JP2678819B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a light-sensitive material using a surface latent image type silver halide photographic emulsion. The present invention relates to a silver halide photographic light-sensitive material which is less sensitive and less desensitized when subjected to pressure.

(Prior Art) In the field market, a light-sensitive material using a silver halide photographic emulsion is used for various purposes, and the market size has been increasing more and more in recent years.

Under these circumstances, especially in photosensitive materials used in markets that require a large amount of prints with a short delivery time, such as photosensitive materials for color printing, rapid development processing time directly improves print production efficiency. Many studies have been made to increase the development speed.

Among them, it is well known that increasing the silver chloride content of a silver halide emulsion used for a light-sensitive material can dramatically improve the development speed.

However, when an emulsion having a high silver chloride content is used, it is difficult to obtain high sensitivity due to high fog, so-called reciprocity law failure in which the sensitivity changes due to changes in exposure illuminance, and further due to temperature changes during exposure. It has been known that there are drawbacks such as a large change in sensitivity.

Various techniques have been disclosed in order to overcome such drawbacks of a silver halide emulsion having a high silver chloride content (hereinafter referred to as a high silver chloride emulsion).

For example, by adding a metal compound of Group VIII to JP-A-51-139323, JP-A-59-171947, or British Patent No. 2109576, high sensitivity is obtained and reciprocity law failure is improved. There is a statement. In addition, Japanese Patent Publication Sho 49
-33781, JP-A-50-23618, JP-A-52-18310, JP-A-58
-15952, 59-214028, 61-67845, German Patents 2226877, 2708466 or U.S. Patent 370358.
The specification No. 4 describes that inclusion of a rhodium compound or an iridium compound achieves a high contrast and an improvement in reciprocity law failure. However, when a rhodium compound is used, a hard emulsion is obtained, but remarkable desensitization occurs, which is not practically preferable. In addition, when an iridium compound is used, a so-called latent image sensitization, in which the development density increases with the passage of time from exposure of the photosensitive material to processing, is often observed, and this is also not practically preferable.

U.S. Pat. No. 4,269,927 discloses that high sensitivity can be obtained by incorporating cadmium, lead, copper, zinc or a mixture thereof into the surface latent image type high silver chloride emulsion grains having a silver chloride content of 80 mol% or more. There is a statement that it will be. However, although these methods have some effect on the increase of sensitivity and the improvement of reciprocity law failure, the sensitivity variation due to the temperature change during exposure is not sufficiently improved, which is not preferable in practice.

Further, as a means for solving the problem of desensitization when a high silver chloride emulsion is used, see, for example, JP-A-58-95736,
Nos. 8-108533, 60-222844 and 60-222845 have various silver halide grains having a high silver bromide content in order to impart high sensitivity to a high silver chloride emulsion. It is disclosed that it is effective to have a different grain structure. However, as a result of examination by the present inventors, according to these techniques, high sensitivity is certainly obtained, but at the same time, desensitization easily occurs when pressure is applied to the emulsion grains, which is a major defect in practical use. It was found that

Further, Japanese Patent Publication No. 48-35373 describes that a black-and-white photographic printing paper having a high contrast can be obtained at a low price by adding a water-soluble iron compound to a silver chloride emulsion obtained by a normal mixing method. But,
In this method, when the amount of the iron compound added is increased in order to obtain high sensitivity, desensitization of the emulsion is apt to occur when pressure is applied, and it is difficult to obtain a sufficient effect.

Further, in JP-A-1-183647, high sensitivity can be obtained by having a silver bromide localized phase inside or on the surface of high silver chloride emulsion grains containing iron ions, and further, it is possible to prevent temperature change during exposure. There is a statement that sensitivity fluctuations can be reduced. However, the introduction of the silver bromide polar phase causes a problem that desensitization is likely to occur when pressure is applied to the emulsion grains.

As described above, by attempting to eliminate the problems of low sensitivity and increase of fog, which are problems when a high silver chloride emulsion is used by introducing these techniques, desensitization easily occurs when pressure is applied to emulsion grains. It turned out that it was not practically preferable.

(Problems to be Solved by the Invention) Therefore, a first object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in rapid processability, has high sensitivity, high contrast and little fog.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which is less susceptible to desensitization when pressure is applied to emulsion grains.

(Means for Achieving the Object) The above objects of the present invention have been achieved by the following silver halide silver photographic light-sensitive materials.

(1) A silver halide photographic light-sensitive material having at least one photosensitive emulsion layer containing a surface latent image type silver halide emulsion on a support, wherein the emulsion layer contains substantially no silver iodide. Characterized in that it contains silver chlorobromide or silver chloride grains of which mol% or more is silver chloride, and the grains are formed in the presence of gelatin having both adenine and guanine contents of 0.5 ppm or less. A silver halide photographic light-sensitive material.

(2) Item (1), wherein the silver chlorobromide or silver chloride grains contain iron ions in an amount of 10 ^-7 to 10 ^-3 mol per mol of silver halide. The silver halide photographic light-sensitive material described in.

(3) 90% or more of the amount of iron ions contained in the silver chlorobromide or silver chloride grains is contained in the surface layer of 50% or less of the volume of the grains. The silver halide photographic light-sensitive material according to the item (2).

(4) No. (1), (2) or (3) characterized in that a silver bromide localized phase having a silver bromide content of less than 70 mol% is contained inside or on the surface of silver halide grains. A silver halide photographic light-sensitive material as described in the above item.

 Hereinafter, the present invention will be described in detail.

The adenine and guanine contents of gelatin used for forming the silver halide grains of the present invention are both 0.5 ppm or less, more preferably 0.2 ppm or less, and further preferably 0.1 ppm or less. The most preferable embodiment is that they are not contained at all.

The adenine and guanine contents in gelatin can be quantified as follows, for example.

30 g of 2N sulfuric acid was added to 10.0 g of gelatin powder, and the mixture was decomposed by heating in a boiling bath.

Add 2 cc of 2% calcium chloride aqueous solution and 2.5 cc of 20% silver nitrate aqueous solution.

After being left refrigerated overnight, the precipitate and the supernatant are sufficiently separated by a centrifugation method.

After adding 5 ml of 1N hydrochloric acid to the precipitate, it is heated and extracted in a boiling bath for 5 minutes.

After centrifugation, transfer the supernatant to a 25cc volumetric flask.

After repeating the operation several times, the hydrochloric acid extract in the measuring flask is adjusted to 25 cc with 2 mol / l sodium acetate aqueous solution.

Using standard liquids of adenine and guanine of known concentrations, the adenine and guanine contents are determined by a commercially available liquid chromatography device.

As the gelatin of the present invention, any gelatin may be used as long as the adenine and guanine contents satisfy the above-mentioned conditions, and so-called alkali-processed gelatin, acid-processed gelatin, gelatin derivatives, modified gelatin, etc. are commonly used in the art. Any of the above can be used.

Further, the step of purifying gelatin so that the adenine and guanine contents satisfy the above conditions may be at any stage before it is subjected to grain formation. Therefore, for example, the adenine and guanine contents may satisfy the above conditions at the time of obtaining the gelatin powder for silver halide grain formation, and the adenine and guanine contents may satisfy the above conditions after obtaining the gelatin powder. You may perform a certain fixed process.

The gelatin of the present invention can be reduced in content of adenine and guanine by, for example, preliminarily purifying by the following means, and can be preferably used in achieving the object of the present invention.

The aqueous gelatin solution is treated with activated carbon.

Wash the gelatin gel with cold water (15 ° C or less).

Adenine and guanine are separated by gel perchromatogram.

The gelatin aqueous solution is passed through an ion exchange resin.

The original adenine and guanine content was 0.5 ppm due to the above purification means alone, repeatedly, or in combination.
It is possible to satisfy the conditions of the present invention with a larger amount of gelatin.

The gelatin of the present invention is used in the grain forming step of a silver halide emulsion as described above, but may be used in any other step such as a redispersion step after precipitation desalting, a post-ripening step, and a finished emulsion to be used for emulsion coating. It can also be used in the preparation process and the like. Further, when the silver halide photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material comprising two or more light-sensitive layers or a non-light-sensitive layer, at least one of them has a salt odor having a silver chloride content of 90 mol% or more. It may be a silver halide or silver chloride emulsion layer, and when the emulsion layer having a high silver chloride content is two or more layers, at least one of them contains adenine or guanine of gelatin used for grain formation of the silver halide emulsion. Both should be 0.5 ppm or less. Further, the gelatin of the present invention can be used in any photosensitive layer or non-photosensitive layer other than the emulsion layer of the present invention.

The silver halide emulsion of the present invention is silver chlorobromide or silver chloride containing substantially 90 mol% or more of silver chloride containing substantially no silver iodide. Substantially free of silver iodide means not more than 0.5 mol%, preferably not more than 0.1 mol%, more preferably not containing it at all. The silver chloride content is 90
It is necessary to be at least mol%, preferably at least 95 mol%, particularly preferably at least 98 mol%. Emulsions made of pure silver chloride other than those containing iron ions as impurities are also preferred.

In the case where the silver halide emulsion of the present invention contains silver bromide, it is also preferable that the silver halide emulsion is provided inside or on the surface of the grain in the form of a silver bromide localized phase having a silver bromide content of less than 70 mol%. .

The lower limit of the silver bromide content of the silver bromide localized phase is 10 mol%.
The above is preferable, and more preferably 20 mol% or more.
Silver chloride is preferred as the silver halide other than silver bromide in the silver bromide localized phase. For measuring the halogen composition of silver halide in the silver bromide localized phase, for example, European Patent (EP) 0,
No. 273,430.

In the present invention, it is preferred that the silver halide emulsion grains contain iron ions. In order to contain iron ions, it is easy to allow a water-soluble iron compound to coexist in the step of forming emulsion grains. These iron compounds are 2
It is a trivalent or trivalent iron ion-containing compound and preferably has water solubility. Particularly preferred are iron complex salts which can be easily incorporated into silver halide grains. Specific examples of these compounds are shown below, but are not limited thereto.

Ferrous arsenate, ferrous bromide, ferrous carbonate, ferrous chloride,
Ferrous citrate, ferrous fluoride, ferrous formate, ferrous gluconate, ferrous hydroxide, ferrous iodide, ferrous lactate, ferrous oxalate, ferrous phosphate Iron, ferrous succinate, ferrous sulfate, ferrous thiocyanate, ferrous nitrate, ferrous ammonium nitrate, basic ferric acetate, ferric albumin, ferric ammonium acetate, bromide Ferric iron, ferric chloride, ferric chromate, ferric citrate, ferric fluoride, ferric formate, glucero-ferric phosphate, ferric hydroxide, ferric acid phosphate Ferric nitrate, ferric nitrate, ferric phosphate, ferric pyrophosphate, sodium ferric pyrophosphate, ferric thiocyanate, ferric sulfate, ferric ammonium sulfate, ferric guanidinium sulfate, Ammonium ferric citrate, potassium hexacyanoferrate (II), potassium pentacyanoammineiron (II), ethylene Ndinitriloiron tetraacetate (III)
Sodium, potassium hexacyanoferrate (III), tris (bipyridyl) iron (III) chloride, potassium pentacyanonitrosylferrate (III) Among these compounds, hexacyanoferrate (II) is particularly preferable.
Acid salt, hexacyanoferrate (III), ferrous thiocyanate or ferric thiocyanate are preferably used.

The above iron compound can be present in the dispersion medium (gelatin or a polymer having a protective colloid property) solution, an aqueous halide solution, an aqueous silver salt solution or any other aqueous solution during the formation of silver halide grains. To be included in. These iron compounds are preferably used in an amount of 10 ⁻⁷ to 10 ⁻³ mol per mol of silver halide, more preferably 10 ^{−6 to} 5 × 10 ⁻⁴ mol.

When the iron compound is contained in the silver halide grains in the present invention, it is preferable that 90% or more of the amount of iron ions contained in the grains is contained in the surface layer of 50% or less of the grain volume. The surface layer of 50% or less of the particle volume means a surface portion corresponding to a volume of 50% or less of the volume of one particle, that is, a so-called shell portion. In this case, 50 of the particle volume
The presence form of iron ions in the surface layer of not more than% is not limited. That is, it may exist uniformly in the surface layer, or may exist locally inside or on the surface of the surface layer to form a so-called sea-island structure. The volume of this surface layer is preferably 40
% Or less, and more preferably 20% or less. To concentrate iron ions in these surface layers,
For example, it can be carried out by forming the silver halide grain core of the portion excluding the surface layer and then supplying the iron compound in time with the supply of the water-soluble silver salt solution and the aqueous halide solution for forming the surface layer. .

In the present invention, a polyvalent metal compound other than iron ions can also be included in the silver halide grains. These include, for example, cobalt, nickel, ruthenium,
Examples thereof include Group VIII metal ions such as rhodium, palladium, osmium, iridium and platinum, or chain ions thereof. In addition to these, metal ions such as copper, gold, zinc, cadmium or lead, or complex ions thereof may be contained in combination.

The photosensitive material according to the present invention has a hydrophilic colloid layer for the purpose of improving the sharpness and the like of an image.
No. 337,490A2, pp. 27-76, a dye capable of being decolorized by treatment (among others, an oxonol dye) is used as the photosensitive material.
Titanium oxide is added so that the optical reflection density at 0 nm is 0.70 or more, or titanium oxide surface-treated with a dihydric or tetrahydric alcohol (such as trimethylolethane) is added to the water resistant resin layer of the support. Weight% or more (more preferably 14% by weight
Above).

Further, in the light-sensitive material according to the present invention, it is preferable to use a color image preservability improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, combination use with a pyrazoloazole coupler is preferred.

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color developing process and / or the aromatic compound remaining after the color developing process. The compound (G) which forms a chemically inert and substantially colorless compound by chemically bonding with an oxidized form of an aromatic amine color developing agent can be used simultaneously or alone, for example, in storage after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent or its oxidized product and the coupler remaining in the film.

Further, the light-sensitive material according to the present invention is added with a fungicide such as those described in JP-A-63-271247 in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Preferably.

The support used in the light-sensitive material according to the present invention may be a white polyester support for display or a support provided with a layer containing a white pigment on the support having a silver halide emulsion layer. You may use. In order to further improve the sharpness, an antihalation layer is preferably provided on the support on the side where the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light.

The photosensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure. In the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ^-4 seconds is preferred.

In the exposure, it is preferable to use a band stop filter described in U.S. Pat. No. 4,880,726.
As a result, light color mixing is removed, and color reproducibility is significantly improved.

The exposed light-sensitive material can be subjected to conventional black-and-white or color development processing. In the case of a color light-sensitive material, bleach-fix processing is preferably performed after color development for the purpose of rapid processing. Particularly when the high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less, for the purpose of accelerating desilvering.

Silver halide emulsions and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied to the light-sensitive material according to the present invention, and processing methods and processing applied to process this light-sensitive material As the additives, those described in the following patent publications, in particular, EP 0,355,660A2 (Japanese Patent Application No. 1-107011) are preferably used.

Further, as cyan couplers, besides diphenylimidazole cyan couplers described in JP-A-2-33144, 3-hydroxypyridine cyan couplers described in European Patent EP 0,333,185A2 (among them, specific examples thereof) 4-equivalent coupler (42) having a chlorine leaving group to give 2-equivalent coupler, couplers (6) and (9)
Are particularly preferred) and the use of cyclic active methylene cyan couplers described in JP-A-64-32260 (in particular, coupler examples 3, 8, and 34 listed as specific examples) are also preferred.

EXAMPLES Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited thereto.

Example 1 Four types of gelatin powders having transmittances shown in Table 1 were prepared (gelatin # 1 to # 4). Gelatin # 1-3
% Aqueous solution of sodium chloride 6.4g added to, N, N ^{- -} dimethyl-2-thione (1% aqueous solution) was added 3.2 ml. An aqueous solution containing 0.2 mol of silver nitrate in this solution,
An aqueous solution containing 0.08 mol of potassium bromide and 0.12 mol of sodium chloride was added and mixed at 52 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.8 mol of silver nitrate and an aqueous solution containing 0.32 mol of potassium bromide and 0.48 mol of sodium chloride were added and mixed at 52 ° C. with vigorous stirring. 52 ° C
After maintaining for 5 minutes, the product was desalted and washed with water. Further, gelatin # 1 (90.0 g) was added, and triethylthiourea was added to perform optimum chemical sensitization. The obtained silver chlorobromide (silver bromide 40 mol%) emulsion was designated as emulsion # 1A-1.

Next, sodium chloride was added to a 3% aqueous solution of gelatin # 1.
3g was added, N, N ^{- -} dimethyl-2-thione (1% aqueous solution) was added 3.2 ml. In this solution, an aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.004 mol of potassium bromide and 0.196 mol of sodium chloride were added and mixed at 52 ° C. with vigorous stirring. Then, add silver nitrate to 0.8
A molar aqueous solution and an aqueous solution containing 0.016 mol of potassium bromide and 0.784 mol of sodium chloride were added and mixed at 52 ° C. with vigorous stirring. After keeping at 52 ° C. for 5 minutes, desalting and washing were performed. Further, gelatin # 1 (90.0 g) was added, and triethylthiourea was added to perform optimum chemical sensitization. The resulting silver chlorobromide emulsion was designated as emulsion # 1B-1.

Emulsion # 1B-1 differs from Emulsion # 1B-1 only in that 0.84 mg and 3.36 mg of potassium hexacyanoferrate (II) trihydrate were added to the sodium chloride aqueous solution to be added at the first time and the second time, respectively. Emulsion # 1B-2.

Next, an emulsion was prepared which was different from emulsion # 1B-1 except that 4.2 mg of potassium hexacyanoferrate (II) trihydrate was added to the aqueous sodium chloride solution to be added for the second time. It was set to 3.

Next, in Emulsion # 1B-1, the silver nitrate aqueous solution and the sodium chloride aqueous solution to be added for the second time are divided into 3: 5, and silver nitrate / sodium chloride is added three times in total, and the third time is added. An emulsion was prepared by adding 4.2 mg of potassium hexacyanoferrate (II) trihydrate to an aqueous solution of sodium chloride, and this was designated as emulsion # 1B-4.

Next, in the emulsion # 1B-4, the ratio of the aqueous silver nitrate solution and the aqueous sodium chloride solution to be added the second and third times was 1: 1.
To prepare Emulsion # 1B-5.

Then, in emulsion # 1B-4, the ratio of the clear silver nitrate aqueous solution and the sodium chloride aqueous solution to be added the second and third times is 3: 1.
And emulsion # 1B-6 was prepared.

Next, in Emulsion # 1B-4, the ratio of the aqueous silver nitrate solution and the aqueous sodium chloride solution added at the second and third times was 7: 1.
And emulsion # 1B-7 was prepared.

Next, the above eight emulsions (# 1A-1, # 1B-1 to # 1B ...
7) means that gelatin used for forming emulsion grains is gelatin #
8 emulsions (# 2A-1, # 2
2B-1 to # 2B-7) were prepared.

Further, the above eight emulsions (# 1A-1, # 1B-1 to # 1B-
7) means that gelatin used for forming emulsion grains is gelatin #
8 emulsions (# 3A-1, # 3
3B-1 to # 3B-7) were prepared.

Further, the above eight emulsions (# 1A-1, # 1B-1 to # 1B-
7) means that gelatin used for forming emulsion grains is gelatin #
8 emulsions (# 4A-1, # 4
4B-1 to # 4B-7) were prepared.

The silver halide grains contained in the 32 types of emulsions thus prepared were almost the same, cubic with an average side length of 0.5 μm, and the coefficient of variation in grain size was 0.08.

Table 2 summarizes the halogen compositions of these emulsions and the sites where iron ions are contained in the grains.

Next, 38.0 g of cyan coupler (a), 17.0 g of color image stabilizer (b) and 35.0 g of (c) were dissolved in 40.0 ml of ethyl acetate and 23.0 g of solvent (d), and this solution was added with 10% dodecylbenzenesulfone. It was emulsified and dispersed in 400 ml of 10% gelatin aqueous solution containing 20 ml of sodium acid salt.

Spectral sensitizing dyes (e) and (f) were added to the silver halide emulsion obtained above at 5.0 × 10 ⁻⁵ mol / mol Ag and 1.0 × 10 ⁻³ mol / mol Ag, respectively, to give a red-sensitive emulsion. A coating solution was prepared by mixing an emulsified dispersion of the above coupler with this to give the composition shown in Table 3, and coated on a paper support laminated on both sides with polyethylene in a layer structure shown in Table 3, 32 A variety of photosensitive materials were created. As a gelatin hardening agent for each layer, 1-oxy 3,5-dichloro-s-triazine sodium salt was used.

The performance of the prepared emulsion was tested using 32 kinds of coated samples (having the same name as the used emulsion).

Each sample was exposed to 250 CMS for 0.1 seconds at room temperature (23 ° C.) through an optical wedge and a red filter, and color development processing was performed using the following developing process and developing solution.

Measure the reflection density of the processed sample created in this way,
A so-called characteristic curve was obtained. The sensitivity was defined as the reciprocal of the exposure amount that gave a density 0.5 higher than the aperture density, and the sensitivity was expressed as a relative value with 100 being the sensitivity for 0.1 second exposure at room temperature of Sample # 1A-1.

Further, the difference between the density corresponding to the exposure amount that was increased by 0.5 in logE from the exposure amount for which the sensitivity was obtained and the density at the point where the sensitivity was obtained was obtained and defined as contrast.

In addition, in order to examine the change when pressure is applied to the photosensitive material, samples before exposure are 2 g, 4 g, 6 g, and 8 g
Sapphire needle with a load of (the radius of the tip of the needle is 0.03 mm)
Was scratched at a speed of 5 cm / sec, and then exposed and developed to determine whether or not desensitization had occurred. The results were determined as follows.

Evaluation Degree of desensitization × × Desensitization is recognized from load 2g × Load 4g 〃 △ Load 6g 〃 ○ Desensitization is recognized even with load 8g ◎ No desensitization even with load 8g These results are shown in Table 4. Shown in.

 Processing process Temperature Time Color development 35 ° C 45 seconds Bleaching and fixing 35 ° C 45 seconds Rinse 30-35 ° C 20 seconds Rinse 30-35 ° C 20 seconds Rinse 30-35 ° C 20 seconds Rinse 30-35 ° C 30 seconds Dry 70- 80 ° C for 60 seconds (Rinse → 3 tank countercurrent method) The composition of each processing solution is as follows.

Color developer Water 800ml ethylenediamine ^{-N, N, N -, N} - - tetramethyl phosphonic acid 1.5g triethylene diamine (1,4-diazabicyclo [2,2,2] octane) 5.0 g Sodium chloride 1.4g Potassium carbonate 25.0 g N- Ethyl-N- (β-methanesulfonamidoethyl)
-3-Methyl-4- aminoaniline sulphate 5.0g N, N-diethylhydroxylamine 4.2g Optical brightener (UVITEX CK Ciba-Geigy) 2.0g Add water 1000ml pH (25 ℃) 10.10 Bleach-fixer water 400ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 18.0 g Ammonium iron (III) diamine tetraacetate 55.0 g Disodium ethylenediamine tetraacetate 3.0 g Ammonium bromide 40.0 g Glacial acetic acid 8.0 g Water 1000 ml pH (25 ℃) 5.50 Rinse Liquid ion-exchanged water (3ppm or less for calcium and magnesium) From the results, the remarkable effect of the present invention can be known. That is, when grains are formed in the presence of gelatin # 1, Sample # 1A-1 using an emulsion having a silver bromide content of 40 mol% has a very low contrast and cannot be put to practical use. Sample # 1 with 100 mol% silver chloride emulsion
With B-1, a high contrast can be obtained, but it has a low sensitivity and is not practical. Increasing the sensitivity by adding iron ions to the silver chloride emulsion (# 1B-2,3) is observed, but the fog density is high and the pressure desensitization is large. By concentrating and containing iron ions on the surface of the particles (# 1B-4 to 7), the method is directed to a method in which high sensitivity can be achieved while maintaining high contrast and pressure desensitization is improved, but it is not sufficient for practical use.

However, when gelatin # 2 of the present invention and silver chloride grains are combined (# 2B-1), high sensitivity and high contrast can be achieved, pressure desensitization is remarkably improved, and fog density is reduced. This effect is remarkably observed in silver chlorobromide grains having a high silver chloride content, and the effect is small in the case of silver chlorobromide grains having a silver bromide content of 40% (# 2A-1). Further, even when iron ions are contained in the silver chloride emulsion, the pressure resistance is not so deteriorated unlike the case of gelatin # 2 (# 2B-2,3). By concentrating and containing iron ions on the surface of the particles, the sensitivity is further enhanced, the contrast is increased, and pressure desensitization is improved (# 2B
-4 to 7).

The above effect is further enhanced when gelatin # 3 is used, and is greatest when gelatin # 4 is used.

Example 2 Gelatin # 1 of sodium chloride 3.3g 3% aqueous solution (described in Example 1) was added, N, N ^{- -} dimethyl-2-thione (1% aqueous solution) was added 3.2 ml. An aqueous solution containing 0.2 mol of silver nitrate in this solution and potassium bromide 0.0
An aqueous solution containing 4 mol and 0.16 mol of sodium chloride was added and mixed at 66 ° C. with vigorous stirring. Then, an aqueous solution containing 0.8 mol of silver nitrate and an aqueous solution containing 0.16 mol of potassium bromide and 0.64 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring. After keeping at 66 ° C. for 5 minutes, the temperature was lowered, desalted and washed with water. Further, 90.0 g of gelatin # 1 was added to adjust the pH and pAg, and then the spectral sensitizing dyes (g) and (h) shown below were each added at 2 × 10 ^-4 mol / molAg.
And triethylthiourea were added, and spectral sensitization and chemical sensitization were performed. Obtained silver chlorobromide (silver bromide 20 mol%)
The emulsion was designated as emulsion # 1B-201.

Next, sodium chloride was added to a 3% aqueous solution of gelatin # 1.
3g was added, N, N ^{- -} dimethyl-2-thione (1% aqueous solution) was added 3.2 ml. An aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.004 mol of potassium bromide and 0.196 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring in this solution. Then, add silver nitrate to 0.8
A molar aqueous solution and an aqueous solution containing 0.016 mol of potassium bromide and 0.784 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring. After keeping at 66 ° C. for 5 minutes, the temperature was lowered, desalted and washed with water. Furthermore, gelatin # 1
After adding 90.0 g and adjusting the pH and pAg, the spectral sensitizing dyes (g) and (h) were each added at 2 × 10 ^-4 mo as in Emulsion # 1B-201.
l / molAg and triethylthiourea were added, and spectral sensitization and chemical sensitization were performed. The obtained silver chlorobromide (silver bromide 2
Emulsion # 1B-202.

Emulsion # 1B-202 differs from emulsion # 1B-202 only in that 0.42 mg and 1.96 mg of potassium hexacyanoferrate (II) trihydrate were added to the first and second aqueous alkali halide solutions, respectively. This was designated as Emulsion # 1B-203.

Next, in emulsion # 1B-202, the silver nitrate aqueous solution and the alkali halide aqueous solution to be added a second time were divided into 7: 1,
We decided to add silver nitrate / alkali halide three times in total, and prepare an emulsion in which 2.11 mg of potassium hexacyanoferrate (II) trihydrate was added to the alkali halide aqueous solution to be added the third time. Emulsion # 1B-204
And

Next, sodium chloride was added to a 3% aqueous solution of gelatin # 1.
3g was added, N, N ^{- -} dimethyl-2-thione (1% aqueous solution) was added 3.2 ml. An aqueous solution containing 0.2 mol of silver nitrate and an aqueous solution containing 0.2 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring in this solution.
Subsequently, an aqueous solution containing 0.7 mol of silver nitrate and an aqueous solution containing 0.7 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring. Further, an aqueous solution containing 0.1 mol of silver nitrate and an aqueous solution containing 2.11 mg of potassium hexacyanoferrate (II) trihydrate and 0.1 mol of sodium chloride were added and mixed at 66 ° C. with vigorous stirring. After keeping at 66 ° C. for 5 minutes, the temperature was lowered, desalted and washed with water. Further, 90.0 g of gelatin # 1 was added to adjust pH and pAg, and then spectral sensitizing dyes (g) and (h) were respectively added at 2 × 10 ⁻⁴ mol / molAg, which was equivalent to 2 mol% based on silver halide. Add silver bromide fine grain emulsion (average grain size 0.05μ) and triethylthiourea,
Spectral sensitization and chemical sensitization were performed. The obtained silver chloride emulsion was designated as emulsion # 1B-205.

In the preparation of these emulsions # B-201 to 205, the temperature at the time of forming silver halide emulsion grains and the addition rate of the reaction solution were changed to prepare emulsions having an average grain size of about 0.46 μm.
Emulsions # 1G-201 to # 1G-205 were prepared by changing the spectral sensitizing dyes to (i) and (j) described later (the addition amounts were 4 × 10 ⁻⁴ mol / molAg and 7 × 10 ⁻⁵ mol / molAg, respectively). And However, the amount of potassium hexacyanoferrate (II) trihydrate added was doubled in each case. In the preparation of emulsions # 1G-201 to # 1G-205, the temperature during the formation of silver halide emulsion grains and the addition of the reaction solution By changing the speed, an emulsion having an average grain size of about 0.53 μm was prepared, and the spectral sensitizing dyes were changed to (e) and (f) of Example 1 (the addition amount was the same as in Example 1) to prepare emulsion # 1R. -201 to # 1R-205.

15 types of emulsions prepared above # 1B-201-205, # 1G-201
To 205, # 1R-201 to 205 desalting and, 15 types only differ with different gelatin # 1 gelatin # 2 added after washing of the emulsion ^{(# 1 - B-201~205,} # 1 - G −201 to 205, # 1 ^- R−2
01-205) was prepared.

Next, # 1B-201-205, # 1G-201-205, # 1R-201-205
And 15 types of emulsions (# 2B-201-2
5, # 2G-201 to 205, # 2R-201 to 205) were prepared.

Next, # 1B-201-205, # 1G-201-205, # 1R-201-205
And 15 kinds of emulsions (# 3B-201-2
5, # 3G-201 to 205, # 3R-201 to 205) were prepared.

Furthermore, # 1B-201 to 205, # 1G-201 to 205, # 1R-201 to 205
And 15 types of emulsions (# 4B-201-2
5, # 4G-201 to 205, # 4R-201 to 205) were prepared.

Table 5 summarizes the halogen composition, grain size, and iron ion content sites in the total 75 types of emulsions. Among these, emulsions # 1B-205, # 1G-205, # 1R
-205, # 1 ^- B-205, # 1 ^- G-205, # 1 ^- R-205, # 2B-2
05, # 2G-205, # 2R-205, # 3B-205, # 3G-205, #
When the halogen composition of 15 kinds of 3R-205, # 4B-205, # 4G-205, and # 4R-205 was analyzed by X-ray diffraction method, silver bromide was found in addition to the main peak of 100 mol% of silver chloride. Content rate 3
A broad diffraction pattern corresponding to 0 to 40% was observed, indicating that these emulsion grains had a silver bromide localized phase.

Next, after corona discharge treatment was applied to the surface of the paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and the emulsion obtained above was used to prepare the emulsions shown in Tables 6 and 7. Multi-layer coating with the combination of composition, layer constitution and emulsion shown in the table,
Twenty-five color photosensitive materials were prepared. Preparation of the coating solution was performed as follows.

Preparation of coating liquid for the first layer Yellow coupler (EXY) 19.1 g, color image stabilizer (Cpd-
1) 4.4 g and 0.7 g of color image stabilizer (Cpd-7), 27.2 ml of ethyl acetate and solvent (solv-3), (Solv-7),
(Solv-8) 4.1g of each was added and dissolved.
% Emulsified in 185 ml of a 10% aqueous solution of gelatin # 1 containing 8.0 ml of sodium dodecylbenzenesulfonate.

The emulsified dispersion of the coupler thus obtained and the silver halide emulsion shown in Table 7 were mixed and dissolved to prepare a coating solution for the first layer so as to have the composition shown in Table 6.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. However, the emulsified dispersion used in the fifth layer coating liquid was used after emulsifying and dispersing, and then the pressure was reduced at 40 ° C. to distill off ethyl acetate.

As a gelatin hardener for each layer, 1-oxy-3,5-
Dichloro-s-triazine sodium salt was used.

Further, (Cpd-10) and (Cpd-11) were added to each layer so that the total amounts were 25.0 mg / m ² and 50.0 mg / m ² , respectively.

Further, 1- (5-methylureidophenyl-5-mercaptotetrazole was added to the blue-sensitive emulsion layer, the edge-sensitive emulsion layer and the red-sensitive emulsion layer, respectively, per mol of silver halide, 8.
5 × 10 ^-5 mol, 7.7 × 10 ^-4 mol, and 2.5 × 10 ^-4 mol were added.

The blue-to-sensitive emulsion layer and the edge-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7- tetrazaindene each per mol of silver halide 1 × 10 ^-4 mol and 2 × 10 ^{- 4} mol was added.

Further, the following dyes (the amount in parentheses represents the coating amount) were added to the emulsion layer to prevent irradiation.

(Solv-3) Solvent O = PO-C ₉ H ₁₉ (iso) ₃ The same test as in Example 1 was performed using the 25 types of coating samples thus obtained. However, exposure of the sample was performed through filters of three colors of blue, edge and red, and the performance of each of the blue-sensitive, edge-sensitive and red-sensitive photosensitive emulsion layers was examined.

The following processing steps and processing solutions were used for the development processing of the sample.

 The results are shown in Table 8.

Treatment process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161ml 17 Bleach fixing 30-35 ℃ 45 seconds 215ml 17 Rinse 30-35 ℃ 20 seconds -10 Rinse 30-35 ℃ 20 seconds -10 Rinse 30-35 ℃ 20 seconds 350ml 10 Dry 70 to 80 ℃ 60 seconds * Replenishment amount per 1m ² of light-sensitive material (3 tanks counterflow to link →) The composition of each processing solution is as follows.

Bleach-fixing solution (same as tank solution and replenisher) Water 400ml Ammonium thiosulfate (70%) 100ml Sodium sulfite 17g Ethylenediaminetetraacetic acid iron (III) ammonium 55g Ethylenediaminetetraacetate disodium 5g Ammonium bromide 40g Water 100ml pH ( 25 ° C) 6.0 Rinse solution (same as tank solution and replenisher) Ion-exchanged water (calcium and magnesium are below 3ppm each) As is clear from the results, the effect of the present invention is remarkable also in the multilayer color light-sensitive material. That is, when grains are formed in the presence of gelatin # 1, Sample # 1-1 prepared using an emulsion having a silver bromide content of 20 mol% has a remarkably low contrast and cannot be put to practical use. . In sample # 1-2 using an emulsion having a silver chloride content of 98 mol%, the contrast is increased but the sensitivity is low, which is not practical.
By adding iron ions to the silver chloride emulsion (# 1-
3) Sensitivity increase is observed, but fog density is high and pressure desensitization is large. By concentrating and containing iron ions on the particle surface (# 1-4), the sensitivity can be enhanced while maintaining high contrast and the pressure desensitization can be improved, but it is not sufficient for practical use. Further, if a silver bromide-localizing layer is provided on the emulsion grains, the sensitivity is further enhanced, but the pressure resistance is deteriorated and the fog density is increased (# 1-5).

However, when gelatin # 2 of the present invention is combined with silver chlorobromide grains having a high silver chloride content (# 2-2), not only high sensitivity and high contrast can be achieved, but also pressure desensitization is remarkably improved and fog density is also improved. Decrease. This effect is remarkably observed in silver chlorobromide grains having a high silver chloride content, and the effect is small in silver chlorobromide grains having a silver bromide content of 20% (# 2).
-1). Even if the silver chloride emulsion contains iron ions,
Unlike the case of gelatin # 2, the pressure resistance does not deteriorate much (# 2-3). By making iron ions concentrated on the surface of the particles, the sensitivity is further increased and the contrast is enhanced, and the pressure desensitization is improved (# 2-4). Further, even when a silver bromide localized layer is provided on the emulsion grains for high sensitivity, deterioration of pressure resistance and increase of fog density can be minimized (# 2-5).

The above effect is further enhanced when gelatin # 3 is used, and is greatest when gelatin # 4 is used.

Further, the gelatin of the present invention exhibits effects such as high sensitivity, high contrast, low fog, and reduced pressure desensitization for the first time when used in emulsion grain formation. Even if it is used, the above effect hardly appears (# 1'-1 to # 1'-5).

(Effects of the invention) As is apparent from the examples, by applying the present invention, high sensitivity and high contrast can be obtained with low fog, and desensitization is less likely to occur when pressure is applied to emulsion grains. An excellent silver halide photographic light-sensitive material can be obtained.

Claims (4)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive emulsion layer containing a surface latent image type silver halide emulsion on a support, wherein the emulsion layer contains substantially silver iodide. 90 mol% or more contains silver chlorobromide or silver chloride particles consisting of silver chloride, and the particles are further formed in the presence of gelatin having both adenine and guanine contents of 0.5 ppm or less. A characteristic silver halide photographic light-sensitive material. 2. The silver chlorobromide or silver chloride grains contain iron ions in an amount of 10 ⁻⁷ to 10 ⁻³ mol per mol of silver halide. The silver halide photographic light-sensitive material as described in 1). 3. 90% or more of the amount of iron ions contained in the silver bromide or silver chloride grains is contained in a surface layer of 50% or less of the volume of the grains. The silver halide photographic light-sensitive material according to claim (2). 4. A silver bromide localized phase having a silver bromide content of less than 70 mol% is contained inside or on the surface of silver halide grains, (1), (2) or The silver halide photographic light-sensitive material described in (3).