JP2001083651A - Photosensitive silver halide emulsion, its preparation and silver halide photographic sensitive material using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic emulsion having high sensitivity by adding an anionic spectral sensitizing dye substantially in the absence of a polyvalent cation which forms a slightly soluble salt with the dye, adding the cation after the sufficient adsorption of the dye and then starting chemical sensitization. SOLUTION: An anionic spectral sensitizing dye is added to an emulsion substantially in the absence of a polyvalent cation which forms a slightly soluble salt with the dye. After the sufficient adsorption of the dye, the cation is added and then chemical sensitization is started to prepare the objective emulsion. By this method, the inter-grain distribution of dye adsorption is improved and the chemical sensitization is efficiently carried out. The polyvalent cation is preferably at least one of calcium, magnesium and strontium ions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic emulsion and a method for producing the same. The present invention particularly relates to a silver halide grain photographic emulsion having excellent photographic sensitivity and a method for producing the same.

The present invention also relates to a silver halide photographic material containing the above silver halide photographic emulsion.

[0003]

BACKGROUND OF THE INVENTION Silver halide photographic emulsions are usually produced by
It comprises a grain formation step, a desalination step, a dispersion step, a spectral sensitization step, and a chemical sensitization step. Spectral sensitization with spectral sensitizing dyes
In recent years, in order to improve the sensitivity / granularity ratio of silver halide photographic emulsions, spectral sensitization is performed by adding a spectral sensitizing dye at or before chemical sensitization in US Pat. No. 4,433,04.
No. 8, etc., it is becoming common.

In recent years, attention has also been paid to calcium in emulsion production and in silver halide photographic materials. For example, a method for producing an emulsion in the presence of a water-soluble metal salt such as calcium nitrate and magnesium sulfate is disclosed in EP 590.
No. 725, which shows that the simultaneous coexistence of a spectral sensitizing dye, a chemical sensitizer, and a water-soluble metal salt is important for sensitization. Also, Japanese Patent Application Laid-Open
No. 174142 discloses a method for producing a silver halide light-sensitive material having excellent storage stability over time by adjusting the calcium content of gelatin in the silver halide light-sensitive material. Nothing is mentioned.

[0005] As described above, the effectiveness of spectral sensitization in the absence of a polyvalent cation of a metal such as calcium during the production of an emulsion and chemical sensitization in the presence of a polyvalent cation of a metal such as calcium are not known. Had not been.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion having a high sensitivity, a method for producing the same, and a silver halide photographic light-sensitive material containing the same.

[0007]

The object of the present invention can be solved by the following method.

(Embodiment 1) The spectral sensitizing dye is added substantially in the absence of a polyvalent cation forming a sparingly soluble salt with the anionic spectral sensitizing dye, and the spectral sensitizing dye is sufficiently adsorbed. A light-sensitive silver halide emulsion produced by adding the cation and then starting chemical sensitization.

(Embodiment 2) Spectral sensitization is carried out by adding a spectral sensitizing dye in a state where calcium, magnesium and strontium are not more than 50 ppm.
A photosensitive iodine odor produced by adding a water-soluble salt of at least one metal selected from calcium, magnesium and strontium to 2500 ppm and thereafter initiating chemical sensitization. Silver halide emulsion.

(Embodiment 3) A spectral sensitizing dye having a solubility in water of 3% by weight or less is prepared under the conditions that the organic solvent and / or the surfactant are not substantially present and the pH is 6 to 8 and 40 to 80 ° C. The photosensitive composition according to aspect 2, wherein the photosensitive composition is manufactured by spectrally sensitizing a dispersion of a spectral sensitizing dye obtained by mechanically pulverizing and dispersing fine particles in an aqueous solvent. Silver iodobromide emulsion.

(Embodiment 4) After dissolving 0.5% by weight or more of an inorganic salt in water substantially free of any of a surfactant, an organic solvent and a silver halide emulsion, a spectral increase of 0.5% by weight or more is performed. 3. The photosensitive iodobromide according to aspect 2, wherein the photosensitive iodobromide is produced by spectral sensitization with a solid fine dispersion of a spectral sensitizing dye obtained by adding a dye and finely dispersing the solid. Silver emulsion.

(Embodiment 5) In the molecular weight distribution measured by the PAGI method, components having a molecular weight of 280,000 or more
%. The photosensitive silver iodobromide emulsion according to any one of Aspects 2 to 4, wherein spectral sensitization and chemical sensitization are performed in the presence of alkali-treated bone gelatin containing at least 10% by weight.

(Embodiment 6) Aspects 2 to 5 characterized by being chemically sensitized with a selenium sensitizer of 2.5 × 10 ⁻⁶ mol / mol silver or more and 5 × 10 ⁻⁵ mol / mol silver or less. 3. The photosensitive silver iodobromide emulsion according to any one of the above items.

(Embodiment 7) Any one of Embodiments 2 to 6, wherein 50% or more of the total projected area of the silver halide grains is occupied by tabular silver halide grains having an aspect ratio of 8 or more. The photosensitive silver iodobromide emulsion according to the embodiment.

(Embodiment 8) The spectral sensitizing dye is added in the substantial absence of a polyvalent cation forming a sparingly soluble salt with the anionic spectral sensitizing dye, and the spectral sensitizing dye is sufficiently adsorbed. A method for producing a photosensitive silver halide emulsion, characterized in that the cation is added after the addition, and then chemical sensitization is started.

(Embodiment 9) Spectral sensitization is carried out by adding a spectral sensitizing dye in a state where calcium, magnesium and strontium are not more than 50 ppm.
Preparation of a photosensitive silver iodobromide emulsion characterized by adding a water-soluble salt of at least one metal selected from calcium, magnesium and strontium so as to be 2500 ppm, and then starting chemical sensitization. Method.

(Embodiment 10) A spectral sensitizing dye having a solubility in water of 3% by weight or less is prepared by adding a spectral sensitizing dye having substantially no organic solvent and / or surfactant and having a pH of 6 to 8, 40 to 80 ° C.
10. The photosensitive silver iodobromide according to aspect 9, wherein the dispersion is spectrally sensitized with a dispersion of a spectral sensitizing dye obtained by mechanically pulverizing and dispersing fine particles in an aqueous solvent under the conditions of Emulsion manufacturing method.

(Embodiment 11) After dissolving 0.5% by weight or more of an inorganic salt in water substantially free of any of a surfactant, an organic solvent and a silver halide emulsion, a spectral increase of 0.5% by weight or more is performed. 10. The method for producing a photosensitive silver iodobromide emulsion according to aspect 9, wherein spectral sensitization is carried out with a solid fine dispersion of a spectral sensitizing dye obtained by adding a dye and finely dispersing the solid.

(Embodiment 12) In the molecular weight distribution measured by the PAGI method, three components having a molecular weight of 280,000 or more
The method for producing a light-sensitive silver iodobromide emulsion according to any one of Embodiments 9 to 11, wherein the spectral sensitization and the chemical sensitization are performed in the presence of alkali-treated bone gelatin containing 0% or more. .

(Embodiment 13) Aspects 9 to 12 characterized by being chemically sensitized with a selenium sensitizer of 2.5 × 10 ⁻⁶ mol / mol silver or more and 5 × 10 ⁻⁵ mol / mol silver or less.
The method for producing a photosensitive silver iodobromide emulsion according to any one of the above aspects.

(Embodiment 14) Any one of Embodiments 9 to 13, wherein at least 50% of the total projected area of the silver halide grains is occupied by tabular silver halide grains having an aspect ratio of 8 or more. The method for producing a photosensitive silver iodobromide emulsion according to the embodiment.

(Embodiment 15) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer provided on a support, the photosensitive halogen according to any one of Embodiments 1 to 7 is provided. A silver halide photographic light-sensitive material containing a silver halide emulsion.

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The present invention relates to a method for producing a silver halide photographic emulsion having improved properties.

The production of a silver halide photographic emulsion usually comprises a grain forming step, a desalting step, a dispersing step, a spectral sensitizing step and a chemical sensitizing step.

One feature of the present invention resides in the spectral sensitization step. The technical concept of the present invention will be described below. First, the addition of the spectral sensitizing dye to a solution containing silver halide grains substantially in the absence of a polyvalent cation that forms a sparingly soluble salt with the anionic spectral sensitizing dye means that the spectral sensitizing dye is added. The purpose is to improve the distribution between particles in the adsorption of the dye. After the spectral sensitizing dye is added to the emulsion, an equilibrium state is reached while repeating adsorption and desorption on the grain surface. In the process of reaching the equilibrium state, in a state in which adsorption and desorption are performed more vigorously, the dye adsorption between particles is averaged, so that the distribution of dye adsorption between particles is improved. Conversely, in the presence of the cation, when the spectral sensitizing dye is adsorbed on the particle surface, it is immobilized and the degree of adsorption and desorption is relatively reduced, so that the distribution of dye adsorption between particles is deteriorated. Next, the effectiveness of adding the cation after the spectral sensitizing dye is sufficiently adsorbed on the particle surface will be described. It is an effective technique to add a chemical sensitizer after adding a spectral sensitizing dye. That is, the spectral sensitizing dye is adsorbed on the particle surface, and the chemical sensitizer is adsorbed on the site where the spectral sensitizing dye is not adsorbed on the particle surface, whereby the sensitizing center can be efficiently formed. The site direct effect of the spectral sensitizing dye is more effective when the dye is immobilized in the presence of the cation. As described above, the present invention provides a method of adding a spectral sensitizing dye to an emulsion in the absence of the cation, improving the interparticle distribution of dye adsorption by sufficiently adsorbing the dye, and adding the cation after dye adsorption. It is essential that the chemical sensitization performed thereafter can be effectively performed.

In the present invention, at least one of calcium ion, magnesium ion and strontium ion is preferable as the polyvalent cation.

The sparingly soluble salt of the anionic spectral sensitizing dye and the polyvalent cation in the present invention will be described. Poor solubility means that the solubility of the salt in water by the anionic spectral sensitizing dye and the polyvalent cation is smaller than the solubility of the anionic spectral sensitizing dye alone in water. Basically, if the solubility of the anionic spectral sensitizing dye is reduced by the polyvalent cation, the effect of the present invention is exhibited. However, the solubility of the anionic sensitizing dye is preferably reduced by a factor of at least 3 due to the polyvalent cation, and more preferably at least 10 times.

In the present invention, calcium, magnesium and strontium in the emulsion after the desalting step and before the spectral sensitization and the chemical sensitization are applied are substantially absent.
Substantially absent means that the lower the content of calcium, magnesium and strontium, the better. Specifically, the content of calcium, magnesium and strontium is 50 ppm or less,
More preferably 35 ppm or less, further preferably 20 ppm
ppm or less. Here, that the content of calcium, magnesium, and strontium is 50 ppm or less means that the content of calcium, magnesium, and strontium is within a specified range.
The contents of calcium, magnesium and strontium are calcium ions, magnesium ions, strontium ions, calcium salts, magnesium salts, strontium salts, etc., for all compounds containing calcium, magnesium and strontium, calcium atoms, magnesium atoms, and strontium. It is represented by the weight in terms of atoms, and is represented by the concentration per unit weight of the emulsion.

The calcium, magnesium and strontium can be determined, for example, by ICP emission spectroscopy.

Next, the spectral sensitization in the present invention will be described.

The spectral sensitizing dye in the present invention can be added by any method. It can be added by dissolving it in water or an organic solvent such as alcohols, glycols, ketones, esters and amides. Further, a spectral sensitizing dye having a solubility in water of 3% by weight or less is used under the condition that substantially no organic solvent and / or surfactant is present and at a pH of 6 to 8 and 40 to 80 ° C.
It is preferable to add a dispersion of the spectral sensitizing dye obtained by mechanically pulverizing and dispersing the fine particles into fine particles in an aqueous system. Here, the solubility in water refers to the solubility at 27 ° C., and the solubility of the spectral sensitizing dye is preferably 1 ×
It is in the range of 10 ^-8 % by weight to 2% by weight. The condition that substantially no organic solvent and / or surfactant is present means that the organic solvent and / or surfactant is 5% or less by weight based on the spectral sensitizing dye, preferably 1% by weight. Or less, more preferably 0.5% by weight or less. Further, as described in JP-A-11-52507, 0.5% by weight or more of an inorganic salt is dissolved in water substantially free of any of a surfactant, an organic solvent and a silver halide emulsion. ,
It is more preferable to add 0.5% by weight or more of the spectral sensitizing dye and to add a solid fine dispersion of the spectral sensitizing dye prepared according to the spectral sensitizing dye dispersion method characterized by finely dispersing the solid. .

The term "substantially free of any of the surfactant, the organic solvent and the silver halide emulsion" means that the surfactant, the organic solvent and the silver halide emulsion are 5 parts by weight relative to the spectral sensitizing dye.
% Or less, preferably 1% by weight or less,
More preferably, it is 0.5% by weight or less. The inorganic salt in the present invention is a salt of a carbon-free acid such as hydrochloric acid, sulfuric acid, nitric acid and the like with an alkali metal, an alkaline earth metal, and ammonium. Specifically, z is lithium chloride, sodium chloride, chloride, or the like. Potassium, rubidium chloride, cesium chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, lithium sulfate, potassium sulfate, sodium sulfate, lithium nitrate, potassium nitrate,
Examples thereof include sodium nitrate and ammonium nitrate. The concentration of these inorganic salts in water is 0.5% by weight or more, preferably 1% by weight or more and 50% by weight or less, more preferably 2% by weight or more and 30% by weight or less. Also,
The concentration of these spectral sensitizing dyes in water is 0.5% by weight or more, preferably 1% by weight or more and 30% by weight or less, more preferably 2% by weight or more and 20% by weight or less. is there.

The photographic emulsion of the present invention is preferably spectrally sensitized by a methine dye or the like to exhibit the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Styryl dyes and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and compound merocyanine dyes.
These dyes may contain any nucleus commonly used in cyanine dyes as a basic heterocyclic nucleus. Examples of such a nucleus include a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, and a pyridine nucleus; and an alicyclic hydrocarbon ring fused to these nuclei. Nuclei; and nuclei in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole Examples include a nucleus, a benzimidazole nucleus, and a quinoline nucleus. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or the complex merocyanine dye includes, as nuclei having a ketomethylene structure, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidin-2,4-dione nucleus, and thiazolidine-2,4-nucleus.
It can have a 5-6 membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, a thiobarbituric acid nucleus.

These spectral sensitizing dyes may be used alone or in combination, and the combination of spectral sensitizing dyes is often used particularly for supersensitization.
Representative examples are U.S. Pat. Nos. 2,688,545 and 2,682,545.
977,229, 3,397,060, 3,5
22,052, 3,527,641, 3,61
7,293, 3,628,964 and 3,66
6,480, 3,672,898, 3,67
9,428, 3,703,377, 3,76
9,301, 3,814,609, 3,83
Nos. 7,862, 4,026,707, British Patent Nos. 1,344,281, 1,507,803, JP-B-43-4936, JP-B-53-12,375, JP-A-52 Nos. -110,618 and 52-109,925.

In addition to the spectral sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Next, calcium added after the spectral sensitization,
The addition of the water-soluble salt of at least one metal selected from magnesium and strontium will be described.

First, the timing of the addition of the water-soluble metal salt will be described. After the spectral sensitizing dye is added to the emulsion, it is adsorbed on the surface of the emulsion grains and eventually reaches an equilibrium state. In the present invention, a water-soluble salt of at least one metal selected from calcium, magnesium and strontium can be added after the spectral sensitizing dye is sufficiently adsorbed on the particle surface. It is preferably added when at least 80% or more of the dye is adsorbed on the particle surface of the spectral sensitizing dye in the equilibrium state, and more preferably 90% or more.

The amount of the spectral sensitizing dye adsorbed is determined by separating the solid layer and the liquid layer by centrifugal sedimentation and measuring the difference between the amount of the spectral sensitizing dye added first and the amount of the spectral sensitizing dye in the supernatant. The amount of the adsorbed spectral sensitizing dye can be determined.

In the present invention, the amount of the water-soluble salt of at least one metal selected from calcium, magnesium and strontium to be added after the spectral sensitizing dye has been sufficiently adsorbed and before the start of chemical sensitization is: The content of calcium, magnesium and strontium in the emulsion after the addition is 100 to 2500 ppm, preferably 20 to 2500 ppm.
0 to 2500 ppm. Of the metals added, calcium is most preferred, followed by strontium and magnesium.

As the water-soluble salt of calcium in the present invention, for example, calcium nitrate and calcium chloride are preferable, and as the water-soluble salt of magnesium, magnesium nitrate, magnesium chloride and magnesium chloride are preferable.
Magnesium nitrate is most preferred, and strontium nitrate is preferred as the water solubility of strontium.

Next, the chemical sensitization in the present invention will be described. In the present invention, it is preferable to perform at least selenium sensitization as the chemical sensitization.

First, selenium sensitization used in the present invention will be described.

As the selenium sensitizer used in the present invention, selenium compounds disclosed in conventionally known patents can be used. Usually, the unstable selenium compound and / or the non-unstable selenium compound is used by adding the selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. As an unstable selenium compound,
JP-B-44-15748, JP-B-43-13489
JP-A-4-25832, JP-A-4-109240
It is preferable to use the compounds described in the above.

Specific examples of unstable selenium sensitizers include, for example, isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids. For example, 2-selenopropionic acid, 2-
Selenobutyric acid), selenoesters, diacylselenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, and colloidal metal selenium.

While the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. Speaking of an unstable selenium compound as a sensitizer of a photographic emulsion, the structure of the compound is not very important as long as selenium is unstable, and the organic portion of the selenium sensitizer molecule carries selenium, It is generally understood by those skilled in the art that it has no role other than to be present in the emulsion in an unstable form. In the present invention, an unstable selenium compound having such a broad concept is advantageously used.

The non-labile selenium compounds used in the present invention include JP-B-46-4553 and JP-B-52-3.
No. 4,492, and JP-B-52-34491. As a non-labile selenium compound,
For example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, 2-selenooxazolidinthione and these Derivatives.

Of these selenium compounds, the following general formulas (I) and (II) are preferred.

Formula (I)

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In the formula, Z ₁ and Z ₂ may be the same or different and each represents an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl) Aralkyl group (eg, benzyl, phenethyl), aryl group (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl), heterocyclic group (eg,
2-pyridyl, 3-thienyl, 2-furyl, _{2-imidazolyl), - NR 1 (R 2} ), - represents the OR ₃ or -SR _4.

R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and represent a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, a heterocyclic group or an acyl group. Alkyl group, an aralkyl group, the aryl group or heterocyclic group, the same examples as Z ₁ and the like. However, R ₁ and R ₂ represent a hydrogen atom or an acyl group (eg, acetyl,
Propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, α-
Naphthoyl, 4-trifluoromethylbenzoyl).

[0053] In formula (I), preferably, Z ₁ represents an alkyl group, an aryl group, or -NR ₁ a (R _2), Z ₂
Represents -NR ₅ (R _6). R ₁ , R ₂ , R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an acyl group.

Formula (I) is more preferably N, N
-Dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N-
Represents an alkyl-N-aryl-arylselenoamide.

General formula (II)

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In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each represents an aliphatic group, an aromatic group, a heterocyclic group, —OR ₇ , —NR ₈ (R ₉ ), or —SR ₁₀ , -Se
R ₁₁ , X represents a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. X represents a halogen atom.

In the general formula (II), Z ₃ , Z ₄ , Z ₅ ,
The aliphatic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl, ethyl,
n-propyl, isopropyl, t-butyl, n-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-pentynyl,
Benzyl, phenethyl).

In the general formula (II), Z ₃ , Z ₄ , Z ₅ ,
The aromatic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (for example, phenyl,
Pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl, 4-methylphenyl).

In the general formula (II), Z ₃ , Z ₄ , Z ₅ ,
The heterocyclic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a saturated or unsaturated 3- to 10-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. Represents a heterocyclic group (for example, 2-pyridyl, 3-thienyl, 2-furyl, 2-thiazolyl, 2-imidazolyl, 2-benzimidazolyl).

In the general formula (II), the cation represented by R ₇ , R ₁₀ and R ₁₁ is an alkali metal atom (for example,
Sodium, potassium) or ammonium. The halogen atom represented by X represents, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the general formula (II), preferably,
Z ₃ , Z ₄ or Z ₅ is an aliphatic group, an aromatic group or —OR ₇
And R ₇ represents an aliphatic group or an aromatic group.

The formula (II) more preferably represents a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate or a triarylselenophosphate.

Specific examples of the compounds represented by formulas (I) and (II) are shown below, but the present invention is not limited thereto.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, and added during chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more of the above-mentioned selenium sensitizers can be used in combination. A combination of an unstable selenium compound and a non-unstable selenium compound is preferred.

The amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the ripening temperature and time, and the like.
1 × 10 ^-8 mol to 1 × 10 ^-4 per mol of silver halide
Molar is preferred. In particular, in order to remarkably obtain the effect of selenium sensitization, the amount is preferably from 2.5 × 10 ⁻⁶ mol to 5 × 10 ⁻⁵ mol. More preferably, it is 2.5 × 10 ⁻⁶ mol or more and 1 × 10 ⁻⁵ mol or less. The temperature of chemical ripening when using a selenium sensitizer is preferably 40 ° C. or higher,
And 80 ° C. or lower. pAg and pH are arbitrary. For example, the effects of the present invention can be obtained in a wide range of pH from 4 to 9.

The selenium sensitization is more effectively achieved by performing the sensitization in the presence of a silver halide solvent.

Examples of the silver halide solvent usable in the present invention include, for example, US Pat. No. 3,271,157.
No. 3,531,289, No. 3,574,62
No. 8, JP-A-54-1019 and JP-A-54-158917
(A) organic thioethers described, for example, in JP-A-53-82408, JP-A-55-77737, and JP-A-55-77737;
(B) thiourea derivatives described in JP-A-2982; and (c) silver halide solvents having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. (D) imidazoles, (e) sulfites described in JP-A-54-100717,
(F) thiocyanate.

Particularly preferred silver halide solvents include:
There are thiocyanate and tetramethylthiourea. The amount of the solvent used varies depending on the kind. For example, in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ mol or more per mol of silver halide and 1 × 10 ⁻² or more.
Mol or less.

The emulsion of the present invention is preferably used in combination with gold sensitization. As a gold sensitizer for gold sensitization, the oxidation number of gold is +1
Valence or +3 valence, and a gold compound usually used as a gold sensitizer can be used. A typical example is
Examples thereof include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, and gold selenide.

The emulsion of the present invention is desirably used in combination with sulfur sensitization in chemical sensitization.

The sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher, for a certain time.

For the above-mentioned sulfur sensitization, known sulfur sensitizers can be used. Examples include thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine and the like. Other, for example, U.S. Pat.
574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, 3,656,955,
German Patent 1,422,869, JP-B-56-249
No. 37 and JP-A-55-45016 can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This amount varies over a considerable range under various conditions such as pH, temperature, silver halide grain size, etc., but is not less than 1 × 10 ⁻⁷ mol per mol of silver halide.
× 10 ^-5 mol or less is preferred.

In the present invention, the start of chemical sensitization refers to the time when at least one of the above-mentioned chemical sensitizers is added to the emulsion.

During the grain formation of the silver halide emulsion of the present invention,
Reduction sensitization can also be performed after grain formation and before or during chemical sensitization, or after chemical sensitization.

The reduction sensitization can be performed by adding a reduction sensitizer to a silver halide emulsion, or by using pAg1
7, a method of growing or ripening in a low pAg atmosphere;
Either a method of growing or ripening in a high pH atmosphere of pH 8 to 11 called high pH ripening can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

Examples of reduction sensitizers include stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid,
Silane compounds, borane compounds and the like are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide as reduction sensitizer,
Dimethylamine borane, ascorbic acid and its derivatives are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide.

The reduction sensitizer is dissolved in water or an organic solvent such as alcohols, glycols, ketones, esters, and amides and added during grain growth. Although it may be added to the reaction vessel in advance, it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide, and silver halide grains may be precipitated using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains grow, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver is
A compound which acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective.
The silver ions generated here may form a silver salt that is hardly soluble in water, such as silver halide, silver sulfide, and silver selenide.
Further, a silver salt easily soluble in water such as silver nitrate may be formed.
The oxidizing agent for silver may be inorganic or organic. As the inorganic oxidizing agent, ozone, hydrogen peroxide and additives thereof (for example, NaBO ₂ .H ₂ O ₂ .3H _{2
O, 2NaCO 3 · 3H 2 O} 2, Na 4 P 2 O 7 · 2H 2 O 2,
_{2Na 2 SO 4 · H 2 O} 2 · 2H 2 O), peroxy acid salts (e.g., _{K 2 S 2 O 8, K} 2 C 2 O 6, K 2 P 2 O 8), peroxy complex compounds (e.g., K ₂ [Ti (O ₂ ) C ₂ O ₄ ] ·
_{3H 2 O, 4K 2 SO 4} · Ti (O 2) OH · SO 4 · 2H 2
O, Na ₃ [VO (O ₂ ) (C ₂ H ₄ ) ₂ .6H ₂ O), permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr ₂ O ₇ ) Oxygenates, halogens such as iodine and bromine, perhalates (eg, potassium periodate), salts of high valent metals (eg, potassium hexacyanoferric acid), and thiosulfonates. is there.

Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-
Bromsuccinimide, chloramine T, chloramine B) are mentioned by way of example.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, inorganic oxidizing agents such as thiosulfonates and organic oxidizing agents such as quinones.

It is a preferred embodiment to use the above-described reduction sensitization and an oxidizing agent for silver in combination. A method of using an oxidizing agent followed by reduction sensitization, a reverse method thereof, or a method of coexisting both can be used. These methods can be applied to both the grain formation step and the chemical sensitization step.

Next, the grain formation of the emulsion of the present invention will be described.

In the present invention, tabular silver halide grains (hereinafter also referred to as tabular grains) are preferably used. The aspect ratio of a tabular grain means the ratio of the diameter to the thickness in silver halide. That is, it is a value obtained by dividing the diameter of each silver halide grain by the thickness. Here, the diameter refers to the diameter of a circle having an area equal to the projected area of the silver halide grains when the grains are observed with a microscope or an electron microscope. Therefore, that the aspect ratio is 8 or more means that the diameter of the circle is 8 times or more the thickness of the particle. In the tabular silver halide grains of the present invention, grains having an aspect ratio of 8 or more occupy 50% or more of the projected area of all silver halide grains, preferably 60%.
That is all.

In the present invention, the average aspect ratio is an average value of the aspect ratios of all tabular grains in the emulsion, and the tabular grains are grains having an aspect ratio of 2 or more. The average aspect ratio of the tabular grains of the present invention is preferably 8 or more.
The above is further preferred, and the value of 16 or more is particularly preferred. The upper limit of each aspect ratio is 50.

As an example of a method of measuring the aspect ratio, there is a method of taking a transmission electron micrograph by a replica method and obtaining the equivalent circle diameter and thickness of each particle. in this case,
The thickness is calculated from the length of the shadow of the replica.

The shape of the tabular grains in the present invention is usually
Hexagon. The hexagonal shape means that the shape of the main plane of the tabular grains has an adjacent side ratio (maximum side length / minimum side length) of 2 or less. Preferably, the adjacent side ratio is 1.6 or less, and more preferably, the adjacent side ratio is 1.2 or less. It goes without saying that the lower limit is 1.0. Particularly in high aspect ratio grains, triangular tabular grains increase in tabular grains. Triangular tabular grains appear when Ostwald ripening has progressed too much. In order to substantially obtain hexagonal tabular grains, it is preferable to shorten the time for ripening as much as possible. For that purpose, it is necessary to devise a method of increasing the ratio of tabular grains by nucleation. JP-A-63 by Saito
As described in JP-A-11928, when silver ions and bromide ions are added to a reaction solution by a double jet method, in order to increase the probability of generation of hexagonal tabular grains, a silver ion aqueous solution and a bromide ion aqueous solution are used. Preferably, one or both solutions contain gelatin.

The hexagonal tabular grains used in the present invention have nucleation and
It is formed by the Ostwald ripening and growing process. Each of these steps is important in suppressing the spread of the particle size distribution, but it is impossible to narrow the spread of the size distribution generated in the previous step in the subsequent step. Care must be taken that the distribution does not spread. An important point in the nucleation process is
This is the relationship between the nucleation time for causing silver ions and bromide ions to be added to the reaction solution by the double jet method to cause precipitation, and the temperature of the reaction solution. JP-A-63-92 by Saito
No. 942 describes that the temperature of the reaction solution during nucleation is preferably in the range of 20 to 45 ° C. in order to improve the monodispersity. Further, JP-A-2-222940 by Zola et al.
The article states that the preferred temperature during nucleation is below 60 ° C.

In order to obtain monodisperse tabular grains having a large aspect ratio, gelatin may be additionally added during grain formation. At this time, the gelatin used is preferably a succinated gelatin. Alternatively, JP-A-10-14889
No. 7 and JP-A-11-143002 are preferably used. The chemically modified gelatin is a gelatin characterized in that at least two carboxyl groups are newly introduced when an amino group in the gelatin is chemically modified, and it is preferable to use a trimellitated gelatin. This gelatin is preferably added before the growth step, and more preferably immediately after the nucleation. The addition amount is at least 40%, preferably at least 60%, particularly preferably at least 80%, based on the weight of the entire dispersion medium during the formation of the particles.

The silver halide of the tabular grain emulsion preferably comprises silver iodobromide or silver chloroiodobromide. Although silver chloride may be contained, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less, or 0 mol%. Regarding the silver iodide content, the coefficient of variation of the grain size distribution of the tabular grain emulsion is preferably 30% or less.
The silver iodide content is preferably at most 20 mol%. By reducing the silver iodide content, the coefficient of variation of the grain size distribution of the tabular grain emulsion can be easily reduced. In particular, the coefficient of variation of the grain size distribution of the tabular grain emulsion is preferably 20% or less, and the silver iodide content is preferably 10 mol% or less.

It is preferable that the tabular grain emulsion has a structure within the grains with respect to silver iodide distribution. In this case, the structure of the silver iodide distribution may be a double structure, a triple structure, a quadruple structure, or even a higher structure.

In the present invention, tabular grains have dislocation lines. Dislocation lines of tabular grains are described, for example, in J. Am. F. Hamilt
on, Photo. Sci. Eng. , 11,57, (1
967) and T.S. Shiozawa, J .; Soc. Pho
t. Sci. Japan, 35, 213, (1972)
Can be observed by a direct method using a transmission electron microscope at a low temperature. That is, silver halide grains taken out from the emulsion with care not to apply enough pressure to generate dislocation lines on the grains are placed on a mesh for observation with an electron microscope, and damaged by electron beams (printout, etc.).
Observation is carried out by a transmission method in a state in which the sample is cooled so as to prevent the above. At this time, the thicker the particle, the more difficult it is for the electron beam to penetrate. Therefore, a clearer image can be observed by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

The average number of dislocation lines per tabular grain of the present invention is preferably 10 or more per grain. More preferably, the average is 20 or more per particle. When dislocation lines are densely present or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count to about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where there are only a few pieces. The average number of dislocation lines per particle is determined as a number average by counting the number of dislocation lines for 100 particles or more. Hundreds of dislocation lines may be observed.

Dislocation lines can be introduced, for example, near the outer periphery of tabular grains. In this case, the dislocation is almost perpendicular to the outer periphery, and a dislocation line is generated from the position of x% of the length from the center of the tabular grain to the side (outer periphery) to the outer periphery. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the start positions of the dislocation lines is similar to the particle shape, but may not be a perfect similar shape and may be distorted. This type of dislocation number is not found in the central region of the grain.
The direction of the dislocation lines is approximately (211) crystallographically, but often meanders, and may intersect each other.

The tabular grains may have dislocation lines almost uniformly over the entire area on the outer periphery, or may have dislocation lines at local positions on the outer periphery. That is, in the case of a hexagonal tabular silver halide grain as an example, dislocation lines may be limited only near six vertices, or dislocation lines may be limited only near one of the vertices. Conversely, dislocation lines may be limited to only sides excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the centers of two parallel main planes of the tabular grains. When dislocation lines are formed over the entire area of the main plane, the direction of the dislocation lines may be approximately (211) crystallographically when viewed from a direction perpendicular to the main plane, but may be in the (110) direction or In some cases, the dislocation lines are formed randomly, and the length of each dislocation line is also random. In some cases, the dislocation lines are observed as short lines on the main plane, and in other cases, they are observed as long lines reaching the side (outer circumference). is there. Dislocation lines are sometimes straight or meandering. They also often intersect with each other.

As described above, the position of the dislocation line may be limited to the outer periphery, the main plane, or a local position, or may be formed by combining these.
That is, they may exist simultaneously on the main plane on the outer periphery.

Introduction of dislocation lines into tabular grains can be achieved by providing a specific high silver iodide phase inside the grains.
In this case, a high silver iodide phase may be provided with a high silver iodide region discontinuously. Specifically, the high silver iodide phase inside the grains is obtained by preparing a base grain, providing a high silver iodide phase, and covering the outside with a phase having a lower silver iodide content than the high silver iodide phase. Can be The silver iodide content of the tabular grains of the base is lower than that of the high silver iodide phase, preferably 0 to 20 mol%, more preferably 0 to 15 mol%.

The high silver iodide phase inside the grains means a silver halide solid solution containing silver iodide. The silver halide in this case is preferably silver iodide, silver iodobromide, or silver chloroiodobromide, but is preferably silver iodide or silver iodobromide (silver iodide content: 10 to 40 mol%). More preferred. In order for the high silver iodide phase inside the grains (hereinafter referred to as the internal silver iodide high phase) to be selectively present on any side, corner, or plane of the base grains, formation of the base grains is required. It is desirable to control the conditions and the conditions for forming the internal high silver iodide phase and the conditions for forming the phase covering the outside. As the conditions for forming the base grains, pAg (the logarithm of the reciprocal of silver ion concentration) and the presence / absence, type and amount of silver halide solvent, and temperature are important factors. By controlling the pAg during the growth of the base grains to 8.5 or less, more preferably 8 or less, the internal high silver iodide phase is formed in the vicinity of the apex of the base grains or at the surface when the internal high silver iodide phase is formed later. It can be selectively present above. On the other hand, the pAg during the growth of the base particles is preferably 8.5 or more, more preferably 9 or more.
By performing the above, the internal high silver iodide phase can be present on the side of the base grain in the subsequent generation of the internal high silver iodide phase. These threshold values of pAg change up and down depending on the temperature and the presence / absence, type and amount of the silver halide solvent. When, for example, thiocyanate is used as the silver halide solvent, the threshold value of the pAg shifts toward a higher value. Particularly important as the pAg during growth is the pAg at the end of the growth of the base particle. On the other hand, even when the pAg at the time of growth does not satisfy the above value, it is possible to control the selected position of the internal silver iodide-rich phase by adjusting the pAg after the growth of the base grains and ripening. is there. At this time, ammonia, amine compounds, thiourea derivatives, and thiocyanate salts are effective as silver halide solvents. The formation of the internal silver iodide-rich phase can use a so-called conversion method. In this method, during the grain formation, there is a method of adding a halogen ion having a lower solubility of a salt for forming a silver ion than a halogen ion forming a grain or a vicinity of the surface of the grain at that time. In the present invention, it is preferable that the amount of the added halogen ions having low solubility is not less than a certain value (related to the halogen composition) with respect to the surface area of the particles at that time. For example, it is preferable to add a certain amount or more of KI to the surface area of the silver halide grains at that time during grain formation. Specifically, it is preferable to add 8.2 × 10 ⁻⁵ mol / m ² or more of iodide salt.

A more preferred method for forming the internal silver-rich iodide phase is to add an aqueous silver salt solution simultaneously with the addition of an aqueous halide salt solution containing an iodide salt.

For example, AgNO is added simultaneously with the addition of the KI aqueous solution.
₃ Add the aqueous solution by double jet. At this time, the addition start time and the addition end time of the KI aqueous solution and the AgNO ₃ aqueous solution may be shifted from each other and may be changed. The addition molar ratio of the AgNO ₃ aqueous solution to the KI aqueous solution is preferably 0.1 or more, more preferably 0.5 or more. More preferably, it is 1 or more. The total added molar amount of the AgNO ₃ aqueous solution may be in the silver excess region with respect to the halogen ions and the added iodine ions in the system. It is preferable that the pAg at the time of addition of the halide aqueous solution containing iodide ions and the addition of the silver salt aqueous solution by the double jet decrease with the addition time by the double jet. The pAg before the start of addition is
It is preferably 6.5 or more and 13 or less. More preferably 7.0
The number is preferably 11 or more. The pAg at the end of the addition is 6.5
More preferably, it is at most 10.0.

In carrying out the above method, it is preferable that the solubility of the mixed silver halide is as low as possible. Therefore, the temperature of the mixed system for forming a high silver iodide phase is preferably 30 ° C. or more and 80 ° C. or less, more preferably 30 ° C. or more and 7 ° C. or less.
0 ° C. or less.

More preferably, the formation of the internal high silver iodide phase can be carried out by adding fine grain silver iodide, fine grain silver iodobromide, fine grain silver chloroiodide or fine grain silver chloroiodobromide. In particular, it is preferable to add fine grain silver iodide.
These fine particles usually have a particle size of 0.01 μm or more and 0.1 μm or less, but 0.01 μm or less or 0.1 μm or less.
Fine particles having a particle size of m or more can also be used.
The methods for preparing these fine silver halide grains are described in JP-A-1-183417, JP-A-2-44335,
No. 183644, No. 1-183645, No. 2-435
Nos. 34 and 2-43535 can be referred to. An internal high silver iodide phase can be provided by adding and ripening these fine grain silver halides. When the fine particles are dissolved by ripening, the above-mentioned silver halide solvent can be used. It is not necessary that all of the added fine particles dissolve and disappear immediately, and it is sufficient that the fine particles dissolve and disappear when the final particles are completed.

The position of the internal silver iodide-rich phase is measured from the center of a hexagon or the like on which the grains are projected, and is preferably in the range of 5 mol% or more and less than 100 mol% based on the silver amount of the whole grains. Preferably 20 mol% or more and less than 95 mol%,
In particular, the content is preferably in the range of 50 mol% or more and less than 90 mol%. The amount of silver halide forming these internal high silver iodide phases is not more than 50 mol%, more preferably not more than 20 mol% of the silver amount of the whole grains in terms of silver amount. These high silver iodide phases are the prescription values for the production of silver halide emulsions, not the values obtained by measuring the halogen composition of the final grains by various analytical methods. The internal silver iodide-rich phase often disappears in the final grain due to recrystallization or the like in the shelling process, and the above-mentioned silver content is all related to the prescribed value.

Therefore, in the final grain, dislocation lines can be easily observed by the above-mentioned method. However, in the internal silver iodide phase introduced for introducing dislocation lines, the silver iodide composition at the boundary continuously changes. For this reason, it is often not possible to confirm it as a clear phase. Regarding the halogen composition of each part of the grain, X-ray diffraction, EPMA (also known as XMA) method (a method of detecting silver halide composition by scanning silver halide grains with an electron beam), and ESCA (also known as XPS) ) Method (a method of irradiating X-rays and dispersing photoelectrons coming out of the particle surface) and the like.

The outer phase covering the inner silver iodide-rich phase is lower than the silver iodide content of the high silver iodide phase, and preferably has a silver iodide content of 0 to 30 mol%, more preferably 0 to 30 mol%. It is 20 mol%, most preferably 0 to 10 mol%.

The temperature and the pAg at the time of forming the outer phase covering the inner silver iodide-rich phase are arbitrary, but the preferred temperature is 3 p.
0 ° C. or higher and 80 ° C. or lower. Most preferably, it is 35 ° C or more and 70 ° C or less. Preferred pAg is 6.5 or more and 1
1.5 or less. In some cases, it is preferable to use the above-mentioned silver halide solvent, and the most preferable silver halide solvent is a thiocyanate salt.

Further, as another method for introducing dislocation lines into tabular grains, there is a method using an iodide ion releasing agent as described in JP-A-6-11782, which is preferably used.

It is also possible to introduce dislocation lines by appropriately combining the method of introducing dislocation lines with the above-described method of introducing dislocation lines.

The distribution of iodine between grains of the silver halide grains used in the present invention is preferably uniform. The silver halide grains of the present invention preferably have an iodine distribution between grains of 20% or less. More preferably 15% or less,
It is particularly preferably at most 10%. If the coefficient of variation of the iodine content distribution of each silver halide is greater than 20%, it is not preferable because the contrast does not become high and the sensitivity decreases when pressure is applied.

The silver halide grains having a narrow intergranular iodine distribution used in the present invention can be prepared by any known method, for example, a method of adding fine particles as disclosed in JP-A-1-183417 or JP-A-2-68538. And the like, using an iodide ion releasing agent, or the like can be used alone or in combination.

The silver iodide content of each grain can be measured by analyzing the composition of each grain using an X-ray microanalyzer. The coefficient of variation of the intergranular iodine distribution is defined as the standard deviation of the silver iodide content and the average iodine content when the silver iodide content of at least 100, more preferably 200 and particularly preferably 300 or more emulsion grains is measured. It is a value defined by a relational expression (standard deviation / average silver iodide content) × 100 = coefficient of variation using silver halide content. The measurement of the silver iodide content of the individual grains is described, for example, in EP 147,868. There may or may not be a correlation between the silver iodide content Yi (mol%) of each grain and the sphere equivalent diameter Xi (microns) of each grain, but it is desirable that there is no correlation. Regarding the structure relating to the silver halide composition of the grains of the present invention,
For example, X-ray diffraction, EPMA (also referred to as XMA) method (a method of detecting silver halide composition by scanning silver halide grains with an electron beam), ESCA (also referred to as XPS) method (X-ray (A method of irradiating photoelectrons emitted from the particle surface by irradiating the particles). In the present invention, the particle surface refers to a region having a depth of about 50 ° from the surface. The halogen composition in such a region can usually be measured by the ESCA method. The inside of the particle means a region other than the above-mentioned surface.

Next, the gelatin used in the present invention will be described. In the present invention, since it is necessary to prepare an emulsion having a low calcium content, it is preferable to use gelatin whose calcium content has been reduced by lime treatment.

In the present invention, high molecular weight gelatin is preferably used. The high molecular weight gelatin used in the present invention refers to an alkali-treated bone gelatin containing 30% or more of a component having a molecular weight of 280,000 or more in a molecular weight distribution measured by the PAGI method. Gelatin used in the present invention contains three components having a molecular weight distribution of 280,000 or more.
It is an alkali-treated bone gelatin containing 0% or more, preferably 35% or more. Gelatin is obtained by decomposing the structure of collagen tissue with alkali or acid to impart water solubility. In the case of alkali-treated gelatin, sub-α (low molecular weight), α (molecular weight 10
10,000), β (molecular weight 200,000), γ (molecular weight 300,000) and a large polymer portion (void; molecular weight greater than 300,000).
The ratio of the components, ie the molecular weight distribution, is determined by the internationally defined PAGI method. The PAGI method is a method of estimating a molecular weight distribution by obtaining a chromatogram of an aqueous gelatin solution by a gel filtration method using high performance liquid chromatography. In the gelatin used in the present invention, the sum of the γ and the void component is 30% or more,
Preferably it is 35%, more preferably 37% or more.

The method for producing such gelatin is roughly classified into the following two methods.

[0124] 1. Method without cross-linking of gelatin Alkali-treated gelatin is produced by removing calcium from raw material bone, immersing in lime treatment to loosen the collagen structure, extracting with warm water, and drying. In general, extraction is performed by setting the extraction temperature in 1 to 7 stages, and the extraction temperature increases with the number of extractions. At that time, the molecular weight distribution of the resulting gelatin can be controlled by adjusting the extraction temperature and time. Gelatin used in the present invention can be prepared by examining these extraction conditions.

[0125] 2. Method Using Gelatin Crosslinking Agent Gelatin used in the present invention is obtained by crosslinking gelatin. As the crosslinking method, there are two methods: a method of crosslinking between gelatin molecules by an enzyme, and a method of adding a crosslinking agent to form a chemical bond between gelatin molecules and crosslinking the gelatin molecules.

As a typical method of the enzyme method used in the present invention, gelatin cross-linked with transglutaminase will be described. The transglutaminase enzyme can crosslink gelatin by a function of catalyzing an acyl transfer reaction between a γ-carboxamide group of a glutamine residue and various primary amines of gelatin, which is a protein. Transglutaminase is derived from animals, plants, and microorganisms.For example, animal-derived ones include mammalian organs such as guinea pig liver, those extracted from blood, and plant-derived ones derived from pea. Extracted and derived from microorganisms are extracted from actinomycetes. In the present invention, any source having transglutaminase activity can be preferably used.

The transglutaminase used in the present invention can be prepared, for example, by the method of Clark et al. (Archives of Biochemis).
try and Biophysics, 79, 338 [1959]), the method of Connel et al. (J. Biological Chemistry, 246, [1971]), the method described in JP-A-4-207149, and the method described in JP-A-6-3077.
Those synthesized by any of the methods described in No. 0 can be preferably used. Examples of these transglutaminases include Acteva (trade name, manufactured by Ajinomoto Co., Inc.).
Transglutaminase activity used in the present invention,
It can be measured by reacting benzyloxycarbonyl L glutaminylglycine with hydroxyamine and determining the amount of hydroxamic acid produced. Based on this measurement, the transglutaminase activity that produces 1 × 10 ⁻⁶ mol of hydrixamic acid per minute is defined as one unit. The transglutaminase used in the present invention varies depending on the gelatin used.
× is preferably added in an amount to produce a 10 ^-6 mol or more of the hydroxamic acid, particularly preferably preferably generates a 1 × 10 ^-5 mol or more hydroxamic acids.

As the cross-linking agent used in the cross-linked gelatin used in the present invention, any cross-linking agent which has hitherto been known as a hardening agent for gelatin can be used. The typical compounds are shown below.

A. Inorganic crosslinking agent (inorganic hardener) Cationic chromium complex; ligands of the complex include hydroxyl group, oxalic acid group, citric acid group, malonic acid group, lactate, tartrate, succinate, acetate, Formate, sulfate,
Chloride, nitrate. Aluminum salts; especially sulfates, potassium alum, ammonium alum.

The above compounds crosslink the carboxyl groups of gelatin.

B. Organic crosslinking agent (organic hardener) Aldehyde-based crosslinkers; the most commonly used is formaldehyde. Effective cross-linking can also be achieved with dialdehyde, for example, glyoxal and succinaldehyde, particularly glutaraldehyde. Diglycolaldehyde, various aromatic dialdehydes, dialdehyde starch, and dialdehyde derivatives of vegetable gums are also used for crosslinking in the present invention.

[0132] 2. N-methylol compounds and other protected aldehyde crosslinkers; N-methylol compounds obtained by condensation of formaldehyde with various aliphatic linear or cyclic amides, ureas and nitrogen-containing heterocycles. Specific examples include 2,3-dihydroxidioxane, acetate esters of dialdehydes and hemiacetals thereof, and 2,5-dimethoxytetrahydrofuran.

3. Ketone crosslinking agents; compounds of diketones and quinones. Well-known diketones include 2,3-butanedione, CH ₃ COCOCH _{3 and the} like. As quinone, p-benzoquinone is well known.

4. Sulfonate and sulfonyl halide; bis (sulfonyl chloride) as a typical compound
And bis (sulfonyl fluoride) s.

[0135] 5. Active halogen compound; a compound having two or more active halogen atoms. Representative compounds include simple bis-α-chloro or bis-α-bromo derivatives of ketones, esters, and amides, bis (2-chloroethylurea), bis (2-chloroethyl) sulfone, and phosphoramidic halides. .

6. Epoxide; butadiene dioxide is a typical compound.

7. Activated olefins; Many compounds having two or more double bonds, especially unsubstituted vinyl groups activated by adjacent electron-withdrawing groups, are effective as gelatin crosslinkers. Examples of this compound include divinyl ketone, resorcinol bis (vinyl sulfonate),
4,6-bis (vinylsulfonate), 4,6-bis (vinylsulfonyl) -m-xylene, bis (vinylsulfonylalkyl) ether or amine, 1,3,5-triacryloylhexahydro-s-triazine, Diacrylamide, 1,3-bis (acryloyl) urea and the like.

Others JP-A-62-215272, p. 475, line 8 to 50
The curing agent described on page 8, line 3 (general formula (HI)
To (H-VIII)) can also be used.

In the production of gelatin used in the present invention, the crosslinking agents mentioned above are added to a gelatin solution to cause gelatin intermolecular crosslinking. The conditions at that time differ depending on each crosslinking agent, but the reaction conditions can be determined by setting a constant reaction temperature and reaction time and measuring the molecular weight distribution of gelatin by the PAGI method. At this time, the progress of crosslinking can be monitored by measuring the viscosity of the gelatin solution. It is desirable that all of the added cross-linking agent be reacted, but if it remains unreacted, after the cross-linking reaction, the gelatin solution can be subjected to ultrafiltration to remove the remaining cross-linking agent. In the present invention, the conditions for the crosslinking reaction can be set by measuring the molecular weight distribution according to the measurement method of the PAGI method. That is, the temperature and time of the crosslinking reaction, the pH of the solution, and the like.

The gelatin used in the present invention may be added at any point during grain formation, but is preferably added after nucleation. The addition amount is at least 10%, preferably at least 30%, more preferably at least 50%, based on the total dispersion medium during the formation of the particles. Further, the gelatin used in the present invention has an effect even if it is added as a dispersed gelatin added after washing the emulsion with water. The addition amount is at least 10%, preferably at least 30%, more preferably at least 50% of the dispersed gelatin added after washing with water. Further, the gelatin used in the present invention is effective even if added before coating. The addition amount is 10% or more of the dispersion medium added before coating, preferably 30%.
% Or more, more preferably 50% or more.

Emulsions used in the present invention, techniques such as layer arrangement which can be used for photographic light-sensitive materials using the emulsions, functional couplers such as silver halide emulsions, dye-forming couplers, DIR couplers, and various additives And development processing are described in EP 0 565 096 A1 (19
(Published October 13, 1993) and the patents cited therein. The following is a list of each item and the corresponding places.

1. 1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to page 62, line 14, 2. Intermediate layer: page 61, lines 36 to 40, 3. Multilayer effect imparting layer: page 62, lines 15 to 18, 4. Silver halide composition: page 62, lines 21 to 25; 5. Silver halide grain habit: page 62, lines 26 to 30, 6. Silver halide grain size: page 62, lines 31 to 34, 7. Emulsion production method: page 62, lines 35 to 40, Silver halide grain size distribution: page 62, 41 to 42
Row, 9. Tabular grains: page 62, lines 43 to 46,10. 10. Internal structure of particle: page 62, lines 47 to 53, Emulsion latent image forming type: page 62, line 54 to page 63, 5
Line, 12. 12. Physical ripening / chemical ripening of emulsion: p. 63, lines 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogged emulsion: p. 63, lines 14 to 31, Non-light-sensitive emulsion: page 63, lines 32-43, 16. 16. Silver coating amount: page 63, lines 49 to 50; Photographic additives: Research Disclosure (R
D) Item 17643 (December 1978), Item 18716 (January 1979)
(January) and Item 307105 (November 1989). The following shows the items and their related descriptions.

Types of Additives RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868 Super sensitizer, page 649, right column Brightener page 24 page 647 page right column page 868 5. 5. Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column, dyes, ultraviolet absorbers Binder page 26 page 651 left column pages 873 to 874 7. 7. Plasticizer, page 27 page 650, right column, page 876 Lubricant Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 9. Static 27 pages 650 pages right column pages 876-877 Inhibitors 10. Matsuto 878-879.

18. Formaldehyde scavenger: 6
Page 4, lines 54-57; 20. Mercapto antifoggant: page 65, lines 1 and 2, Release agent such as fogging agent: page 65, lines 3-7, 21. Dye: page 65, lines 7-10, 22. General color couplers: p. 65, lines 11 to 13, 23. Yellow, magenta and cyan couplers: page 65, 1
Lines 4 to 25, 24. Polymer coupler: page 65, lines 26 to 28, 25. Diffusible dye-forming couplers: p. 65, lines 29 to 31, 26. Colored coupler: page 65, lines 32-38, 27. General functional couplers: p. 65, lines 39 to 44, 28. Bleach accelerator releasing coupler: page 65, lines 45-48, 29. Development accelerator releasing coupler: page 65, lines 49 to 53, 30. Other DIR couplers: page 65, line 54 to page 66, 4
Line, 31. Coupler dispersion method: page 66, lines 5-28, 32. Preservatives / fungicides: page 66, lines 29-33, 33. Type of photosensitive material: page 66, lines 34 to 36, 34. Photosensitive layer thickness and swelling speed: page 66, line 40 to page 67, 1
Row, 35. Back layer: page 67, lines 3 to 8, 36. Overall development processing: page 67, lines 9-11, 37. Developer and developer: page 67, lines 12 to 30, 38. 39. Developer additive: page 67, lines 31 to 44, Reverse processing: page 67, lines 45 to 56, 40. Processing solution opening ratio: page 67, line 57 to page 68, line 12, 41. Developing time: page 68, lines 13 to 15, 42. Bleach-fixing, bleaching, fixing: page 68, 16 lines-page 69, 31
Row, 43. Automatic developing machine: page 69, lines 32 to 40, 44. Rinsing, rinsing, stabilization: page 69, line 41 to page 70, line 18
Row, 45. Processing solution replenishment, reuse: page 70, lines 19-23, 46. 47. Built-in developer sensitive material: page 70, lines 24-33, Developing temperature: 70 pages 34-38, 48. Use for film with lens: page 70, lines 39-41.

The bleaching solution described in European Patent No. 602600 containing a 2-pyridinecarboxylic acid or 2,6-pyridinedicarboxylic acid, a ferric salt such as ferric nitrate, and a persulfate is also used. It can be used preferably. In the use of this bleaching solution, it is preferable to interpose a stopping step and a washing step between the color developing step and the bleaching step,
It is preferable to use an organic acid such as acetic acid, succinic acid, and maleic acid for the stop solution. In addition, this bleaching solution contains p
Organic acids such as acetic acid, succinic acid, maleic acid, glutaric acid, adipic acid, etc.
It is preferable to contain the compound in a range of 2 mol / liter (hereinafter, liter is also referred to as “L”).

[0146]

EXAMPLES Example 1 (Preparation of Emulsion Em-1) An aqueous solution 12 containing 1.0 g of low molecular weight gelatin having a molecular weight of 15,000, and 1.0 g of KBr.
00 ml (hereinafter, ml is also referred to as “mL”) was kept at 35 ° C. and stirred vigorously. AgN
30 mL of an aqueous solution containing 1.9 g of O ₃ , 1.5 g of KBr
And 30 mL of an aqueous solution containing 0.7 g of low-molecular-weight gelatin having a molecular weight of 15,000 were added over 30 seconds by a double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. 6 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After ripening, 35 g of succinated gelatin was added.
The pH was adjusted to 5.5. 150 mL of an aqueous solution containing 30 g of AgNO ₃ and an aqueous solution of KBr were mixed by a double jet method to obtain 1
Added over 6 minutes. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Furthermore, AgN
An aqueous solution containing 110 g of O ₃ and an aqueous KBr solution were added by a double jet method over 15 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, an AgI fine grain emulsion having a size of 0.03 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was maintained at −25 mV. 132 mL of an aqueous solution containing 35 g of AgNO ₃ and an aqueous KBr solution were added over 7 minutes by the double jet method. The potential at the end of the addition is -20 m
The addition of the aqueous KBr solution was adjusted to V. After the temperature was raised to 40 ° C., 5.6 g of Compound 1 was added in terms of KI, and a 0.8 M aqueous sodium sulfite solution was added to 64 c
c was added. Further, an aqueous NaOH solution was added to raise the pH to 9.0 and maintained for 4 minutes to rapidly generate iodide ions. Then, the pH was returned to 5.5. After the temperature was returned to 55 ° C., 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After the addition is completed, AgNO ₃ , 7
250 mL of an aqueous solution containing 0 g and an aqueous KBr solution were added over 20 minutes while maintaining the potential at 60 mV. At this time, 1.0 × 10 ⁻⁵ mol of yellow blood salt was added to 1 mol of silver. After washing with water, 80 g of lime-processed gelatin having a calcium concentration of 1 ppm was added, and the pH was adjusted to 5.8 and pAg at 40 ° C.
It adjusted to 8.7 and was set to Em-1.

Compound 1

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The content of calcium, magnesium and strontium in the emulsion Em-1 was measured by ICP emission spectroscopy.
And 1 ppm (total 18 ppm).

(Preparation of Em-2) The preparation of Em-1 was carried out in the same manner as Em-1 except that the lime-treated gelatin added after washing with water was changed to 72 g of lime-treated gelatin and 8 g of gelatin containing 3600 ppm of calcium. Em-2 was prepared. The calcium content of Em-2 is 4
6 ppm, and the total amount of calcium, magnesium and strontium was 49 ppm.

(Preparation of Em-3) The preparation of Em-1 was carried out in the same manner as Em-1 except that the lime-treated gelatin added after washing with water was changed to 56 g of lime-treated gelatin and 24 g of gelatin containing 3600 ppm of calcium. Em-3 was prepared. The calcium content of Em-3 was 100 ppm, and the total amount of calcium, magnesium and strontium was 103 ppm.

(Preparation of Em-4) Em-4 was prepared in the same manner as Em-1, except that the lime-treated gelatin added after washing with water was changed to 80 g of gelatin containing 3600 ppm of calcium. did. Em-
4 has a calcium content of 300 ppm and a total amount of calcium, magnesium and strontium of 30 ppm.
It was 3 ppm.

(Spectral sensitization and chemical sensitization) (Preparation of Em-1-A) The above emulsion was heated to 56 ° C. First, 1 g of a pure AgBr fine grain emulsion having a size of 0.05 μm was added thereto in terms of Ag and shelled. Next, the spectral sensitizing dyes 1, 2, and 3 were added in an amount of 5.8 per mole of silver, respectively.
5 × 10 ^-4 mol, 3.06 × 10 ^-4 mol, 9.00 × 1
0 ^-6 mol was added. When a spectral sensitizing dye is added and the adsorption of the spectral sensitizing dye reaches 20% of the adsorption amount in an equilibrium state,
235 ppm of calcium nitrate was added. The amount of spectral sensitizing dye adsorbed is determined by separating the solid and liquid layers by centrifugation and measuring the difference between the amount of spectral sensitizing dye initially added and the amount of spectral sensitizing dye in the supernatant. The amount of the spectral sensitizing dye was determined. After addition of calcium nitrate, potassium thiocyanate,
Chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea, and compound 4 were added for optimal chemical sensitization. N,
N-dimethylselenourea is 3.40 per mole of silver.
× 10 ^-6 mol was added. Emulsion Em-1-A was prepared by adding Compound 3 20 minutes before the end of chemical sensitization and adding Compound 2 at the end of chemical sensitization.

Spectral sensitizing dye 1

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Spectral sensitizing dye 2

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Spectral sensitizing dye 3

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Compound 2

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Compound 3

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(Em-1-AA) European Patent 590725
Em-1-AA was prepared in the same manner as Em-1-A, except that the spectral sensitizing dye, calcium nitrate and the chemical sensitizer were simultaneously added according to the above procedure.

(Em-1-B) In the preparation of Em-1-A, when a spectral sensitizing dye was added and the adsorption of the spectral sensitizing dye reached 50% of the adsorption amount in an equilibrium state, calcium nitrate was added. Is added in the same manner as Em-1-A, except that
m-1-B was prepared.

(Em-1-C) In the preparation of Em-1-A, when a spectral sensitizing dye was added and the adsorption of the spectral sensitizing dye reached 80% of the adsorption amount in an equilibrium state, calcium nitrate was added. Is added in the same manner as Em-1-A, except that
m-1-C was prepared.

(Em-1-D) In the preparation of Em-1-A, when a spectral sensitizing dye was added and the adsorption of the spectral sensitizing dye reached 90% of the adsorption amount in an equilibrium state, calcium nitrate was added. Is added in the same manner as Em-1-A, except that
m-1-D was prepared.

(Em-1-CA to Em-1-CD) Em
In the preparation of -1-C, Em-1-CA and Em- were respectively carried out in the same manner as Em-1-C except that the amounts of calcium nitrate to be added were 55, 95, 2435, and 4985 ppm, respectively. 1-CB, Em-1-C
C, Em-1-CD was prepared.

(Em-2-A, Em-3-A, Em-4
-A) In the preparation of Em-1-C, the emulsion used was E
Em-1 except for changing to m-2, Em-3 and Em-4
-C and Em-3-A, respectively.
A, Em-4-A was prepared.

(Em-1-E, Em-1-F, Em-1
-G) In the preparation of Em-1-C, Em-1-E and Em-1 were respectively performed in the same manner as Em-1-C except that magnesium nitrate, strontium nitrate and zinc nitrate were added instead of calcium nitrate. -F and Em-1-G were prepared.

On a cellulose triacetate film support provided with an undercoat layer, the emulsions Em-1-A to 1-G which had been subjected to the above chemical sensitization under the coating conditions shown in Table 1 below were provided with a protective layer. It was applied to prepare a sample.

[0166]

[Table 1]

These samples were left under the conditions of 40 ° C. and 70% relative humidity for 14 hours. Thereafter, exposure was performed for 1/100 second through a continuous wedge with a gelatin filter SC-50 manufactured by FUJIFILM Corporation.

Using a negative processor FP-350 manufactured by Fuji Photo Film Co., Ltd., processing was performed by the method described below (until the cumulative replenishment amount of the liquid became three times the mother liquid tank capacity).

(Processing Method) Process Processing Time Processing Temperature Replenishment Color Developing 3 min 15 sec 38 ° C. 45 mL Bleaching 1 min 00 sec 38 ° C. 20 mL All bleach solution overflows into bleach fixing tank Bleach fixing 3 min 15 sec 38 30 ° C water washing (1) 40 seconds 35 ° C Countercurrent piping system from (2) to (1) Water washing (2) 1 minute 00 seconds 35 ° C 30mL Stable 40 seconds 38 ° C 20mL Drying 1 minute 15 seconds 55 ° C * The replenishment amount is 35 mm width / 1.1 m length (corresponding to 24 Ex. 1 line) Next, the composition of the processing solution will be described.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Iodine 1.5 mg potassium hydroxide-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 5.5 Add water and add 1.0 L 1.0 L pH (potassium hydroxide And adjusted with sulfuric acid) 10.05 10.10.

(Bleaching solution) Common to tank liquid and replenisher (unit: g) Ferric ammonium ammonium diamine tetraacetate dihydrate 20.0 Disodium ethylene diamine tetraacetate 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH ₃ ) _{2 N-CH 2 -CH 2 -SS} -CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) 15.0 mL water to make 1.0 L pH (adjusted with aqueous ammonia and nitric acid) 6.3 .

(Bleach-fixing solution) Tank solution (g) Replenisher (g) Ethylenediaminetetraacetate ammonium dihydrate 50.0-Ethylenediaminetetraacetic acid disodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Aqueous ammonium thiosulfate (700 g / L) 240.0 mL 400.0 mL Ammonia water (27%) 6.0 mL-Add water 1.0 L 1.0 L pH (adjusted with ammonia water and acetic acid) 7.2 7.3.

(Washing solution) Tank water and replenisher common tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400) The mixture was passed through a mixed-bed column packed with to treat the calcium and magnesium ion concentrations at 3 mg / L or less, and then 20 mg / L of sodium diisocyanurate and 0.15 g / L of sodium sulfate were added. P of this liquid
H was in the range 6.5-7.5.

(Stabilizing solution) Common to tank liquid and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 Disodium ethylenediaminetetraacetate 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 1.0 L with water added to pH 8.5.

The density of the treated sample was measured with a green filter. The sensitivity was represented by the relative value of the reciprocal of the exposure required to give a density of fog plus 0.2. Also, RM
The S granularity is uniformly exposed with a light amount giving a density of 0.2, and after performing the development processing described above, published by Macramin Co., Ltd.
The Theory of Photographic Process "6
It was measured by the method described on page 19. Table 2 shows the obtained results.

[0176]

[Table 2]

From Table 2, it was found that spectral sensitization substantially in the absence of calcium and then chemical sensitization in the presence of calcium are important for sensitization. The effects described on the left were also exhibited in the presence of magnesium, strontium, and zinc. However, in the presence of zinc, the granularity was poor due to the aggregation of the particles.

Example 2 (Preparation of solid fine dispersion of spectral sensitizing dye 1) Solid fine dispersions of spectral sensitizing dyes 1 to 3 were prepared as follows. Table 3
As shown in the preparation conditions, after dissolving the inorganic salt in ion-exchanged water, a spectral sensitizing dye was added and dispersed at 2000 rpm for 20 minutes using a dissolver blade at 60 ° C. Solid fine dispersions of dyes 1 to 3 were prepared.

[0179]

[Table 3]

(Preparation of Em-1-H)
In the preparation of 1-C, Em-1 was prepared in the same manner as Em-1-C, except that a dye was added in the form of the fine solid dispersion described above.
-H was produced.

(Preparation 2 of solid fine dispersion of spectral sensitizing dye)
99 parts by weight of water was added to 1 part by weight of the spectral sensitizing dye 1, and the pH was adjusted to 7.0. Next, the temperature of the aqueous solution was adjusted to 60 ° C., and the mixture was stirred with a high-speed stirrer (dissolver) at 800 rpm for 60 minutes to obtain a dispersion in which the spectral sensitizing dye 1 was solid-dispersed. Similarly, a solid dispersion of the spectral sensitizing dye 1 and the spectral sensitizing dye 2 was obtained.

(Preparation of Em-1-I) Em-1-I was prepared in the same manner as Em-1-H except that the dispersion prepared in Preparation 2 of the above-mentioned solid fine dispersion of the spectral sensitizing dye was added. Was prepared.

Coating films of emulsions Em-1-H and Em-1-I were prepared in the same manner as described in Example 1, and the photographic properties were evaluated in the same manner as in Example 1. Table 4 shows the results.

[0184]

[Table 4]

From Table 4, it was found that adding a spectral sensitizing dye in the form of a solid fine dispersion resulted in higher sensitivity. In particular, Em-1-H spectrally sensitized with a solid microdispersion concentrated by the presence of a salt was most preferred.

Example 3 In the preparation of Em-1 in Example 1, the gelatin added after washing with water (alkali-treated bone gelatin having a molecular weight of 280,000 or more and 28%) was added to a component having a molecular weight of 280,000 or more.
Em-5 was prepared in the same manner as Em-1, except that the alkali-treated bone gelatin contained 0% (prepared by the method described in the detailed description without gelatin cross-linking). The content of calcium, magnesium and strontium in Em-5 was 18 ppm as in Em-1.

The preparation of Em-1-H in Example 2 was repeated except that the emulsion was changed from Em-1 to Em-5.
Em-5-A was produced in the same manner as for m-1-H. A coating film was prepared by the method described in Example 1, and the photographic properties were evaluated. Table 5 shows the results.

[0188]

[Table 5]

As shown in Table 5, the components having a molecular weight of 280,000 or more
%, Further sensitization was achieved by using alkali-treated bone gelatin.

Example 4 Em-5-A was prepared in the same manner as in Example 3 except that the chemical sensitization was carried out using the selenium sensitizer amounts shown in Table 6.
A-5, Em-5-B to Em-5-F
Was prepared. A coating film was prepared in the same manner as described in Example 1, and the photographic properties were evaluated. Table 6 shows the results.

[0191]

[Table 6]

From Table 6, it was found that the addition of the selenium sensitizer in an amount of 2.5 × 10 ⁻⁶ mol to 5 × 10 ⁻⁵ mol per mol of silver is particularly effective for increasing the sensitivity.

Example 5 Emulsions Em-6, Em-7 and Em-8 were prepared by adjusting the growth potential to 0, -15 and -20 mV in the preparation of the emulsion Em-5 in Example 3. Em-5
Table 7 shows the average aspect ratio of Em-8 to Em-8 and the ratio of particles having an aspect of 8 or more. In addition, the Em-
In the preparation of 5-A, the emulsions were em-
m-6 in the same manner as Em-5-A, except that the amount of the sensitizer was reduced to an optimum level.
-A, Em-7-A and Em-8-A were produced. A coated film was prepared in the same manner as described in Example 1,
The photographic properties were evaluated. Table 7 shows the results.

[0194]

[Table 7]

From Table 7, it was found that particularly when the grains having an aspect ratio of 8 or more occupy 50% or more of the total projected area, the sensitization was remarkable.

Example 6 A silver halide emulsion Em-B to Em-B was prepared by the following production method.
O was prepared.

(Preparation of Em-B) 1200 mL of an aqueous solution containing 1.0 g of low molecular weight gelatin having a molecular weight of 15,000, 1.0 g of KBr was kept at 35 ° C., and vigorously stirred. A
gNO ₃ , 30 mL of an aqueous solution containing 1.9 g, KBr1.
30 mL of an aqueous solution containing 5 g and 0.7 g of low molecular weight gelatin having a molecular weight of 15,000 was added by a double jet method over 30 seconds to form nuclei. At this time, the excess concentration of KBr was kept constant. 5 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After ripening, 35 g of trimellitated gelatin containing 35 μmol of methionine per gram and having a molecular weight of 100,000 and a trimellitization ratio of 98% was added. p
H was adjusted to 5.5. 150 mL of an aqueous solution containing 30 g of AgNO ₃ and an aqueous solution of KBr
Added over minutes. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Further, AgNO ₃ ,
An aqueous solution containing 110 g and an aqueous KBr solution were added by a double jet method over 15 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, the size is 0.
An AgI fine grain emulsion having a particle size of 03 µm was prepared to have a silver iodide content of 3.8
% While simultaneously accelerating the flow and adding the silver potential at -25 mV. 132 mL of an aqueous solution containing 35 g of AgNO ₃ and an aqueous KBr solution were added over 7 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition became -20 mV. Temperature 40 ° C
After that, 8.0 g of Compound 6 in terms of KI was added, and 64 cc of a 0.8 M aqueous sodium sulfite solution was further added. Further, an aqueous NaOH solution was added to raise the pH to 9.0 and maintained for 4 minutes to rapidly generate iodide ions. Then, the pH was returned to 5.5. After returning the temperature to 55 ° C,
Add 1 mg of sodium benzenethiosulfonate,
Further, 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was added. After the addition, 250 mL of an aqueous solution containing 70 g of AgNO ₃ and an aqueous KBr solution were adjusted to a potential of 60 mV.
Over 20 minutes. At this time, 1.0 × 10 ⁻⁵ mol of yellow blood salt was added to 1 mol of silver. After washing with water, 80 g of lime-processed gelatin having a calcium concentration of 1 ppm was added, and the mixture was adjusted to pH 5.8 and pAg 8.7 at 40 ° C.

The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy, and found to be 15 ppm, 2 ppm and 1 ppm, respectively.

The temperature of the above emulsion was raised to 56 ° C. First, 1 g of a pure AgBr fine grain emulsion having a size of 0.05 μm was added thereto in terms of Ag and shelled. Next, spectral sensitizing dye 1,
2, 3 in the form of the solid fine dispersion described in Example 2 were each 6.50 × 10 ^-4 mol, 3.4 mol per mol silver.
0 × 10 ^-4 mol and 1.00 × 10 ^-5 mol were added. When the spectral sensitizing dye was added and the adsorption of the spectral sensitizing dye reached 90% of the adsorption amount in the equilibrium state, calcium nitrate was added so that the calcium concentration became 250 ppm. The amount of spectral sensitizing dye adsorbed is determined by separating the solid and liquid layers by centrifugation and measuring the difference between the amount of spectral sensitizing dye initially added and the amount of spectral sensitizing dye in the supernatant. The amount of the spectral sensitizing dye was determined. After the addition of calcium nitrate, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea, and compound 4 were added for optimal chemical sensitization. N, N-dimethylselenourea was added in an amount of 4.00 × 10 ⁻⁶ mol per mol of silver. At the end of chemical sensitization, Compound 2 and Compound 3 were added to prepare Em-B.

Compound 6

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(Preparation of Em-C) In the preparation of Em-B
The amount of KBr added after nucleation was changed to 1.5 g,
35 μmol / g of trimellitated gelatin
Thionine-containing phthalation rate 9 with a molecular weight of 100,000
Replace Compound 6 with 7% phthalated gelatin and replace Compound 6 with Compound
7, and the added amount of compound 7 was 7.1 g in terms of KI.
And quantify the amount of spectral sensitizing dye added before chemical sensitization.
7.80 × 10 for photosensitizing dyes 1, 2, and 3, respectively
^-FourMol, 4.08 × 10^-FourMol, 1.20 × 10^-FiveMole
N, N-dimethyl added during chemical sensitization
The amount of selenourea is 5.00 × 10 ^-6Than to change to mole
Outside, Em-C was prepared in the same manner as Em-B.

Compound 7

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(Preparation of Em-E) Em in Example 1
In the preparation of -1-C, 35 g of succinated gelatin was changed to adding 15 g of succinated gelatin and 20 g of the above-mentioned trimellitated gelatin, and the amount of Compound 1 added was changed to KI.
The amount was changed to 8.0 g in terms of conversion, and the spectral sensitizing dyes added before the chemical sensitization were changed to spectral sensitizing dyes 4, 5, and 6, and the added amounts of each were 7.73 × 10 ^-4 mol, 1 .65 × 10 ^-4
Mol, except that it is 6.20 × 10 ^-5 mol.
Em-E was prepared in the same manner as described above.

Spectral sensitizing dye 4

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Spectral sensitizing dye 5

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Spectral sensitizing dye 6

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(Preparation of Em-F) In the preparation of Em-B, 35 g of trimellitated gelatin was changed to adding 20 g of succinated gelatin and 15 g of phthalated gelatin, and the added amount of Compound 6 was converted to KI. 9.2 g, and the spectral sensitizing dyes added before chemical sensitization were changed to spectral sensitizing dyes 4, 5, and 6, and the added amount of each was 8.50 × 1.
0 ^-4 mol, 1.82 × 10 ^-4 mol was prepared Em-F in the same manner as Em-B except that the 6.82 × 10 ^-5 mol.

(Preparation of Em-G) In the preparation of Em-C, 35 g of phthalated gelatin was changed to 15 g of trimellitated gelatin and 20 g of phthalated gelatin, and the spectral sensitizing dye added before chemical sensitization was spectrally sensitized. The dyes were changed to 4, 5, and 6, and the added amount of each was 1.00 × 10 ^-3 mol;
Em-G was prepared in the same manner as Em-C, except that it was 15 × 10 ⁻⁴ mol and 8.06 × 10 ⁻⁵ mol.

(Preparation of Em-J) In the preparation of Em-B, the spectral sensitizing dyes added before chemical sensitization were changed to spectral sensitizing dyes 7 and 8, and the added amount of each was 7.65 × 10 5 ^-Four
Em-J was prepared in the same manner as Em-B except that the mol was 2.74 × 10 ⁻⁴ mol.

Spectral sensitizing dye 7

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Spectral sensitizing dye 8

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(Preparation of Em-L) (Preparation of silver bromide seed emulsion) An average sphere equivalent diameter of 0.6 μm, an aspect ratio of 9.0, and 1.16 mol of silver per kg of emulsion, containing 66 g of gelatin. A silver tabular emulsion was prepared.

(Growth Process 1) 1.2 g of potassium bromide and 9
Aqueous solution 12 containing succinated gelatin with a succinating rate of 8%
0.3 g of modified silicone oil was added to 50 g. 0.
After the silver bromide tabular emulsion containing 086 mol of silver was added, the mixture was stirred at 78 ° C. An aqueous solution containing 18.1 g of silver nitrate and the silver iodide fine particles having a particle size of 0.037 μm were added so as to be 5.4 mol with respect to silver to be added. Further, at this time, an aqueous potassium bromide solution was added while adjusting the pAg to be 8.1 with a double jet.

(Growth Process 2) After adding 2 mg of sodium benzenethiosulfonate, 0.45 g of 3,5-disulfocatechol disodium salt, thiourea dioxide 2.
5 mg was added.

Further, an aqueous solution containing 95.7 g of silver nitrate and an aqueous solution of potassium bromide were accelerated by a double jet to obtain an aqueous solution.
Added over minutes. At this time, the silver iodide fine particles of 0.037 μm were added in a molar amount of 7.0 mol with respect to the added silver. At this time, the amount of potassium bromide in the double jet was adjusted so that the pAg became 8.1. After the addition,
2 mg of sodium benzenethiosulfonate were added.

(Growth Process 3) An aqueous solution containing 19.5 g of silver nitrate and an aqueous solution of potassium bromide were added by a double jet over 16 minutes. At this time, the amount of the aqueous potassium bromide solution was adjusted so that the pAg became 7.9.

(Addition of sparingly soluble silver halide emulsion 4) After adjusting the host particles to pAg 9.3 with an aqueous potassium bromide solution, the above silver iodide fine grain emulsion 25 of 0.037 μm was prepared.
g was added rapidly within 20 seconds.

(Formation of outermost shell layer 5) 34.9 g of silver nitrate
Was added over 22 minutes. This emulsion was tabular grains having an average aspect ratio of 9.8 and an average equivalent sphere diameter of 1.4 μm, and the average silver iodide content was 5.5 mol.

[Chemical sensitization] After washing with water, the succination ratio was 98.
% Succinated gelatin and calcium nitrate at 40 ° C
And adjusted to pH 5.8 and pAg 8.7. The temperature was raised to 60 ° C., and 5 × 10 ⁻³ mol of a 0.07 μm silver bromide fine grain emulsion was added. After 20 minutes, spectral sensitizing dyes 9, 10 and 11 were added. Thereafter, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea, and compound 4 were added to perform optimal chemical sensitization. Compound 3 was added 20 minutes before the end of the chemical sensitization, and Compound 5 was added at the end of the chemical sensitization. Here, the optimal chemical sensitization means that the spectral sensitizing dye and each compound are added in an amount of 10 ^-1 to 10 ^-8 mol per ¹ mol of silver halide so that the sensitivity at the time of exposure at 1/100 is maximized. Means you have selected from a range.

Spectral sensitizing dye 9

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Spectral sensitizing dye 10

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Spectral sensitizing dye 11

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Compound 4

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Compound 5

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(Preparation of Em-O) An aqueous gelatin solution (1250 mL of distilled water, 48 g of deionized gelatin, 0.75 g of KBr) was charged into a reaction vessel equipped with a stirrer, and the temperature of the solution was maintained at 70 ° C. To this solution was added 276 mL of an aqueous solution of AgNO ₃ (containing 12.0 g of AgNO ₃ ) and an aqueous solution of KBr having an equimolar concentration while maintaining the pAg at 7.26 over 7 minutes by a controlled double jet addition method. Then, the temperature was lowered to 68 ° C., and thiourea dioxide (0.05 wt.
%) Was added.

Subsequently, 592.9 mL of an AgNO ₃ aqueous solution
(Including 108.0 g of AgNO ₃ )
A mixed aqueous solution of r and KI (2.0 mol% KI) was added over 18 minutes and 30 seconds by a controlled double jet addition method while maintaining the pAg at 7.30. Five minutes before the end of the addition, 18.0 m of thiosulfonic acid (0.1 wt%) was added.
L was added.

The obtained grains were cubic grains having an equivalent sphere diameter of 0.19 μm and an average silver iodide content of 1.8 mol%. E
m-O was re-dispersed by desalting and washing with a normal flocculation method, and then at 40 ° C., pH 6.2 and pAg.
Adjusted to 7.6. Subsequently, Em-O was subjected to the following spectral and chemical sensitization.

First, spectral sensitizing dye 10, spectral sensitizing dye 1
1. Spectral sensitizing dyes 12 were added per mole of silver.
37 × 10 ^-4 mol / mol, KBr 8.82 × 10 ^-4 mol / mol, sodium thiosulfate 8.83 × 10 ^-5 mol / mol, aqueous potassium thiocyanate 5.95 × 10 ^-4 mol / mol and chloride Potassium goldate 3.07 × 10 ^-5 mol /
Aging was performed at 68 ° C. by adding mol. The aging time was adjusted so that the sensitivity at the exposure of 1/100 second was the highest.

Spectral sensitizing dye 12

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For the preparation of (Em-D, H, I, K, M, N) tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. Further, according to the examples of JP-A-3-237450, gold sensitization was carried out in the presence of the spectral sensitizing dyes shown in Table 8 and sodium thiocyanate.
Sulfur sensitization and selenium sensitization are applied. Emulsions D, H,
I and K contain optimum amounts of Ir and Fe. Emulsion M, N
Is subjected to reduction sensitization during grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. Table 8 shows the addition amount of the spectral sensitizing dye used for each emulsion.

[0231]

[Table 8]

Spectral sensitizing dye 13

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[0233]

[Table 9]

In Table 9, dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

Preparation of Support The support used in this example was prepared by the following method.

1) First layer and undercoat layer For a polyethylene naphthalate support having a thickness of 90 μm, a treatment atmosphere pressure of 0.2 Torr was applied to both surfaces of each support.
r, partial pressure of H ₂ O in atmosphere gas 75%, discharge frequency 30
The glow discharge treatment was performed at a frequency of 2500 kHz, an output of 2500 W, and a treatment intensity of 0.5 kV · A · min / m ² . A coating solution having the following composition was applied as a first layer on the support at a coating amount of 5 mL / m ² using a bar coating method described in Japanese Patent Publication No. 58-4589.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by weight 10% aqueous dispersion. Secondary aggregate having a primary particle diameter of 0.005 μm and an average particle diameter of 0.05 μm) Gelatin 0.5 parts by weight Water 49 parts by weight Polyglycerol polyglycidyl ether 0.16 parts by weight Poly (degree of polymerization 20) oxyethylene 0.1 parts by weight Sorbitan monolaurate.

Further, after the first layer was applied, it was wound around a stainless steel core having a diameter of 20 cm, and was heat-treated at 110 ° C. (Tg of PEN support: 119 ° C.) for 48 hours, heat-treated and annealed. Thereafter, a coating solution having the following composition was applied to the side opposite to the first layer side as an undercoat layer for the emulsion at a coating amount of 10 mL / m ² by using a bar coating method.

Gelatin 1.01 parts by weight Salicylic acid 0.30 parts by weight Resorcin 0.40 parts by weight Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 parts by weight Water 3.53 parts by weight Methanol 84.57 parts by weight n -Propanol 10.08 parts by weight.

Further, a second layer and a third layer, which will be described later, are sequentially coated on the first layer, and finally, a color negative photosensitive material having a later-described composition is overlaid on the opposite side to form a silver halide emulsion. A transparent magnetic recording medium with a layer was produced.

2) Second layer (transparent magnetic recording layer) Dispersion of magnetic material Co-coated γ-Fe ₂ O ₃ magnetic material (average major axis length: 0.25 μm)
m, S _BET : 39 m ² / g, Hc: 831 Oe, σs:
77.1 emu / g, σr: 37.4 emu / g) 11
Then, 00 parts by weight, 220 parts by weight of water and 165 parts by weight of a silane coupling agent [3- (poly (degree of polymerization: 10) oxyethynyl) oxypropyl trimethoxysilane] were added and kneaded well with an open kneader for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. for 24 hours to remove water, and then heat-treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.

Further, the mixture was kneaded again with an open kneader for 4 hours according to the following formulation.

The above-mentioned surface-treated magnetic particles 855 g, diacetyl cellulose 25.3 g, methyl ethyl ketone 136.3 g, cyclohexanone 136.3 g Further, the following formulation was finely dispersed in a sand mill (1/4 G sand mill) at 2,000 rpm for 4 hours. did. As the medium, glass beads having a diameter of 1 mm were used.

The above kneading liquid 45 g diacetyl cellulose 23.7 g methyl ethyl ketone 127.7 g cyclohexanone 127.7 g Further, a magnetic substance-containing intermediate liquid was prepared according to the following formulation.

Preparation of Magnetic Substance-Containing Intermediate Solution 674 g of the above magnetic substance fine dispersion liquid 24280 g (solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g After mixing these, The mixture was stirred with a disper to prepare a "magnetic substance-containing intermediate liquid".

An α-alumina abrasive dispersion used in the present invention was prepared according to the following formulation.

(A) Sumicorundum AA-1.5 (average primary particle diameter 1.5 μm, specific surface area 1.3 m ² / g) Preparation of particle dispersion Sumicorundum AA-1.5 152 g Silane coupling agent KBM903 (Shin-Etsu Silicone Co., Ltd.) 0.48 g Diacetylcellulose solution 227.52 g (solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Ceramic-coated sand mill (1/1)
(4G sand mill) at 800 rpm for 4 hours. As the media, zirconia beads having a diameter of 1 mm were used.

(B) Colloidal silica particle dispersion (fine particles) "MEK-ST" manufactured by Nissan Chemical Industries, Ltd. was used.

This is a dispersion of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium, and has a solid content of 30%.

Preparation of Second Layer Coating Solution The above magnetic substance-containing intermediate solution 19053 g Diacetyl cellulose solution 264 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion “MEK-ST” [Dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Industries, Ltd.) Diluent 203 g (solid content 20%, diluent solvent: methyl ethyl ketone) / Cyclohexanone = 1/1) methyl ethyl ketone 170 g cyclohexanone 170 g.

The coating solution obtained by mixing and stirring the above was applied by a wire bar so as to have an application amount of 29.3 mL / m ² . Drying was performed at 110 ° C. The thickness of the dried magnetic layer was 1.0 μm.

3) Third Layer (Higher Fatty Acid Ester Slip Agent-Containing Layer) Preparation of Dispersion Stock Solution of Slip Agent The following solution A was heated and dissolved at 100 ° C., added to Solution A, and dispersed with a high-pressure homogenizer. Was prepared.

[0253] A solution following compound 399 parts by weight of _{C 6 H 13 CH (OH)} (CH 2) 10 COOC 50 H 101 The following compound 171 parts by weight of _{n-C 50 H 101 O (} CH 2 CH 2 O) 16 H Cyclohexanone 830 Parts by weight.

Liquid A Cyclohexanone 8600 parts by weight.

Preparation of Spherical Inorganic Particle Dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.

Isopropyl alcohol 93.54 parts by weight Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) Compound 1-1: (CH ₃ O) ₃ Si— (CH ₂ ) ₃ —NH ₂ ) 5.53 parts by weight Compound 2-1 2.93 parts by weight

Embedded image 88.00 parts by weight of Sea Hosta KEP50 (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.).

After stirring with the above formulation for 10 minutes, the following is further added.

252.93 parts by weight of diacetone alcohol While cooling the above liquid with ice and stirring, an ultrasonic homogenizer “SONIFIER450 (BRANSON CORPORATION)
)) For 3 hours to obtain a spherical inorganic particle dispersion c1.
Was completed.

Preparation of Spherical Organic Polymer Particle Dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation.

XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by weight Methyl ethyl ketone 120 parts by weight Cyclohexanone 120 parts by weight (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone) = 1/1).

While cooling with ice and stirring, an ultrasonic homogenizer “SONIFIER450 (BRANSON CORPORATION)
(2) for 2 hours to obtain a dispersion liquid c2 of spherical organic polymer particles.

Preparation of Third Layer Coating Solution The following was added to 542 g of the above-mentioned slip agent dispersion stock solution to prepare a third layer coating solution.

Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g The above-mentioned Seahosta KEP50 dispersion liquid [c1] 53.1 g The above-mentioned spherical organic polymer particle dispersion liquid [c2] 300 g FC431 2.65 g (3M Corporation) BYK310 5.3 g (manufactured by BYK Chemi Japan KK, solid content 25%).

The above third layer coating solution was coated on the second layer by 10.3
It was applied at a coating amount of 5 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

4) Coating of Photosensitive Layer Next, on the side opposite to the support of the back layer obtained above, each layer having the following composition was applied in multiple layers to prepare a color negative film.

(Composition of Photosensitive Layer) The main materials used for each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow Coupler H: Gelatin hardener (Specific compounds are described below, followed by a symbol, followed by a numerical value, followed by a chemical formula.)

The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.122 0.07 μm Silver Iodobromide Emulsion Silver 0.01 Gelatin 0.919 ExC-1 0.002 ExC-3 0.002 Cpd -2 0.001 HBS-1 0.005 HBS-2 0.002.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.055 Gelatin 0.425 ExF-1 0.002 Solid Disperse Dye ExF-9 0.120 HBS-1 0.074.

Third layer (low-sensitivity red-sensitive emulsion layer) Em-D silver 0.577 Em-C silver 0.347 ExC-1 0.188 ExC-2 0.011 ExC-3 0.075 ExC-40 .121 ExC-5 0.010 ExC-6 0.007 Cpd-2 0.025 Cpd-4 0.025 Cpd-7 0.050 Cpd-8 0.050 HBS-1 0.114 HBS-5 0.038 Gelatin 1.474.

Fourth Layer (Medium Speed Red Sensitive Emulsion Layer) Em-B Silver 0.431 Em-C Silver 0.432 ExC-1 0.154 ExC-2 0.068 ExC-3 0.018 ExC-40 .103 ExC-5 0.023 ExC-6 0.010 Cpd-2 0.036 Cpd-4 0.028 Cpd-7 0.010 Cpd-8 0.010 HBS-1 0.129 Gelatin 1.086.

Fifth layer (high-sensitivity red-sensitive emulsion layer) Em-A silver 1.108 ExC-1 0.180 ExC-3 0.035 ExC-6 0.029 Cpd-2 0.064 Cpd-40 077 Cpd-7 0.040 Cpd-8 0.040 HBS-1 0.329 HBS-2 0.120 Gelatin 1.245.

Sixth layer (intermediate layer) Cpd-1 0.094 Cpd-9 0.369 Solid disperse dye ExF-4 0.030 HBS-1 0.049 Polyethyl acrylate latex 0.088 Gelatin 0.886.

Seventh Layer (Layer that Gives Layered Effect to Red Sensitive Layer) Em-J Silver 0.293 Em-K Silver 0.293 Cpd-4 0.030 ExM-2 0.120 ExM-3 0.016 ExY -1 0.016 ExY-6 0.036 Cpd-6 0.011 HBS-1 0.090 HBS-3 0.003 HBS-5 0.030 Gelatin 0.610.

Eighth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Em-H Silver 0.329 Em-G Silver 0.333 Em-I Silver 0.088 ExM-2 0.378 ExM-3 0.047 ExY-1 0.017 HBS-1 0.098 HBS-3 0.010 HBS-4 0.077 HBS-5 0.548 Cpd-5 0.010 Gelatin 1.470.

Ninth Layer (Medium Speed Green Sensitive Emulsion Layer) Em-F Silver 0.457 ExM-2 0.032 ExM-3 0.029 ExM-4 0.029 ExY-1 0.007 ExC-6 010 HBS-1 0.065 HBS-3 0.002 HBS-5 0.020 Cpd-5 0.004 Gelatin 0.446.

Tenth layer (high-sensitivity green-sensitive emulsion layer) Em-E silver 0.794 ExC-6 0.002 ExM-1 0.013 ExM-2 0.011 ExM-3 0.030 ExM-40 017 ExY-5 0.003 Cpd-3 0.004 Cpd-4 0.007 Cpd-5 0.010 HBS-1 0.148 HBS-5 0.037 Polyethyl acrylate latex 0.099 Gelatin 0.939.

Eleventh layer (yellow filter layer) Cpd-1 0.094 Solid disperse dye ExF-2 0.150 Solid disperse dye ExF-5 0.010 Oil-soluble dye ExF-7 0.010 HBS-1 0.049 Gelatin 0.630.

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Em-O silver 0.112 Em-M silver 0.320 Em-N silver 0.240 ExC-1 0.027 ExY-1 0.027 ExY-2 0.890 ExY-6 0.120 Cpd-2 0.100 Cpd-3 0.004 HBS-1 0.222 HBS-5 0.074 Gelatin 2.058.

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Em-L silver 0.714 ExY-2 0.211 Cpd-2 0.075 Cpd-3 0.001 HBS-1 0.071 gelatin 0.678.

Fourteenth layer (first protective layer) 0.07 μm silver iodobromide emulsion Silver 0.301 UV-1 0.211 UV-2 0.132 UV-3 0.198 UV-4 0.026 F -18 0.009 S-1 0.086 HBS-1 0.175 HBS-4 0.050 gelatin 1.984.

Fifteenth layer (second protective layer) H-1 0.400 B-1 (1.7 μm in diameter) 0.050 B-2 (1.7 μm in diameter) 0.150 B-3 0.050 S- 10.20 Gelatin 0.750.

Further, in order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coating properties of each layer, W-1 to W-6, B-4 to B -6, F
-1 to F-17, and lead salts, platinum salts, iridium salts, and rhodium salts.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the eleventh layer was dispersed by the following method.

ExF-2 wet cake (containing 17.6% by weight of water) 2.800 kg Sodium octylphenyldiethoxymethanesulfonate (31% by weight aqueous solution) 0.376 kg F-15 (7% aqueous solution) 011 kg Water 4.020 kg Total 7.210 kg (adjusted to pH = 7.2 with NaOH).

After the slurry having the above composition was coarsely dispersed by stirring with a dissolver, using an agitator mill LMK-4,
Circumferential speed 10m / s, discharge rate 0.6kg / min, 0.3m
The dispersion was dispersed until the absorbance ratio of the dispersion became 0.29 at a filling rate of zirconia beads of m diameter of 80% to obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm.

Similarly, ExF-4 and ExF-9
Was obtained. The average particle size of the fine dye particles was 0.28 μm and 0.49 μm, respectively. ExF-5
Was dispersed by a microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.

The compounds used for forming each layer are shown below.

[0289]

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[0290]

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[0291]

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[0292]

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[0293]

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[0294]

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[0295]

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[0296]

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[0297]

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[0298]

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[0299]

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The color negative photosensitive material prepared as described above was used as a sample 001. Sample 001 was used as the sample.
Exposure was performed for 1/100 second through a gelatin filter SC-39 and a continuous wedge.

The development was performed by an automatic developing machine F manufactured by Fuji Photo Film Co., Ltd.
Performed as follows using P-360B. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in Hatsumei Kyokai Disclosure Technique No. 94-4992.

The processing steps and the composition of the processing solution are shown below.

(Processing Step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5L Fixing (1) 50 seconds 38.0 ° C-5L Fixing ( 2) 50 seconds 38.0 ℃ 8 mL 5L water washing 30 seconds 38.0 ℃ 17 mL 3L stable (1) 20 seconds 38.0 ℃-3L stable (2) 20 seconds 38.0 ℃ 15 mL 3L drying 1 minute 30 seconds 60.0 ℃ * replenishment amount Is per 35 m of photosensitive material and 1.1 m in width (equivalent to 24 Ex. 1 line).

The stabilizing solution and the fixing solution were of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm in width of the photosensitive material and 1.1 m in width.
2.5 mL, 2.0 mL, and 2.0 mL, respectively. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The opening area of the above processor is 10 with color developing solution.
0cm ² , 120cm ^{2 for} bleaching solution, about 1 other processing solution
00 cm ² .

The composition of the processing solution is shown below.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium 0.3 0.3 Sodium sulfite 3.9 5.9. 3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3mg-4-Hydroxy -6-methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino Aniline sulfate 4.5 6.5 Add water 1.0 L 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Water was added and 1.0 L 1.0 L pH [adjusted with ammonia water] 4.6 4.0.

(Fixing (1) tank liquid) A 5/95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid (pH:
6.8).

(Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 mL 720 mL (750 g / L) Imidazole 721 Ammonium methanethiosulfonate 515 Ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 13 39 Add water 1.0L 1.0L pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45.

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 m.
g / L or less, followed by sodium diisocyanurate 20 mg / L and sodium sulfate 150 mg / L
Was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) 1,2-benzo Isothiazolin-3-one sodium 0.10 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0. 75 Add water to 1.0 L pH 8.5.

The concentration of the treated sample was measured with a red filter. The sensitivity was read by the relative value of the reciprocal of the exposure required to give a density of fog density plus 0.2. As a result, results similar to those obtained in Examples 1 to 5 were obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/09 G03C 1/09 7/00 510 7/00 510

Claims (15)

[Claims] 1. The method according to claim 1, wherein said spectral sensitizing dye is added substantially in the absence of a polyvalent cation which forms a sparingly soluble salt with an anionic spectral sensitizing dye, and after said spectral sensitizing dye is sufficiently adsorbed. A light-sensitive silver halide emulsion prepared by adding the cation and thereafter initiating chemical sensitization. 2. Spectral sensitization is performed by adding a spectral sensitizing dye in a state where calcium, magnesium and strontium are 50 ppm or less, and thereafter, calcium, magnesium and strontium are added.
100 to 2500p for magnesium and strontium
pm, a water-soluble salt of at least one metal selected from the group consisting of calcium, magnesium and strontium is added, followed by starting chemical sensitization. Silver halide emulsion. 3. A method for preparing a spectral sensitizing dye having a solubility in water of 3% by weight or less under the conditions of substantially no organic solvent and / or surfactant and pH 6 to 8 and 40 to 80 ° C. 3. The photosensitive iodine according to claim 2, wherein the photosensitive iodine is produced by spectral sensitization with a dispersion of a spectral sensitizing dye obtained by mechanically pulverizing and dispersing fine particles in an aqueous solvent. Silver bromide emulsion. 4. After dissolving 0.5% by weight or more of an inorganic salt in water substantially free of any of a surfactant, an organic solvent and a silver halide emulsion, 0.5% by weight or more of a spectral sensitizing dye. 3. A photosensitive silver iodobromide according to claim 2, wherein the photosensitive silver iodobromide is produced by spectral sensitization with a solid fine dispersion of a spectral sensitizing dye obtained by adding the compound and finely dispersing the solid. emulsion. 5. The method according to claim 1, wherein the spectral sensitization and the chemical sensitization are carried out in the presence of an alkali-treated bone gelatin containing at least 30% of a component having a molecular weight of 280,000 or more in a molecular weight distribution measured by the PAGI method. 5. The photosensitive silver iodobromide emulsion according to any one of 2 to 4. 6. 2.5 × 10 ⁻⁶ mol / mol silver or more 5 × 1
0 ^-5 mol / mol photosensitive silver iodobromide emulsion according to any one of claims 2 to 5 by silver following selenium sensitizer, characterized in that it is chemically sensitized. 7. 50% of the total projected area of the silver halide grains
7. The photosensitive silver iodobromide emulsion according to claim 2, wherein the above is occupied by tabular silver halide grains having an aspect ratio of 8 or more. 8. Addition of the spectral sensitizing dye in the substantial absence of a polyvalent cation that forms a sparingly soluble salt with the anionic spectral sensitizing dye, and after the spectral sensitizing dye is sufficiently adsorbed. A method for producing a photosensitive silver halide emulsion, comprising adding the cation and then starting chemical sensitization. 9. Spectral sensitization is performed by adding a spectral sensitizing dye in a state where calcium, magnesium and strontium are not more than 50 ppm, and thereafter, calcium, magnesium and strontium are added.
100 to 2500p for magnesium and strontium
producing a light-sensitive silver iodobromide emulsion, wherein a water-soluble salt of at least one metal selected from calcium, magnesium and strontium is added so as to obtain a pm, and then chemical sensitization is started. Method. 10. A spectral sensitizing dye having a solubility in water of not more than 3% by weight under the condition of substantially no organic solvent and / or surfactant and at a pH of 6 to 8 and 40 to 80 ° C.
10. The photosensitive silver iodobromide emulsion according to claim 9, wherein the emulsion is spectrally sensitized with a dispersion of a spectral sensitizing dye obtained by mechanically pulverizing and dispersing fine particles in an aqueous solvent. Method. 11. A spectral sensitizing dye of 0.5% by weight or more after dissolving 0.5% by weight or more of an inorganic salt in water substantially free of any of a surfactant, an organic solvent and a silver halide emulsion. 10. A method for producing a photosensitive silver iodobromide emulsion according to claim 9, wherein the emulsion is spectrally sensitized with a solid fine dispersion of a spectral sensitizing dye obtained by finely dispersing a solid. 12. The spectral sensitization and the chemical sensitization are carried out in the presence of an alkali-treated bone gelatin containing a component having a molecular weight of 280,000 or more in a molecular weight distribution measured by the PAGI method of 30% or more. 12. The method for producing a photosensitive silver iodobromide emulsion according to any one of 9 to 11. 13. More than 2.5 × 10 ^-6 mol / mol silver and 5 ×
13. The method according to claim 9, wherein the chemical sensitization is carried out with a selenium sensitizer of 10 ^-5 mol / mol silver or less.
The method for producing a photosensitive silver iodobromide emulsion described in the above item. 14. A total projected area of 50 of silver halide grains.
% Or more is occupied by tabular silver halide grains having an aspect ratio of 8 or more.
5. The method for producing a photosensitive silver iodobromide emulsion according to any one of the above. 15. A light-sensitive silver halide emulsion according to claim 1, wherein the light-sensitive silver halide emulsion comprises at least one light-sensitive silver halide emulsion layer on a support. A silver halide photographic light-sensitive material comprising: