JP3528077B2 - Method for producing silver halide emulsion and silver halide photographic material - Google Patents

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, and more specifically, it relates to a silver halide emulsion having high sensitivity but little fog, reciprocity law failure characteristics and improved storage stability. The present invention relates to a manufacturing method and a silver halide photographic light-sensitive material using the same.

[0002]

2. Description of the Related Art While silver halide color photographic light-sensitive materials are said to be mature products with extremely high degree of perfection, required performances are wide-ranging such as high sensitivity, high image quality, and little performance fluctuation due to storage conditions. Further, in the future, it is necessary to take into consideration rapid processing suitability by accelerating the development progress, and the required level thereof has been increasing more and more in recent years.

Particularly in terms of high sensitivity, due to recent technological advances in digital cameras, in order to maintain the superiority of silver halide light-sensitive materials, fog is kept low, and further high sensitivity is achieved at the same time. Needs to be converted.

Sensitization technology for sensitizing a silver halide emulsion, that is, sensitization technology relates to a method for producing a silver halide emulsion, chemical sensitization of a silver halide emulsion, and spectral sensitization of a silver halide emulsion. Various methods are known, such as a method for designing a silver halide light-sensitive material, a method for developing a silver halide light-sensitive material, and the like. Among them, the most preferable and essential method is the method of exposing a silver halide crystal. It is to reduce inefficiency in the process and improve quantum efficiency. Chemical sensitization is one of the means, and there are chalcogen sensitization such as sulfur sensitization, selenium sensitization, and tellurium sensitization, precious metal sensitization using a precious metal such as gold, and reduction sensitization using a reducing agent. , These are used alone or in combination. Above all, when sulfur sensitization or selenium or tellurium sensitization is used in combination with gold sensitization, a marked increase in sensitivity can be obtained, but at the same time, fog also increases. In particular, compared to gold-sulfur sensitization, gold-selenium and tellurium sensitization causes a particularly large increase in fog, and a technique for suppressing the occurrence of fog, a fog at the time of storage, and a sensitization technique development with less sensitivity fluctuation have been desired. In addition, many practical silver halide grains have a grain size distribution and an average silver iodide content distribution, and are optimally spectrally sensitized and optimally chemically sensitized by such a system. However, the level of uniformity between and within silver halide grains has not reached a sufficient level.

Patents disclosing methods for adding photographic additives include, for example, JP-A Nos. 4-12344 and 4-125.
No. 633, No. 5-80445, No. 7-219094, etc., but these are different from the present invention because they are intended to be uniformly adsorbed on a silver halide such as adsorbing an adsorbent at a low temperature. Is.

The order of addition of gold sensitizers and chalcogen sensitizers and the interval between the addition timings are disclosed in JP-A-5-127289 and JP-A-7-209791. The combination of the temperature history and the order of addition of the sensitizer is not described, and it cannot be a known example of the present invention.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to provide a method for producing a silver halide emulsion having high sensitivity but little fog, improved reciprocity law failure characteristics and storability, and a silver halide photograph using the same. Providing a photosensitive material.

[0008]

The above object of the present invention has been achieved by the following constitution.

(1) In the method for producing a silver halide emulsion in which chemical ripening is carried out after adding a silver halide adsorbing substance, the emulsion temperature is higher after chemical ripening after the silver halide adsorbing substance is added but before chemical ripening. The chemical aging is gold
Add the sensitizer and mix uniformly, then add the chalcogen sensitizer.
And a method for producing a silver halide emulsion, characterized in that the addition is carried out in the presence of a nucleophile .

[0010]

[0011]

( 2 ) The method for producing a silver halide emulsion as described in 1 above, which is a silver halide emulsion comprising silver halide grains that have been reduction-sensitized in the grain forming process.

( 3 ) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on at least one side of a support, wherein at least one of the silver halide emulsion layers is as described in 1 or 2 above. A silver halide photographic light-sensitive material comprising a silver halide emulsion produced by the production method.

The present invention will be described in detail below.

In the present invention, there are various cases in which the emulsion temperature after the addition of the silver halide-adsorptive substance and before the chemical ripening is higher than that during the chemical ripening can be considered. Can be mentioned. When the emulsion temperature is T, Further, in each of the above 1 to 3, it is also possible to raise the temperature and then lower the temperature during adsorption, or conversely, to lower the temperature and then raise the temperature, or it is possible to repeat it twice or more. The preferred operations in the present invention are the following two cases. That is, in a method for producing a silver halide emulsion used for a silver halide photographic light-sensitive material, a case where an adsorptive substance added after the desalting step is added at a high temperature and then adsorbed at a high temperature, and then the temperature is lowered to perform chemical ripening. In this case, the adsorptive substance is added at a low temperature, then the temperature is raised to adsorb the adsorbent substance, and the temperature is further lowered to perform chemical aging. The term "during adsorption" refers to the process of adsorbing onto silver halide grains after the addition of the adsorptive substance has been completed for 3 minutes to 60 minutes and after stirring to make the mixture uniform.

When the adsorbing substance is added at a high temperature and then the temperature is lowered to perform chemical aging, the adsorbing substance is 55 ° C. or more and 70 ° C. or more.
It is preferably added at a temperature of not higher than 0 ° C, and the subsequent chemical ripening is preferably performed at a temperature of 30 ° C or higher and 50 ° C or lower, more preferably 35 ° C or higher and 45 ° C or lower. Further, in this case, it is preferable that the temperature difference between the addition of the adsorptive substance and the chemical aging is 5 ° C. or more, more preferably 10 ° C. or more.

When the adsorptive substance is added at a low temperature and then the temperature is raised and then the temperature is lowered and the chemical aging is carried out, the temperature is 30 ° C. or higher.
At 0 ° C or below, first add an adsorptive substance and homogenize it, then
The temperature is preferably raised to 5 ° C or higher and 70 ° C or lower, and the subsequent chemical ripening is preferably performed at 30 ° C or higher and 50 ° C or lower, more preferably 35 ° C or higher and 45 ° C or lower.
That is, in the latter case, it is preferable that there is a temperature difference of 5 ° C. or more between the time of heating after the addition of the adsorptive substance and the time of chemical aging, and it is more preferable that the temperature difference is 10 ° C. or more. In the present invention, the adsorptive substance is a sensitizing dye,
Nitrogen-containing heterocyclic compounds and the like can be mentioned, but as a substance preferably used, a sensitizing dye can be mentioned.

The chemical ripening of the present invention, it added a chalcogen sensitizer were uniformly mixed by adding the gold sensitizer. The addition of the chalcogen sensitizer after the gold sensitizer is added and uniformly mixed means that the gold sensitizer is added before the chalcogen sensitizer. The gold sensitizer is preferably added 5 minutes or more before the chalcogen sensitizer is added, and 10 minutes or more before the addition.
Within minutes is more preferable.

[0019] In the present invention, you chemical ripening in the presence of a nucleophilic agent. As the nucleophile preferably used in the present invention,
For example, sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, and sodium hydrogen sulfite, mercaptos such as thiosalicylic acid, thioglycolic acid, cysteine, thiolactic acid, and 2-mercaptobenzothiazole, phosphines such as triphenylphosphine, and tributylphosphine. , 3-Methylbenzothiazolium iodide, 3-allylthiazolium iodide, 2-hydroxymethyl-3-ethylbenzothiazolium iodide, etc. Thiazolium salts showing nucleophilicity by ring opening, ethanesulfin Acid, sulfinic acid such as sodium benzenesulfinate, methanesulfinic acid, thiosulfinic acid such as benzenethiosulfinic acid, hydrazines such as methylhydrazine and phenylhydrazine, ethanolamine, ethyl Amines such as Njiamin, Hidorosamu acids, and a hydroxyl amine such as N- methylhydroxylamine. In the present invention, a thiazolium salt represented by the following general formula (I) or a compound having a ring opened between the carbon atoms substituted by S and R ₁ in the general formula (I) is particularly preferable as the nucleophile.

[0020]

[Chemical 1]

In the formula, R ₁ is a hydrogen atom or an optionally substituted alkyl group, preferably an alkyl group having 1 to 6 carbon atoms, m is 0 or 1, and when m is 1, Z is In the atomic group necessary for forming a condensed benzene ring, R ₂ is substituted on this benzene ring, when m is 0, R ₂ is substituted on the 4- or 5-position of the thiazolium ring, R ₂ is a hydrogen atom, An optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group, or alkoxy group, or an electron-withdrawing group, and in the case of an alkyl group, an alkenyl group, an alkynyl group, or an alkoxy group, preferably having 6 or less carbon atoms. When n is 2 or more, a plurality of R _{2 s} may be the same or different, and R _{2 s} may be linked to each other to form a condensed ring. n is 0, 1 or 2 when m is 0, and m is 1
In the case of, it is 0 or 1-3. R ₃ is a hydrogen atom or an optionally substituted alkyl group, alkenyl group, alkynyl group or aralkyl group, and in the case of an alkyl group, an alkenyl group or an alkynyl group, preferably has 6 or less carbon atoms, and X ⁻ is an anion. And 1 is 0 or 1.

The thiazolium salt represented by the general formula (I) is preferably one in which the thiazolium ring is easily opened by hydrolysis or the like.

The alkyl group represented by R ₁ includes, for example, a methyl group and a propyl group. Examples of the C 1-6 alkyl group, alkenyl group, alkynyl group and alkoxy group represented by R ₂ include a methyl group, an ethyl group, a hexyl group, an allyl group, a propargyl group and a methoxy group. Examples of the group capable of substituting for R ₁ and R ₂ include, for example,
Examples thereof include a hydroxy group, a carboxyl group, an amino group, a carbamoyl group, a sulfamoyl group and a halogen atom. Examples of the electron withdrawing group represented by R ₂ include a halogen atom, a carboxyl group, a trifluoromethyl group, a cyano group, a nitro group, a sulfo group, an aminosulfonyl group, an alkoxycarbonyl group, and an acyl group. Multiple R
_{When 2} is linked to form a condensed ring, for example, naphthothiazonium and the like can be mentioned. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group represented by R ₃ include methyl group, propyl group, butyl group, hexyl group, allyl group, propargyl group and benzyl group. Examples of the group substituted with these include a sulfone group, a hydroxyl group, an optionally substituted amino group, a halogen atom, a sulfo group, an aminosulfonyl group, an acyl group or a heterocyclic group. Examples of the anion represented by X ⁻ include a halide ion, a nitrate ion, a phosphate ion, a chlorate ion, or an anion derived from an organic substance. However, when R _{1 to} R ₃ have an anionic group, l is 0. The following compounds may be mentioned as specific compounds of the general formula (I).

[0024]

[Chemical 2]

[0025]

[Chemical 3]

The compound of the general formula (I) of the present invention is known as a compound for activating a non-labile selenium sensitizer in US Pat. No. 3,442,653 and the like. JP-A-8-5
No. 4701 discloses that fog and sensitivity are improved by using in combination with an unstable selenium sensitizer, which is essentially unnecessary for activation. However, the use of the nucleophile in the composition of the present invention having a temperature change during the process of spectral sensitization and chemical sensitization and its effect have not been known.

The nucleophile of the present invention may be added at any time after the desalting after the grain formation and before the end of the chemical sensitization, but between the adsorbent addition and the chalcogen sensitizer addition. It is preferable to add the compound. The addition amount of the nucleophile of the present invention is not uniform depending on the type of silver halide emulsion used, the type of compound used, and ripening conditions,
1 × 10 ^-7 mol to 1 × 10 ^-1 per mol of silver halide
It is preferably molar. More preferably 1 × 10 ^-6
It is from 1 mol to 1 × 10 ^-2 mol. The method of adding these compounds may be a method of adding them by dissolving them in a single solvent or a mixed solvent of water or an organic solvent such as methanol, or a method of adding them in advance by mixing with a gelatin solution, depending on the properties of the compound to be used. A method disclosed in JP-A-4-140739, that is, a method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used.

The sensitizer used in the present invention will be described below. Specific examples of the sulfur sensitizer used in the present invention include 1,3-diphenylthiourea, triethylthiourea, thiourea derivatives such as 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, and dithicarbamic acids. Preferred are polysulfide organic compounds, thiosulfates, simple sulfur, and the like. As the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable. Other US Patent No. 1,57
4,944, 2,410,689, 2,27
8,947, 2,728,668, 3,50
No. 1,313, No. 3,656,955, etc.,
The sulfur sensitizers described in West German Application Publication (OLS) 1,422,869, JP-A-56-24937 and JP-A-55-45016 can be used.

As the selenium sensitizer used in the present invention, an unstable selenium compound capable of reacting with silver nitrate in an aqueous solution to form a precipitate of silver selenide is preferably used. For example, US Patent Nos. 1,574,944 and 1,602,
592, 1,623,499 and JP-A-60-15.
No. 0046, JP-A-4-25832 and JP-A-4-1092.
40, No. 4-147250 and the like. Examples of useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylseleno). Urea, N,
N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenyl Carbonylselenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamides (eg selenoacetamide, N, N-dimethylselenobenzamide etc.), selenocarboxylic acids and selenoesters (eg 2-selenopropion). Acid, methyl-3-selenobutyrate, etc., selenophosphates (eg, tri-
p-triselenophosphate, etc.) and selenides (dimethyl selenide, triphenylphosphine selenide, pentafluorophenyl-diphenylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenoamides and selenides.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patent specifications. US Patent No. 1,5
74,944, 1,602,592, 1,62
3,499, 3,297,466, 3,29
7,447, 3,320,069, 3,40
8,196, 3,408,197, 3,44
2,653, 3,420,670, 3,59
1,385, French Patent 2,693,038,
No. 2,093,209, Japanese Patent Publication No. 52-34491,
52-34492, 53-295 and 57-2.
2090, JP-A-59-180536, 59-1.
85330, 59-181337, 59-18
7338, 59-192241, 60-150.
No. 046, No. 60-151637, No. 61-2467
38, JP-A-3-42221, JP-A-3-24537,
No. 3-111838, No. 3-116132, No. 3-
No. 148648, No. 3-237450, No. 4-168
No. 38, No. 4-25832, No. 4-32831, No. 4-96059, No. 4-109240, No. 4-14.
0738, 4-140739, 4-14725.
No. 0, No. 4-184331, No. 4-190225,
No. 4-191729, No. 4-195035, British Patent Nos. 255,846, 861,984, and H.S.
E. Journal of Pho by Spencer et al.
magazine of scientific science, Volume 31, 15
It is also disclosed in research papers such as 8 to 169 (1983).

Tellurium sensitizers and sensitizing methods used in the present invention are described in US Pat. Nos. 1,623,499, 3,320,069, 3,772,031, and 3,531. 289, 3,655,394, British Patents 235,211, 1,121,469, 1,295,462, 1,396,696, Canadian Patent 800,958. , Japanese Patent Application Laid-Open No. 4-20464. Specifically, phosphine tellurides (eg, butyl-diisopropylphosphine telluride, tributylphosphine telluride, etc.), telluroureas (eg, N, N-dimethylethylene tellurourea,
N, N-diphenylethylene tellurourea etc.), telluroamides and the like.

In noble metal sensitization, Research
Noble metal salts such as gold, platinum, palladium and iridium described in Disclosure magazine 307 volume 307105 can be used, and gold sensitization is particularly preferable. Examples of useful gold sensitizers include chloroauric acid, gold thiosulfate, gold thiocyanate and the like, and US Pat. No. 2,597,8.
No. 56, No. 5,049, 485, Japanese Patent Publication No. 44-157
48, JP-A-1-147537 and 4-70650.
And the like, such as the organic gold compounds disclosed in the publications.
When the sensitization method using a gold complex salt is performed, it is preferable to use a gold ligand such as thiosulfate, thiocyanate or thioether as an auxiliary agent, and particularly thiocyanate is preferably used. When performing the chemical sensitization of the present invention, two or more kinds of the above-mentioned sulfur sensitizer, selenium sensitizer and tellurium sensitizer may be combined.

The amount of the sulfur sensitizer, selenium sensitizer, tellurium sensitizer and gold sensitizer added is not uniform depending on the kind of silver halide emulsion, the kind of compound used and the ripening conditions.
Usually 1 × 10 ⁻⁹ mol to 1 × per mol of silver halide
It is preferably 10 ⁻⁵ mol. More preferably 1 ×
It is 10 ⁻⁸ mol to 1 × 10 ⁻⁴ mol.

The above-mentioned various sensitizers may be added according to the properties of the compound to be used, by adding them by dissolving in an organic solvent such as water or methanol alone or in a mixed solvent, or by adding them in advance with a gelatin solution. The method disclosed in JP-A-4-140739 also by a method of mixing and adding,
That is, a method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used.

In reduction sensitization, Research
The reducing compounds described in Disclosure magazine 307 volume 307105 and JP-A-7-78685 can be used. Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compound (eg, dimethylamineborane, etc.), hydrazine compound (eg, hydrazine, p-tolylhydrazine, etc.),
Examples thereof include polyamine compounds (eg, diethylenetriamine, triethylenetetramine, etc.), stannous chloride, silane compounds, reductones (eg, ascorbic acid, etc.), sodium sulfite, aldehyde compounds, hydrogen gas and the like. In addition, Japanese Patent Application Nos. 8-277938 and 8-251.
High pH disclosed in 486, 8-182035, etc.
Alternatively, reduction sensitization may be performed in an atmosphere containing excess silver ions.

Examples of the sensitizing dye used in the present invention include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, oxonols, merostyryl and streptocyanines. Examples thereof include polymethine dyes. Particularly effective sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, and sensitizing dyes belonging to complex merocyanine dyes. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing effect by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing effect of the sensitizing dye is included in the emulsion. May be.

The addition amount of such a dye largely depends on the kind of silver halide emulsion, and in the case of a usual and preferred silver halide grain size of 0.2 to 1.5 μm, 1 × 10 ⁻ per mol of silver halide. It is preferably ⁶ mol to 1 × 10 ⁻⁴ mol. To incorporate the sensitizing dyes used in the present invention in the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion, or water or methanol, ethanol,
It may be added to the emulsion by dissolving it in a water-miscible organic solvent such as n-propyl alcohol, isopropyl alcohol, acetone, acetonitrile or 2-methoxyethanol, alone or in a mixed solvent. In the present invention, JP-A-5-29
No. 7496, No. 6-186657, a substantially water-insoluble sensitizing dye is added in a solid state without using an organic solvent in order to uniformly and effectively adsorb the sensitizing dye on the surface of silver halide grains. Is preferred.

The silver halide emulsion used in the present invention is
Various antifoggants and stabilizers may be incorporated for the purpose of preventing fog during the production process of the light-sensitive material, storage or processing, and stabilizing photographic performance. Specifically, tetrazaindenes, azoles, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzimidazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, thioketo compounds, and further benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonic acid amide, hydroquinone derivatives, aminophenol derivatives, gallic acid Examples thereof include derivatives and ascorbic acid derivatives.

In the present invention, chemical sensitization may be performed in the presence of a silver halide solvent. The silver halide solvent used in the present invention includes U.S. Pat. No. 3,271,157.
No. 3,574,628, JP-A-54-1019.
No. 54-158917, organic thioethers described in JP-A Nos. 53-82408 and 55-55
No. 77737, No. 55-2982, etc., and thiourea derivatives described in JP-A No. 53-144319, halogenated compounds having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom. Silver solvent, JP-A-5
Imidazoles described in JP-A-4-100717,
Examples thereof include sulfite and thiocyanate.

Next, the silver halide emulsion of the present invention will be described. The shape and halogen composition of the silver halide grain used in the present invention are not particularly limited. However, the preferred form of silver halide grains differs depending on the application. For example, the following tabular grains are preferable as the silver halide grains used in the color negative film.

The details will be described below. Tabular grains are classified into twins crystallographically. A twin is a silver halide crystal having one or more twin planes within one grain. The morphology of twins is classified by Klein and Moiser in the article Photographie Correspondents (Pho).
tographish Korresponden
z) Volume 99, p100, Volume 100, p57.

The tabular grains in the present invention preferably have two or more twin planes parallel to the principal plane. The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, the tabular grains contained are
A sample is prepared by coating a silver halide photographic emulsion on a support so that the principal planes thereof are oriented in parallel. This is cut with a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. The presence of twin planes can be confirmed by observing this section with a transmission electron microscope.

The distance between two twin planes in a tabular grain is
In observing the section using the transmission electron microscope,
Arbitrarily select 1000 or more tabular grains showing a cross section cut substantially perpendicular to the main plane, and select the shortest distance between two twin planes among the even twin planes parallel to the main plane. It is obtained by obtaining each particle and averaging them.

In the present invention, the average distance between twin planes is preferably 0.01 μm to 0.05 μm, more preferably 0.013 μm to 0.025 μm.

In the present invention, the distance between twin planes is a factor that influences the supersaturated state during nucleation, such as gelatin concentration, gelatin species, temperature, iodine ion concentration, pBr, p.
It can be controlled by appropriately selecting the combination of various factors such as H, the ion supply rate, and the stirring rotation speed. Generally, the higher the supersaturation state of nucleation, the narrower the distance between twin planes.

Details of the supersaturation factor are described in, for example, JP-A-63-92924 or 1-213363.
You can refer to the description such as No.7.

The average thickness of the tabular grains in the present invention can be obtained by observing the section using the above-mentioned transmission electron microscope, similarly obtaining the thickness of each grain, and averaging. The average thickness of tabular grains is 0.05
μm to 1.5 μm is preferable, and 0.07 is more preferable.
μm to 0.50 μm.

The average grain size of the tabular grains in the present invention is represented by an arithmetic mean of circle-equivalent diameters of projected areas of the silver halide grains (diameters of circles having the same projected area as the silver halide grains). 0.1 to 5.0 μm is preferable, and 0.2 to 2.5 μm is more preferable.

The particle size can be obtained, for example, by magnifying the particles with an electron microscope from 10,000 times to 70,000 times and measuring the particle size on the print or the area at the time of projection (measurement). It is assumed that the number of particles is 1000 or more indiscriminately.

In the tabular grains according to the present invention, the aspect ratio (particle size / grain thickness) of 5 or more is 50% or more of the total projected area, and preferably the aspect ratio of 8 or more is the total projected area. It is 50% or more.

The silver halide grains of the present invention are preferably monodisperse silver halide emulsions. In the present invention, the monodisperse emulsion is preferably 25% or less when the breadth of the distribution is defined by (standard deviation / average grain size) × 100 = grain size distribution (coefficient of variation of grain size) [%], and more It is preferably 20% or less, more preferably 16% or less. Here, the average particle size and standard deviation are obtained from the above-mentioned average particle size.

The tabular grain in the present invention is preferably a grain composed of a core serving as a core and a shell coating the core, and the shell is formed of one layer or more layers.

When the tabular grains of the present invention are composed of the above core / shell type grains, the halogen composition of the core and the shell can be arbitrarily selected, but the proportion of the core is 1 to 60% of the total amount of silver in the grains. Is preferably 4-40%
Is more preferable.

In the present invention, when the silver iodide contents of the core and the shell are different from each other, the difference in the silver iodide contents of the core part and the shell part preferably has a sharp boundary, and the difference between the core and the shell is between the core and the shell. It is also preferable to use at least one intermediate layer.

When the tabular grains in the present invention contain core / shell type silver halide grains having the above-mentioned intermediate layer, the preferable volume of the intermediate layer is 0.1 to 0.1% of the total amount of silver in the grains.
20%, more preferably 0.5 to 10%.

The difference between the silver iodide contents of the intermediate layer and the shell is that the silver iodide content of the intermediate layer is 2 m with respect to the silver iodide content of the shell.
It is preferably higher than ol%.

The average silver iodide content of the tabular grains in the present invention is 10 mol% or less, preferably 7 mol% or less, and more preferably 4 mol% or less.

In the present invention, the halogen composition of the tabular grains may be any of silver bromide, silver iodide and silver chloride, and may be silver iodobromide, silver chloroiodide, silver chlorobromide or the like. Although mixed crystals can be used, grains mainly containing silver iodobromide as described above are preferable.

The distribution state of silver iodide in the above core / shell type silver halide grains can be detected by various physical measurement methods, and is described in, for example, the proceedings of the 1981 Annual Meeting of the Photographic Society of Japan. As described above, it can be investigated by measuring luminescence at a low temperature or by an X-ray diffraction method.

In the present invention, various methods well known in the art can be used for forming tabular grains. That is, the single jet method, the controlled double jet method, the controlled triple jet method, etc. can be used in any combination, but in order to obtain highly monodisperse grains, the formation of silver halide grains is required. It is important to control pAg in the liquid phase to be adjusted according to the growth rate of silver halide grains. As the pAg value, a region of 7.0 to 11.5 is used, preferably 7.5 to 11.0, and more preferably 8.
A region of 0 to 10.5 can be used.

In determining the addition rate, JP-A-54 is used.
The technologies described in JP-A-48521 and JP-A-58-49938 can be referred to.

In the present invention, a known silver halide solvent such as ammonia, thioether or thiourea may be present during the production of tabular grains, or a silver halide solvent may not be used.

The tabular grains used in the present invention may be either grains in which the latent image is mainly formed on the surface or grains in which the latent image is mainly formed.

The tabular grains in the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium. here,
An aqueous solution containing a dispersion medium is one in which a protective colloid is formed in an aqueous solution by a substance that can form a hydrophilic colloid such as gelatin (a substance that can serve as a binder), and preferably contains a colloidal protective gelatin. It is an aqueous solution.

When gelatin is used as the protective colloid in carrying out the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in Arthur Guice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

Hydrophilic colloids other than gelatin that can be used as protective colloids include, for example, gelatin derivatives, graft polymers of gelatin and other polymers,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
There are various types of synthetic hydrophilic polymeric substances such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers.

In the case of gelatin, it is preferable to use one having a jelly strength of 200 or more in the Paggy method.

The tabular grain in the present invention is at least one selected from the group consisting of cadmium salt, zinc salt, lead salt, thallium salt, iron salt, rhodium salt, iridium salt and indium salt (including complex salt) in the process of growing the grain. A metal ion can be added by using a seed so that these metal elements can be contained inside the particle and / or on the surface of the particle.

The tabular grains in the present invention may be those in which unnecessary soluble salts have been removed after the growth of silver halide grains has been completed, or the tabular grains may be contained as they are.

Further, as in the method described in JP-A-60-138538, desalting can be carried out at any point of silver halide growth. When removing the salts, Research Disclosure (Research Disc)
Closure, hereinafter abbreviated as RD) No. 17643, Item II. More specifically, in order to remove the soluble salt from the emulsion after the precipitation or after the physical ripening, a Nudel water washing method performed by gelatinizing gelatin may be used, and inorganic salts, anionic surfactants, Anionic polymer (eg polystyrene sulfonic acid) or gelatin derivative (eg acylated gelatin, carbamoylated gelatin, etc.)
You may use the precipitation method (flocculation) which utilized.

In the present invention, the silver iodide content and the average silver iodide content of each silver halide grain are determined by the EPMA method (Electron Probe Micro Ana).
It can be obtained by using the (lyzer method). According to this method, a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared, and elemental analysis of an extremely minute portion can be performed as compared with X-ray analysis by electron beam excitation by irradiating an electron beam. By this method, the halogen composition of each grain can be determined by obtaining the characteristic X-ray intensity of silver and iodide emitted from each grain. When the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content can be determined from the average thereof.

The tabular grains used in the present invention preferably have a more uniform silver iodide content between grains. EP
When the distribution of silver iodide content between grains is measured by the MA method, the relative standard deviation is preferably 30% or less, more preferably 20% or less.

The halide composition on the surface of tabular grains is XPS.
Method (X-ray Photoelectron Spe
It is determined as follows by the ctrocopy method: X-ray photoelectron spectroscopy. Here, the surface is the outermost layer of the grain including the outermost surface of the silver halide grain and refers to the depth from the outermost surface of the grain to 50 Å. That is, the sample is 1 × 1
It was cooled to -110 ° C or lower in an ultrahigh vacuum of 0 ^-8 torr or less, and MgKα was used as an X-ray for a probe with an X-ray source voltage of 15
Irradiation with kV, X-ray source current 40 mA, Ag3d5 / 2,
The electrons of Br3d and I3d3 / 2 are measured. Sensitivity factor (Sensitiv)
It is corrected by using an intensity factor), and the halide composition of the surface is obtained from the intensity ratio of these.

The XPS method has heretofore been disclosed in JP-A-2-241 as a method for obtaining the silver iodide content on the surface of silver halide grains.
No. 88, etc.

In the tabular grain of the present invention, the silver iodide content on the grain surface is preferably higher than the average silver iodide content of the grain. That is, it is preferable that the relationship of silver iodide content on the grain surface / average silver iodide content = 1.1 to 20 is satisfied, and more preferably, silver iodide content on the grain surface / average silver iodide content. = 1.3 to 10 is satisfied.

In the tabular grains of the present invention, it is preferable that 50% or more of all projected areas have 5 or more dislocation lines per grain. The dislocation of silver halide grains is described in, for example, J. F. Hamilton, Photo. Sci.
Eng. , Vol11, 57 (1967) and T.W. S
hiozawa, J .; Soc. Photo. Sc
i. It can be observed by a direct method using a transmission electron microscope at low temperature described in Japan, vol 35, 213 (1972). That is, the silver halide grains taken out carefully so as not to apply pressure to dislocations from the emulsion, put them on a mesh for electron microscope observation, and to prevent damage (printout etc.) by electron beam In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for an electron beam to pass therethrough. Therefore, a high pressure type (200 μm for particles having a thickness of 0.25 μm)
It can be observed more clearly by using an electron microscope of kV or more).

From the photograph of the grains obtained by such a method, the position and the number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be determined.

The position of the dislocation line is preferably near the outer periphery of the tabular grain, near the ridgeline, or near the apex. More specifically, from the center of the main plane of the tabular grain to the main plane. When a straight line parallel to is drawn toward the side surface of the grain and the length of the straight line to the outer surface is L, 50% or more of the total projected area of the grain is 5 or more dislocation lines per grain. Is preferably in the region from the outside to 0.50 L to L, and more preferably, 50% or more of the total projected areas have 0.70 L to 10 L or more dislocation lines per grain. It is particularly preferable that 50% or more of the total projected area of the grains have 20 or more dislocation lines per grain in the region of 0.80L to L from the outside. Is what you are doing. The direction of the dislocation line is approximately from the center toward the outer surface (side surface), but it often meanders.

As the method of introducing dislocation lines, for example, an aqueous solution containing iodine ions such as potassium iodide and a water-soluble silver salt solution are added by a double jet method, a method of adding only a solution containing iodine ions, or an iodide Using a known method such as a method of adding a fine grain emulsion containing silver or a method of using an iodine ion releasing agent as described in JP-A-6-11781, the origin of dislocation lines at a desired position Dislocations can be formed. Among these methods, the method of adding a fine grain emulsion containing silver iodide and the method of adding an iodine ion releasing agent are preferable.

Known photographic additives which can be used in the silver halide photographic light-sensitive material of the present invention are described in RD17643, page 25.
VIII-A to page 27, XIII, RD18716, 650
Page 651, RD308119, Page 1003 Item VIII-A-
1012, page XXI-E, and specific examples of various couplers are RD17643, page 25, VII-C to G, RD30.
8119, p. 1001 VII-C to G. In the present invention, the above-mentioned RD17643, page 28 XV
Section II, RD 18716, pp. 647-8 and RD3081.
The supports described on page 19, 1009, section XVII can be used. For the photosensitive material, the above-mentioned RD30811 is used.
Auxiliary layers such as a filter layer and an intermediate layer described in item VII-K on page 9,1002 can be provided. The light-sensitive material may have various layer structures such as the forward layer, the reverse layer, and the unit structure described in RD308119, Item VII-K.

[0081]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 [Preparation of emulsion EM-1] << Nucleation step >> The following reaction mother liquor (Gr-1) in a reaction vessel.
Was maintained at 30 ° C., and the pH was adjusted to 1.96 with 1N sulfuric acid while stirring at a stirring speed of 400 rotations / minute using the mixing and stirring apparatus described in JP-A-62-160128. Then, using the double jet method, the (S-1) liquid and the (H-1) liquid were added at a constant flow rate for 1 minute to perform nucleation.

(Gr-1) Alkali-treated inactive gelatin (average molecular weight 100,000) 40.50 g Potassium bromide 12.40 g Finish with distilled water to 16.2 (S-1) Silver nitrate 862.5 g Distilled water 4. Finish to 06l (H-1) Potassium bromide 604.5g Finish to 4.06l with distilled water << Aging step >> After the completion of the nucleation step, the solution (G-1) is added, and the mixture is heated to 60 ° C for 30 minutes. The temperature was raised. During this period, the silver potential of the emulsion in the reaction vessel (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to 6 mV using a 2N potassium bromide solution. Subsequently, an aqueous ammonia solution was added to adjust the pH to 9.3, and the pH was held for 7 minutes, and then the pH was adjusted to 6.1 using an aqueous acetic acid solution. During this period, the silver potential was adjusted to 6 mV by using a 2N potassium bromide solution.
Controlled to.

(G-1) Alkali-treated inactive gelatin (average molecular weight: 100,000) 173.9 g HO (CH ₂ CH ₂ O) _m {CH (CH ₃ ) CH ₂ O} _19.8 (CH ₂ CH ₂ O) _n 10% by weight methanol solution of H (m + n = 9.77) 5.80 ml Finish to 4.22 l with distilled water << Particle growth step >> After completion of the aging step, the double jet method is used to obtain the solution (S-1). And (H-1) liquid while accelerating the flow rate (the ratio of the addition flow rate at the end to the start is about 12
Double) added in 37 minutes. After the addition was completed, the (G-2) solution was added, and the stirring rotation speed was adjusted to 550 rpm, then, while accelerating the flow rates of the (S-2) solution and the (H-2) solution (at the end (The ratio of the addition flow rate at the beginning is about 2 times) 40 minutes. During this period, the silver potential of the emulsion was controlled to 6 mV by using a 2N potassium bromide solution. After the completion of the addition, the temperature of the emulsion in the reaction vessel was lowered to 40 ° C over 15 minutes. Thereafter, the silver potential in the reaction vessel was adjusted to -39 mV using a 3N potassium bromide solution, and subsequently 407.5 g of the (F-1) solution was added, followed by the (S-2) solution and the (H- 3) The liquid was added over 25 minutes while accelerating the flow rate (the ratio of the addition flow rate at the end time to the addition flow rate at the start time was about 1.2 times). (S-2) Silver nitrate 2.10 kg Finish with distilled water to 3.53 l (H-2) Potassium bromide 859.5 g Potassium iodide 24.45 g Finish with distilled water to 2.11 l (H-3) Potassium bromide 587.0 g Potassium iodide 8.19 g Finish to 1.42 l with distilled water (G-2) Ocein gelatin 284.9 g HO (CH ₂ CH ₂ O) _m {CH (CH ₃ ) CH ₂ O} _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10 wt% methanol solution 7.75 ml Distilled water makes 1.93 l (F-1) 3 wt% gelatin and silver iodide grains (average grain size) Fine grain emulsion (*) having a diameter of 0.05 μm 407.5 g * The method for preparing the fine grain emulsion is as follows: 5000 m of a 6.0 wt% gelatin solution containing 0.06 mol of potassium iodide.
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added to 1 liter over 10 minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After forming the particles, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.
The finished weight was 12.53 kg.

After completion of the above grain growth, JP-A-5-726
After desalting according to the method described in No. 58, gelatin is added and dispersed, and the pH is 5.80 at 40 ° C., pAg.
Was adjusted to 8.06. The emulsion thus obtained was EM-
Set to 1.

From an electron micrograph of the obtained emulsion grains,
It was confirmed to be tabular grains having an average particle size of 1.50 μm (average value of circle conversion diameter of projected area), aspect ratio of 7.4 (50% or more of total projected area), and particle size distribution of 15.0%. .

This emulsion EM-1 was subdivided into emulsions A to G by the following method.

[0088] The part of the emulsion EM-1 "Preparation of Emulsion A" was heated and dissolved in 55 ℃, 4 × 10 ^-4 mol per mol of silver halide sensitizing dye SD-1, S
D-2 (8 × 10 ^-5 mol) and SD-3 (5 × 10 ^-5 mol) were added, and after 20 minutes while maintaining the temperature at 55 ° C., sodium thiosulfate pentahydrate 5.5 × 10 ^-6 mol, penta Fluorophenyl-diphenyl-phosphine selenide 2.5 × 10 ^-6 mol, 3.2 × 10 ^-6 mol of chloroauric acid and 3.5 × 10 ^-4 mol of potassium thiocyanate were mixed at 2 minute intervals. It was added and aged so that the sensitivity was optimized. At the end of ripening, a stabilizer ST-1 and an antifoggant AF-1 were added, the temperature was lowered, and the mixture was cooled and solidified to obtain an emulsion A.

[0089] The part of the emulsion EM-1 "Preparation of Emulsion B" was heated and dissolved in 35 ° C. was added a sensitizing dye of the emulsion A the same amount, and the temperature was raised to 62 ° C. after 20 minutes. Emulsion B was prepared by adding the same chemical sensitizer as in the preparation of emulsion A and ripening to this emulsion.

<< Preparation of Emulsion C >> 6 parts of emulsion EM-1 was used.
Dissolve by heating at 5 ° C and add the same amount of sensitizing dye as in Emulsion A.
Hold for 0 minutes. Then, the temperature was lowered to 60 ° C. over 1 minute.
Emulsion C was prepared by adding the same chemical sensitizer as in the preparation of emulsion A and ripening to this emulsion.

<< Preparation of Emulsion D >> 6 parts of emulsion EM-1 was prepared.
Dissolve by heating at 5 ° C and add the same amount of sensitizing dye as in Emulsion A.
Hold for 0 minutes. Then, the temperature was lowered to 55 ° C. over 1 minute.
Emulsion D was prepared by adding the same chemical sensitizer as in the preparation of emulsion A and ripening to this emulsion.

<< Preparation of Emulsion E >> 6 parts of emulsion EM-1 was used.
Dissolve by heating at 5 ° C and add the same amount of sensitizing dye as in Emulsion A.
Hold for 0 minutes. Then, the temperature was lowered to 45 ° C. over 1 minute.
Emulsion E was prepared by adding the same chemical sensitizer as in the preparation of emulsion A and ripening to this emulsion.

<< Preparation of Emulsion F >> 3 parts of emulsion EM-1
It was dissolved by heating at 5 ° C. and the same amount of sensitizing dye as in Emulsion A was added.
After 1 minute, the temperature was raised to 65 ° C. and maintained for 20 minutes. Then, the temperature was lowered to 60 ° C. over 1 minute. Emulsion F was prepared by adding the same chemical sensitizer as in the preparation of emulsion A and ripening to this emulsion.

<< Preparation of Emulsion G >>
It was dissolved by heating at 5 ° C. and the same amount of sensitizing dye as in Emulsion A was added.
After 1 minute, the temperature was raised to 65 ° C. and maintained for 20 minutes. Then, the temperature was lowered to 45 ° C. over 1 minute. Emulsion G was prepared by adding the same chemical sensitizer as in the preparation of emulsion A and ripening to this emulsion.

Magenta coupler M-1 dissolved in ethyl acetate and tricresyl phosphate (OIL-1) was added to each of the obtained emulsions, and the mixture was emulsified and dispersed in an aqueous solution containing a dispersion aid (SU-1) and gelatin. Dispersion, spreading agent (SU-
2) and a hardening agent (H-1, H-2) were added to prepare coating solutions, and the coating solutions were respectively coated on the subbed cellulose triacetate support by a conventional method and dried to give Samples 101 to 107. It was made.

A method for preparing a sample coated with a single emulsion layer will be described below. Each weight shows the coating amount per m ² .

[0097] <Coating prescription>   From the support side   First layer: green-sensitive silver halide emulsion layer   Emulsion (listed in Table 1) Coating silver amount 1.5g   Magenta coupler- (M-1) 0.33g   Tricresyl phosphate (OIL-1) 0.50 g   Gelatin 3.5g   Second layer: surface protection layer   PM-1 0.15g   PM-2 0.04g   Gelatin 0.65g

[0098]

[Chemical 4]

[0099]

[Chemical 5]

The sample obtained as described above was used for 5400
Wedge exposure was performed for 1/100 second through a Toshiba glass filter Y-48 using a K light source, and development processing was performed according to the following processing steps.

The sensitivity of each sample was such that the green density was fog +0.
Sample N is expressed by the reciprocal of the exposure amount that gives an optical density of 15.
o. It was shown as a relative value with the value of 101 as 100.

Further, in order to evaluate the fog generated during storage, the sample was subjected to a condition of a temperature of 23 ° C. and a relative humidity of 65%.
After the humidity was controlled for 4 hours, it was sealed in a resin can and allowed to stand at a temperature of 55 ° C. for 5 days. Each of these samples was treated together with the samples stored in the refrigerator, and the difference in the minimum density value of the obtained characteristic curve was evaluated as the fog rise width during storage.
The results are shown in Table 1.

(Processing step) << Standard color development processing >> Processing step Processing time Processing temperature Replenishment amount * Color development 2 minutes 30 seconds 38 ± 0.3 ° C. 780 cc Bleach 45 seconds 38 ± 2.0 ° C. 150 cc Fixed 1 minute 30 seconds 38 ± 2.0 ° C. 830 cc stability 60 seconds 38 ± 5.0 ° C. 830 cc dry 1 minute 55 ± 5.0 ° C .- * Replenishment amount is a value per 1 m ² of the 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 sulfate 2.5 g sodium chloride 0.6 g 4-amino- 3-Methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to 1 liter and potassium hydroxide or 20% sulfuric acid was added. Use to adjust pH to 0.06.

Color developing 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-methyl-N-ethyl-N- (β-hydroxylethyl) Aniline sulfate 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water was added to make 1 liter, and potassium hydroxide or 20% was used to adjust the pH to 10. Adjust to 18.

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. PH to 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.

Fixer 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 with 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 using 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 (L-77 manufactured by UCC) 0.1 g Ammonia water 0.5 cc Water was added to make 1 liter, and the pH was adjusted to 8.5 with ammonia water or 50% sulfuric acid.

[0112]

[Table 1]

As is clear from Table 1, silver halide adsorption
Emulsion higher than during chemical ripening after adding chemicals and before chemical ripening
An emulsion with low fog and high sensitivity was obtained by passing through the temperature .
Further, it can be seen that the fog rise during storage is small and stable.

<< Preparation of Emulsions HM >> Emulsions H to M were prepared by changing the order and timing of addition of the chemical sensitizers shown in Table 2 in the preparation method of Emulsion E. sample
Sample No. 2 coated with a single emulsion layer in the same manner as Nos. 101 to 107
01 to 206 were produced and evaluated for fog, sensitivity and storability. However, the relative sensitivities in the table are represented by setting 1/100 second exposure of the sample 101 in Table 1 to 100.

[0115]

[Table 2]

The effect of Sample 105 was outstanding in Table 1, but from Table 2, the fog and the sensitivity were improved by adding the gold sensitizer during the chemical ripening before the chalcogen sensitizer. It can be seen that is further improved.

<< Preparation of Emulsions L to V >> In the preparation method of Emulsion L, the nucleophile was added in an amount of 7.5 × 10 ⁻⁵ mol per mol of silver halide, and the kind and addition of the nucleophile shown in Table 3 were added. Emulsion N to Emulsion T were prepared at different times.
Comparative Emulsions U and V were prepared according to the type and addition time of the nucleophile shown in Table 3 in the preparation method of Emulsions A and B in Table 1. Using the above emulsions, single emulsion layer coating samples 301 to 309 were prepared in the same manner as sample numbers 101 to 107, and fog, sensitivity, storability and low illuminance failure characteristics were evaluated. However, the relative sensitivity in the table is 1/100 second exposure of sample 308 is 10
Expressed as 0.

[0118]

[Table 3]

As is clear from Table 3, by using the compound of the present invention, higher sensitivity can be achieved and low illuminance failure characteristics can be improved. Meanwhile, sample 30
8 and 309, even when the compound of the present invention was used in the chemical ripening method of the present invention having no temperature change, the effect of improving low illumination failure was slight.

Example 2 [Preparation of Emulsion EM-2] In the grain growth step of Emulsion EM-1, Solution (S-1) and Solution (H-1) were added for 37 minutes while accelerating the flow rate. Add (R-1) solution to the lash, and after addition is complete,
-2) Solution was added and the stirring speed was adjusted to 550 rpm, and then (S-2) solution and (H-2) solution were added over 40 minutes while accelerating the flow rate. During this period, the silver potential of the emulsion was controlled to 6 mV by using a 2N potassium bromide solution.
After the above addition, emulsion (EM-1) was prepared in the same manner as emulsion (EM-1) except that (T-1) solution was rush added and the emulsion temperature in the reaction vessel was lowered to 40 ° C over 15 minutes. Prepared. From an electron micrograph of the obtained emulsion grains, it was confirmed that the grains were almost the same as those of the emulsion EM-1.

(R-1) Thiourea dioxide 26.6 mg Finished with distilled water to 46.5 ml (T-1) Sodium ethanethiosulfonate 880 mg Finished with distilled water to 293.3 ml This emulsion EM-2 was divided into small portions. By the method shown below,
Emulsion W to emulsion Z were prepared.

<< Preparation of Comparative Emulsion W >> A part of Emulsion EM-2 was dissolved by heating at 55 ° C., and 4 × 10 ⁻⁴ mol of sensitizing dye SD-1 and 8 of SD-2 were added per mol of silver halide. × 10 ^-5
And SD-3 (5 × 10 ^-5 mol) were added, 20 minutes after maintaining at 55 ° C., nucleophile I-2 (7.5 × 10 ^-5 mol) was added, and 15 minutes later chloroauric acid 3 was added. A mixed solution of 0.0 × 10 ^-6 mol and potassium thiocyanate 3.7 × 10 ^-4 mol was added, and 1
After 5 minutes, sodium thiosulfate pentahydrate, 5.8 × 10 ⁻⁶ mol,
Pentafluorophenyl-diphenyl-phosphine selenide 3.0 × 10 ^-6 mol was added every 2 minutes to give 1/1
It was aged so that the 00 second sensitivity was optimum. At the end of ripening, stabilizer ST-1 and antifoggant AF-1 were added, the temperature was lowered, and the mixture was cooled and solidified to obtain emulsion W.

<< Preparation of Comparative Emulsion X >> A part of Emulsion EM-2 was dissolved by heating at 35 ° C., the same amount of sensitizing dye as Emulsion W was added, and 20 minutes later, the temperature was raised to 62 ° C. Emulsion X was prepared by adding the same chemical sensitizer as in the preparation of emulsion W and ripening to this emulsion.

<< Preparation of Emulsion Y >>
Dissolve by heating at 5 ° C and add the same amount of sensitizing dye as Emulsion W.
After holding for 0 minutes, the nucleophile I-2 of the present invention was added and held for 15 minutes. Then, the temperature was lowered to 45 ° C. over 1 minute. Emulsion Y was prepared by adding the same chemical sensitizer as in the preparation of emulsion W and ripening to this emulsion.

<< Preparation of Emulsion Z >> 3 part of emulsion EM-2 was used.
The mixture was heated to 5 ° C. and dissolved, and the same amount of sensitizing dye as that of Emulsion W was added.
After 1 minute, the temperature was raised to 65 ° C., the temperature was maintained for 20 minutes, the nucleophile I-2 of the present invention was added, and the temperature was maintained for 15 minutes. Then 1 minute 4
The temperature was lowered to 5 ° C. Emulsion Z was prepared by adding the same chemical sensitizer as in the preparation of emulsion W and ripening to this emulsion.

Sample Nos. 101 to 10 for each of the resulting emulsions
Single emulsion coating samples 401 to 404 were prepared in the same manner as in No. 7, and the same processing and evaluation were performed. The results are shown in Table 4.

[0127]

[Table 4]

As can be seen from Table 4, the embodiment of the present invention has a remarkable effect on the reduction-sensitized silver halide grains during the grain formation process.

Example 3 A multilayer color photographic light-sensitive material sample 501 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support having an undercoat layer.

The addition amount is expressed in grams per 1 m ² .
However, silver halide and colloidal silver are converted into the amount of silver, and the sensitizing dye (indicated by S) is shown by the number of moles per 1 mole of silver.

[0131] The characteristics of the above silver iodobromide are shown below (the average particle size is the length of one side of a cube having the same volume).

Emulsion No. Average grain size (μm) Average AgI amount (mol%) Diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 b 0.40 8.0 1.4 1.4 c 0.60 7.0 3. 1 d 0.74 7.0 5.0 e 0.60 7.0 4.1 f 0.65 8.7 6.5 h 0.65 8.0 1.4 i 1.00 8.0 2. 0 j 0.05 2.0 1.0 As a typical example of the formation of silver halide grains of the present invention, JP-A-1-183417 and 1-183644.
No. 1-183645, No. 2-166442, and Japanese Patent Application No. 9-9423.

In addition to the above composition, the dispersion aid SU-
1, coating aids SU-2, SU-3, SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-11, two types of polyvinylpyrrolidone (AF-12) having a weight average molecular weight of 10,000 and a weight average molecular weight of 1,100,000, inhibitors AF-13, AF-1, A
F-15, hardening agents H-1, H-2 and preservative Ase-1
Was added.

The structures of the compounds used in the above samples are shown below.

[0135]

[Chemical 6]

[0136]

[Chemical 7]

[0137]

[Chemical 8]

[0138]

[Chemical 9]

[0139]

[Chemical 10]

[0140]

[Chemical 11]

[0141]

[Chemical 12]

[0142]

[Chemical 13]

[0143]

[Chemical 14]

As described above, a photosensitive material sample 501 was prepared.
Sample No. Emulsion N of the present invention used in the tenth layer of sensitive material in construction of the 501, comparative emulsion U prepared in Example 1, to prepare a sample 502 and 503 was changed to V same processing and evaluation as in Example 1 As a result, the sample 501 of the present invention showed high sensitivity to the comparative samples 502 and 503, small fog, and excellent low illuminance failure characteristics.

[0145]

According to the present invention, there is provided a method for producing a silver halide emulsion having high sensitivity, less fog, improved reciprocity law failure characteristics and storability, and a silver halide photographic light-sensitive material using the same. I was able to do something.

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03C 1/015-1/09

Claims (3)

(57) [Claims] 1. A method for producing a silver halide emulsion in which chemical ripening is carried out after addition of a silver halide-adsorptive substance. However, the chemical ripening requires a gold sensitizer.
Add the chalcogen sensitizer and mix evenly.
And a method for producing a silver halide emulsion, which is carried out in the presence of a nucleophile . 2. A method of reduction sensitization during grain formation.
The method for producing a silver halide emulsion according to claim 1 , which is a silver halide emulsion comprising silver rogenide grains . 3. Less on at least one side of the support
Both silver halide emulsions having one silver halide emulsion layer
In a true light-sensitive material, at least the silver halide emulsion layer
A further layer is produced by the production method according to claim 1 or 2.
Ha containing a prepared silver halide emulsion
Silver halide photo-sensitive material.