contrast silver halide photographic sensitive material suppressing a change in performance such as sensitivity and fog with the lapse of time. CONSTITUTION:This silver halide photographic sensitive material having at least one silver halide emulsion layer on one side of the base contains 2.0X10<-4>-5.0X10<->mol/m<2> (expressed in terms of Cl ions) water-soluble inorg. chloride in the backing layer formed on the other side of the base by coating. At the time of packing this sensitive material, relative humidity is regulated to 30-60%.

Description

[Detailed description of the invention]

0001

FIELD OF INDUSTRIAL APPLICATION This invention relates to a silver halide photographic material with improved storage stability over time.

0002

BACKGROUND OF THE INVENTION Photosensitive materials for printing plate making need to have high contrast in order to obtain good halftone dot quality. For this reason, the so-called Lith development method has been used in the past, but due to its poor retention, recently it has been possible to develop so-called PQ or MQ types, which contain a relatively high concentration of sulfites, by using a contrast enhancer. Photosensitive materials that can be used with developing solutions have been developed. As such a contrast enhancing agent, for example, a tetrazolium compound disclosed in Japanese Patent Publication No. 59-17825 is known, but the use of such a contrast enhancing agent causes problems such as an increase in fog over time. However, when a fog suppressant is used to prevent such fog, the sensitivity decreases and there is a problem with stability over time.

0003

OBJECTS OF THE INVENTION In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material which has ultra-high contrast and also has stable sensitivity and fog over time.

0004

[Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material having at least one silver halide emulsion layer on a support, in which a water-soluble Chlorine ion amount of inorganic chloride 2.0×
This is achieved by a silver halide photographic material containing 10-4 to 5.0 x 10-3 mol/m2 and having a relative humidity of 30 to 60 RH% during packaging.

The present invention will be explained in detail below.

Examples of the inorganic chloride to be contained in the backing layer of the present invention include zinc chloride, aluminum chloride, yttrium chloride, cadmium chloride, potassium chloride, calcium chloride, cobalt chloride, strontium chloride, cesium chloride, iron chloride, and sodium chloride. , nickel chloride, barium chloride, magnesium chloride, manganese chloride, lithium chloride, rubidium chloride, and the like. Among these, it is preferable to use sodium chloride and potassium chloride.

[0007] The amount of chlorine ions added is 2.0×
10-4 to 5 x 10-3 mol/m2, preferably 3.
It is 4 x 10-4 to 2.6 x 10-3 mol/m2. Furthermore, the relative humidity of the photosensitive material of the present invention at the time of packaging is 30 to 60%.
, preferably 40-55%.

Next, as the tetrazolium compound used in the photosensitive material of the present invention, a compound represented by the following general formula [T] is preferable.

[0009]

[Chemical formula 1]

[In the formula, R1, R2 and R3 each represent a hydrogen atom or a substituent, and X- represents an anion. ]
First, in the above general formula [T], preferable examples of the substituents represented by R1 to R3 include alkyl groups (for example, methyl, ethyl, cyclopropyl, propyl, isopropyl,
cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), amino group, acylamino group (e.g. acetylamino), hydroxyl group, alkoxy group (e.g. methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.), acyloxy group (e.g. acetyloxy), Halogen atoms (e.g. fluorine, chlorine, bromine, etc.),
Carbamoyl group, acylthio group (e.g. acetylthio)
, alkoxycarbonyl groups (e.g. ethoxycarbonyl), carboxyl groups, acyl groups (e.g. acetyl),
Cyano group, nitro group, mercapto group, sulfooxy group,
Examples include groups such as aminosulfoxy groups.

[0011] Examples of the anion represented by Acid radicals of organic acids, anionic activators, specifically lower alkylbenzenesulfonate anions such as p-toluenesulfonate anions, p
-Higher alkylbenzenesulfonate anions such as dodecylbenzenesulfonate anions, higher alkylsulfate ester anions such as lauryl sulfate anions, borate anions such as tetraphenylboron, dialkyl sulfosuccinates such as di-2-ethylhexylsulfosuccinate anions Anions, polyether alcohol sulfate ester anions such as cetyl polyethenoxysulfate anions, higher aliphatic anions such as stearate anions, and polymers with acid groups such as polyacrylate anions can be mentioned.

Specific examples of the compounds represented by the general formula [T] used in the present invention are listed in Table T below, but the compounds of the present invention are not limited thereto.

[0013]

[Table 1]

[0014] The tetrazolium compound used in the present invention is described, for example, in Chemical Review (Chemical Review).
It can be easily synthesized according to the method described in Vol. 55, pp. 335-483.

The tetrazolium compound represented by the general formula [T] of the present invention is contained in an amount of about 1 mg or more per mole of silver halide contained in the silver halide photographic light-sensitive material of the present invention.
It is preferred to use up to about 2 g, preferably from about 10 mg to about 2 g.

The tetrazolium compound represented by the general formula [T] used in the present invention may be used alone or in combination of two or more in an appropriate ratio.

The silver halide used in the silver halide photographic material of the present invention is not particularly limited, but silver chloride or silver chlorobromide is preferred. The composition of silver chlorobromide is AgC
l/AgBr=100/0 to 2/98, preferably AgCl/AgBr=90/10 to 40
The molar ratio is /60. The average grain size of the silver halide grains is preferably 0.10 μm to 0.50 μm, and the coefficient of variation expressed by (standard deviation of grain size)/(average grain size) x 100 is 1.
It is more preferable to have a narrow particle size distribution of 5% or less. For the silver halide used in the present invention, various sensitizers, sensitizing dyes, stabilizers, etc. can be used. The silver halide and tetrazolium compounds according to the invention are incorporated into the hydrophilic colloid layer, and the hydrophilic colloid used particularly advantageously in the invention is gelatin. Hydrophilic colloids other than gelatin can also be used. These hydrophilic colloids can also be applied to layers that do not contain silver halide, such as antihalation layers, protective layers, intermediate layers, etc. As the support used in the present invention, various supports used in the photosensitive material industry, such as polyester films, can be used. The photographic material of the present invention is preferably coated with a protective layer of gelatin having an appropriate thickness, preferably 0.1 to 10 .mu.m, particularly preferably 0.8 to 2 .mu.m. The hydrophilic colloid layer used in the present invention may optionally contain various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, antistain agents, and pH adjusters. , antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, etc. may be used within the range that does not impair the effects of the present invention. can. In particular, in the present invention, the amount of chlorine ions of water-soluble inorganic chloride in the backing layer is 2.0 x 10-4 to 5 x 10-3 mol/
m2, preferably 3.4 x 10-4 to 2.6 x 10-3
As the water-soluble inorganic chloride which is preferably added in a proportion of mol/m2, NaCl and KCl are particularly preferred.

As the developing agent used for developing the silver halide photographic light-sensitive material of the present invention, T. H. The Theory of the Photographic Process, 4th Edition by James
photographic Process, Fourt
h Edition) pages 291-334 and Journal of the American Chemical Society (Jo
urnal of THe American Chem
ical Society) Volume 73, Page 3,100 (1
951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the present invention, the effects of the present invention will not be impaired and This can be mentioned as one of the characteristics. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, adjusting the pH with caustic alkali, alkali carbonate, or amines used in general black and white developers and providing a buffer function, inorganic development inhibitors such as potassium bromide, organic development inhibitors such as benzotriazole, and ethylenediamine. Metal ion scavengers such as tetraacetic acid, methanol,
Development accelerators such as ethanol, benzyl alcohol and polyalkylene oxide, surfactants such as sodium alkylarylsulfonate, natural saponins, sugars or alkyl esters of the above compounds, hardeners such as glutaraldehyde, formalin and glyoxal, It is optional to add an ionic strength adjusting agent such as sodium sulfate. The developing solution of the present invention includes Japanese Patent Application Laid-Open No. 56-106244
Amino compounds such as alkanolamines described in No. 1 can be used.

[0019] In addition, L. F. A. Meson, “Photographic Processing Chemistry”, Focal
Those described in Press Publishing (1966), pages 226-229, U.S. Patent No. 2,193,015, U.S. Pat.

Various other processing techniques known in the photographic industry may be used.

Furthermore, in the present invention, when packaging the photosensitive material, the relative humidity is kept at 30-60%, preferably 40-55%.
It is important to set it as a percentage.

[0022]

EXAMPLES The present invention will be explained in more detail with reference to specific examples below.

Example 1 [Preparation method of emulsion (A)] A silver chlorobromide emulsion was prepared using the following solutions A, B and C. <Solution A> Ossein gelatin

17g Polyisopropylene-polyethylene oxydisuccinate sodium 10% ethanol aqueous solution
5ml
Distilled water

1280ml <Solution B> Silver nitrate

170g distilled water

410ml<
Solution C> Sodium chloride

45.0g potassium bromide

27.4g Rhodium trichloride trihydrate
28 μg Polyisopropylene oxydisuccinate sodium salt 10% ethanol solution

3ml ossein gelatin

11g distilled water

407ml
After solution A was kept at 40° C., sodium chloride was added so that the EAg value became 160 mV. Next, JP-A-57-9
Solution B and solution C were added by a double jet method using the mixer described in No. 2523 and No. 57-92524.

As shown in Table 1, the addition flow rate was gradually increased over the total addition time of 80 minutes.
The addition was carried out while keeping the value constant. EAg value is 160
5 minutes after the start of the addition, the EAg value was changed to 120 mV using a 3 ml/l aqueous sodium chloride solution, and this value was maintained thereafter until the completion of mixing. To keep the EAg value constant, EAg was
The value was controlled.

[0025]

[Table 2]

To measure the EAg value, a metal silver electrode and a double junction type saturated Ag/AgCl reference electrode were used (the electrode configuration was a double junction disclosed in JP-A-57-197534). ). or,
A variable flow rate roller tube metering pump was used to add solutions B and C. Furthermore, during the addition, the emulsion was sampled and observed using an electron microscope to confirm that no new particles were generated within the system. During the addition, the pH value of the system was controlled to be kept constant at 3.0 using a 3% aqueous nitric acid solution. After adding liquids B and C, the emulsion becomes 10
After Ostwald ripening for a minute, desalting and washing with water were carried out by a conventional method, and then 600 ml of an aqueous solution of ossein gelatin (containing 30 g of ossein gelatin) was added and dispersed by stirring at 55° C. for 30 minutes, and the volume was adjusted to 750 ml. After gold-sulfur sensitization was performed on emulsion (A), 500 mg of potassium bromide was added per mole of silver halide, and then 3 sensitizing dye A was added per mole of silver halide contained in the emulsion.
After stagnation for 10 minutes, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added as a stabilizer, and 100 mg of sensitizing dye B was added per mole of silver halide contained in the emulsion. did.

[0027]

[Case 2]

Next, per mole of silver halide, general formula [T
] Add 700 mg of tetrazolium compound T-11,
Furthermore, 300 mg of sodium p-dodecylbenzenesulfonate
, 2 g of styrene-maleic acid copolymer and 15 g of styrene-butyl acrylate-acrylic acid copolymer latex (average particle size approximately 0.25 μm) were added, Ag
It was coated onto a polyethylene terephthalate film base which had been subbed as described in Example (1) of JP-A-59-19941 so that the amount of gelatin was 4.0 g/m2 and the amount of gelatin was 2.00/m2.

At that time, a protective layer containing 10 mg/m2 of bis-(2-ethylhexyl)sulfosuccinate as a spreading agent and formalin as a hardening agent was simultaneously coated so that the amount of gelatin was 1.0 g/m2. .

[0030]

[Chemical formula 3]

Gelatin
2.
4g/m2 Surfactant: saponin
0.1g
/m2 :S-1

6mg/m2 colloidal silica

100mg/m2 prescription (4) [Backing protective layer composition] Gelatin

1g/m2 Matting agent: Monodispersed polymethyl methacrylate with an average particle size of 5.0μm

50mg/m2 Surfactant: S-2
10mg/m2
Hardener: Glyoxal
25mg/m2
:H-1
35mg/
m2 Water-soluble inorganic chloride
Amounts shown in Table 2

003
2]

[C4]

The exposed sample was processed in an automatic processor using a developing solution and a fixing solution according to the following formulation.

<Development processing conditions> (Process) (Temperature) (Time) Development 28°C
Fix for 30 seconds at 28℃
Wash with water for about 20 seconds at room temperature
Dry for about 20 seconds at 50℃
15 seconds <Developer prescription> (Composition A) Pure water (ion exchange water)
150ml
Ethylenediaminetetraacetic acid disodium salt
2g diethylene glycol

50g potassium sulfite (55% w/v aqueous solution)
100ml
potassium carbonate
50g
hydroquinone
15g 5-
Methylbenzotriazole
200mg 1-phenyl-5-
Mercaptotetrazole 3
0mg Potassium hydroxide Adjust the pH of the working solution to 10.
Amount to make 4 Potassium bromide

4.5g (composition B) Pure water (ion exchange water)
3ml
diethylene glycol
50g Ethylenediaminetetraacetic acid disodium salt
25mg acetic acid (90% aqueous solution)
0.
3ml 5-nitroindazole
110mg
1-phenyl-3-pyrazolidone
700mg Butylamine diethanolamine
15g When using a developer, add the above composition A to 500ml of water.
The compositions were dissolved in the order of composition B and made up to 1 liter for use. <Fixer formulation> (Composition A) Ammonium thiosulfate (72.5% w/v aqueous solution)


240ml sodium sulfite
1
7g Sodium acetate trihydrate
6.5g
boric acid
6g
Sodium citrate dihydrate
2g acetic acid (9
0% w/w aqueous solution)
13.6ml (composition B) Pure water (ion exchange water)
17ml
Sulfuric acid (50% w/w aqueous solution)
4.7g aluminum sulfate
(Aqueous solution with Al2O3 equivalent content of 8.1% w/w)
26.5 g When using a fixer, the above composition A and composition B were dissolved in 500 ml of water in that order, and the final volume was made up to 1 liter. The pH of this fixer was about 4.3. The film thus prepared was subjected to a aging test for surrogate evaluation and then exposed to wedge light using a tungsten light source. Evaluation of stability over time was carried out by the following method. In other words, divide one half into two parts and heat it at 23℃ for 4 minutes.
After controlling the humidity at 8RH%, polyvinyl acetate (thickness 100μm)
sealed with moisture-proof material laminated with
Heat treatment was performed for 72 hours in a thermostat at 0RH%.

The relative sensitivity of the sample obtained by processing is
．． It is expressed as an exposure amount logE value that gives a value of 0, and is a relative value with a sample left untreated as 100. For fogging, the density of the unexposed film was measured. In addition, adhesion was also evaluated, with ◯ indicating good and × indicating a problem in practical use.

The results are shown in Table 2.

[0037]

[Table 3]

From the results in Table 2, it can be seen that the samples of the present invention have high sensitivity, have little change in sensitivity over time, and have improved fog increase.

[0039]

[Effect of the invention] The present invention provides high contrast,
Moreover, it was possible to provide a silver halide photographic material with improved performance fluctuations such as sensitivity and fog over time.

Claims (1)

[Claims] Claim 1: In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a backing layer coated on the side opposite to the emulsion layer contains chloride ions of a water-soluble inorganic chloride. Amount 2.0×10-4~5.0×
10-3 mol/m2, and the relative humidity at the time of packaging is 3.
A silver halide photographic material characterized by having a RH% of 0 to 60%.