JP2681675B2 - Highly sensitive silver halide photographic light-sensitive material with less fog and excellent storage stability over time. - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having high sensitivity, less fog generation, and excellent storage stability over time. Regarding

[Background of the Invention]

The silver halide color photographic light-sensitive material is required to have various performances, and among them, high sensitivity, high image quality and improvement in storage stability over time are the most important.

In particular, increasing the sensitivity of the silver halide emulsion itself can be used as a technique for obtaining a high-sensitivity photographic light-sensitive material, and it is also possible to use a silver halide emulsion having a smaller grain size than in the past to obtain high-quality photographs. It can be used as a technique for obtaining a photosensitive material and can be said to be an extremely effective technique.

As a method for sensitizing a silver halide photographic light-sensitive material,
Many methods are known in the art. Spectral sensitization using sensitizing dyes; Noble metal sensitization using salts of precious metals such as gold, platinum and iridium; Sulfuric acid sensitization using sodium thiosulfate, thioacetamide, allylisothiourea, etc. in addition to active gelatin; colloidal selenium and selenoureas Sensitization using selenium; reduction sensitization using monovalent tin salt, polyamine, hydrazine derivative; development acceleration using polyonium salt of nitrogen, phosphorus or sulfur, or polyalkylene glycol. In the actual photographic industry, these sensitizing techniques are appropriately combined according to the purpose to produce a desired silver halide photographic light-sensitive material, but a technique capable of sufficiently satisfying storage stability has not yet been established. .

In order to improve such a defect, a method of adding various antifoggants to a light-sensitive material has been tried.

In particular, U.S. Patents 1,758,576, 2,304,962, 2,697,
040, 2,697,099, 2,824,001, 2,476,536
No. 2,843,491, 3,251,691 and British Patent 403,789.
No. 893,428, the mercapto compounds described in JP-B-58-9939, etc. are effective in suppressing the fog,
The sensitivity is remarkably deteriorated, and it has not reached a satisfactory level because of deterioration in sensitivity and fog due to storage over time.

As described above, it has been extremely difficult to obtain a silver halide emulsion having high sensitivity, less fog, and good storage stability over time.

[Object of the invention]

In view of the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, low fog, and improved storage stability over time.

[Configuration of the invention]

As a result of various studies to solve the above-mentioned object of the present invention, it was found that the problem can be solved by chemical aging under the following environment.

That is, the object of the present invention is to achieve substantial chemical ripening with a pAg value of 6.0.
To 8.8, and a photosensitive layer having a silver halide emulsion which has been subjected to a process of increasing the pAg value by adding a compound which forms a sparingly soluble salt with silver ions before or during the start of chemical ripening. Is achieved with a silver halide photographic light-sensitive material.

The present invention is based on the following findings found by the present inventors. That is, it is well known by those skilled in the art that how much pAg is set in the case of chemically ripening an emulsion is well known to those skilled in the art, and pAg 4 to 5
A sensitizing method of aging at a certain degree has been known for a long time. However, if pAg is simply set low and chemical ripening is performed, chemical ripening will be completed in a short time, but instability of fog, for example, increase in fog due to storage over time,
Or there may be a problem in reproducibility when the same chemical aging is applied. If an antifoggant or the like is used together as a countermeasure, another problem occurs as described above, and it is not a drastic solution.

However, as a result of various studies by the present inventors, pA
Even when g is 8.8 or less, the chemical ripening proceeds in the range of 6.0 to 8.8 by increasing the pAg value by adding a compound that forms a poorly soluble salt with silver ions during the chemical ripening. It was found that a silver halide light-sensitive material having high sensitivity, low fog, and good storability with time can be obtained as compared with the case of performing chemical ripening at a higher pAg value.

 The present invention will be described in more detail below.

In the present invention, chemical ripening refers to sensitizing silver halide grains with a chemical sensitizer when forming a silver halide emulsion.

In the present invention, chemical ripening can be achieved by any chemical sensitizing means, and the chemical sensitizer used is not particularly limited.

As the chemical sensitizer that can be advantageously used in the present invention,
Examples thereof include noble metal sensitizers, sulfur sensitizers, selenium sensitizers and reduction sensitizers.

As the sulfur sensitizer, in addition to active gelatin, a sulfur compound such as sodium thiosulfate, thiourea, and allyl isothiocyanate can be used.

As the selenium sensitizer, active and inactive selenium compounds can be used.

Reduction sensitizers include monovalent tin salts, polyamines, bisalkylaminosulfides, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives.

As the noble metal sensitizer, gold compounds and compounds such as ruthenium, rhodium, palladium, iridium and platinum can be used.

A combination of a noble metal sensitizer and a sulfur sensitizer is preferable as the chemical sensitizer capable of more fully exerting the objects and effects of the present invention.

The addition amount of the chemical sensitizer at the time of chemically ripening the silver halide emulsion according to the present invention can be appropriately set depending on the silver halide grains used.

Next, the substantial chemical ripening referred to in the present invention will be described.

The chemical ripening start step refers to a step of adding a chemical sensitizer, and in this step, the time when the chemical sensitizer is added is the start of chemical ripening.

The above chemical ripening can be stopped by a method known in the art. As a method of ending the chemical ripening, a method of lowering the temperature, a method of lowering the pH, a method of using a chemical ripening stopper, etc. are known. Is preferred.
Examples of the chemical aging inhibitor include halides (eg, potassium bromide, sodium chloride, etc.), organic compounds used as antifoggants or stabilizers (eg, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, etc.) is known. These are used alone or in combination with complicated compounds.

The time when the chemical ripening is completed is the time when the operation for ending the chemical ripening is performed.

In the present invention, the substantial chemical ripening time means the time between the start of chemical sensitization and the end of chemical sensitization.

The pAg value when subjected to substantial chemical ripening is 6.0 to 8.8, but its preferable value is in the range of 7.0 to 8.2, and more preferably in the range of 7.4 to 8.0. The pAg value at the time of substantial chemical aging preferably satisfies at least 1/3 of the substantial chemical aging time satisfying the above conditions, and particularly at least 2/3 of the first half of this substantial chemical aging time satisfies the above conditions. It is preferable to satisfy.

Next, the “compound that forms a poorly soluble salt with silver ion” (hereinafter abbreviated as pAg value increasing agent) in the present invention will be described.

As a pAg value-increasing agent, at least 0 by adding it during the chemical ripening between pAg 6.0 to 8.8.
The compound is not particularly limited as long as it is a compound other than a halide ion having a pAg value of 02 (preferably 0.05) or more.
However, particularly preferred compounds include thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, sodium selenocyanate, selenocyanates such as ammonium selenocyanate, carbonates such as sodium carbonate and potassium carbonate, sodium sulfite. , Potassium sulfite, and other sulfites. Among these, the most preferable compound group is thiocyanate.

The amount of these pAg value increasing agents added varies depending on the composition of the silver halide emulsion used, the grain size, crystal habit, etc.
Usually, it is preferably 0.0005 to 1 per mol of silver halide.
It is 0 g, more preferably 0.001 to 0.5 g, and particularly preferably 0.005 to 0.2 g.

The pAg value increasing agent may be added either before or after the start of substantial chemical ripening, but in the case of the start, it is preferably added during the first half of the substantial chemical ripening time. Particularly preferably, it is added prior to the addition of the chemical sensitizer.

The silver halide color photographic light-sensitive material of the present invention can contain various components in addition to the above essential components.

In the present invention, the silver halide emulsion includes a conventional silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride as a photosensitive silver halide. Although any of those used for emulsions can be used, silver bromide, silver iodobromide and silver chloroiodobromide are particularly preferable.

The photosensitive silver halide grains used in the above silver halide emulsion may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, may be grown after forming seed grains, or may be grown by various commonly used methods.

Further, the halogen composition of the silver halide grains may be changed by using a conversion method at any step of the formation thereof.

The silver halide grain can contain various metal elements inside the grain and / or on the grain surface, and can also be provided with a reduction sensitizing nucleus by placing it in a suitable reducing atmosphere.

Further, the silver halide emulsion may be one in which unnecessary soluble salts are removed after the growth of silver halide grains is completed,
Alternatively, it may be contained as it is.

In the present invention, the silver halide grain in the silver halide emulsion may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain. Further, it may have any crystal form.

The average grain size of the above silver halide grains is 0.05 to 3.0.
μm is preferable, and more preferably 0.1 to 2.0 μm.

In the present invention, as the silver halide emulsion, those having any grain size distribution can be used. That is, an emulsion having a wide grain size distribution (referred to as "polydisperse emulsion") may be used, or an emulsion having a narrow grain size distribution (referred to as "monodisperse emulsion") may be used.

The above silver halide emulsions may be used as a mixture of two or more kinds of silver halide emulsions formed separately.

The silver halide color photographic light-sensitive material of the present invention can be applied to, for example, color negative and positive films, and color photographic paper.

When the silver halide photographic light-sensitive material of the present invention is used for color, it may be monochromatic or polychromatic. A multi-color silver halide photographic light-sensitive material is usually composed of a silver halide emulsion layer containing magenta, yellow, and cyan couplers as a photographic coupler, and a non-photosensitive material in order to reproduce a color by a subtractive method. The layer has a structure in which an appropriate number of layers and a layer order are laminated on the support, and the number of layers and the layer order can be arbitrarily set depending on the priority performance and the purpose of use.

Known photographic additives can be used in the silver halide photographic emulsion of the present invention.

Known photographic additives include, for example, compounds described in Research Disclosure RD-17643 and RD-18716 shown in the following table.

In the emulsion layer of the light-sensitive material according to the present invention, an aromatic primary amine developer (for example, p-phenylenediamine derivative, aminophenol derivative, etc.) is used in color development processing.
A dye-forming coupler is used which forms a dye by a coupling reaction with the oxidant. The dye-forming couplers are usually selected so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A magenta dye-forming coupler is used in the emulsion layer and a cyan dye-forming coupler in the red emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared in a manner different from the above-mentioned combination depending on the purpose.

It is desirable that these dye-forming couplers have a group having 8 or more carbon atoms in the molecule, which makes the coupler non-diffusible. Also, these dye-forming couplers need only reduce two molecules of silver ions, even if they are four-equivalent, in which four molecules of silver ions need to be reduced in order to form one molecule of dye. Either of two equivalents may be used. Dye-forming couplers are colored couplers having a color correcting effect and development inhibitors, development accelerators, bleaching accelerators, developers, silver halide solvents, toning agents by coupling with oxidized developing agents. Compounds that release photographically useful fragments, such as hardeners, foggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers are included. Among them, couplers which release a development inhibitor with development to improve the sharpness of an image and the granularity of an image are called DIR couplers. Instead of the DIR coupler, a DIR compound which releases a development inhibitor at the same time as a colorless compound is formed by a coupling reaction with an oxidized product of a developing agent may be used.

The DIR couplers and DIR compounds used are those in which an inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group, and which are removed by the coupling reaction. (A timing DIR coupler and a timing DIR compound) in which an inhibitor is released by an intramolecular nucleophilic reaction, an intramolecular electron transfer reaction, or the like. Further, as the inhibitor, those having a diffusivity after release and those having a low diffusivity can be used alone or in combination depending on the application. A colorless coupler that performs a coupling reaction with an oxidized form of an aromatic primary amine developer but does not form a dye (also referred to as a competitive coupler) can be used in combination with a dye-forming coupler.

As the yellow dye-forming coupler, known acylacetanilide-based couplers can be preferably used. Of these, benzoylacetanilide and pivaloylacetoanilide compounds are advantageous.

Specific examples of yellow color-forming couplers that can be used include, for example, U.S. Patents 2,875,057, 3,265,506, 3,408,194, and 3,5.
No. 51,155, No. 3,582,322, No. 3,725,072, No. 3,891,44
No. 5, West German Patent 1,547,868, West German Patent Application 2,219,917
No. 2,261,361, No. 2,414,006, British Patent 1,425,02
No. 0, JP-B-51-10783, JP-A-47-26133, JP-A-48-7
No. 3147, No. 50-6341, No. 50-87650, No. 50-123342
Nos. 50-130442, 51-21827, 51-102636
No. 52-82424, No. 52-115219, and No. 58-95346.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indazolone couplers and the like can be used.

Specific examples of magenta coloring couplers that can be used are, for example, U.S. Pat.Nos. 2,600,788, 2,983,608, 3,062,653,
3,127,269, 3,311,476, 3,419,391, 3,5
19,429, 3,558,319, 3,582,322, 3,615,50
No. 6, No. 3,834,908, No. 3,891,445, West German Patent 1,810,4
No. 64, West German Patent Application (OLS) 2,408,665, 2,417,945
No. 2,418,959, No. 2,424,467, JP-B-40-6031
JP-A-49-74027, JP-A-49-74028, JP-A-49-129538
No. 50-60233, No. 50-159336, No. 51-20826,
Nos. 51-26541, 52-42121, 52-58922, 53
-55122 and Japanese Patent Application No. 55-110943.

As the cyan dye-forming coupler, a known phenol or naphthol coupler can be used.

For example, a phenol-based coupler substituted with an alkyl group, an acylalkyl group, a ureido group, or the like, a naphthol-based coupler formed from a 5-aminonaphthol skeleton, a di-equivalent naphthol-based coupler having an oxygen atom introduced as a leaving group, or the like is available. Be represented.

Specific examples of the cyan coloring coupler that can be used include, for example, U.S. Patent No. 3,779,763, JP-A-58-98731, and JP-A-60-37557.
No. 2,895,826, No. 60-225155, No. 60-222
No. 853, No. 59-185335, U.S. Pat.No. 3,488,193, No. 60-185335
No. 237448, No. 53-52423, No. 54-48237, No. 56-2714
No. 7, Japanese Patent Publication No. 49-11572, JP-A No. 61-3142, and No. 61-9652.
No. 3, No. 61-39045, No. 61-50136, No. 61-99141
No. 61-105545 and the like.

Examples of the light-sensitive material to which the silver halide photographic light-sensitive material of the present invention can be applied include various color and black-and-white light-sensitive materials. For example, color negative film for photography, color reversal film, color photographic paper, color positive film, color reversal photographic paper, color positive photosensitive material for direct positive, heat development, silver die bridge, etc., and for X ray photography, squirrel, It can be used for black-and-white photographic light-sensitive materials such as those for microscopic use, general photography, and black-and-white photographic paper.

〔Example〕

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

Example 1 Multi-layer color photographic element sample-10 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support. The amount added in the silver halide photographic light-sensitive material indicates the weight (g) per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of conversion.

Layer composition of sample No. 1 First layer: Antihalation layer (HC-1) Black colloidal silver 0.20 UV absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.20 Gelatin 1.5 Second layer; Intermediate layer ( IL-1) UV absorber (IL-1) 0.01 High boiling point solvent (Oil-1) 0.01 Gelatin 1.5 Third layer; Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.9 Odor Silver halide emulsion (Em-2) 0.6 Sensitizing dye (S-1) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.5 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 1.0 Cyan coupler (C-2) 0.05 Colored cyan coupler (CC-1) 0.05 DIR compound (D-1) ) 0.002 High boiling point solvent (Oil-1) 0.5 Gelatin 1.5 4th layer; High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 2.0 Sensitizing dye (S-1) 2.0 × 10 ^-4 (1 mol / silver ) Sensitizing dye (S-2) 2.0 × 10 -4 ( mol / mole of silver) Sensitizing dye (S-3) 0.1 × 10 -4 ( mol / mole of silver) Cyan Coupler (C-2) 0.015 cyan Coupler (C-3) 0.25 Colored cyan coupler (CC-1) 0.015 DIR compound (D-2) 0.05 High boiling point solvent (Oil-1) 0.3 Gelatin 1.5 Fifth layer; Intermediate layer (IL-2) Gelatin 0.5 Sixth Layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 1.0 Sensitizing dye (S-4) 5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-5) 1 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.5 Colored magenta coupler (CM-1) 0.01 DIR compound (D-3) 0.02 DIR compound (D-4) 0.020 High boiling solvent (Oil -2) 0.4 Gelatin 1.0 7th layer; Intermediate layer (IL-3) Gelatin 0.8 8th layer; High sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-3) 1.3 Sensitization Containing (S-6) 1.5 × 10 -4 ( mol / mole of silver) Sensitizing dye (S-7) 2.5 × 10 -4 ( mol / mole of silver) Sensitizing dye (S-8) 0.5 × 10 - ⁴ (mol / silver 1 mol) Magenta coupler (M-2) 0.05 Magenta coupler (M-3) 0.15 Colored magenta coupler (CM-2) 0.05 DIR compound (D-3) 0.01 High boiling solvent (Oil-3) 0.5 Seratin 1.0 9th layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 Color stain inhibitor (SC-1) 0.1 High boiling point solvent (Oil-3) 0.1 Gelatin 0.8 10th layer; Low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (S-10) 7 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.5 Yellow coupler (Y-2) 0.1 DIR compound (D-2) 0.01 High boiling point solvent (Oil-3) 0.3 Gelatin 1.0 11th layer; High-sensitivity blue-sensitive emulsion layer (BH) Silver bromide emulsion (Em-4) 0.4 iodobromide emulsion (Em-1) 0.3 Sensitizing dye (S-9) 1 × 10 -4 ( mol / mole of silver) Sensitizing dye (S-10) 3 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.30 Yellow coupler (Y-2) 0.05 High boiling point solvent (Oil-3) 0.1 Gelatin 1.1 12th layer; 1st protective layer (PRO-1) ) Fine grain silver iodobromide emulsion (average particle size 0.08 μmAg 12 mol%) 0.4 UV absorber (UV-1) 0.10 UV absorber (UV-2) 0.05 High boiling solvent (Oil-1) 0.1 High boiling solvent (Oil-) 4) 0.1 Formalin scavenger (HS-1) 0.5 Formalin scavenger (HS-2) 0.2 Gelatin 1.0 13th layer; 2nd protective layer (PRO-2) Surfactant (SU-1) 0.005 Alkali-soluble mat Agent (average particle size 3 μm) 1.10 Gelatin 0.6 Em−1: average particle size 0.46 μm, average silver iodide 7.0 mol%, monodisperse surface low silver iodide containing emulsion Em-2: flat Emulsion of uniform grain size 0.30 μm, average silver iodide content 2.0 mol%, monodisperse and uniform composition Em-3: average grain size 0.81 μm average silver iodide content 7.0 mol% monodisperse surface low iodine Emulsion containing silver iodide Em-4: average grain size 0.95 μm, average silver iodide content: 8.0 mol%, monodisperse (width of distribution: 14%) surface low silver iodide (0.5 mol%) containing type Emulsion In addition to the above composition for each layer, coating aid Su-2, stabilizer
Stb-1 and antifoggant AF-1 were added.

Further, a silver halide emulsion used in the eighth layer of Sample-101 was prepared under various chemical ripening conditions as shown in Table 1 and replaced with the silver halide emulsion of the eighth layer of Sample-101. , Samples-102 to 110 were prepared.

H-2 _{[(CH 2 = CHSO 2 CH 2} ) 3 CCH 2 SO 2 (CH 2) 2 N (CH 2) 2 SO 3 K For each of the produced samples 101 to 110, 55 ° C, 60%
Each of the samples left for 1 week under RH conditions and the samples immediately after production were subjected to wedge exposure using white light, and then subjected to the following development processing.

Processing step (38 ° C) Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 3 minutes 15 seconds Fixing 6 minutes 30 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry The processing solution composition used in each processing step is as follows. It is as follows.

(Color developing solution)

4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1.

(Bleach)

Ethylenediaminetetraacetic acid iron ammonium salt 100. g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.1 g Glacial acetic acid 10.0 ml Water is added to adjust the pH to 6.0 using ammonia water.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 and pH is adjusted to 6.0 using acetic acid.

(Stabilizing solution)

 Formalin (37% aqueous solution) 1.5 ml Conidax (Konica) 7.5 ml Add water to make 1.

For each of the obtained samples, the green (G) concentration was measured,
The relative sensitivity and fog density were determined.

The relative sensitivity was calculated as the reciprocal of the exposure amount required to obtain the density of the minimum density + 0.3, and Sample-101 was set to 100,
The other samples (102-110) are shown as relative sensitivity to sample-101. Table 2 shows these results.

As is clear from the results of Table-2, the sample using the emulsion chemically ripened under the conditions of the present invention has high sensitivity,
Further, the occurrence of fog was small, and the storage stability was further excellent, and the increase in fog and the decrease in sensitivity could be suppressed.

Further, when the same experiment was conducted with a blue-sensitive emulsion layer and a red-sensitive emulsion layer, almost the same results were obtained, and the effect of the present invention was confirmed.

Example 2 A sample 201 (comparative) of a multilayer color light-sensitive material was prepared by sequentially coating each layer having the following composition from the support side onto a triacetyl cellulose film support which was subjected to an undercoating process. The coating amount of each component is shown in g / m ² . However, for silver halide, the coating amount converted to silver, and for couplers, silver 1
It is shown by the number of moles per mole.

First layer: antihalation layer Ultraviolet absorber U-1 0.3 Ultraviolet absorber U-2 0.4 High boiling point solvent O-1 1.0 Black colloidal silver 0.24 Gelatin 2.0 Second layer: Intermediate layer 2,5-di-t-octylhydroquinone 0.1 High-boiling point solvent O-1 0.2 Gelatin 1.0 Third layer: low-sensitivity red-sensitive silver halide emulsion layer Silver iodobromide (AgI4) spectrally sensitized with red sensitizing dyes (S-1) and (S-2) Mol% average particle size 0.25 μm) 0.5 coupler Cp-1 0.1 high boiling solvent O-2 0.6 gelatin 1.3 fourth layer: high-sensitivity red-sensitive silver halide emulsion layer red sensitizing dyes (S-1) and (S-2) ) Spectrally sensitized with silver iodobromide (AgI2 mol% average particle size 0.60 μm) 0.8 coupler Cp-1 0.2 high boiling solvent O-2 1.2 gelatin 1.8 fifth layer: intermediate layer 2,5-di-t- Octyl hydroquinone 0.1 High boiling point solvent O-1 0.2 Gelatin 0.9 6th layer: Low sensitivity red sensitive halogen Silver Oxide Emulsion Layer Silver iodobromide spectrally sensitized with green sensitizing dyes (S-3) and (S-4) (AgI 4 mol% average particle size 0.25 μm) 0.6 coupler Cp-2 0.04 coupler Cp-3 0.01 High boiling point solvent O-3 0.5 Gelatin 1.4 Seventh layer: high-sensitivity green-sensitive silver halide emulsion layer Silver iodobromide spectrally sensitized with green sensitizing dyes (S-3) and (S-4) (AgI2 mol) % Average particle size 0.60 μm) 0.9 Coupler Cp-2 0.10 Coupler Cp-3 0.02 High boiling point solvent O-3 1.0 Gelatin 1.5 8th layer: Intermediate layer Same as 5th layer 9th layer: Yellow filter layer Yellow colloidal silver 0.1 2 , 5-Di-t-octylhydroquinone 0.1 High boiling point solvent O-1 0.2 Gelatin 0.9 10th layer: low-sensitivity blue-sensitive silver halide emulsion layer Iodobromide spectrally sensitized by blue sensitizing dye (S-5) Silver (AgI 4 mol% average particle size 0.35 μm) 0.6 Coupler Cp-4 0.3 High boiling point solvent O-3 0.6 Gelatin 1.3 Eleventh layer: High-sensitivity blue-sensitive silver halide emulsion layer Silver iodobromide (AgI2 mol% average particle size 0.90 μm) spectrally sensitized with a blue sensitizing dye (S-5) 0.9 Coupler Cp-4 0.5 High Boiling point solvent O-3 1.4 Gelatin 2.1 12th layer: first protective layer UV absorber U-1 0.3 UV absorber U-2 0.4 High boiling point solvent O-3 0.6 2,5-di-t-octylhydroquinone 0.1 Gelatin 1.2 Thirteenth layer: Second protective layer Non-photosensitive fine grain silver halide emulsion made of silver iodobromide having an average grain size of 0.08 μm and 1 mol% of silver iodide 0.3 Polymethylmethacrylate grains (diameter 1.5 μm) Surfactant- 1 Gelatin 0.7 In addition to the above composition, gelatin hardening agent-1 and a surfactant were added to each layer.

(Compound used) The silver halide emulsions of the photosensitive silver halide emulsion layers except the 10th layer of Sample-201 were chemically ripened using sodium thiosulfate and chloroauric acid while keeping the temperature of the reaction tank at 55 ° C. .

The pAg value during the chemical aging was 9.2, and it was aged for 90 minutes. on the other hand,
The conditions for chemical ripening of the silver halide emulsion for the 10th layer are shown in Table 3.

Further, various silver halide emulsions for use in the tenth layer of Sample-201 were prepared under the conditions shown in Table 3,
In place of 0 layer silver halide emulsion, sample-202 to 207
Was prepared.

For each of the produced samples 201 to 207, 55 ° C, 60%
Each of the one left for 1 week under RH condition and the one just after production was subjected to wedge exposure using white light, and then subjected to the following development processing.

Processing time Development time Processing temperature First development 6 minutes 38 ℃ Washing with water 2 minutes 38 ℃ Reversing 2 minutes 38 ℃ Color development 6 minutes 38 ℃ Adjusting 2 minutes 38 ℃ Bleaching 6 minutes 38 ℃ Fixing 4 minutes 38 ℃ Washing with water 4 minutes 38 ℃ Stable 1 minute normal temperature drying The processing liquid composition used in the above processing step is as follows.

First developer Sodium tetrapolyphosphate 2g Sodium sulfite 20g Hydroquinone monosulfonate 30g Sodium carbonate (monohydrate) 30g 1-Phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0.1% solution) 2ml Water added 1000ml Inversion solution Nitrilotrimethylenephosphonic acid-6 sodium salt 3g Stannous chloride (dihydrate) 1g p- Aminophenol 0.1g Sodium hydroxide 8g Glacial acetic acid 15ml Water added 1000ml Color developer Sodium tetrapolyphosphate 3g Sodium sulfite 7g Sodium triphosphate (dihydrate) 36g Potassium bromide 1g Potassium iodide (0.1% solution) 90ml Water Sodium oxide 3g Citrazine acid 1.5g N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline / sulfate 11g 2,2-Ethylenedithiodiethanol 1g Water was added to 1000ml Adjustment liquid sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0.4ml Glacial acetic acid 3ml Water was added 1000ml Bleaching solution Sodium ethylenediaminetetraacetate (dihydrate) 2g Ammonium ethylenediaminetetraacetate (III) (dihydrate) 120g Ammonium bromide 100g Water is added 1000ml Fixer ammonium thiosulfate 80g Sodium sulfite 5g Sodium bisulfite 5g Water is added 1000 ml Stabilizer Formalin (37% by weight) 5 ml Conidax (Konica Corporation) 5 ml Water was added to each sample 1000 ml The blue density of each sample was measured to determine the relative sensitivity and maximum color density (D max) .

As for the relative sensitivity, the reciprocal of the exposure amount required to obtain a blue density of 0.5 was obtained and the sample-201 was set to 100, and the other samples (202 to 207) were shown as the relative sensitivity to the sample 201.

 The results are shown in Table-4.

As is clear from the results in Table 4, the samples using the emulsion chemically ripened under the conditions of the present invention have high sensitivity,
Furthermore, it showed excellent storability over time and was able to suppress changes in sensitivity and reductions in maximum density.

Further, similar experiments were carried out with a red-sensitive emulsion layer and a linear-sensitive emulsion layer, and similarly good results were obtained, and it was confirmed that the effects of the present invention were exhibited regardless of the difference in color sensitivity. .

Example 3 Color reversal light-sensitive material sample-30 in which the following first to eleventh layers were provided on a paper support coated on both sides with polyethylene.
Created 1. The coating amount of each component is shown in g / m ² . However, with respect to silver halide, it is indicated by a coating amount converted to silver.

1st layer (antihalation layer) Black colloidal silver ...... 0.10 Gelatin ...... 1.5 2nd layer (1st red sensitive layer) Cyan coupler C-1 ...... 0.080 Cyan coupler C-2 ...... 0.16 Antifading agent A-1 ...... 0.12 Anti-fading agent A-2 ...... 0.06 High boiling point solvent O-1 ...... 0.18 AgBrI spectrally sensitized with red sensitizing dye (S-1, S-2)
(AgI 3.0 mol%, average particle size 0.4 μm) …… 0.14 Gelatin …… 0.81 Third layer (second red sensitive layer) Cyan coupler C-1 …… 0.043 Cyan coupler C-2 …… 0.085 Anti-fading agent A -1 …… 0.064 Anti-fading agent A-2 …… 0.032 High boiling point solvent O-1 …… 0.097 AgBrI spectrally sensitized with red sensitizing dye (S-1, S-2)
(AgI 3.0 mol%, average particle size 0.8 μm) …… 0.16 Gelatin …… 0.98 Fourth layer (first intermediate layer) Mixing inhibitor AN-1 …… 0.020 Mixing inhibitor AN-2 …… 0.060 High boiling point solvent O-2: 0.13 Gelatin: 0.90 Fifth layer (first green-sensitive layer) Magenta coupler C-3: 0.25 Anti-fading agent A-3: 0.067 Anti-fading agent A-4: 0.12 High boiling point solvent O -1 ...... 0.19 AgBrI (AgI3.Sg) spectrally sensitized with a green sensitizing dye (S-3).
0 mol%, average particle diameter 0.4 μm) 0.15 Gelatin 0.93 Sixth layer (second green sensitive layer) Magenta coupler C-3 0.15 Anti-fading agent A-3 0.040 Anti-fading agent A-4 …… 0.070 High boiling point solvent O-1 …… 0.11 AgBrI (AgI3.
0 mol%, average particle size 0.7 μm) 0.15 Gelatin 0.83 7th layer (second intermediate layer) Yellow colloidal silver 0.20 Mixing inhibitor AN-1 ...... 0.014 Mixing inhibitor AN-2 ...... 0.046 High boiling point solvent O-2 …… 0.096 Gelatin …… 0.90 Eighth layer (first blue sensitive layer) Yellow coupler C-4 …… 0.24 Antifading agent A-1 …… 0.096 Antifading agent A-5 …… 0.048 High Boiling point solvent O-3 ...... 0.048 AgBrI spectrally sensitized with blue sensitizing dye (S-4) (AgI3.
0 mol%, average particle size 0.4 μm) 0.15 Gelatin 0.95 9th layer (2nd blue sensitive layer) Yellow coupler C-4 0.32 Anti-fading agent A-1 0.13 Anti-fading agent A-5 …… 0.064 High boiling point solvent O-3 …… 0.064 AgBrI spectrally sensitized with blue sensitizing dye (S-4) (AgI3.
0 mol%, average particle size 0.8 μm) 0.13 Gelatin 0.93 10th layer (UV absorbing layer) UV absorber U-1 ...... 0.45 UV absorber U-2 ...... 0.15 Color mixture inhibitor AN-1 0.033 High-boiling point solvent O-3 0.37 Gelatin 1.87 11th layer (protective layer) Gelatin 0.50 In addition to the above, a surfactant, a hardener, and an anti-irradiation dye are contained.

O-1 di-2-ethylhexyl phthalate O-2 di-isodecyl phthalate O-3 di-nonyl phthalate The silver halide emulsion used in each color-sensitive layer is described in JP-A-59-17.
No. 8447 was prepared by the method of Example 1 of Public Relations. Each emulsion of the photosensitive silver halide emulsion layer except for the third layer of Sample-301 was desalted and washed with water, and then 55 ° C in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate at pAg.
The optimum chemical ripening was performed at = 9.0.

On the other hand, the conditions for chemical ripening of the third layer silver halide emulsion are shown in Table 5.

Further, various silver halide emulsions for use in the third layer of Sample-301 were prepared under the conditions shown in Table 5 and replaced with the silver halide emulsion of the third layer of Sample-301. 3
10 were produced.

For each of the prepared samples 301 to 310, 55 ° C, 60% R.
Wedge exposure was performed using white light for each of those left for 5 days under H condition and those immediately after production, and then the following development processing was performed. Processing step Processing time (processing temperature) First development (monochrome development) 1 minute 15 seconds (38 ℃) Washing with water 1 minute 30 seconds Light fog 100lux or more 1 second or more Second development (color development) 2 minutes 15 seconds (38 ℃) Water washing 45 seconds Bleach fixing 2 minutes (38 ℃) Water washing 2 minutes 15 The composition of the treatment liquid used in the above treatment step is as follows.

(First developer) Potassium sulfite 3.0g Sodium thiocyanate 1.0g Sodium bromide 2.4g Potassium iodide 8.0mg Potassium hydroxide (48%) 6.2ml Potassium carbonate 14g Sodium hydrogencarbonate 12g 1-Phenyl-4-methyl-4 -Hydroxymethyl-3
-Pyrazolidone 1.5g Hydroquinone monosulfonate 23.3g Water added 1.0 (pH 9.65) (Color developer) Benzyl alcohol 14.6ml Ethylene glycol 12.6ml Potassium carbonate (anhydrous) 26g Potassium hydroxide 1.4g Sodium sulfite 1.6g 3,6 -Dithiaoctane-1,8-diol 0.24g Hydroxylamine sulfate 2.6g 4-N-ethyl-N-β- (methanesulfonamidoethyl) -2-methyl-p-phenylenediamine sesquisulfate 5.0g Water added 1.0 (Bleach-fixing solution) Ammonium salt of ethylenediaminetetraacetate diiron complex
1.56 mol solution 115 ml Sodium metabisulfite 15.4 g Ammonium thiosulfate (58%) 126 ml 5-mercapto-1,2,4-triazole 0.4 g Water was added 1.0 (pH = 6.5) Was measured to determine the relative sensitivity and the maximum color density (D max).

The relative sensitivity was determined by calculating the reciprocal of the exposure required to obtain a red reflection density of 1.7 and setting Sample 301 as 100
302 to 310 are shown as relative sensitivity to sample 301.

 The results are shown in Table-6.

As is clear from the results shown in Table 6, the sample using the emulsion chemically ripened under the conditions of the present invention has high sensitivity and shows excellent storability over time, and suppresses a change in sensitivity and a decrease in maximum density. I was able to.

〔The invention's effect〕

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity, low fog and improved storability can be obtained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-58-125612 (JP, A)

Claims (1)

(57) [Claims] 1. A thiocyanate, a selenocyanate, which undergoes substantial chemical ripening within a pAg value range of 6.0 to 8.8, and which forms a sparingly soluble salt with silver ions before or during the start of chemical ripening. A silver halide photographic light-sensitive material comprising at least one light-sensitive layer having a silver halide emulsion which has undergone a process of increasing the pAg value by adding at least one selected from carbonate and sulfite.