JPH0869079A - Silver halide emulsion and silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To obtain a photosensitive material high in sensitivity and superior in secular preserability and latent image stability by subjecting the insides of silver halide grains to reduction sensitization and adding a specified compound after forming silver halide grains before chemical sensitization. CONSTITUTION: The silver halide grains undergo reduction sensitization in the insides of them and at least one kind of the compound having an acid dissociation constant of <=1×10<-8> and a solubility product of <=1×10<-10> with silver ions is added after the growth of the silver halide grains and before the chemical sensitization and this compound is represented by formula I, preferably, by formula II, and in formulae I and II, Z is an atomic group necessary to form a hetero ring, and each of R1 -R3 is an H atom or a substituent. The reduction sensitization in the inside of grains is carried out by adding a reducing agent to a silver halide emulsion or a mixed solution for the growth of the grains or ripening or growing the grains in the conditions of a low pAg of <=7pAg or a high pH of >=7.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a halogenated silver halide emulsion having high sensitivity, low fog, long-term storage stability and latent image stability. The present invention relates to a silver photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, performance requirements for silver halide light-sensitive materials for photography have become more and more severe, and higher level requirements for various photographic characteristics such as sensitivity, fog and graininess and storability. Is occurring. Particularly in recent years, with the spread of compact cameras and film with a camera mechanism generally called a film with a lens, high sensitivity has become an essential condition for the photographic light-sensitive material. Also, due to the daily use of photography and the spread of applications, silver halide light-sensitive materials have come to be stored under various environments and used under various conditions, and the stability of photographic performance during storage of light-sensitive materials has also been improved. There is a strong demand.

In the prior art, prevention of electron-hole recombination using an internal high iodine type core / shell emulsion or improvement of latent image forming efficiency by selective growth of chemically sensitized nuclei, or Many sensitization techniques have been studied such as improvement of electron transfer efficiency from a sensitizing dye using a supersensitizer to a silver halide crystal, but in the environment actually used by the user as described above. A more comprehensive combination of technologies is required to maintain high sensitivity.

Although many techniques have been disclosed so far in order to achieve high sensitivity, reduction sensitization can be mentioned as the most typical method.

As a method of reduction sensitization, a method of applying it to the surface of silver halide grains, a method of applying it during the growth of silver halide grains, or when a seed crystal is used for grain growth, reduction sensitization of seed crystals is carried out in advance. It is known how to apply. Also,
As a concrete means, for example, Carroll is disclosed in US Pat.
No. 487,850 uses a tin compound, and Roue
2,512,925 with polyamine compounds, Ference in UK Patent 789,823 with thiourea dioxide and Collier Photographic Science.
and Engineering Volume 23, Item 111, Dimethylamine Borane, Stannous Chloride, Hydrazine, High pH Aging, Low pHAg.
Adopted aging.

Further, JP-A-2-136852 and JP-A-2-196232 disclose the use of ascorbic acid as a reducing agent.
However, these reduction sensitization methods have a problem that although the sensitization is achieved, the reduction sensitization effect is decreased with time, or fog is increased under the condition of heat or temperature. .

Further, in Japanese Patent Application Laid-Open No. 5-197059, a fog change is suppressed while maintaining high sensitivity by doping a reduction-sensitized emulsion with a polyvalent metal such as Cd, but the effect of improving the fog change is satisfactory. It has not reached a certain level, which is why the user actually has a satisfactory low fog under the condition of a certain level of heat temperature as used in the market.
Unfortunately, no effective technology for maintaining high sensitivity was found.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, excellent storage stability over time and latent image stability.

[0009]

The above object of the present invention is achieved by any one of the following constitutional requirements.

A silver halide emulsion characterized by satisfying the following conditions (1) and (2):

(1) The inside of the grain is sensitized by reduction.

(2) At least one selected from compounds represented by the following general formula [I], having an acid dissociation constant of 1 × 10 ^-8 or less and a solubility product with silver ion of 1 × 10 ^-10 or less. Add one type after silver halide grain formation and before chemical sensitization.

[0013]

[Chemical 3]

In the formula, Z represents an atomic group necessary for forming a heterocycle.

The silver halide emulsion as described above, wherein the compound represented by the general formula [I] is represented by the following general formula [II].

[0016]

[Chemical 4]

In the formula, R ₁ , R ₂ and R ₃ may be the same or different and each represents a hydrogen atom or a substituent.

The reduction sensitizing means passes through (a) an atmosphere of pAg of 7 or less during ripening or grain growth of silver halide, or (b) an atmosphere of pH of 7 or more without using an ammonium compound. A silver halide emulsion as described above or described above, which is prepared by any of the above.

A silver halide photographic light-sensitive material, comprising at least one silver halide emulsion layer containing the silver halide emulsion described above.

The present invention will be described in detail below.

The inside of the silver halide grain of the present invention is reduction-sensitized.

The reduction sensitization is carried out by adding a reducing agent to a silver halide emulsion or a mixed solution for growing grains. Alternatively, a silver halide emulsion or a mixed solution for grain growth may be used at a low pAg of pH 7 or lower, or at pH 7
It is carried out by aging or grain growth under the above high pH conditions. A method in which these methods are combined is a preferred embodiment in the present invention.

A preferred reducing agent used for reduction sensitization of the silver halide grains of the present invention is thiourea dioxide,
Examples thereof include ascorbic acid and its derivatives, and stannous salt. Other suitable reducing agents include borane compounds, hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines and sulfites and the like. The addition amount is preferably 10 ^-2 to 10 ^-8 mol per mol of silver halide.

A silver salt may be added for low pAg ripening or grain growth, but a water-soluble silver salt is preferred, and silver nitrate is preferred as the water-soluble silver salt. During aging
The pAg is suitably 7 or less, preferably 6 or less, more preferably 1 to 3 (here, pAg = −log [Ag ⁺ ]).

High pH ripening or grain growth is carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for grain growth. As the alkaline compound, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia or the like can be used. In the method of adding ammoniacal silver nitrate for silver halide formation, an alkaline compound excluding ammonia is preferably used because the effect of ammonia decreases.

As a method for adding the silver salt or alkaline compound for reduction sensitization, rush addition may be performed, or addition may be performed over a certain period of time. In this case, the flow rate may be added at a constant flow rate, or the flow rate may be changed like a function. Also, the required amount may be added in several divided portions. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, they may be present in the reaction vessel, or they may be mixed in the soluble halide solution and added together with the halide. Furthermore, the addition may be performed separately from the soluble silver salt and the soluble halide.

In the preparation of the silver halide emulsion of the present invention, when the crystal growth form from silver grains is used,
The low pAg ripening is preferably performed by adding silver nitrate after the seed emulsion is formed, that is, between the steps immediately before desalting of the seed grains and after desalting. Particularly, it is preferable to add silver nitrate after the desalting of the seed particles for aging, and the aging temperature is 40 ° C or higher, 50
C to 80C is preferred. The aging time is preferably 30 minutes or more and 50 to 150 minutes.

In the form grown from seed particles, high p
When H aging is performed, the volume of the grains after growth is
It is necessary to grow the particles through the environment of pH 7 or more at least once before the portion corresponding to 70% grows, and the pH 7 is reached until the portion corresponding to 50% of the volume of the grown grains grows. It is more preferable to grow the particles through the above environment at least once, and the pH should be adjusted to 8% by the time the portion corresponding to 40% of the volume of the grown particles grows.
It is particularly preferable to grow the particles through the above environment at least once.

An oxidizing agent can be used in the silver halide emulsion of the present invention. The following can be used as the oxidizing agent. For example, hydrogen peroxide (water) and its adducts: H ₂ O ₂ , NaBO ₂ , H ₂ O ₂ -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 etc. Peroxy acid salt: K ₂ S ₂ O ₃ , K ₂ C ₂ O ₃ , K
₄ P ₂ O ₃ , K ₂ [Ti (O ₂ ) C ₂ O ₄ ] -3H ₂ O. Peracetic acid, ozone, iodine,
Examples thereof include bromine and thiosulfonic acid compounds.

The addition amount of the oxidizing agent used in the present invention is influenced by the type of the reducing agent, the reduction sensitizing conditions, the addition timing of the oxidizing agent, and the adding conditions, but it is 10 ⁻ per mol of the reducing agent used. ^{2-10 -5} mol are preferred.

The oxidizing agent may be added at any time during the silver halide emulsion manufacturing process. It can also be added prior to the addition of the reducing agent.

Further, after adding the oxidizing agent, a reducing substance may be newly added in order to neutralize the excess oxidizing agent. These reducing substances are substances capable of reducing the above-mentioned oxidizing agent, sulfinic acids, di- and trihydroxybenzenes, chromanes, hydrazine and hydrazides, p-phenylenediamines, aldehydes, aminophenols, Examples include endiols, oximes, reducing sugars, phenidones, sulfites, and ascorbic acid derivatives. The amount of the reducing substance is preferably an amount per mole ^10-3 to ³ moles of the oxidizing agent to be used is.

The position where the silver halide grain according to the present invention is subjected to reduction sensitization may be inside the grain, and preferably, the substantial growth of silver halide is 50 in terms of silver halide amount.
%, Reduction sensitization is preferably carried out before the completion of the process, and the time point when substantial growth is started is more preferred.

Here, the inside of the particle means 50 from the outermost surface of the particle.
Refers to the part excluding parts up to Å.

In the present invention, the silver halide amount of 50% means a protective colloid in which the silver halide grains are grown during the period from the start to the end of the substantial growth of the silver halide grains in the present invention. It refers to 50% of the total weight of silver halide formed in the aqueous solution containing it.

The "substantial growth" of silver halide grains in the silver halide emulsion of the present invention means that halide ions and silver are added to an aqueous solution containing a protective colloid (gelatin) in which the silver halide grains are grown. A silver halide emulsion in which ions are supplied as a water-soluble alkali halide and a water-soluble silver salt, or as silver halide fine particles, from the end of nucleation of silver halide grains to the end of grain growth. This is a manufacturing process, and does not include a manufacturing process of a silver halide emulsion after the desalting process after the growth of the silver halide grains.

The term “nuclear generation completion” means a state in which the size and number of nuclei have been determined after the generation of nuclei.

The silver halide grains of the present invention are preferably prepared by an acidic method or a neutral method, in which the growth is carried out without using an ammonium compound, and most preferably, a neutral method is carried out without using an ammonium compound. . The ammonium compound as used herein refers to a general compound that releases ammonium ions in an aqueous solution, such as aqueous ammonia, an ammonium compound, an ammonium salt, an ammonia complex salt, or an ammonium oxide. Known silver halide solvents such as thioether and thiourea can be used as long as they are not ammonium compounds.

The silver halide emulsion of the present invention is preferably grown from seed grains.

In the present invention, the seed particles are, as is generally known in the art, nucleated and grown in a batch different from that of substantial growth, and then desalted to give a substantial growth. Refers to particles that can previously be present in the reaction vessel.

The gelatin according to the present invention is used as a dispersion medium during the above-described substantial growth in order to effectively bring out the effects of the present invention, and is also used during nucleation. Good.

It is generally known in the art that an aqueous gelatin solution is added to a desalted emulsion, the mixture is stirred and dispersed at a certain temperature for several tens of minutes, and then distilled water is added to once finish the emulsion. However, it is most preferable to use the gelatin according to the present invention as the gelatin in this gelatin aqueous solution and to use it as a dispersion medium during the above-described substantial growth.

The silver halide emulsion of the present invention comprises a core consisting essentially of silver iodobromide, an iodobromide which covers the core and has a silver iodide content lower than that of silver iodobromide. Silver iodobromide composed of a shell consisting essentially of silver or silver bromide is preferred.

The core may contain silver iodide uniformly, or may have a multilayer structure composed of layers having different silver iodide contents. In the latter case, the silver iodide content of the layer having the highest silver iodide content is 5 mol% or more, more preferably 10 mol% or more, and the silver iodide content of the shell is the core. Of the highest silver iodide content phase, the silver iodobromide content of the shell is preferably 5 mol% or less.

The halogen composition on the surface of the silver halide grain of the present invention is 7 mol% or less, more preferably 5 mol% or less.

The expression "consisting essentially of silver iodobromide" is mainly composed of silver iodobromide, but may contain silver chloride within a range not impairing the effects of the present invention. means.

The silver halide grain of the present invention is at least one selected from the group consisting of cadmium salt, zinc salt, lead salt, thallium salt and iridium salt (including complex salt) in the step of forming and / or growing the grain. Can be used to add these metal elements to the inside and / or the surface of the particles, and by placing them in an appropriate oxidizing atmosphere, they act on the metallic silver inside and / or on the surface of the particles. Then, it may be converted into silver ions.

The silver halide grain of the present invention may be either a grain in which a latent image is mainly formed on the surface or a grain in which the latent image is mainly formed. The size of silver halide is 0.05 to 5.0 μm. , Preferably 0.1-3.0μ
m.

The silver halide emulsion of the present invention may be one in which unnecessary soluble salts have been removed after the growth of silver halide grains has been completed, or may be contained as it is. When removing the salts, Research Disclosure (hereinafter abbreviated as RD)
It can be carried out based on the method described in Item 17643, Item II. More specifically, in order to remove the soluble salt from the emulsion after precipitation or physical ripening, a Nudel water washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants and anions may be used. A precipitation method (flocculation) using a hydrophilic polymer (eg polystyrene sulfonic acid) or a gelatin derivative (eg acylated gelatin, carbamoylated gelatin, etc.) may be used.

The silver halide emulsion of the present invention can be further chemically sensitized by a conventional method. That is, sulfur sensitization, selenium sensitization, tellurium sensitization, a noble metal sensitization method using a noble metal compound such as gold can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more kinds. A dye that does not have a spectral sensitizing effect by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, contains a supersensitizer that enhances the sensitizing effect of the sensitizing dye in the emulsion. Is also good.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion of the present invention.

A coupler is used in the emulsion layer of the silver halide color photographic light-sensitive material of the present invention. Further, by a coupling with a competing coupler having an effect of color correction and an oxidized product of a developing agent, a development accelerator, a developer, a silver halide solvent, a toning agent, a hardener, a fogging agent, an antifoggant,
Compounds that release photographically useful fragments such as chemical sensitizers, spectral sensitizers and desensitizers can be used.

The silver halide color photographic light-sensitive material of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer and an antiirradiation layer. In these layers and / or in the emulsion layer, a dye which flows out from the above-mentioned silver halide color photographic light-sensitive material or is bleached may be contained.

The silver halide color photographic light-sensitive material of the present invention includes a matting agent, a lubricant, an image stabilizer, a formalin scavenger, an ultraviolet absorber, an optical brightener, a surfactant, and
A development accelerator or a development retarder can be added.

As the support used in the present invention, polyethylene laminated paper, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

Next, the compound represented by the general formula [I] or [II] will be described.

In the general formula [I], Z is a compound having the above acid dissociation constant and the solubility product with silver ion.
Can be selected any heterocyclic compound, but is preferably a polycyclic heterocyclic compound, and further particularly preferred examples include, for example, a substituted or unsubstituted benzimidazole ring, benzotriazole ring, purine Ring, 8-
An azapurine ring and a pyrazolopyrimidine ring can be mentioned.

Examples of the substituent represented by R ₁ , R ₂ and R ₃ include alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group,
Pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc.), alkenyl group
(Eg vinyl group, allyl group etc.), alkynyl group (eg propargyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), heterocyclic group (eg pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group) Group, furyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group, tetrazolyl group, etc., halogen atom (for example, chlorine atom, bromine atom, iodine atom, fluorine atom) Etc.), alkoxy groups (eg, methoxy group, ethoxy group, propyloxy group, pentyloxy group, cyclopentyloxy group, hexyloxy group, cyclohexyloxy group, octyloxy group, dodecyloxy group, etc.),
Aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxy Carbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamide group (eg,
Methylsulfonylamino group, ethylsulfonylamino group, butylsulfonylamino group, hexylsulfonylamino group, cyclohexylsulfonylamino group, octylsulfonylamino group, dodecylsulfonylamino group, phenylsulfonylamino group, etc., sulfamoyl group (for example, aminosulfonyl group) , Methylaminosulfonyl group,
Dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group,
Naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc., ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc., acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, Naphthylcarbonyl group, pyridylcarbonyl group, etc., carbamoyl group (eg, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentyl) Minocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarboxylic N group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc., amide group (eg, Methylcarbonylamino group, ethylcarbonylamino group, etc., sulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group) , 2-pyridylsulfonyl group, etc.), amino group (eg, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecyl group) Amino group, an anilino group, naphthylamino group, 2-pyridylamino group), a cyano group, a nitro group, a carboxyl group,
Examples thereof include a hydroxyl group. These groups may also be alkyl groups (eg methyl, ethyl, propyl,
Isopropyl group, butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group, dodecyl group, etc.), halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), alkoxy group ( For example, methoxy group, ethoxy group, 1,1-dimethylethoxy group, hexyloxy group, dodecyloxy group, etc.),
Aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, 2-ethylhexylcarbonyl group) Etc.), aryloxycarbonyl group (eg phenoxycarbonyl group, naphthyloxycarbonyl group etc.), alkenyl group (eg vinyl group, allyl group etc.), heterocyclic group (eg 2-pyridyl group, 3-pyridyl group, 4 -Pyridyl group, morpholyl group, piperidyl group, piperazyl group, pyrimidyl group, pyrazolyl group, furyl group, etc.), alkynyl group (eg, propargyl group, etc.), amino group (eg, amino group, N, N-dimethylamino group, Anilino group, etc.), hydroxy group, cyano group, sulfo group, carboxyl group, sulfonamide A group (eg, methylsulfonylamino group, ethylsulfonylamino group,
Butylsulfonylamino group, octylsulfonylamino group, phenylsulfonylamino group, etc.) and the like.

In the present invention, any compound represented by the general formula [I] having an acid dissociation constant of 1 × 10 ^-8 or less and a solubility product with silver ion of 1 × 10 ^-10 or less is effective. Can be used for

The acid dissociation constant is one measured at room temperature, and is, for example, "Large Organic Chemistry", Annex 2 (published by Asakura Shoten) or TH.
James The Theory of Photographic Process 4th Edition (Macmil
lan company) etc. In addition, there are several methods for measuring the acid dissociation constant.
Pp. 524 to 552, published by Maruzen, etc. The acid dissociation constant of the compound of the present invention represented by the general formula [I] is 1 × 10 ⁻⁸ or less as described above. However, it was revealed from the results of the study by the present inventors that a surprisingly large effect can be obtained particularly in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻¹⁸ .

The compounds of the present invention also have a solubility product with silver ions of 1 × 10 ^-10 or less as described above. A compound having a solubility product exceeding this, that is, a compound having a smaller ability to form a salt with silver ions, cannot be expected to have the desired effect (improvement in stability over time).

For the measurement and calculation of the solubility product, "New Experimental Chemistry Course, Vol. 1" (Maruzen), pages 233 to 250 can be referred to.

Specific examples of the compound represented by the general formula [I] used in the present invention are shown below, but the present invention is not limited thereto.

[0065]

[Chemical 5]

[0066]

[Chemical 6]

[0067]

[Chemical 7]

[0068]

Embedded image

R ₁ , R ₂ and R ₃ of the compound represented by the general formula [II] of the present invention can be arbitrarily selected, but preferably R ₁ is a —NH ₂ group and R ₂ , R ₂ is R ₂ . ₃ is a hydrogen atom or R
₁ is R ₂ is -NH ₂ group, or R ₁ with an -OH group, R _2, R ₃ is -OH group. Further, as Z in the above-mentioned general formula [I], any hetero ring can be adopted, and particularly preferred are benzimidazole ring, benztriazole ring, purine ring, 8-azabulin ring and pyrazolopyrimidine ring.

The addition amount of the compounds represented by the general formulas [I] and [II] of the present invention is from 2 × 10 ^-7 to 1 mol of silver halide.
It is preferable to use 1 × 10 ⁻² mol, and further 2 × 10 ⁻⁷
-5 × 10 ^-3 mol is preferred.

In the method of adding the compound of the present invention, the compound may be added as a solid, but it is preferably added in a solution state.
As the solvent, water or a water-miscible solvent such as methanol is preferably used. The compounds of the present invention may be used alone or in combination of two or more.

[0072]

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

Example 1 << Preparation of Twin Seed Emulsion (T-1) >> A seed emulsion having two parallel twin planes was prepared by the following method with reference to the description in Japanese Patent Application No. 3-341164. (T-1) was prepared.

(Solution A) Ocein gelatin 80.0 g Potassium bromide 47.4 g HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m ± n = 9.77) 0.48 ml of 10% by weight methanol solution Add water 8000.0 ml (Solution B) Silver nitrate 1200.0 g Add water 1600.0 ml (Solution C) Ocein gelatin 32.2 g Potassium bromide 790.0 g Potassium iodide 70.34 g Water 1600.0 ml (D liquid) Ammonia water (28%) 470.0 ml Using the stirring device described in Japanese Patent Laid-Open No. 62-160128, liquid A and liquid C are vigorously stirred at 40 ° C. and liquid B and liquid C are double-jetted. Method was added in 7.7 minutes to generate nuclei. During this time, pBr
Kept at 1.60.

Thereafter, the temperature was lowered to 20 ° C. over 35 minutes. Furthermore, the D liquid was added in 1 minute, and then the mixture was aged for 5 minutes. The KBr concentration during aging was 0.03 mol / l, and the ammonia concentration was 0.66 mol / l.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. When the seed emulsion grains were observed with an electron microscope, the average grain size was 0.225 μm and the ratio of twin parallel twin planes was 75% in terms of the number of all grains.

<< Preparation of Emulsion (Em-1) >> 5 shown below
An emulsion (Em-1) was prepared using the various solutions.

(Solution A-1) Ocein gelatin 66.5 g Distilled water 3227.0 ml HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m ± n = 9.77) 2.50 ml of 10 wt% methanol solution Seed emulsion (T-1) (*) 98.5 g Finish with distilled water to 3500 cc (Solution B-1) 3.5N silver nitrate aqueous solution 4702.0 ml (Solution C-1) Bromide Potassium 2499.0g Finished to 6000cc with distilled water (Solution D-1) Fine grain emulsion consisting of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05μm) (*) Preparation method: 0.06 mol of potassium iodide To 5000 ml of a 6.0% by weight gelatin solution, 2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes.
The temperature during fine particle formation was controlled at 40 ° C. The finished weight is
It was 12.53 Kg.

(Solution E-1) 1.75N Potassium Bromide Aqueous Solution Necessary amount Solution A-1 was added to a reaction vessel and stirred vigorously.
Solution B-1 to solution D-1 were added according to the simultaneous mixing method according to Table 1 to grow a seed crystal to prepare a core / shell type silver halide emulsion.

Here, (1) solution B-1, solution C-1 and solution D-1 addition rates, (2) solution B-1 and solution C
The addition rate of -1 was changed in a function-like manner with respect to time so as to correspond to the critical growth rate of silver halide grains, and in addition to the growing seed emulsion, small grains were generated and polydispersion was achieved by Ostwald ripening. It was properly controlled so that it would not occur.

The temperature of the solution in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 8.8 over the entire area of crystal growth. Solution E-1 was added as needed for pAg control. pH was not controlled, but pH was maintained during grain growth.
It was kept in the range of H5.0-6.0. Table 1 also shows the amount of silver added and the silver iodide content of the silver halide phase during the formation with respect to the addition time of the addition solution.

After grain growth, desalting treatment was carried out according to the method described in Japanese Patent Application No. 3-41314, 1.19 l of 20% by weight gelatin aqueous solution was added and dispersed at 50 ° C. for 30 minutes, and then at 40 ° C. pH.
Was adjusted to 5.80 and pBr was adjusted to 3.55.

The silver halide grains contained in the obtained silver halide emulsion were monodisperse tabular halogen having an average grain size of 1.34 μm (diameter in terms of projected area circle), an average aspect ratio of 2.6 and a grain size distribution of 18%. It was a silver halide grain.

[0084]

[Table 1]

<< Preparation of Emulsion (Em-2) >> Emulsion (Em-
In the preparation of 1), 52.47 minutes after the addition of the solution B-1 to the solution D-1 was started, the pH was adjusted to 8.0 with a 10% aqueous potassium hydroxide solution, and after the particle growth, the desired amount of Desalted according to the method described in Hira 3-41314, 20
An emulsion (Em-2) was prepared in exactly the same manner except that 1.19 l of a gelatin aqueous solution of wt% was added, the mixture was stirred for 20 minutes, and then pH was adjusted to 5.80 and pBr to 3.55 at 40 ° C.

The history of pH in the reaction vessel was as follows.

Time (minutes) from the start of addition of Solution B-1 to Solution D-1 pH in the reaction vessel 52.47 8.00 76.48 7.51 150.13 6.40 176.09 6.36 239.00 5.84 << Preparation of emulsion (Em-3) >> Emulsion In the preparation of (Em-1), addition of Solution B-1 to Solution D-1 was started and
After 2.47 minutes, the addition was interrupted and the p was added using a 3.5N silver nitrate aqueous solution.
After adjusting Ag to 6.0 and aging for 10 minutes, pAg was returned to 8.8 with a 3.5N potassium bromide aqueous solution, and addition of solution B-1 to solvent D-1 was restarted, and further solution B-1 to solution D-1. 150.13 minutes after the start of the addition of, the pH was adjusted to 6.0 with acetic acid,
After grain growth, desalting treatment was performed according to the method described in JP-A-4-59351, and 1.19 l of a 20% by weight gelatin aqueous solution was added.
Was added and dispersed at 50 ° C. for 15 minutes, then pBr was adjusted to 1.5 with a 3.5N potassium bromide aqueous solution at 50 ° C., and the emulsion (Em-2) of the present invention was added to the stirred silver halide emulsion. Emulsion (Em-3) was prepared in exactly the same manner except that the solution H-0 used in the preparation was added for 30 seconds, the mixture was stirred for 20 minutes, and then the pH was adjusted to 5.80 and pBr to 3.55 at 40 ° C. did.

<< Preparation of Emulsion (Em-4) >> Emulsion (Em-
In the preparation of 1), an emulsion (Em-4) was prepared in exactly the same manner except that the solution K-1 below was added 52.47 minutes after the addition of the solutions B-1 to D-1 was started.

(Solution K-1) Aqueous solution containing thiourea dioxide in an amount of 1 × 10 ^-6 mol per mol of silver in emulsion (Em-4). Table 2 shows emulsions (Em-1) to (Em-). The characteristics of 4) are shown.

[0090]

[Table 2]

Emulsions Em-1 to E thus obtained
For m-4, sensitizing dyes (SD-1), (SD-2),
Optimum spectral sensitization and chemical sensitization were performed using (SD-3), sodium thiosulfate, chloroauric acid and ammonium thiocyanate.

The general formula [I] or [II] of the present invention
The compound represented by was added as described in Table 3.

The acid dissociation constant (pKa value) of the compound used,
The solubility product with silver ion (pKsp [Ag]) is shown in logarithmic notation.

[0094] After completion of the aging, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 1-phenyl-5-mercaptotetrazole were added and stabilized.

Table 3 shows the prepared emulsions.

[0096]

[Table 3]

[0097]

[Chemical 9]

(Preparation of Sample 101) Sample 101, which is a multilayer color light-sensitive material, was prepared by providing each layer having the composition shown below on a cellulose acetate film support which was subbed.

In all of the following Examples, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Further, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in the number of moles per mole of silver halide.

First layer: antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point organic solvent (Oil-1) 0.16 Gelatin 1.23 Second layer: Intermediate layer High boiling point organic solvent (Oil-2) 0.17 Gelatin 1.27 Third layer; low-sensitivity red-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.50 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content) Ratio 2.0 mol%) 0.21 Sensitizing dye (SD-1) 2.8 × 10 ^-4 Sensitizing dye (SD-2) 1.9 × 10 ^-4 Sensitizing dye (SD-3) 1.9 × 10 ^-5 Sensitizing dye (SD -4) 1.0 × 10 ^-4 Cyan coupler (C-1) 0.48 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.021 DIR compound (D-1) 0.020 High boiling point solvent (Oil-1) 0.53 Gelatin 1.30 4th layer; Medium-sensitive red-sensitive layer Silver iodobromide emulsion (average grain size 0.52 μm, silver iodide content 8.0 mol%) 0 .62 Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 8.0 mol%) 0.27 Sensitizing dye (SD-1) 2.3 × 10 ⁻⁴ Sensitizing dye (SD-2) 1.2 × 10 ⁻⁴ Sensitizing dye (SD-3) 1.6 × 10 ^-5 Sensitizing dye (SD-4) 1.2 × 10 ^-4 Cyan coupler (C-1) 0.15 Cyan coupler (C-2) 0.18 Colored cyan coupler (CC-1) 0.030 DIR compound (D-1) 0.013 High boiling point solvent (Oil-1) 0.30 Gelatin 0.93 Fifth layer; high-sensitivity red-sensitive layer Em-a 1.27 Cyan coupler (C-2) 0.12 Colored cyan coupler (CC-1) 0.013 High boiling point solvent (Oil-1) 0.14 Gelatin 0.91 6th layer; Intermediate layer High boiling point organic solvent (Oil-2) 0.11 Gelatin 0.80 7th layer; Low sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, Silver iodide content 8.0 mol%) 0.61 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.20 Sensitizing dye (SD-4) 7.4 × 10 ^-5 Sensitizing dye (SD-5) 6.6 × 10 ^-4 Magenta coupler (M-1) 0.18 Magenta coupler (M-2) 0.44 Colored magenta coupler (CM-1) 0.12 High boiling point Solvent (Oil-2) 0.75 Gelatin 1.95 Eighth layer; Medium sensitivity green sensitive layer Silver iodobromide emulsion (average grain size 0.59 μm, silver iodide content 8.0 mol%) 0.87 Sensitizing dye (SD-6) 2.4 × 10 ^-4 Sensitizing dye (SD-7) 2.4 × 10 ^-4 Magenta coupler (M-1) 0.058 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.070 DIR compound (D-2) 0.025 DIR Compound (D-3) 0.002 High boiling point solvent (Oil-2) 0.50 Gelatin 1.00 9th layer; High sensitivity green sensitive layer Silver iodobromide emulsion I 1.27 Magenta coupler (M-2) 0.084 Magenta coupler (M-3) 0.064 Colored magenta coupler (CM-1) 0.012 High boiling point solvent ( il-1) 0.27 High boiling point solvent (Oil-2) 0.012 Gelatin 1.00 10th layer; Yellow filter layer Yellow colloidal silver 0.08 Color stain inhibitor (SC-2) 0.15 Formalin scavenger (HS-1) 0.20 High boiling point solvent (Oil) -2) 0.19 gelatin 1.10 11th layer; intermediate layer formalin scavenger (HS-1) 0.20 gelatin 0.60 12th layer; low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average grain size 0.38 μm, silver iodide content 3.0 mol) %) 0.22 Silver iodobromide emulsion (average grain size 0.27 μm, silver iodide content 2.0 mol%) 0.03 Sensitizing dye (SD-8) 4.9 × 10 ⁻⁴ Yellow coupler (Y-1) 0.75 DIR compound (D -1) 0.010 High-boiling solvent (Oil-2) 0.30 Gelatin 1.20 13th layer; Medium-sensitive blue-sensitive layer Silver iodobromide emulsion (average grain size 0.59 µm, silver iodide content 8.0 mol%) 0.30 Sensitizing dye ( SD-8) 1.6 × 10 ^-4 sensitizing dye (SD-9) 7.2 × 10 -5 Ieroka LAR (Y-1) 0.10 DIR compound (D-1) 0.010 High boiling point solvent (Oil-2) 0.046 Gelatin 0.47 14th layer; high sensitivity blue sensitive layer Silver iodobromide emulsion (average grain size 1.00 μm, silver iodide) Content ratio 10.0 mol%) 0.85 Sensitizing dye (SD-8) 7.3 × 10 ^-5 Sensitizing dye (SD-9) 2.8 × 10 ^-5 Yellow coupler (Y-1) 0.11 High boiling solvent (Oil-2) 0.046 Gelatin 0.80 15th layer; 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 UV absorber (UV-2) 0.10 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Formalin scavenger (HS-1) 0.40 Gelatin 1.31 16th layer; 2nd protective layer Alkali-soluble matting agent (Average particle size 2 μm) 0.15 Polymethylmethacrylate (Average particle size 3 μm) 0.04 Lubricant (WAX-1) 0.04 Gelatin 0.55 In addition to the composition, a coating aid Su-1, a dispersion aid Su-
2, viscosity modifier V-1, hardeners H-1, H-2, stabilizer ST-1, antifoggant AF-1, dye AI-1, AI
-2, weight average molecular weight: 10,000 and weight average molecular weight: 1,
100,000 of two AF-2 and preservative DI-1 were added. The amount of DI-1 added was 9.4 mg / m ² .

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

[0102]

[Chemical 10]

[0103]

[Chemical 11]

[0104]

[Chemical 12]

[0105]

[Chemical 13]

[0106]

Embedded image

[0107]

[Chemical 15]

[0108]

Embedded image

[0109]

[Chemical 17]

[0110]

[Chemical 18]

(Preparation of sample 102) Em of the fifth layer of sample 101
Sample 102 was prepared in the same manner as sample 101 except that -a was changed to Em-b.

(Preparation of Sample 103) Em of Fifth Layer of Sample 101
Sample 103 was prepared in the same manner as Sample 101, except that -a was changed to Em-c.

(Preparation of Sample 104) Em of Fifth Layer of Sample 101
A sample 104 was prepared in the same manner as the sample 101 except that -a was changed to Em-d.

(Preparation of sample 105) Em of the fifth layer of sample 101
Sample 105 was prepared in the same manner as sample 101, except that -a was changed to Em-e.

(Preparation of sample 106) Em of the fifth layer of sample 101
Sample 106 was prepared in the same manner as Sample 101, except that -a was changed to Em-f.

(Preparation of sample 107) Em of the fifth layer of sample 101
Sample 107 was prepared in the same manner as sample 101, except that -a was changed to Em-g.

(Preparation of Sample 108) Em of Fifth Layer of Sample 101
Sample 108 was prepared in the same manner as Sample 101, except that -a was changed to Em-h.

(Preparation of sample 109) Em of the fifth layer of sample 101
Sample 109 was prepared in the same manner as Sample 101, except that -a was changed to Em-i.

(Preparation of sample 110) Em of the fifth layer of sample 101
Sample 110 was prepared in the same manner as Sample 101, except that -a was changed to Em-j.

(Preparation of sample 111) Em of the fifth layer of sample 101
Sample 111 was prepared in the same manner as Sample 101, except that -a was changed to Em-k.

(Preparation of sample 112) Em of the fifth layer of sample 101
Sample 112 was prepared in the same manner as Sample 101, except that -a was changed to Em-1.

(Preparation of Sample 113) Em of the fifth layer of Sample 101
Sample 113 was prepared in the same manner as Sample 101, except that -a was changed to Em-m.

The above samples 101 to 113 were divided into four, and samples I to IV were prepared as follows. Sample I was subjected to wedge exposure according to a conventional method and immediately subjected to development processing according to the following processing steps. Sample II is 55 after wedge exposure.
The same development treatment was carried out after leaving it for 7 days under the condition of ° C and a relative humidity of 80%. Sample III was left for 5 days under the conditions of 60 ° C. and 40% relative humidity, then exposed to wedges, and subjected to the same development processing. Sample IV was left for 7 days under the conditions of 30 ° C. and 90% relative humidity, then exposed to wedges, and subjected to the same development processing.

Then, the density of each of the samples I to IV was measured with a red filter. As for the sensitivity of each sample, the red density is the fog density +0.
It is expressed by the reciprocal of the exposure amount that gives an optical density of 15, and is shown as a relative value when the value of Sample I is 100.

(Treatment process) Treatment process Treatment time Treatment temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ℃ 780cc Bleach 45 seconds 38 ± 2.0 ℃ 150ml fixation 1 minute 30 seconds 38 ± 2.0 ℃ 830ml stability 1 Min 38 ± 5.0 ℃ 830ml Dry 1 minute 55 ± 5.0 ℃-* Replenishment amount is the value per 1m ² of light-sensitive material.

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

Color developer and color replenisher developer Replenisher Replenisher Water 800cc 800cc Potassium carbonate 30g 35g Sodium hydrogencarbonate 2.5g 3.0g Potassium sulfite 3.0g 5.0g Sodium bromide 1.3g 0.4g Potassium iodide 1.2mg-hydroxylamine sulfate Salt 2.5g 3.1g Sodium chloride 0.6g-4-Amino-3-methyl-N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5g 6.3g Diethylenetriaminepentaacetic acid 3.0g 3.0g Potassium hydroxide 1.2g 2.0 g Add 1 liter of water and use potassium hydroxide or 20% sulfuric acid to adjust the color developer to pH 10.06 and the replenisher to pH 10.18.
Adjust to.

Bleaching solution and bleach replenishing solution Bleaching solution Replenishing solution Water 700cc 700cc 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125g 175g Ethylenediaminetetraacetic acid 2g 2g Sodium nitrate 40g 50g Ammonium bromide 150g 200g Glacial acetic acid 40g 56g Water Then, the bleaching solution is adjusted to pH 4.4 and the replenisher is adjusted to pH 4.0 using ammonia water or glacial acetic acid.

Fixing Solution and Fixing Replenishing Solution Fixing Solution Replenishing Solution Water 800 cc 800 cc Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g Ammonia water or glacial acetic acid was used as the fixer at pH 6.2 Adjust the replenisher to pH 6.5 and add water to make 1 liter.

Stabilizer and stable replenisher water 900 cc p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylol urea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzisothiazolin-3-one 0.1 g siloxane (UC-L-77 ) 0.1g Ammonia water 0.5cc Add water to make 1 liter, then use ammonia water or 50%
Adjust to pH 8.5 with sulfuric acid.

The results are shown in Table 4.

[0132]

[Table 4]

As shown in Table 4, it can be seen that the samples using the emulsion of the present invention have high sensitivity, low fog, latent image stability, and excellent storage stability over time.

[0134]

EFFECT OF THE INVENTION High sensitivity, low fog and excellent latent image stability,
It was possible to obtain a silver halide emulsion excellent in stability over time and a photographic light-sensitive material using the same.

Claims (4)

[Claims] 1. A silver halide emulsion characterized by satisfying the following conditions (1) and (2). (1) The inside of the grain is reduction-sensitized. (2) Represented by the following general formula [I] and having an acid dissociation constant of 1
At least one selected from the compounds having a solubility product with silver ions of 1 × 10 ^-8 or less and 1 × 10 ^-10 or less should be added after chemical sensitization after silver halide grain formation. Embedded image [In the formula, Z represents an atomic group necessary for forming a heterocycle. ] 2. The compound represented by the general formula [I] is
A compound represented by the following general formula [II]:
The described silver halide emulsion. Embedded image [In the formula, R ₁ , R ₂ and R ₃ may be the same or different and each represents a hydrogen atom or a substituent. ] 3. The reduction sensitizing means passes through (a) an atmosphere of pAg of 7 or less during ripening or grain growth of silver halide, or (b) pH without using an ammonium compound.
The silver halide emulsion according to claim 1 or 2, wherein the silver halide emulsion is prepared under an atmosphere of 7 or more. 4. A silver halide photographic light-sensitive material containing the silver halide emulsion according to claim 1 in at least one silver halide emulsion layer.