JPH07225440A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material using a silver halide emulsion contg. silver halide particles each having (100) faces as principal planes, less liable to fog and almost free from a change of fog due to a change in processing by specifying the structure of silver halide particles in an emulsion layer and incorporating a mercury compd. into a sensitive material. CONSTITUTION:This silver halide photographic sensitive material has at least one photosensitive silver halide emulsion layer on the base and contains a mercury compd. In the emulsion layer, flat platy silver halide particles each having >=50mol% silver chloride content, (100) faces as principal planes and an aspect ratio (diameter thickness) of >=1.5 and subjected to gold-chalcogen sensitization account for >=30% of the total projection area of all silver halide particles. 'Principal planes' are stipulated as a pair of parallel faces having the largest area among the faces of each crystal forming practically rectangular prism- shaped emulsified particles and the fact that principal planes are (100) faces can be investigated by an electron beam diffraction method or an X-ray diffraction method.

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 photographic light-sensitive material using an emulsion having a high silver chloride content, which is excellent in rapid processing property, particularly high sensitivity, low fog and fog due to processing fluctuation. The present invention relates to a photographic light-sensitive material that hardly changes.

[0002]

2. Description of the Related Art In everyday life, I often come across scenes and materials that I want to take photos of,
The camera used for shooting is not necessarily carried or prepared. Moreover, there are many other opportunities like this, and there is a potentially strong demand for an imaging system that can handle them.

In response to such a demand, a so-called lens-equipped film system has been developed and is becoming popular with many people. One of the supporting elements of this system is a high-sensitivity color negative photosensitive material. A relatively dark lens with a large depth of field is required to cover from short-distance photography to long-distance photography with an inexpensive fixed-focus plastic lens, and a high-sensitivity color negative photosensitive material is used to compensate for this. Become. Therefore,
As a film with a lens, a film having an ISO of about 400 is used. In addition, very recently, an ultra-high-sensitivity color negative of ISO 800, which has hitherto been regarded as an ultra-high-sensitivity region, has been used for a film with a lens and has been well received by the market.

On the other hand, another desire when taking a picture is that one wants to see it immediately after taking it. To meet this demand, so-called instant color films have been sold, but they have not reached the level of being widely accepted in terms of price and image quality. In order to meet the demand for rapid development, it is advantageous to use silver halide grains having a high solubility and high silver chloride content. In the field of color paper, a silver halide emulsion having a high solubility is already available. Silver chloride is the mainstream. However,
High silver chloride emulsions can only be cubic with (100) faces by the usual method.

It is well known by those skilled in the art that tabular grains are suitable in terms of performance required for color photographic materials, so-called sensitivity, graininess, sharpness and color sensitization efficiency. Therefore, efforts have been made for flattening for the purpose of applying the high silver chloride emulsion to color photographic materials.

For flattening high silver chloride grains, the main plane is (11
1) is, for example, US Pat. No. 4,783,398.
No. 4,952,491 and the like. However, the (111) plane of high silver chloride is unstable in terms of surface shape, and there are many problems in terms of manufacturing stability.

On the other hand, regarding high silver chloride tabular grains whose main planes are (100) planes, see EP 0 534 395.
A1 and U.S. Pat. No. 5,264,337. However, these tabular grains having the (100) plane as the main plane have problems such as high fogging and a significantly large fogging change due to process variation, and a solution to these problems is strongly desired. It was

[0008]

DISCLOSURE OF THE INVENTION The present invention provides a silver halide photographic light-sensitive material containing high silver chloride grains having excellent rapid processability, which has a low fog and a small (100) face with a change in process. Another object of the present invention is to provide a photographic light-sensitive material using a tabular silver halide emulsion whose main plane is.

[0009]

The above-mentioned objects of the present invention have been achieved by the following. (1) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, 30% or more of the total projected area of silver halide grains in the emulsion layer contains silver chloride. When the ratio is 50 mol% or more, the main plane is (10
0) plane is a tabular grain sensitized with gold chalcogen having an aspect ratio (diameter / thickness) of 1.5 or more, and a mercury compound is contained in the light-sensitive material. Photographic material. (2) The silver halide photographic light-sensitive material as described in (1) above, wherein a silver salt that is less soluble than silver chloride is present on the surface of the tabular grains. (3) The silver halide photographic light-sensitive material as described in (1) above, wherein the tabular grains are sensitized with gold chalcogen in the presence of a spectral sensitizing dye. (4) The silver halide photographic light-sensitive material as described in (1) above, wherein the tabular grains are reduction-sensitized.

In the present invention, gold chalcogen sensitization (10
0) The combined use of a mercury compound in the tabular emulsion enables a significant reduction in fog to be realized without a reduction in sensitivity. Although the mechanism of action is not always clear, an amalgam state is formed by the silver nuclei and mercury in the mercury compound, which is unintentionally formed when the high silver chloride (100) tabular emulsion is prepared,
It is conceivable that the fog can be reduced.

The contents of the present invention will be described in detail below.

The silver chloride content of tabular silver halide grains having a (100) plane as the principal plane and having a silver chloride content of 50 mol% or more (hereinafter also referred to as "tabular grains") used in the present invention. Is preferably 75 mol% or more,
It is more preferably 90 mol% or more, and most preferably 95 mol% or more.

The silver halide emulsion used in the present invention is a silver halide emulsion containing at least a dispersion medium and the above-mentioned silver halide grains, and 10% of the total projected area of all silver halide grains in the emulsion. Or more, preferably 35 to 100
%, And more preferably 60 to 100% is (10
It is a tabular silver halide grain having a (0) plane. The term "projected area" as used herein means the projected area of silver halide emulsion grains when they are arranged on a substrate in a state where they do not overlap each other and tabular grains are arranged such that the principal planes thereof are parallel to the substrate surface. Further, the principal plane refers to two parallel maximum outer surfaces in one tabular grain. The aspect ratio (diameter / thickness) of the tabular grains is 1.5 or more, preferably 2 or more,
It is more preferably 3 to 25, still more preferably 3 to 15. Here, the diameter means that when the particles are observed with an electron microscope,
It shall refer to the diameter of a circle having an area equal to the projected area of the grain. The thickness means the distance between the main planes of tabular grains. The diameter of the tabular silver halide grains is preferably 10 μm or less, more preferably 0.2 to 5 μm, and 0.2
˜3 μm is more preferred. Further, the thickness is preferably 0.7 μm or less, more preferably 0.03 to 0.3 μm, and 0.
05-0.2 μm is more preferable. The grain size distribution of the tabular grains is preferably monodisperse, and the coefficient of variation is preferably 40% or less, more preferably 20% or less.

The "principal plane" is defined as a set of parallel planes having the largest area among the crystal surfaces forming substantially rectangular parallelepiped emulsion grains, and the fact that the principal plane is the (100) plane is determined by electron beam diffraction. Method or X-ray diffraction method. A substantially rectangular parallelepiped emulsion grain means that the main plane is (100)
Although it is formed from a plane, it may have (111) crystal faces from 1 to 8. That is, a rectangular parallelepiped 8
One to eight of the four corners may have a sharpened shape.

The two parallel main planes used in the present invention are (100) planes, and the silver chloride content of the grains is 50 mol%.
Emulsions containing high silver chloride tabular grains as described above are described in European Patent No. 0,534,395A1 and US Pat. No. 5,264,337, or Japanese Patent Application No. 5-26405.
It can be prepared according to the following method described in No. 9. From the viewpoint of production stability and monodispersity of particle size, a method of producing through a process including each process of nucleation, ripening and growth is preferable. 1) Nucleation process The tabular nuclei, which are the nuclei of tabular grains, have a high production ratio under the condition that the introduction of lattice defects easily occurs. As a method for obtaining plate nuclei with high reproducibility and a high production ratio, a method utilizing halogen conversion of product nuclei is effective. In this method, first, silver halide nucleation is performed, and subsequently, a halogen ion which forms a more insoluble silver halide is introduced to perform halogen conversion. More specifically, the halogen composition structure of the nucleus formed during nucleation has, for example, a structure of (AgX ₁ | AgX ₂ ) or (AgX ₁ | AgX ₄ | AgX ₃ ). This structure can be formed, for example, by simultaneously adding a silver salt aqueous solution and a halide salt aqueous solution and changing the halogen composition of the halide aqueous solution discontinuously.
Alternatively, an aqueous solution of a halide salt is added to the dispersion medium solution, then an aqueous solution of a silver salt is added to form AgX ₁ , then another aqueous solution of a halide salt is added, and then an aqueous solution of a silver salt is added, ( An AgX ₁ | AgX ₂ ) structure can be prepared, or a combination thereof can be prepared.

AgX ₁ and AgX ₂ and AgX ₁ and Ag
X ₄ , AgX ₄ and AgX ₃ are Cl-content or Br-
The contents differ by 25 to 100 mol%, preferably 50 to 100 mol%, more preferably 75 to 100 mol%.
Further, in addition to the difference in Cl-content or Br-content, or the I-content is 5 to 100 mol%, preferably 10 to 100.
They differ by mol%, more preferably 30-100 mol%. In addition, there may be mentioned an embodiment in which the difference in Cl-content or the difference in Br-content complies with the above definition and the difference in I-content is 0 to 5 mol%. The molar ratio of AgX ₁ : AgX _{2 in} the case of (AgX ₁ | AgX ₂ ), and (AgX ₁ | Ag
The molar ratio of AgX ₁ : AgX ₂ : AgX _{3 in} (X ₄ | AgX ₃ ) can be variously changed, and the molar ratio that provides the most preferable embodiment of the present invention can be selected and used.

The grain equivalent to a circle, which is the core of tabular grains, has a projected grain diameter of preferably 0.15 μm or less, and 0.02 to 0.02 μm.
0.1 μm is more preferable, and 0.01 to 0.1 μm is still more preferable.

The dispersion medium concentration of the dispersion medium solution at the time of nucleation is 0.
01 to 10% by weight is preferable, and 0.02 to 5% by weight is more preferable. 1-10 are preferable and, as for pH, 2-9 are more preferable. The temperature is preferably 10 to 80 ° C, and 30 to 60
C is more preferred. The excess Br-concentration is preferably 10 ^-2 mol / liter or less, more preferably 10 ^-2.5 mol / liter or less. Excess Cl- concentration is pCl = 0.8-3.0
Is preferred, and 1.2 to 2.8 is more preferred.

At the time of nucleation, a dispersion medium may be included in the silver salt aqueous solution and / or the halide salt aqueous solution added to enable uniform nucleation. The dispersion medium concentration is preferably 0.01% by weight or more, more preferably 0.02 to 2% by weight, still more preferably 0.05 to 1% by weight. A low molecular weight gelatin having a molecular weight of 3,000 to 60,000, preferably 8,000 to 40,000 is more preferable. Furthermore, it is more preferable that the aqueous solution of silver salt and the aqueous solution of halide salt are directly added to the liquid through a porous material addition system having 3 to 10 ¹⁵ , preferably 30 to 10 ¹⁵ pores. For details, see Japanese Patent Laid-Open No. 3-
No. 21339, No. 4-193336, and Japanese Patent Application No. 4-24
The description of No. 0283 can be referred to. Gelatin having a lower methionine content has a higher frequency of defect formation. From the gelatin having a methionine content of 1 to 60 μmol / g, the most preferable gelatin can be selected and used according to each case.

By lowering the concentration of excess halogen ions or the concentration of excess silver ions during nucleation, the mixing ratio of twinned grains can be reduced.

A silver salt aqueous solution and a halide salt aqueous solution are added by a simultaneous mixing method to a dispersion medium solution containing at least a dispersion medium and water with stirring to form nuclei. The concentration of Cl-in the dispersion medium solution during nucleation is preferably 10 ^-1.5 mol / liter or less, and the silver ion concentration is preferably 10 ^-2 mol / liter or less. The pH is preferably 2 or more, more preferably 5 to 10. The gelatin concentration is preferably 0.01 to 3% by weight,
0.03 to 2% by weight is more preferable.

The temperature during nucleation is not limited, but usually 1
0 degreeC-80 degreeC is preferable, and 20-70 degreeC is more preferable. The addition rate of the silver salt aqueous solution is preferably 0.3 to 20 g / min, and more preferably 0.5 to 15 g / min, per liter of the container solution. The pH of the container solution is not particularly limited, but usually pH 1 to 11, preferably pH 3 to 10 is used. The most preferable pH value can be selected and used according to the combination of excess silver ion concentration, temperature, and the like.

It is preferable that substantially no NH3 is allowed to coexist in the nucleation process. Here, substantially means that the silver halide solvent concentration d0 is preferably d0 ≤ 0.5 mol / liter, more preferably d0 <0.1 mol / liter, and further preferably d0 <0.02 mol / liter. Point to. It is preferable that substantially no silver halide solvent other than NH ₃ is allowed to coexist in the nucleation and growth processes. Here, “substantially” means the same as the d1 concentration regulation. As a silver halide solvent other than NH ₃ , thioethers, thioureas,
Antifoggants such as thiocyanates, organic amine compounds and tetrazaindene compounds can be mentioned, and thioethers, thioureas and thiocyanates are preferable.

2) Aging Process It is not possible to separately prepare tabular grain nuclei during nucleation. Therefore, in the next ripening process, Ostwald ripening causes the tabular grains to grow and the other grains to disappear. The aging temperature is 40 ° C or higher, preferably 45 to 90 ° C, more preferably 50 to 80 ° C.

In the present invention, it is preferable that the silver halide solvent is not substantially coexistent during ripening.
Here, “substantially” complies with the above rules.

The pH during aging is 1 to 12, preferably 1.
It is 5-8, more preferably 1.7-6.

As the dispersion medium for nucleation, ripening and growth, a conventionally known dispersion medium for silver halide emulsions can be used, but the methionine content is particularly preferably 0-5.
0 μmol / g, more preferably 0 to 30 μmol / g gelatin can be preferably used. When the gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are formed, which is preferable. Also, Japanese Examined Patent Publication No. 52-16365, Journal of the Photographic Society of Japan, 29 volumes (1), 17, 22 (1966), 30 volumes (1),
10, 19 (1967), 30 volumes (2), 17 (1)
967), 33 (3), 24 (1967). Further, the crystal habit controlling agent described in European Patent 0534395A1 can be used in combination. The dispersion medium concentration is 0.1 to
10 wt% is preferable, and the control agent is preferably 10 ^-1 to
10 ⁻⁶ mol / liter, more preferably 10 ⁻² to 10 ⁻⁵
It can be used in mol / liter. These can be added at any time from before nucleation to the end of growth. It can be added in the form of additional addition to the existing dispersion medium, or can be added after removing the existing dispersion medium by centrifugation or the like. 3) Growth process After increasing the tabular grain ratio by aging, a solute is added next to further grow the tabular grains. As the solute addition method, 1) a solution addition method (a method of adding a silver salt aqueous solution and a halide salt aqueous solution), 2) a fine grain emulsion addition method of previously forming fine silver halide grains and adding the fine grains,
3) A method of using both in combination. In order to preferentially grow the tabular grains in the edge direction, it is necessary to grow the tabular grains at a low supersaturation concentration within a range that does not undergo Ostwald ripening. That is, it is necessary to control the concentration at a low supersaturation level with high accuracy. 2)
The method (1) is more preferable because it enables this.

In the fine grain emulsion addition method, the diameter is 0.15 μm or less, preferably 0.1 μm or less, more preferably 0.1 μm or less.
A silver halide fine grain emulsion having a grain size of 06 μm or less is added, and tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or intermittently. The fine grain emulsion can be continuously prepared by supplying an aqueous solution of silver salt and an aqueous solution of halide salt in a mixer provided in the vicinity of the reaction vessel, and can be continuously added to the reaction vessel immediately or in advance in another vessel. It is also possible to add it continuously or intermittently after it is prepared in a batch manner.
It is preferable that the fine particles are substantially free of twin grains. The term “substantially free of” means that the twin grain number ratio is 5% or less, preferably 1% or less, more preferably 0.5% or less.

The halogen composition of the fine grains may be silver chloride, silver bromide, silver iodide, or a mixed crystal of two or more thereof.

The solution conditions during grain growth are the same as the above-mentioned aging conditions. This is because both are steps in which tabular grains are grown by Ostwald ripening and other fine particles are eliminated, and they are mechanically the same. For details of the method for adding a fine grain emulsion, see Japanese Patent Application No. 2-142635,
The description in JP-A-4-77261 and JP-A-1-183417 can be referred to. In order to form fine particles having substantially no twin planes, the excess halogen ion concentration or the excess silver ion concentration is preferably 10 ^-2 mol / liter or less, and the silver salt aqueous solution and the halide salt aqueous solution are simultaneously mixed and added. It may be added by a method.

The fine particle formation temperature is preferably 50 ° C. or lower,
5-40 degreeC is more preferable, and 10-35 degreeC is still more preferable. The dispersion medium preferably has a molecular weight of 2000 to 6 × 10.
⁴ , more preferably 5000-4 × 10 ⁴ low molecular weight gelatin, preferably 30% by weight or more, more preferably 6
Gelatin occupying 0% by weight or more, and more preferably 80% by weight or more is preferable. The dispersion medium concentration is preferably 0.02% by weight or more, more preferably 0.1 to 5% by weight.

Dislocation lines can be introduced into the grains during the grain formation by the halogen composition gap method, the halogen conversion method, the epitaxial growth method and a combination thereof. The pressure fog characteristics and reciprocity law characteristics and the color sensitization characteristics are further improved, which is preferable. Regarding this, JP-A-63-2
20238, 64-26839, JP-A-2-1276
35, ibid 3-189642, ibid 3-175440, ibid 2
-123346, European Patent 0460656A1 Journal
of Imaging Science, 32 volumes, 160-177 (19
88) can be referred to.

The obtained particles may be used as host particles to form epitaxial particles for use. Further, particles having dislocation lines inside may be formed using the particles as a core.
In addition, using the grains as a substrate, a silver halide layer having a halogen composition different from that of the substrate is laminated,
It is also possible to make particles of various known particle structures.

Further, a shallow inner latent emulsion may be formed by using the tabular grains as a core. It is also possible to form core / shell type particles. Regarding this, JP-A-59-
133542, 63-151618, U.S. Pat. Nos. 3,206,313, 3,317,322, 3,761,276, 4,269,927, 3,367,778. Can be referred to.

The most important parameter for finally obtaining a silver halide grain having a high aspect ratio is the pAg at the time of ripening and growth, as described above.

High silver chloride (100) used in the present invention
Tabular grains are chalcogen sensitized (sulfur sensitized, selenium sensitized,
Tellurium sensitization) and gold sensitization are required to be performed at any step in the production process of the silver halide emulsion. It is also preferable to combine two or more chalcogen sensitization methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. There are a type in which chemically sensitized nuclei are embedded inside a grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface.

The combination of chalcogen sensitization and metal sensitization which can be preferably carried out in the present invention is described by James (TH Jam).
es), The Photographic Process, 4th
Edition, published by Macmillan, 1977, (TH Jame
s, The Theory of the Photo
graphic Process, 4th ed, Ma
cmillan, 1977) 67-76, using active gelatin, and Research Disclosure, Vol. 120, 1974, 4
Mon, 20088; Research Disclosure, 34.
Vol., June 1975, 13452, U.S. Pat. No. 2,64.
No. 2,361, No. 3,297,446, No. 3,7
73,031, No. 3,857,711, No. 3,
901,714, 4,226,018, and 3,904,415, and British Patent 1,31.
PAg 5-10, pH as described in 5,755
5 to 8 and a temperature of 30 to 80 ° C., sulfur, selenium,
It can be tellurium, gold or multiple combinations of these sensitizers. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. The gold compound is preferably used in combination with thiocyanate or selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
711, 4,226,018 and 4,0.
The sulfur-containing compounds described in No. 54,457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitizer. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526 and the above-mentioned Daffin. "Photographic Emulsion Chemistry", pages 138-143.

The emulsion of the present invention is preferably combined with gold sensitization. The amount of the gold sensitizer is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, and more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol, per mol of silver halide. The preferred range of the thiocyan compound or selenocyan compound is 5 × 10 ^-2 to 1 × 10 ^-6 .

The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is 1 × per mol of silver halide.
It is 10 ⁻⁴ to 1 × 10 ⁻⁷ mol, more preferably 1
It is ^{x10 -5 to} 5x10 ^-7 mol.

Selenium sensitization is a preferable chalcogen sensitizing method for the emulsion of the present invention. In selenium sensitization,
Using a known unstable selenium compound, specifically, for example, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketones, selenamides A selenium compound such as can be used. Selenium sensitization is preferably used in combination with sulfur sensitization, metal sensitization, or both.

It is preferred that the high silver chloride (100) tabular silver emulsion of the present invention is subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, pAg1 called silver ripening.
No. 7, a method of growing or aging in a low pAg atmosphere, or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

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

Known examples of reduction sensitizers are stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, or two or more kinds of 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 the range of 10 ^-7 to 10 ^-3 mol is suitable 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. It may be added to the reaction vessel in advance, but it is preferable to add it at an appropriate time during grain growth. Further, a reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or the water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. What is an oxidizing agent for silver?
It refers to a compound that acts on metallic silver to convert it into silver ions. In particular, a compound capable of converting extremely fine silver grains, which are a by-product in the process of forming silver halide grains and the process of chemical sensitization, into silver ions is effective. The silver ions generated here are, for example, silver halide, silver sulfide,
May form a sparingly soluble silver salt such as silver selenide,
Further, a silver salt which is easily soluble in water such as silver nitrate may be formed.
The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidant include ozone, hydrogen peroxide and its adducts (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 OH), peroxy acid salts (eg K ₂ S ₂ O ₈ , K
₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ) and peroxy complex compounds (for example, 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 (e.g., KMnO _4), oxygen acid salts, such as chromates (e.g., K ₂ Cr ₂ O ₇₎ There are halogen elements such as iodine and bromine, perhalogenates (eg potassium periodate), salts of high-valent metal (eg potassium hexacyanoferrate) and thiosulfonates.

As the organic oxidant, for example, p
-Quinones such as quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B).

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents and quinone type organic oxidizing agents.
It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. It can be selected from the method of using an oxidant and then the reduction sensitization, the reverse method thereof, or the method of coexisting both. These methods can be selectively used in the grain forming step and the chemical sensitization step.

On the surface of the tabular grains having a high silver chloride content, the principal plane of which is the (100) plane of the present invention, it is preferable to make a silver salt, which is less soluble than silver chloride, exist. Examples of silver salts that are less soluble than silver chloride include silver bromide, silver iodide, silver iodobromide, silver thiocyanate, silver selenocyanate, and mixed crystals thereof. It is preferably silver halide.
The amount of the silver salt, which is less soluble than silver chloride, is 20 mol% or less, preferably 10 mol% or less, based on the whole grains.
More preferably 5 mol% or less, 0.001 mol%
That is all.

As a method for allowing a silver salt, which is less soluble than silver chloride, to exist on the surface of the tabular grains, a method of adding a halide salt aqueous solution and a silver salt aqueous solution having a corresponding composition by a double jet method, a fine grain emulsion addition method, and A method of using a sustained release agent of bromide ion or iodine ion can be mentioned.

In the method of adding the water-soluble halide salt and the water-soluble silver salt by a double jet, the halogen ion is added in a free state even if the aqueous solution of the halide salt is diluted and added. There is a limit in trying to reduce the locality between particles. This is especially difficult for tabular grains. On the other hand, the method of adding a fine grain emulsion or the method of using a sustained-release agent is a preferable method for forming a salt, which is less soluble than silver chloride, uniformly on the surface of the grains.

The average spherical phase equivalent diameter of the fine particles in the fine grain emulsion addition method is preferably 0.1 μm or less, more preferably 0.06 μm or less. The fine particles are continuously prepared by supplying an aqueous solution of a silver salt and an aqueous solution of a salt capable of forming a silver salt having a solubility lower than that of silver chloride in a mixer provided in the vicinity of the reaction vessel, and immediately adding to the reaction vessel. Alternatively, it can be added after it is prepared in a batch manner in advance in another container. The method using a sustained-release agent is described in JP-B-1-28594.
2. Japanese Patent Application No. 5-58039 and the like.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate and starch derivatives. Sugar derivative; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone,
A wide variety of synthetic hydrophilic polymeric substances such as single or copolymers such as polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole can be used.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Ph
oto. Japan. No. 16. P30 (1966)
You may use the enzyme-treated gelatin as described in,
Further, a hydrolyzate or an enzymatic hydrolyzate of gelatin can also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature for washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3-8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. As a method of washing with water, a noodle washing method, a dialysis method using a semipermeable membrane,
It can be selected and used from a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added at the time of grain formation, when the grains are modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. For example, Mg, Ca, Sr, B
a, Al, Sc, Y, La, Cr, Mn, Fe, Co,
Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, O
s, Ir, Pt, Au, Cd, Tl, In, Sn, P
Metals such as b and Bi can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides or hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example, CdBr ₂ , CdCl ₂ , Cd (NO ₃ )
₂ , Pb (NO ₃ ) ₂ , Pb (CH ₃ COO) ₂ , K ₃
[Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe (C
N) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ RhCl ₆ ,
Metal compounds such as K ₄ Ru (CN) ₆ can be mentioned.
The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl.
These may use only one type of metal compound, but may use two types or three or more types in combination.

The metal compound is water or methanol, aceto
It is preferable to add it after dissolving it in a suitable organic solvent such as
Good Aqueous hydrogen halide solution to stabilize the solution
(Eg HCl, HBr) or halogenated alkali
(Eg KCl, NaCl, KBr, NaBr)
A method of adding can be used. If necessary, acid
・ Alkali may be added. Metal compounds form particles
Even if added to the previous reaction vessel, it must be added in the middle of particle formation
You can also In addition, a water-soluble silver salt (for example, AgNO ₃)Ah
Or an alkali halide aqueous solution (for example, NaCl,
KBr, KI) and continuously during the formation of silver halide grains.
Can also be added. Furthermore, water-soluble silver salt, halogen
Prepare a solution independent of alkali chloride and
You may add continuously in time. Further various addition methods
It is also preferable to combine

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se, and Te, cyanates, thiocyanates, selenocyanates, carbonates,
Phosphate and acetate may be present.

The base grains of the present invention can be subjected to at least one of palladium sensitization and noble metal sensitization at any step of the silver halide emulsion production step. It is preferable to combine two or more sensitizing methods.

In the noble metal sensitization, for example, a noble metal salt of platinum or palladium can be used. The palladium compound means a divalent or tetravalent palladium salt.
Preferred palladium compounds are P ₂ PdX ₆ or R ₂
It is represented by PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, for example, K ₂ PdCl ₄ ,
(NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (N
H ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ PdC
₁₆ or K ₂ PdBr ₄ is preferred. The palladium compound is preferably used in combination with thiocyanate or selenocyanate.

The mercury compound used in the present invention includes
Known mercury compounds can be used. For example, mercuric salts and mercuric salts described in US Pat. No. 2,728,664, mercury oxides described in US Pat. No. 3,615,620, or British Patent 742,219, 7th
42, 222, U.S. Pat. Nos. 2,728,663 and 2,728,666, and complex compounds such as molecular compounds of a mercuric salt and an organic compound containing a basic nitrogen atom. To be The mercury salt preferably used is an inorganic salt or an organic salt, for example, mercuric acetate or mercuric acetate, mercuric formate; mercuric oxalate or mercuric acid; mercuric bromoiodide or mercuric bromochloride. Mixed halides such as dimercury, such as chlorides, bromides, fluorides and iodides; mercuric nitrate or mercuric acid and mercuric sulfate or mercuric acid. From the viewpoint of solubility, acetic acid and a mercury salt of hydrohalic acid are preferable. When an oxide compound is used, mercuric oxide is preferred because it has a higher solubility than mercuric oxide.

The mercury compound used in the present invention can be added at any time during the production of the light-sensitive material. That is, it can be added to the silver halide emulsion during the production of the silver halide emulsion, or can be added to the emulsion immediately before coating it on the support. The preferred addition time is during the production of silver halide emulsion, preferably before the completion of chemical sensitization, and more preferably before the start of desalting step. The layer containing the mercury compound may be a silver halide emulsion layer or a hydrophilic colloid layer adjacent to the silver halide emulsion layer, but a silver halide emulsion layer is preferred.

The addition amount of the mercury compound used in the present invention is 10 ^-9 to 10 ^-2 mol per mol of silver, and more preferably 1 mol.
It is 0 ^-8 to 10 ^-4 mol.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, for example triazaindenes, tetra Azaindenes (especially 4-hydroxy substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) chitraazaindenes), pentaazaindenes can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,94
No. 7 and Japanese Patent Publication No. 52-28660 can be used. JP-A-63-63 is one of the preferred compounds.
There are compounds described in No. 212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to adding the effect of preventing fog and stabilizing during the preparation of the emulsion, the crystal wall of the grain is controlled, the grain size is reduced, the solubility of the grain is reduced, and the chemical sensitization is controlled. It can be used for various purposes such as controlling the arrangement of dyes.

As the spectral sensitizing dye to be adsorbed on the base grains of the present invention, there is a methine dye, and therefore the photographic emulsion finally obtained is spectrally sensitized with methine dyes and the like. It is preferable to exhibit. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus,
Imidazole nuclei, tetrazole nuclei, pyridine nuclei; nuclei in which alicyclic hydrocarbon rings are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, for example, indolenine nuclei, benzindolenine Nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus,
The benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus and quinoline nucleus can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, for example, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2
5-6 membered heterocyclic nuclei can be applied, such as -thioxazolidine-2,4-dione nuclei, thiazolidine-2,4-dione nuclei, rhodanin nuclei and thiobarbituric acid nuclei.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,972.
7,229, 3,397,060, 3,5
No. 22,052, No. 3,527,641, No. 3,
617, 293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377,
No. 3,769,301, No. 3,814,609
No. 3,837,862, No. 4,026,70
7, British Patent Nos. 1,344,281 and 1,50
No. 7,803, Japanese Patent Publication No. 43-4936, No. 53-12
No. 375, JP-A Nos. 52-110618 and 52-10.
No. 9925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

The preferred time of addition of the spectral sensitizing dye of the present invention is after the formation of the base grains and before the addition of the fine grains. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but U.S. Pat. Nos. 3,628,969 and 4,
It is also possible to add spectral sensitization at the same time as the chemical sensitizer as described in JP-A No. 225,666 and to perform chemical sensitization at the same time as described in JP-A-58-113928. It can be carried out prior to the sensitization, or it can be added before the completion of silver halide grain precipitation to start the spectral sensitization. Furthermore, US Pat. No. 4,255,666
It is also possible to add these said compounds separately, as taught in US Pat. No. 6,096,097, ie to add some of these compounds prior to chemical sensitization and the rest after chemical sensitization. And at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective. Is.

When the emulsion obtained in the present invention is used as a light-sensitive material, various additives described above are used, but various additives other than the above can be used depending on the purpose.

More specifically, these additives are described in Research Disclosure Item 17643 (December 1978) and Item 18716 (December 1979).
Mon) and Item 308119 (December 1989)
Month), and the relevant parts are summarized in Table 1 below.

[0076]

[Table 1]

Techniques such as layer arrangement which can be used in combination with the photographic light-sensitive material of the present invention, silver halide emulsions, dye-forming couplers, functional couplers such as DIR couplers, various additives and the like, and development processing are as follows: European Patent 05650
96A1 (published October 13, 1993) and the patents cited therein. The items and corresponding description points are listed below. 1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to 62
Page 14 line 2. Middle layer: page 61, lines 36-40 3. Multilayer effect imparting layer: Page 62, lines 15-18 4. Silver halide halogen composition: page 62, lines 21-25 5. Crystal habit of silver halide grains: p. 62, lines 26-30 6. Silver halide grain size: p. 62, lines 31-34 7. Emulsion manufacturing method: Page 62, lines 35-40 8. Silver halide grain size: p. 62, lines 41-42 9. Tabular grains: page 62, lines 43 to 46 10. Internal structure of grains: page 62, lines 47 to 53 11. Emulsion latent image formation type: page 62, line 54 to page 63, line 5. 12. Physical and chemical ripening of emulsion: Page 63, lines 6-9 13. Mixed use of emulsion: page 63, lines 10-13 14. Fogging emulsion: page 63, lines 14-31 15. Non-photosensitive emulsion: page 63, lines 32-43. 16. Coating silver amount: Page 63, lines 49-50. 17. Photographic Additives: Research Disclosure (R
D) 17643, 18716 and 307105 (page 64) 18. Formaldehyde scavenger: pages 64-5
Line 7 19. Mercapto-type antifoggant: Page 65, lines 1-2. 20. Fogging agent and other release agents: Page 65, lines 3-7 21. Dye: Page 65, lines 7-10 22. Color couplers in general: Page 65 11 ~ Line 13 23. Yellow, magenta and cyan couplers: page 65 1
4 to 25 lines 24. Polymer couplers: page 65, lines 26 to 28 25. Diffusible dye forming couplers: page 65, lines 29 to 31 26. Colored couplers: page 65, lines 32 to 38 27. Functional couplers in general: page 65 39 ~ 44 line 28. Bleach accelerator releasing coupler: page 65 lines 45-48 29. Development accelerator releasing coupler: page 65 lines 49-53 30. Other DIR couplers: page 65 lines 54-66 4
Line 31. Coupler dispersion method: Page 66, lines 5 to 28 32. Preservative / antifungal agent: Page 66, lines 29 to 33 33. Type of sensitive material: Page 66, lines 34 to 36 34. Photosensitive layer film thickness and swelling speed : Page 66 line 40 to page 67 line 1 35. Back layer: page 67 line 3 to line 36. General development process: page 67 line 9 to 11 37. Developer and developer: page 67 line 12 to 30 38. Development Liquid additive: page 67, lines 31 to 44 39. Reversal processing: page 67, lines 45 to 56 40. Processing liquid opening ratio: page 67, line 57 to page 68, line 12 41. Development time: page 68, lines 13 to 15 42. Bleach-fix, bleach-fix, page 68, line 16 to page 69, 31.
Line 43. Automatic processor: page 69, lines 32-40 44. Washing, rinsing, stabilizing: page 69, line 41-page 70 18
Line 45. Replenishment and re-use of processing solution: Page 70, Lines 19 to 23 46. Built-in developer sensitive material: Page 70, Lines 24 to 33 47. Development processing temperature: Page 70, Lines 34 to 38 48. Use for film with lens : 70 pages, lines 39-41

The silver halide light-sensitive material of the present invention is described in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, No. 59-218443, No. 61-23805.
It is also applicable to the photothermographic materials described in No. 6, European Patent No. 210,660A2, and the like.

[0079]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 Preparation of emulsion a 1200 ml of gelatin aqueous solution (gelatin 28
g, NaCl 4.0 g, N, N'-dimethylimidazoline-2-thione (containing 3.2 ml of 1% aqueous solution) is added thereto, the temperature is set to 52 ° C., and 200.0 ml of AgNO ₃ aqueous solution (AgNO is added while stirring). ₃ including 32.0 g) and Na
200.0 ml of an aqueous Cl solution (containing 11.0 g of NaCl) was added and mixed for 24 minutes. (Step A) 523.0 ml of AgNO ₃ aqueous solution (AgNO ₃ 156.9
g) and 523.0 ml of NaCl aqueous solution (NaCl5
(Including 4.0 g) was added and mixed for 26 minutes and 09 seconds while maintaining 52 ° C. Then, AgBr fine grain emulsion described later was added in an amount of 6.6 × 10 ⁻³ mol and ripened for 5 minutes. And 2- [5-phenyl-2- {2- [5-phenyl-3- (2-sulfonatoethyl) benzoxazoline-2-ylidenemethyl] -1-butenyl} -3-benzoxazolio] pyridinium ethanesulfonate. Salt 28
6.7 mg was added. The obtained emulsion a was cubic and had an average equivalent spherical diameter of 1.02 μm. Preparation of AgBr fine grain emulsion 1200 ml of gelatin aqueous solution (M3 gelatin 2
4g, containing 0.09g KBr, pH 3.0),
While stirring at a temperature of 23 ° C., an AgNO ₃ aqueous solution 240.
0 ml (AgNO ₃ 60.0 g, M3 gelatin 2.0 g,
1M HNO ₃ (including 1.0 ml) and KBr aqueous solution 24
0.0 ml (KBr 42.0 g, M3 gelatin 2.0 g,
1M KOH (including 1.0 ml) at 90 cc / min for 2 minutes 40
Simultaneous mixed addition was performed for 2 seconds. After stirring for 30 seconds, pH 4.
0, adjusted to pBr 3.2. The obtained AgBr fine grain emulsion had an average equivalent spherical diameter of 0.04 μm. Preparation of emulsion b 1200 ml of gelatin aqueous solution (gelatin 28
g, NaCl 4.0 g, N, N′-dimethylimidazoline-2-thione (3.2% of 1% aqueous solution) is added], the temperature is set to 52 ° C., and 200.0 ml of AgNO ₃ aqueous solution is added with stirring ( AgNO ₃ (including 32.0 g) and N
200.0 ml of aCl aqueous solution (containing 11.0 g of NaCl) was added and mixed for 24 minutes. (Step A) 523.0 ml of AgNO ₃ aqueous solution (AgNO ₃ 156.9
g, mercuric chloride 0.02 × 10 ^-7 per mol Ag
523.0 ml of solution (containing 54.0 g of NaCl) was added and mixed for 26 minutes and 09 seconds while maintaining 52 ° C. Subsequently, the AgBr fine grain emulsion described above was added in an amount of 6.6 × 10 ⁻³ mol and ripened for 5 minutes. And 2
-[5-phenyl-2- {2- [5-phenyl-3-
286.7 mg of (2-sulfonatoethyl) benzoxazoline-2-ylidenemethyl] -1-butenyl} -3-benzoxazolio] ethanesulfonic acid pyridinium salt was added. The obtained emulsion b was cubic and had an average equivalent spherical diameter of 1.02 μm. Emulsions c and d shown in Table 1 were obtained by changing only the addition amount of mercuric chloride from Emulsion b. Preparation of emulsion e 1200 ml of gelatin aqueous solution (gelatin 18.
0 g, pH 4.3] was added, the temperature was raised to 45 ° C., and 12.0 ml of AgNO ₃ aqueous solution (AgN
(Including 2.40 g of O ₃ ) and 12.0 ml of NaCl aqueous solution
(Containing 0.83 g of NaCl) was simultaneously added and mixed at 24 ml / min. After stirring for 1 minute, AgNO ₃ aqueous solution 1
30 ml / mi of 9.0 ml (containing 0.38 g of AgNO ₃ ) and 19.0 ml of KBr aqueous solution (containing 0.27 g of KBr).
Simultaneous addition at n was mixed. After stirring for 1 minute, AgNO ₃
36.0 ml of an aqueous solution (containing 7.20 g of AgNO ₃ ) and N
36.0 ml of aCl aqueous solution (including 2.48 g of NaCl)
Was mixed at 48 ml / min. Next, add 20.0 ml of NaCl aqueous solution (including 2.0 g of NaCl) to adjust the pH.
Was set to 4.8. (Step A) After ripening at 70 ° C. for 16 minutes, the AgCl fine grain emulsion was A
0.987 mol was added in an amount of g and the mixture was aged for 35 minutes. Further, AgBr fine grain emulsion was added in an amount of 0.013 mol and ripened for 6 minutes.

Next, the temperature was lowered to 35 ° C., and the emulsion was washed with water by a precipitation washing method according to a conventional method. Then, an aqueous gelatin solution is added to bring the temperature to 40 ° C., the pH of the emulsion is 6.4, pCl
Adjusted to 2.8. The obtained emulsion e was a tabular emulsion having a (100) plane as a main plane and grains having an aspect ratio of 2 or more occupied 86% of the total projected area. Preparation of AgCl fine particle emulsion 1200 ml of gelatin aqueous solution (24 g of gelatin having an average molecular weight of 30,000 (hereinafter referred to as M3 gelatin), NaC)
90 g of AgNO ₃ aqueous solution (AgN).
O ₃ 225.0 g, M3 gelatin 9.0 g, 1M HN
O ₃ containing 2.3 ml) and aqueous NaCl 900.0ml
(NaCl 77.4 g, M3 gelatin 9.0 g, 1M
KOH (containing 2.3 ml) was simultaneously mixed and added at 90 cc / min for 10 minutes. After stirring for 30 seconds, pH 4.0, pC
Adjusted to l1.7. The obtained AgCl fine grain emulsion had an average equivalent spherical diameter of 0.06 μm.

Preparation of emulsion f 1200 ml of gelatin aqueous solution (gelatin 18.
0 g, pH 4.3] is added, the temperature is brought to 45 ° C.,
While stirring, 12.0 ml of AgNO ₃ aqueous solution (AgNO ₃
2.40g) and 12.0ml NaCl solution (Na
Cl (containing 0.83 g) was simultaneously added and mixed at 24 ml / min. After stirring for 1 minute, 19.0 ml of AgNO ₃ aqueous solution
(Containing 0.38 g of AgNO ₃ ) and KBr aqueous solution 19.
0 ml (containing 0.27 g of KBr) was simultaneously added and mixed at 30 ml / min. After stirring for 1 minute, AgNO ₃ aqueous solution 3
48 ml of 6.0 ml (containing 7.20 g of AgNO ₃ ) and 36.0 ml of NaCl aqueous solution (containing 2.48 g of NaCl)
/ Min at the same time. Next, NaCl aqueous solution 20.
0 ml (containing 2.0 g of NaCl) was added to adjust the pH to 4.8.
And (Step A) After ripening at 70 ° C. for 16 minutes, the AgCl fine grain emulsion was A
0.987 mol (containing 2 × 10 ⁻⁹ mol of mercuric chloride per mol of Ag) was added in a g amount, and the mixture was aged for 35 minutes. Further, AgBr fine grain emulsion was added in an amount of 0.013 mol and ripened for 6 minutes.

Next, the temperature was lowered to 35 ° C., and the emulsion was washed with water by a precipitation washing method according to a conventional method. Then, an aqueous gelatin solution is added to bring the temperature to 40 ° C., the pH of the emulsion is 6.4, pCl
Adjusted to 2.8. The obtained emulsion f was a tabular emulsion having a (100) plane as a main plane and grains having an aspect ratio of 2 or more occupied 86% of the total projected area. Preparation of AgCl fine particle emulsion 1200 ml of gelatin aqueous solution (24 g of gelatin having an average molecular weight of 30,000 (hereinafter referred to as M3 gelatin), NaC)
90 g of AgNO ₃ aqueous solution (AgN).
O ₃ 225.0 g, M3 gelatin 9.0 g, 1M HN
2.3 ml of O _{3 and} mercuric chloride 2 × 1 per mol of Ag
0 ^-7 including moles) and aqueous NaCl 900.0ml (Na
Cl 77.4g, M3 gelatin 9.0g, 1M KOH
(Containing 2.3 ml) was simultaneously mixed and added at 90 cc / min for 10 minutes. After stirring for 30 seconds, pH 4.0, pCl1.
Adjusted to 7. Emulsions g and h shown in Table 1 were obtained by changing only the addition amount of mercuric chloride from emulsion f.

Emulsions a to h were chemically sensitized as follows.

First, thiourea dioxide was added and held for 16 minutes for reduction sensitization. Next, the sensitizing dye ExS-
7 was added. Further, potassium thiocyanate, potassium chloroaurate, sodium thiosulfate and N, N-dimethylselenourea were added for aging. The amount of each compound added at the time of the chemical sensitization and the aging time are 1/10 described later.
The sensitivity of 0 second exposure was adjusted to be optimum.

After the completion of chemical sensitization, the following compounds were added and coated on a triacetyl cellulose film support having an undercoat layer together with a protective layer by a simultaneous extrusion method so that the amount of silver was 0.5 g / m ^2. Then, samples 1 to 8 were obtained. (1) Emulsion layer-Emulsion ... Emulsions 1-8-Compound 1 represented by the following structural formula shown in Chemical formula 4 below-Tricresyl phosphate-Stabilizer 4-hydroxy-6-methyl-1,3,3 Three
a, 7-Tetrazaindene ・ Coating aid sodium dodecylbenzenesulfonate (2) Protective layer ・ Polymethylmethacrylate fine particles ・ 2,4-dichloro-6-hydroxy-s-triazine sodium salt ・ Gelatin Sensitto these samples Exposure for measurement (1/100
Second) and the following color development processing was performed.

[0087] * For stability, the countercurrent system from (3) to (1) was adopted.

The composition of the processing liquid is shown below. (Color developer) Ethylene dian tetraacetic acid 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid 2-sodium salt 0.3 g Potassium carbonate 30.0 g Sodium chloride 5.0 g Disodium-N, N-bis (sulfonate ethyl) ) Hydroxylamine 6.0 g 4- [N-ethyl-N- (β-hydroxylethyl) amino] -2-methylaniline sulfate 5.0 g Water was added to 1.0 liter pH (with potassium hydroxide and sulfuric acid. Adjustment) 10.00

(Bleaching Solution) 1,3-Diaminopropanetetraacetic acid ammonium ferric acid monohydrate 140 g 1,3-Diaminopropanetetraacetic acid 3 g Ammonium bromide 80 g Ammonium nitrate 15 g Hydroxyacetic acid 25 g Acetic acid (98%) 40 g Water was added. 1.0 liter pH (adjusted with aqueous ammonia and acetic acid) 4.3

(Fixer) Ethylenediaminetetraacetic acid disodium salt 15 g Ammonium sulfite 19 g Imidazole 15 g Ammonium thiosulfate (70 WT%) 280 ml Water was added to 1.0 liter pH (adjusted with ammonia water and acetic acid) 7.4

(Stabilizing Solution) Sodium p-toluenesulfinate 0.03 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.2 g Ethylenediamon tetraacetic acid disodium salt 0.05 g 1,2, 4-triazole 1.3 g 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 g Water was added to 1.0 liter pH (adjusted with ammonia water and acetic acid) 8.5 Treatment The density of the finished sample was measured with a green filter.

The sensitivity was defined as the reciprocal of the exposure amount that gives a density of fog + 0.2, and was expressed as a relative value with the value of Sample 1 as 100. The values of sensitivity and fog are shown in Table 2 below.

From Table 2, it can be seen that by flattening the shape of the emulsion grains and by using a mercury compound together, the sensitivity can be reduced and the fluctuation in fog can be reduced.

[0094]

[Table 2]

Example 2 Using the emulsions a and E prepared in Example 1, mercuric acetate was added immediately before coating, and the effect of the present invention was observed. The addition amount of mercuric acetate is as shown in Table 3. Application samples 9 to 16 were prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 3. From Table 3, it can be seen that even if the mercury compound is added immediately before coating, the same effect as in Example 1 can be obtained.

[0096]

[Table 3]

Example 3 On a subbed cellulose triacetate film support,
Each layer having the composition shown below was applied in multiple layers to prepare Sample 101, which is a multilayer color light-sensitive material. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First layer (antihalation layer) Black colloidal silver Silver 0.09 Gelatin 1.30 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS- 1 0.15 HBS-2 0.02

Second layer (intermediate layer) ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver chlorobromide emulsion A Silver 0.25 Silver chlorobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium-Sensitivity Red-Sensitive Emulsion Layer) Silver Chlorobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver chlorobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver chlorobromide emulsion E Silver 0.15 Silver chlorobromide emulsion F Silver 0.10 Silver chlorobromide emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.88

9th layer (high-sensitivity green-sensitive emulsion layer) Silver chlorobromide emulsion D Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.00

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.70

11th layer (low-sensitivity blue-sensitive emulsion layer) Silver chlorobromide emulsion I Silver 0.09 Silver chlorobromide emulsion J Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.73 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 x 10-3 HBS-1 0.32 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion 1 (prepared in Example 1) Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd -3 1.0 x 10 ^-3 HBS-1 0.070 Gelatin 0.70

13th layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 gelatin 1.2

14th layer (second protective layer) Silver chloride emulsion L Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S- 1 0.20 Gelatin 0.70

[0112]

[Chemical 1]

[0113]

[Chemical 2]

[0114]

[Chemical 3]

[0115]

[Chemical 4]

[0116]

[Chemical 5]

[0117]

[Chemical 6]

[0118]

[Chemical 7]

[0119]

[Chemical 8]

[0120]

[Chemical 9]

[0121]

[Chemical 10]

[0122]

[Chemical 11]

[0123]

[Chemical 12]

[0124]

[Chemical 13]

[0125]

[Chemical 14]

[0126]

[Chemical 15]

[0127]

[Chemical 16]

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0129]

[Table 4]

In Table 4, (1) Emulsions I to K were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to H were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) Preparation of tabular grains is described in US Pat. No. 5,264,3
It is prepared according to the example of No. 37.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
was μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

Samples 102 to 108 were prepared by changing the emulsion of the twelfth layer (high-sensitivity blue-sensitive emulsion layer) from emulsion a to emulsions b to f prepared in Example 1. These samples 1
01-108 exposure for sensitometry (1/100
Seconds) and the following color development processing was performed.

[0134] * For stability, the countercurrent system from (3) to (1) was adopted.

The composition of the processing liquid is shown below. (Color developer) Diethylenetriaminepentaacetic acid 3.0 g Potassium carbonate 30.0 g Sodium chloride 5.0 g Diethylhydroxylamine 5,0 g 4- [N-ethyl-N- (β-hydroxylethyl) amino] -2-methylaniline sulfate Salt 5.0 g Water added 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.00

(Bleach) 1,3-Diaminopropanetetraacetic acid ammonium ferric acid monohydrate 140 g 1,3-Diaminopropanetetraacetic acid 3 g Ammonium bromide 85 g Ammonium nitrate 18 g Ammonia water (27%) 10 g Acetic acid (98%) 50 g Potassium carbonate 10 g Water was added to 1.0 liter pH (adjusted with ammonia water and acetic acid) 4.3

(Fixer) Ethylenediaminetetraacetic acid disodium salt 2 g Sodium sulfite 14 g Sodium bisulfite 10 g Ammonium thiosulfate (70 WT%) 210 ml Ammonium thiocyanate 160 g Thiourea 2 g Water was added to 1.0 liter pH (ammonia water and acetic acid Adjusted by 6.5)

(Stabilizer) Surfactant [C ₁₀ H ₂₁ —O— (CH ₂ CH ₂ O) —H] 0.2 g Polymaleic acid (average molecular weight 2000) 0.1 g 1,2-benzisothiazoline-3- On 0.05 g Hexamethylenetetramine 5.5 g Water was added to 1.0 liter pH (adjusted with ammonia water and acetic acid) 8.5

The results obtained are shown in Table 5. It can be seen that the sensitivity and fog in the leg characteristic curve for the yellow color image are similar to those obtained for the single layer coated sample of Example 1.

[0140]

[Table 5]

Example 4 Preparation of Emulsion A 1582 ml of gelatin aqueous solution (gelatin-1) was placed in a reaction vessel.
(Deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) 21 g, HNO ₃ 1N solution 8 ml, pH 4.3, NaCl-1 solution (Na in 100 ml)
13 ml of Cl (including 10 g) was added, and while maintaining the temperature at 40 ° C., Ag-1 solution (20 g of AgNO _{3 in} 100 ml) was added.
And X-1 solution (NaCl 7.05 in 100 ml).
(including g) was simultaneously mixed and added at 62.4 ml / min in 15.6 ml portions. After stirring for 3 minutes, Ag-2 solution (containing AgNO ₃ 2 g in 100ml) and X-2 solution (in 100 ml K
(Including 1.4 g Br) were co-mixed in 28.2 ml portions at 80.6 ml / min. After stirring for 3 minutes, Ag-1 solution and X-
Solution 1 was simultaneously added at 62.4 ml / min in an amount of 46.8 ml. After stirring for 2 minutes, 203 ml of gelatin aqueous solution (gelatin-1 15 g, NaCl 1.3 g, adjusted to pH 6 with NaOH 1N solution) was added to adjust pCl to 1.65,
The temperature was raised to 75 ° C. and aging was carried out for 42 minutes. AgCl fine grain emulsion (average grain diameter 0.1 μm) 4.2 × 10 ^-2
It was added for 20 minutes at a rate of addition of AgCl of mol / min. After aging for 10 minutes after the addition, a flocculating sedimentation agent was added and the temperature was adjusted to 35
It was lowered to ℃ and washed with sedimented water. Add gelatin aqueous solution, 60
The pH was adjusted to 6.0 at ° C. A transmission electron micrograph image (hereinafter referred to as a TEM image) of the replica of the particles was observed.
The resulting emulsion was high silver chloride (100) tabular grains containing 0.44 mol% of AgBr based on silver. (Average aspect ratio 6.3, average thickness 0.2μ, average Dc 1.25
μ). Sample 13 of Example 1 of Japanese Patent Application No. 5-272346
Chemical sensitization was carried out according to the procedure described above to obtain Emulsion A. An emulsion prepared in the same manner as Emulsion A, except that Ag-1 solution was added with 10 ⁻⁷ mol of mercuric oxide per mol of Ag was designated as B. Emulsions A and B were coated in the same manner as in Example 1 of Japanese Patent Application No. 5-272346 and exposed and developed. The sample containing mercury showed low fog.

Example 5 A sample was prepared in the same manner as in Example 3, except that mercuric oxide was added to the emulsion coating solution in an amount of 5 × 10 ^-8 mol per mol of silver halide. The sample containing mercury had even lower fog than the corresponding sample of Example 3.

[0143]

INDUSTRIAL APPLICABILITY The present invention has excellent rapid processability (10
It was found that, in an emulsion containing tabular high-silver-chloride grains having the (0) plane as the principal plane, the combined use of a mercury compound brings about an excellent effect on the color sensitization sensitivity and the change in fog during processing changes.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 1/34

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, wherein the total projected area of silver halide grains in the emulsion layer is 3
0% or more has a silver chloride content of 50 mol% or more, the main plane is the (100) plane, and the aspect ratio (diameter / thickness) is 1.5.
A silver halide photographic light-sensitive material comprising the above-mentioned gold chalcogen-sensitized tabular grains and containing a mercury compound in the light-sensitive material. 2. A silver halide photographic light-sensitive material according to claim 1, wherein a silver salt which is less soluble than silver chloride is present on the surface of the tabular grains. 3. The tabular grain is gold chalcogen sensitized in the presence of a spectral sensitizing dye.
The described silver halide photographic light-sensitive material. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the tabular grains are reduction-sensitized.