JPH0764242A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material containing a diffusion-resistant dye good in absorption spectrum characteristics by forming a photographic layer having a fine solid dispersion of specified dye particles. CONSTITUTION:At least one of the photographic constituent layers formed on a support contains the fine solid dispersion of at least one kind of dye represented by the formula; B=CH-N=A in which A is an acid nucleus, preferably, such as 5-pyrazolone, hydroxypyridone, barbituric acid, or isoxazolone, especially, 5-pyrazolone; and B is a basic nucleus having at least one carboxylic group, preferably, such as oxazole, benzoxazole, indolenine, or pyridine, and each of A and B is optionally substituted by alkyl, aryl, or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material containing a novel dye, and more particularly to a halogenated silver halide photographic light-sensitive material containing a novel diffusion-resistant dye having improved outflow decolorization during rapid processing. The present invention relates to a silver photographic light-sensitive material.

[0002]

2. Description of the Related Art Silver halide photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials) are required to have excellent image quality characteristics such as sharpness and color reproducibility. In order to counter the property, further shortening of processing time, that is, rapid processing suitability is required.

In a light-sensitive material, a light absorption filter,
For the purpose of preventing halation, preventing irradiation or adjusting the sensitivity of the photosensitive emulsion, it is well known to incorporate a dye into the constituent layer of the light-sensitive material in order to absorb light of a specific wavelength. Coloring the hydrophilic colloid layer with a dye has been conventionally performed.

Of the constituent layers of the light-sensitive material described above, the filter layer is usually positioned above the light-sensitive emulsion layer or between the emulsion layer and another emulsion layer, and the incident light reaching the emulsion layer is preferable. It plays a role in changing the spectral composition. Further, the antihalation layer is provided between the photosensitive emulsion layer and the support or on the back surface of the support for the purpose of improving the sharpness of the image, and is provided at the interface between the emulsion layer and the support or the back surface of the support. It absorbs harmful reflected light and improves the sharpness of the image.

Further, the sharpness of an image is improved by coloring a light-sensitive emulsion layer with a dye to absorb harmful reflected light or scattered light to silver halide grains to prevent irradiation. Has also been done.

Recently, dyes (hereinafter referred to as "YC dyes") intended to replace yellow colloidal silver in color photographic light-sensitive materials.
Application) and dyes for dyeing a crossover cut layer in an X-ray photographic light-sensitive material, dyes for dyeing a non-light-sensitive emulsion layer in a printed photographic light-sensitive material, and so on.

The dye used for such purpose has, of course, good absorption spectrum characteristics depending on the purpose of use, and is, for example, completely decolorized during the development process and easily removed from the light-sensitive material during the development process. It does not cause residual color contamination due to dye after processing, does not adversely affect fog or desensitization on photosensitive emulsion, does not diffuse from colored layer to other layers, photosensitive material or solution. It must have excellent stability over time and satisfy various conditions such as no discoloration.

To date, many studies have been conducted for the purpose of finding dyes satisfying the above-mentioned conditions, for example, US Pat. Nos. 3,540,887, 3,544,325, and 3,560,214.
Nos. 3,037,078, and JP 51-3623, and benzylidene dyes, and British Patent 506,385 and JP 39-39.
22069 proposes an oxonol dye, US Pat. No. 2,493,747 proposes a merocyanine dye, and US Pat. No. 1,845,404 proposes a styryl dye.

Some of these conventional dyes have a relatively small effect on the emulsion performance and have the ability to be bleached / eluted / erased in the processing step, but from the viewpoint of diffusion resistance. It was not enough. That is, when a specific layer of a plurality of emulsion layers is selectively colored and used as a filter layer or an antihalation layer, not only the diffusion to other layers is remarkable, but the light absorption effect is lowered,
There was a defect that it gave an unfavorable effect to other layers such as sensitivity deterioration, gradation change and fog abnormality. The dye itself is made resistant to diffusion as a means for preventing diffusion and migration of the dye to other layers, for example, U.S. Patents 2,538,008 and 2,539,009.
No. 4,420,555, JP-A-61-204630, 62-32460
Nos. 63-184749 and the like are disclosed, but all of these dyes have the disadvantage that they are not excellent in decolorizing property or solubility in a processing solution, and therefore, residual color contamination is increased.

Further, as a method for fixing a dissociative dye using a mordant to make it resistant to diffusion, for example, US Pat. No. 2,548,564,
Nos. 3,625,694 and 4,124,386 are disclosed.

However, in the method using a mordant, for example, gelatin which is a binder in the light-sensitive material constituting layer forms an aggregate with the mordant or increases the viscosity, which causes serious problems such as uneven coating and cissing. There are drawbacks that cause troubles, the diffusion between layers is not sufficiently suppressed, the elution and decolorization during processing are poor, and a high pH processing bath is required.
There was a drawback that it was inferior in suitability for rapid processing.

[0012] As a separate method, a dye whose pKa of the dye itself is molecularly designed to be easily dissolved in a high pH solution is used.
Dispersed in a hydrophilic colloid layer having a low pH as a solid fine particle dispersion, for example, U.S. Pat.Nos. 4,855,221 and 4,857,446,
4,948,717, JP-A-52-92716, 55-155350,
55-155351, 56-12639, 63-197943, JP-A-2-
110453, 2-1838-9, 2-191942, 2-264247
No. 2-264936, No. 2-277044, No. 4-37841, and World Patent No. 88/04794 are disclosed.

However, this method requires the dye molecules
As a result, the type of dye is structurally limited to give pKa, and there is a drawback that a dye having a desired absorption wavelength is difficult to obtain, and decolorizing property in rapid processing is not sufficient,
There is a drawback that residual color contamination occurs. Therefore, the decolorizing property is good,
There is a strong need for diffusion resistant dyes having the desired spectral characteristics.

[0014]

Therefore, a first object of the present invention is to have good absorption spectrum characteristics and diffusion resistance in a light-sensitive silver halide emulsion layer or a non-light-sensitive colloid layer. It is intended to provide a silver halide photographic light-sensitive material containing a dye.

A second object of the present invention is to provide a silver halide photographic light-sensitive material containing a dye which is excellent in elution and decolorization during the photographic processing step and is suitable for rapid processing.

A third object of the present invention is to provide a silver halide photographic light-sensitive material containing a dye which does not adversely affect the photographic characteristics such as fog and desensitization of the light-sensitive silver halide emulsion. It is in.

[0017]

The above object of the present invention can be achieved by the following constitutions.

(1) A silver halide photographic light-sensitive material having on a support at least one photographic constituent layer containing at least one dye represented by the following formula [I].

General formula [I] B = CH-N = A In the formula, A represents an acidic nucleus and B represents a basic nucleus. However,
It has at least one carboxy group in the molecule.

(2) In the dye represented by the general formula [I] of (1) above, the acidic nucleus A is 5-pyrazolone, hydroxypyridone, barbituric acid, thiobarbituric acid,
The silver halide photographic light-sensitive material according to (1) above, which is oxazolone, isoxazolone, rhodanine, hydantoin, thiohydantoin, indandione, oxazolidinedione, or pyrazolidinedione.

(3) In the dye represented by the general formula [I] of (1), the basic nucleus B is pyridine, quinoline, oxazole, benzoxazole, pyrrole, indole or indolenine. Silver halide photographic light-sensitive material.

The dye represented by formula (I) according to the present invention will be described below.

The acidic nucleus represented by A in the general formula [I] is
Preferred are 5-pyrazolone, hydroxypyridone, barbituric acid, thiobarbituric acid, oxazolone, isoxazolone, rhodanine, hydantoin, thiohydantoin, indandione, oxazolidinedione, and pyrazolidinedione. More preferred are 5-pyrazolone, hydroxypyridone, barbituric acid and isoxazolone, and even more preferred is 5-pyrazolone.

The basic nucleus represented by B in the general formula [I] is preferably pyridine, quinoline, oxazole,
Benzoxazole, pyrrole, indole, indolenine. More preferred are oxazole, benzoxazole, indolenine and pyridine.

Acid nucleus A and basic nucleus B of the general formula [I]
May have a substituent, and examples of the substituent include an alkyl group (eg, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, n-hexyl group, etc.), Halogen atom (eg, each atom such as chlorine, bromine, iodine, fluorine, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group), heterocyclic group (eg, pyrrolidyl group,
Pyridyl group, furyl group, thienyl group, etc.), carboxyl group, nitro group, hydroxyl group, mercapto group, amino group (eg amino group, diethylamino group etc.), alkyloxy group (eg methyloxy group, ethyloxy group, n-butyloxy group) , N-octyloxy group, isopropyloxy group, etc.), aryloxy group (phenyloxy group, naphthyloxy group, etc.), carbamoyl group (eg, aminocarbonyl group, methylcarbamoyl group, n-pentylcarbamoyl group, phenylcarbamoyl group, etc.) , Amide group (eg, methylamide group, benzamide group, n-octylamide group, etc.), aminosulfonylamino group (eg, aminosulfonylamino group, methylaminosulfonylamino group, anilinosulfonylamino group, etc.), sulfamoyl group (eg, sulfamoyl group) , Meth Sulfamoyl group, phenylsulfamoyl group, etc. n- butyl sulfamoyl group),
Sulfonamide group (eg methanesulfonamide group, n-
Heptanesulfonamide group, benzenesulfonamide group, etc.), sulfinyl group (eg methylsulfinyl group,
Ethylsulfinyl group, phenylsulfinyl group, octylsulfinyl group, etc.), alkyloxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, 2-hydroxyethyloxycarbonyl group, n-
Octyloxycarbonyl group etc.), aryloxycarbonyl group (eg phenyloxycarbonyl group, naphthyloxycarbonyl group etc.), alkylthio group (eg methylthio group, ethylthio group, n-hexylthio group etc.), arylthio group (eg phenylthio group, naphthylthio group) Groups), alkylcarbonyl groups (eg acetyl group, ethylcarbonyl group, n-butylcarbonyl group, n-octylcarbonyl group etc.), arylcarbonyl groups (eg benzoyl group, p-methanesulfonamidobenzoyl group, p-carboxybenzoyl group) Group, naphthoyl group, etc.), cyano group, ureido group (eg, methylureido group, phenylureido group, etc.), thioureido group (eg, methylthioureido group, phenylthioureido group, etc.), alkylsulfonyl group (eg, methylsulfone group) Group, ethylsulfonyl group, n-
Butylsulfonyl group, n-octylsulfonyl group, etc.), arylsulfonyl group (for example, phenylsulfonyl group,
p-hydroxyphenylsulfonyl group) and the like.

Next, typical examples of the dye of the present invention will be given.

[0027]

[Chemical 1]

[0028]

[Chemical 2]

[0029]

[Chemical 3]

[0030]

[Chemical 4]

[0031]

[Chemical 5]

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

The dye represented by the general formula [I] used in the present invention is described in US Pat. No. 2,646,409 and JP-A-58-120245.
Can be synthesized according to the method described in No.

Specific synthetic examples are shown below.

Synthesis Example 1 (Exemplary Dye-10) 2-Methylbenzoxazole Ethiodide 11.6 g, 1- (P
-Carboxy) phenyl-3-ethoxycarbonyl-4-isonitroso-5-pyrazolone 12.2g, anhydrous sodium acetate 4.9
A mixture of g and 250 ml of acetic anhydride was heated and stirred under reflux for 30 minutes. After allowing the reaction solution to cool, the precipitated crystals were collected by filtration and recrystallized from ethanol to obtain 3.5 g of Dye (10).
The structure of the compound was confirmed by NMR. The λmax of the methanol solution of this dye was 494 nm.

Synthesis Example 2 (Exemplary Dye-23) 5-Methylsulfonyl-2,3,3-trimethylindolenin Ethiodide 19.7 g, 1- (P-carboxy) phenyl-3-ethoxycarbonyl-4-isonitroso-5 -A mixture of pyrazolone 15.3 g and acetic anhydride 200 ml was heated and stirred under reflux for 30 minutes.
The reaction solution was allowed to cool and then poured into 500 ml of water, and the precipitated crystals were taken in a furnace and dried. By recrystallizing from acetic acid, 10.5 g of dye (23) was obtained. The structure of the compound was confirmed by NMR. The λmax of the methanol solution of this dye was 530 nm.

The dye of the present invention comprises a silver halide emulsion layer,
It can be used by being contained in other hydrophilic colloid layers. The dye of the present invention can be dissolved in an organic solvent or a weakly alkaline aqueous solution to be contained in the layer. Preferably, the dye of the present invention can be contained as a solid fine particle dispersion.

The solid fine particle dispersion means a state of being dispersed as a solid having a size that is substantially diffusion resistant in the layer. Specifically, for example, the method described in JP-A-63-197943 can be used in which a surfactant (nonionic surfactant) is used for emulsion dispersion and stabilization with a gelatin solution.

The solid fine particle dispersion is prepared by dissolving a dye in a weak alkaline solution and adjusting the pH to weakly acid to produce a fine particle dispersion, or a known method of forming fine particles in the presence of a dispersant, for example, It can be prepared by ball milling, sand milling, colloid milling, roller milling and the like. The fine particles in the solid fine particle dispersion preferably have an average particle diameter of 0.01 to 10 μm, particularly preferably 0.01 to 1 μm. The preferable amount of the dye used in the present invention is not uniform depending on the type of the dye, the characteristics of the light-sensitive material and the like, but it is preferably 1 mg to 1 g per m ² of the light-sensitive material of the present invention, particularly preferably 10 mg to 500 mg. Is. 0.0 as the optical density
Used to be 5 to 3.0.

In the present invention, the photographic constituent layer is, for example,
A blue-sensitive emulsion layer, a green-sensitive emulsion layer, a red-sensitive emulsion layer, an undercoat layer, an intermediate layer, a protective layer, a filter layer, an antihalation layer and an antiirradiation layer, and the dye of the present invention is
Further, it can be used as a photosensitive layer or a non-photosensitive layer.
Furthermore, a backing layer on the side opposite to the photosensitive layer side, a protective layer,
It can also be used in a hydrophilic layer such as an undercoat layer. When used for the hydrophilic layer on the side opposite to the photosensitive layer side, the layer closest to the support is preferred.

The dyes of the present invention may be used in combination of two or more kinds in order to obtain a desired absorption wavelength depending on the color sensitivity of the light-sensitive material, and, if necessary, known dyes conventionally used with the dyes of the present invention. You may use combining the dye for use.

The hydrophilic colloid layer can contain various gelatins, synthetic or natural polymers as hydrophilic binders. For example, gelatin derivative, graft polymer of gelatin and other polymer, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
A homopolymer or copolymer of vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide or the like can be used.

The silver halide emulsion used in the light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide,
Any of those commonly used in silver halide emulsions such as silver chloroiodobromide and silver chloride can be used. The silver halide grains may be any of cubic, octahedral, dodecahedral, tetrahedral or tabular shapes, and a mixture of grains of various shapes may be used. Preferred are particles having a regular shape and a narrow particle size distribution. The average grain size of the silver halide grains is preferably 0.02 to 3.0 μm, more preferably 0.05 to 2.0 μm. The thickness of tabular silver halide grains is 0.05 to 1.
It is preferably 0 μm, more preferably 0.05 to
It is 0.4 μm. The grain size distribution of silver halide grains is (standard deviation of grain size / average grain size) x 100 = width of grain size distribution
When the breadth of distribution is defined by (%), it is preferably 20% or less, more preferably 15% or less.

Various known sensitization methods can be used for the silver halide emulsion, and when chemical sensitization is used, a sulfur sensitization method, a reduction sensitization method, a noble metal sensitization method or the like is used alone or in combination. be able to. In addition, a sensitizing dye can be used to optically sensitize a desired wavelength range.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. Especially when it is used for printing plate making, a tetrazolium compound or a hydrazine compound known as a so-called contrast adjusting agent is added. Good. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the emulsion layer of the color photographic light-sensitive material.

As the yellow dye-forming coupler, known acylacetanilide type couplers can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

Specific examples of the yellow coupler include, for example, British Patent 1,077,874, Japanese Patent Publication No. 45-40757, and Japanese Patent Laid-Open No. 47-103.
No. 1, 47-26133, 48-94432, 50-87650, 5
1-3631, 52-115219, 54-99433, 54-133329
No. 56-30127, U.S. Patent No. 2,875,057, and No. 3,253,924.
No., No. 3,265,506, No. 3,408,194, No. 3,551,155, No.
3,551,156, 3,664,841, 3,725,072, 3,73
0,722, 3,891,445, 3,900,483, 3,929,484
No., No. 3,933,500, No. 3,973,968, No. 3,990,896,
4,012,259, 4,022,620, 4,029,508, 4,0
57,432, 4,106,942, 4,133,958, 4,269,93
No. 6, No. 4,286,053, No. 4,304,845, No. 4,314,023,
4,336,327, 4,356,258, 4,386,155, 4,4
No. 01,752 etc.

As the magenta dye forming coupler, 5-pyrazolone type couplers, pyrazolobenzimidazole type couplers, pyrazoloazole type couplers and open chain acylacetonitrile type couplers can be preferably used.

Specific examples of magenta couplers that can be advantageously used include Japanese Patent Application Nos. 58-164882, 58-167326 and 58-206321.
No. 58, No. 58-214863, No. 58-217339, No. 59-24653, No. 40-6031, No. 40-6035, No. 45-40757, No. 47-274.
11, 49-37854, JP-A-50-13041, 51-26541
No. 51, No. 51-37646, No. 51-105820, No. 52-42121, No. 5
3-123129, 53-125835, 53-129035, 54-485
No. 40, No. 56-29236, No. 56-75648, No. 57-17950, No.
57-35858, 57-146251, 59-99437, British patent
1,252,418, U.S. Patents 2,600,788, 3,005,712,
3,062,653, 3,127,269, 3,214,437, 3,2
53,924, 3,311,476, 3,419,391, 3,519,429
Issue 3,558,319, Issue 3,582,322, Issue 3,615,506,
No. 3,658,544, No. 3,705,896, No. 3,725,067, No. 3,7
58,309, 3,823,156, 3,834,908, 3,891,44
No. 5, No. 3,907,571, No. 3,926,631, No. 3,928,044,
3,935,015, 3,960,571, 4,076,533, 4,1
33,686, 4,237,217, 4,241,168, 4,264,72
No. 3, No. 4,301,235, No. 4,310,623, etc.

As the cyan dye forming coupler, naphthol type couplers and phenol type couplers can be preferably used.

Specific examples of cyan couplers that can be advantageously used include British Patents 1,038,331 and 1,543,040, Japanese Patent Publication No. 48-3.
6894, JP-A-48-59838, 50-137137, 51-1468
No. 28, No. 53-105226, No. 54-115230, No. 56-29235,
56-104333, 56-126833, 57-133650, 57-
155538, 57-204545, 58-118643, 59-31953
No. 59-31954, 59-59656, 59-124341, 5
9-166956, U.S. Patents 2,369,929, 2,423,730,
2,434,272, 2,474,293, 2,698,794, 2,772,
No. 162, No. 2,801,171, No. 2,895,826, No. 3,253,924
No., No. 3,311,476, No. 3,458,315, No. 3,476,563, No.
3,591,383, 3,737,316, 3,758,308, 3,76
7,411, 3,790,384, 3,880,661, 3,926,634
No. 4, No. 4,004,929, No. 4,009,035, No. 4,012,258,
4,052,212, 4,124,396, 4,134,766, 4,1
38,258, 4,146,396, 4,149,886, 4,178,18
No. 3, No. 4,205,990, No. 4,254,212, No. 4,264,722,
4,288,532, 4,296,199, 4,296,200, 4,29
No. 9,914, No. 4,333,999, No. 4,334,011, No. 4,386.155
No. 4,401,752, No. 4,427,767, etc.

Further, by coupling with a colored coupler having a color correcting effect, a competing coupler and an oxidized product of a developing agent, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, a hardener and a hardener. Compounds that release photographically useful fragments such as film agents, fogging agents, antifoggants, chemical sensitizers and spectral sensitizers and sensitizers are used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an anti-irradiation layer, and these layers and / or emulsion layers may flow out of the light-sensitive material during development or It may contain a dye to be bleached.

A formalin scavenger, a fluorescent whitening agent, a matting agent, a slipping agent, an image stabilizer, a surfactant, an antifoggant, a development accelerator, a development retarder or a bleaching accelerator can be added to the light-sensitive material. .

As the support of the photosensitive material, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

To obtain an image using the light-sensitive material of the present invention, generally known photographic processing can be carried out after exposure.

Known additives and the like that can be used in the present invention include, for example, Research Disclosure (RD) N.
No. 17643 (December 1978), No. 18716 (November 1979) and No. 308119 (December 1989), and their description locations are shown below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 IV Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII

[0063]

EXAMPLES Specific examples of the present invention will be given below, but the mode for carrying out the present invention is not limited to these.

Example 1 In this example, a silver halide photographic light-sensitive material was prepared as follows.

First, an emulsion was prepared as follows.

(A) Preparation of Monodisperse Emulsion By using the double jet method while maintaining 60 ° C., pAg = 8, and pH = 2 as conditions for the reaction kettle, iodine containing 2 mol% of silver iodide having an average grain size of 0.3 μm was used. A monodisperse cubic emulsion of silver bromide was obtained.
According to electron microscope observation, the generation rate of twins was 1% or less in number. This emulsion was used as a seed crystal and further grown as follows.

The gelatin aqueous solution was kept at 40 ° C. in the reaction vessel, and the above seed crystals were added.
I adjusted it to 9.5.

After adjusting the pAg to 7.3 with an ammoniacal silver ion solution, a solution containing ammoniacal silver ions, potassium iodide and potassium bromide was added by the double jet method while keeping the pH and pAg constant, and the iodide was added. A silver iodobromide layer containing 30 mol% of silver was formed.

After adjusting the pH to 9 and pAg to 9.0 using acetic acid and silver bromide, an ammoniacal silver ion solution and potassium bromide were simultaneously added and grown to 90% of the grain size after growth.

At this time, the pH was gradually lowered from 9.0 to 8.20.

After adding potassium bromide solution to pAg = 11, further adding ammoniacal silver ion solution and potassium bromide
The pH was gradually lowered to pH 8 and allowed to grow, with an average particle size of 0.
A silver iodobromide emulsion containing 7 μm and 2 mol% of silver iodide was obtained.

During the preparation of the emulsion, the following sensitizing dye (A) was added at 300 mg and silver sensitizing dye (B) at 15 mg per mol of silver in the emulsion to obtain an emulsion.

[0073]

[Chemical 9]

Next, as shown below, a desalting step for removing excess salt was carried out.

The silver halide emulsion solution was kept at 40 ° C. and the following compound (a) (exemplified compound II-1 shown in JP-A-58-140322) was added to precipitate silver halide grains. After discharging the supernatant, pure water at 40 ° C was further added. Then, magnesium sulfate is added and the silver halide grains are allowed to settle again, and the supernatant is removed. This was repeated once and gelatin was added to obtain an emulsion having pH 6.0 and pAg 8.5.

[0076]

[Chemical 10]

The emulsion obtained above was kept at 55 ° C., chloroauric acid and hypo were added for chemical sensitization, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added. A photosensitive emulsion was obtained. This is designated as emulsion (A).

T-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10.0 per mol of silver halide as an additive to the photosensitive emulsion of (A) above. g Diethylene glycol 5.0g Nitrophenyl-triphenylphosphonium chloride 50mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 4.0g 2-Mercaptobenzimidazole-5-sodium sulfonate 5.0mg

[0079]

[Chemical 11]

[0080]

[Chemical 12]

Matting agent composed of polymethylmethacrylate having an average particle size of 3.5 μm 7 mg Colloidal silica having an average particle size of 0.013 μm 70 mg 2-Hydroxy-4,6-dichlorotriazine sodium 30 mg Samples using the above coating solutions, such as the following 1-1 was created.

Sample 1-1 As the subbing liquid, glycidyl methacrylate 50 Wt%, methyl methacrylate 10 wt%, butyl methacrylate 40 wt
% Copolymer was diluted to a concentration of 10% by weight, and an aqueous copolymer dispersion was applied to both surfaces to obtain an undercoated support. Then the emulsion layer so that 3.2 g / m ² as a one-sided silver on the support, a protective layer such that the 0.98 g / m ² as a one-sided amount of gelatin was simultaneous double side coated with coating speed 140 m / min.

Sample 1-2 Sample 1-1 was coated so that a crossover cut layer containing a dye shown in Table 1 was inserted between the emulsion layer and the subbing layer. The dye was added by dissolving the dye in methanol containing a small amount of triethylamine and then adding it to an aqueous gelatin solution to adjust the pH to 6.0 to obtain a coating solution.

Samples 1-3 to 1-10 Coating was performed in the same manner as in Sample 1-2 so that a crossover cut layer was inserted. However, as the method of adding the dye, solid fine particles were dispersed and the dye was added. Sample 1-2 to 1-10
The amount of the dye added was 40 mg / m ² per 1 m ^{2 on} both sides. The amount of gelatin was 0.4 g / m ² .

The collective fine particle dispersion of the dye was performed by ball mill dispersion according to the following procedure. Water and a surfactant alkanol XC were put in a ball mill container, each dye was added, beads of zirconium oxide were put, the container was sealed, and the ball mill dispersion was carried out for 4 days.

The samples thus obtained were evaluated as follows.

(Measurement of sensitometry) Using the standard light B described in "New Edition, Data Book of Illumination" as a light source, the exposure time is 0.1 seconds, 3.2 cms is non-filtered so that the same light amount is obtained on both sides of the film. Exposed. The above sample is SRX
Using a -501 automatic developing machine (manufactured by Konica Corporation), processing was carried out for 45 seconds with an XD-SR developing solution, and after fixing and drying, the sensitivity of each sample was determined. The sensitivity was represented by the relative sensitivity with the sensitivity in the case of Sample 1-1 in Table 1 taken as 100, by calculating the reciprocal of the amount of light required to increase the blackening density by 1.0.

(Evaluation of MTF) An MTF chart containing a rectangular wave made of lead of 0.5 to 10 lines / mm was put on a fluorescent screen KO.
It was brought into close contact with the back surface of the front side of -250 (manufactured by Konica Corp.) and irradiated with X-rays so that the density of the portion of the film surface not covered by the lead chart was about 1.0 on both surfaces.

The sample irradiated with X-rays as described above was developed in the same manner as described above, and the recorded rectangular wave pattern was recorded on a Sakura Microdensitometer M-5 type (manufactured by Konica Corporation). Used and measured. The aperture size at this time is 300 μm in the direction parallel to the rectangular wave and in the direction perpendicular to it.
It was 25 μm and the magnification was 20 times. MT obtained
The F value is representatively shown by the value of spatial frequency 2.0 line / mm.

[0090]

[Chemical 13]

[0091]

[Table 1]

As described above, the sample of the present invention has improved sharpness as compared with the comparative sample, although the sensitivity is less decreased.

On the other hand, instead of the monodisperse emulsion (A), the following polydisperse emulsion (B) and tabular grains (C) were prepared.

(B) Preparation of Polydisperse Emulsion The following four kinds of solutions were prepared by the normal mixing method.

Solution A Silver nitrate 100 g Ammonia water (28%) 78 ml Water is added 240 ml Solution B Ocein gelatin 8 g Potassium bromide 80 g Potassium iodide 1.3 g Water is added 550 ml Solution C ammonia solution 6 ml Glacial acetic acid 10 ml Water 34 ml D Liquid 226ml Glacial acetic acid Add water to make 400ml.

Solution B and solution C were poured into a reaction kettle for emulsion preparation and stirred with a propeller-type stirrer at a rotation speed of 300 rpm to keep the reaction temperature at 55 ° C.

Next, the solution A is divided into a ratio of 1 volume: 2 volumes,
One volume, 100 ml, was added over 1 minute. Ten
After continuing stirring for 1 minute, add 200 ml of the remaining 2 volumes of solution A to 1
It was put in over 0 minutes. Stirring was continued for another 30 minutes. Then, the solution D was added to adjust the pH of the solution in the reaction vessel to 6.0, and the reaction was stopped.

The silver halide grains had an average grain size of 0.56 μm and a dispersity of 0.32. The silver iodide content is 1.2
It was mol%.

(C) Preparation of tabular grains KBr 10.5 g and thioether compound [HO (CH ₂ ) ₂ S were added to 1 liter of water.
_{(CH 2) 2 S (CH} 2) 2 0H] 0.5wt% aqueous solution 10 ml, and gelatin 30
g was added and dissolved, and the mixture was kept at 70 ° C.

While stirring in this solution, 30 ml of an aqueous silver nitrate solution (0.88 mol / l) and 30 ml of an aqueous solution of potassium iodide and potassium bromide (molar ratio 3.5: 96.5) (0.88 mol / l) were used in the double jet method. To obtain grains having an average grain size of 0.60 μm and a silver iodide content of 3.5 mol%. After the addition of the mixed solution was completed, the temperature was lowered to 40 ° C. Condensate of sodium naphthalene sulfonate and formalin and M
24.6 g / AgX1 mol of gSO ₄ was added to each to lower the pH to 4.0 for desalting, and then 15 g of gelatin / AgX1
An emulsion was prepared by adding moles.

Regarding the emulsions obtained in the above (B) and (C),
Chemical sensitization was performed. That is, ammonium thiocyanate, chloroauric acid and hypo were added to perform gold-sulfur sensitization.

After completion of the chemical sensitization, 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene was added. After that, 150 mg of potassium iodide / 1 mol of AgX and the sensitizing dyes (A) and (B) were added in the same amounts as in the case of the emulsion (A) to carry out spectral sensitization. The emulsions thus obtained are referred to as emulsions (B) and (C), respectively.

Additives similar to those of (A) were added to the photosensitive emulsions of (B) and (C) to prepare emulsion coating solutions. Using these coating liquids and the above-mentioned protective layer liquid, solid fine particle dispersion addition was carried out using the dye of the present invention in the same manner as described above, and coating was carried out so as to insert a crossover cut layer. A sample with less deterioration in sensitivity and improved sharpness was obtained.

Example 2 The following photographic constituent layers were provided on the undercoated cellulose acetate ester film having a thickness of 115 μm.

(Composition of Photographic Constituting Layer) The coating amount of silver halide and colloidal silver is g / m ² in terms of metallic silver.
The amounts are expressed in units, the amounts added in g / m ² for couplers, additives and gelatin, and the sensitizing dyes are expressed in moles per mole of silver halide in the same layer. The sample 2-1 is shown below.

Sample 2-1 First layer: antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (Oil-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer Compound (SC-1) 0.15 High boiling point solvent (Oil-2) 0.17 Gelatin 1.27 Third layer: Low sensitivity red sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.50 Silver iodobromide emulsion (average Grain size 0.27 μm, silver iodide content 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ^-4 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD- ⁴ ) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling point solvent (Oil-1) 0.53 Gelatin 1.30 4th layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8.0 mol) %) 0.62 Silver iodobromide emulsion (average grain size 0.38 .mu.m, a silver iodide content of 8.0 mol%) 0.27 Sensitizing dye (SD─1) 2.3 × 10 ^-4 Sensitizing dye (SD─2) 1.2 × 10 ^{- 4} Sensitizing dye (SD-3) 1.6 × 10 ^-5 Sensitizing dye (SD- ⁴ ) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler (CC-1) ) 0.030 DIR compound (D-1) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer: high-sensitivity red-sensitive layer Silver iodobromide emulsion (EM-1) 1.27 Sensitizing dye (SD-1) 1.3 × 10 ^-4 Sensitizing dye (SD-2) 1.3 × 10 ^-4 Sensitizing dye (SD-3) 1.6 × 10 ^-5 Cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91 Sixth layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (Oil-2) 0.11 Gelatin 0.80 Seventh layer: Low sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm Silver iodide content 8.0 mol%) 0.61 Silver iodobromide emulsion (average particle diameter 0.27 [mu] m, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD─4) 7.4 × 10 ^-5 Sensitizing dye (SD -5) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling point solvent (Oil-2) 0.75 Gelatin 1.95 8th layer: Medium sensitivity green-sensitive layer silver iodobromide emulsion (average grain size 0.59 .mu.m, a silver iodide content of 8.0 mol%) 0.87 sensitizing dye (SD─6) 2.4 × 10 ^-4 sensitizing dye (SD─7) 2.4 × 10 ^{- 4} Magenta coupler (M-1) 0.058 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.50 Gelatin 1.00 9th layer: High sensitivity green sensitive layer Silver iodobromide emulsion (EM-1) 1.27 Sensitizing dye (SD-6) 1.4 × 10 ^-4 Sensitizing dye (SD-7) 1 .4 × 10 ^-4 Magenta coupler (M-2) 0.084 Magenta coupler (M-3) 0.064 Colored magenta coupler (CM-1) 0.012 High boiling solvent (Oil-1) 0.27 High boiling solvent (Oil-2) 0.012 Gelatin 1.00 10th layer: Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil-2) 0.19 Gelatin 1.10 11th layer: Intermediate layer Formalin scavenger ( HS-1) 0.20 Gelatin 0.60 Layer 12: Low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.22 Silver iodobromide emulsion (average grain size 0.27 μm, Silver iodide content 2.0 mol%) 0.03 Sensitizing dye (SD-8) 4.9 × 10 ^-4 Yellow coupler (Y-1) 0.75 DIR compound (D-1) 0.010 High boiling solvent (Oil-2) 0.30 Gelatin 1.20 13th layer: Medium sensitivity blue sensitive layer Silver iodobromide emulsion (average Diameter 0.59 .mu.m, a silver iodide content of 8.0 mol%) 0.30 Sensitizing dye (SD─8) 1.6 × 10 ^-4 Sensitizing dye (SD─9) 7.2 × 10 ^-5 Yellow coupler (Y─1) 0.10 DIR compound (D-1) 0.010 High boiling solvent (Oil-2) 0.046 Gelatin 0.47 14th layer: High-sensitivity blue-sensitive layer Silver iodobromide emulsion (EM-1) 0.85 Sensitizing dye (SD-8) 7.3 × 10 ^-5 Sensitizing dye (SD-9) 2.8 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling point solvent (Oil-2) 0.046 Gelatin 0.80 15th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 UV absorber (UV-2) 0.10 High boiling solvent (Oil-1) 0.07 High boiling solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 16th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate (average particle size 3 μm 0.04 Lubricant (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, a coating aid Su-1, a dispersion aid Su-2, a viscosity modifier, a hardener H-1, H-2, Stabilizer ST-1, Antifoggant AF-1, Weight average molecular weight: 1
Two types of AF-2 with 000 and weight average molecular weight of 1,100,000
And the preservative DI-1 was added. The amount of DI-1 added is 9.
It was 4 mg / m ² .

[0107]

[Chemical 14]

[0108]

[Chemical 15]

[0109]

[Chemical 16]

[0110]

[Chemical 17]

[0111]

[Chemical 18]

[0112]

[Chemical 19]

[0113]

[Chemical 20]

[0114]

[Chemical 21]

Next, in place of the yellow colloidal silver of the 10th layer in the above sample 2-1, the dyes of the present invention shown in Table 2 were added as a solid dispersion to prepare samples 2-2 to 2-10. It was made.

Samples 2-1 to 2-10 prepared as described above
After exposure to wedge, the following processing steps were carried out to determine the sensitivity of the blue-sensitive emulsion layer and the fog of the green-sensitive emulsion layer. The sensitivity was obtained from the reciprocal of the exposure amount required to give a density of fog + 0.1, and shown as a relative value with Sample 2-1 as 100. In addition, the fog is shown as an increase in the density of each sample when the processing after the bleaching step is performed except for the color development step in the processing step. The results are also shown in Table 2.

[Treatment Process] Treatment process Treatment time Treatment temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C 780cc. Bleach 45 seconds 38 ± 2.0 ° C 150cc. Settling 1 minute 30 seconds 38 ± 2.0 ° C 830cc. Stability 60 seconds 38 ± 5.0 ℃ 830cc. Drying 1 minute 55 ± 5.0 ℃ − * Replenishment amount is the value per 1 m ² of light-sensitive material.

The following color developing solution, bleaching solution, fixing solution, stabilizing solution and its replenishing solution were used.

Color developer water 800 cc. Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulphate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl-N -Ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g Diethylenetriaminepentaacetic acid 3.0g Potassium hydroxide 1.2g Add water to make 1 liter and add potassium hydroxide or 20%
Adjust to pH 10.06 with sulfuric acid.

Color development replenisher water 800 cc. Potassium carbonate 35 g sodium hydrogen carbonate 3 g potassium sulfite 5 g sodium bromide 0.4 g hydroxylamine sulfate 3.1 g 4-amino-3-methyl-N-ethyl-N- (β-hydroxylethyl ) -Aniline sulfate 6.3g Potassium hydroxide 2g Diethylenetriaminepentaacetic acid 3.0g Add water to make 1 liter and add potassium hydroxide or 20%
Adjust to pH 10.18 with.

Bleaching solution Water 700 cc. 1,3 Diaminopropanetetraacetic acid iron (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make 1 liter and aqueous ammonia or glacial acetic acid was used. Adjust to pH 4.4.

Bleaching Replenisher Water 700 cc. 1,3 Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting to pH 4.4 with aqueous ammonia or glacial acetic acid Add water to make 1 liter.

Fixing solution Water 800 cc. Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.2 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher water 800 cc. Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 with aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilizer and stable replenisher Water 900 cc. Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UCC) L-77) 0.1g Ammonia water 0.5cc. Add water to make 1 liter, then use ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

[0126]

[Table 2]

[0127]

The silver halide photographic light-sensitive material according to the present invention contains a diffusion resistant dye, which is excellent in elution and decoloring property during development processing and excellent in rapid processing suitability.

Further, the dye does not adversely affect photographic characteristics such as fog and desensitization.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material comprising at least one photographic constituent layer containing a solid fine particle dispersion of a dye represented by the following general formula [I] on a support. General formula [I] B = CH-N = A [In formula, A represents an acidic nucleus and B represents a basic nucleus. However, it has at least one carboxy group in the molecule. ] 2. The acid nucleus A is 5-pyrazolone, hydroxypyridone, barbituric acid, thiobarbituric acid, oxazolone, isoxazolone, rhodanine, hydantoin, thiohydantoin, indandione, oxazolidinedione, pyrazolidinedione. 2. The silver halide photographic light-sensitive material according to claim 1, wherein 3. The silver halide photographic light-sensitive material according to claim 1, wherein the basic nucleus B is pyridine, quinoline, oxazole, benzoxazole, pyrrole, indole or indolenine.