JPH05341419A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce fog and to improve pressure characteristics while maintaining high sensitivity by forming an emulsion layer contg. flat platy silver halide particles having introduced dislocation and a specified aspect ratio by the half or more of the total projection area of all the silver halide particles in the emulsion layer. CONSTITUTION:This silver halide photographic sensitive material has an emulsion layer contg. flat platy silver halide particles having dislocation introduced in the presence of a solvent for silver halide as shown by the expression and has >=3.0 aspect ratio by >=50% of the total projection area of all the silver halide particles in the emulsion layer. In the formula, (m) is 0 or an integer of 1-12 and each of X1 and X2 is S, Se, Te or O. Flat platy particles are particles each having plural twin faces parallel to each other and a flat platy external shape but the aspect ratio is not limited. Particles having no twin faces and >=2 aspect ratio are included in flat platy particles but flat platy particles having twin faces are preferable. The aspect ratio of flat platy particles means the ratio of the diameter to the thickness.

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 silver halide photographic light-sensitive material which has high sensitivity, less fog and improved pressure characteristics. It is a thing.

[0002]

2. Description of the Related Art In recent years, the demand for photographic silver halide emulsions has become more and more stringent, and a high level of photographic performance such as high sensitivity, excellent graininess and sharpness has been made. In response to such demands, the use technology of tabular grains intended to improve sensitivity including improvement of color sensitizing efficiency by a sensitizing dye, improve sensitivity / granularity relationship, improve sharpness, and improve covering power is described in US Patent No. 4,434,226
No. 4,414,310, No. 4,433,04
No. 8, No. 4,414, 306, No. 4, 459, 3
No. 53. Also, JP-A-58-11393
0, 58-113934, 59-119350.
Also discloses a multi-layer color photographic light-sensitive material using a tabular silver halide emulsion having an aspect ratio of 8 or more in a high-sensitivity layer and having high sensitivity and improved graininess, sharpness and color reproducibility. There is.

However, the dye also has a property of desensitizing a silver halide emulsion, and usually, the optimum spectral sensitization is carried out only in an amount much smaller than the amount in which the dye produces a continuous monolayer on the surface of emulsion grains. At present, the feeling is not achieved and the merit of tabular grains is not utilized.

Regarding the observation of the dislocation of silver halide grains, [1] CRBerry, J.Appl.Phys ., 27, 6 36 (1956) [2] CRBerry, DCSkilman, J.Appl.Phys. , 35, 2
165 (1964) [3] JFHamilton, J.Phot.Sci.Eng. , 11 , 57 (1967) [4] T.Shiozawa, J.Soc.Phot.Sci.Jap. , 34 , 16 (1971) [5 ] T.Shiozawa, J.Soc.Phot.Sci.Jap. , 35 , 213 (197
2) and the like, and it is possible to observe dislocations in the crystal by X-ray diffraction or low-temperature transmission electron microscopy, and by intentionally giving strain to the crystal It is mentioned that dislocations occur.

Although the silver halide grains in these documents do not have dislocations intentionally inserted during the formation of photographic emulsions, silver halide grains in which dislocations are positively introduced are disclosed in JP-A-63-220238, It is described in JP-A-1-201649. According to these patents, tabular grains having dislocation lines introduced to some extent are superior in photographic characteristics such as sensitivity and pressure characteristics to tabular grains having no dislocation lines, and when these are used in a light-sensitive material, sharpness and graininess are obtained. However, it is already insufficient for the recent demands for photographic light-sensitive materials.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material which has high sensitivity, less fog and improved pressure characteristics.

[0007]

As a result of intensive studies by the present inventors, the objects of the present invention have been achieved by the following means (1) to (3).

(1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, tabular halogen having an aspect ratio of 3.0 or more in which dislocations are introduced in the presence of a silver halide solvent. A silver halide photographic light-sensitive material characterized by containing silver halide grains in an amount of 50% or more of the total projected area of silver halide grains in the emulsion layer.

(2) A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, a flat plate having an aspect ratio of 3.0 or more in which dislocations are introduced in the presence of the following general formula (I). A silver halide photographic light-sensitive material, characterized in that it contains 50% or more of the total projected area of silver halide grains in the emulsion layer.

[0010]

[Chemical 2] In the formula, m represents 0 or an integer of 1 to 12, and X ₁ and X
₂ represents a sulfur atom, a selenium atom, a tellurium atom or an oxygen atom.

(3) A photosensitive material packaging unit provided with an exposure function, which comprises using the silver halide photographic photosensitive material described in (1).

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

First, the tabular silver halide grains used in the present invention will be described in detail.

The tabular grain is a grain having a plurality of parallel twin planes and a tabular outer shape, and its aspect ratio is not limited. Further, grains having no twin plane and an aspect ratio of 2 or more are also included in the tabular grains, but tabular grains having twin planes are preferable.
An example of the latter is A. Mignot et al. In Journal of Cryst. Growth 2
Anisotropically grown normal crystal grains as reported in Vol. 3, p. 207 (1974).

In tabular grains, the aspect ratio is
It means the ratio of diameter to thickness in silver halide grains. That is, it is a value obtained by dividing the diameter of each silver halide grain by the thickness. Here, the diameter is the diameter of a circle having an area equal to the projected area of a silver halide grain when observed with an optical microscope or an electron microscope. Therefore, the aspect ratio of 3.0 or more means that the diameter of this circle is 3.0 times or more the thickness of the particles.

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

In the tabular grains used in the present invention,
The average aspect ratio is 3.0 or more, preferably 3.0 to 20.0, and particularly preferably 3.0 to 8.0. The proportion of tabular grains in the total projected area of silver halide grains in one emulsion layer is 50% or more, preferably 70% or more, and particularly preferably 85% or more.

In the tabular grains used in the present invention, the average grain diameter is 0.2 to 10.0 μm, preferably 0.3 to 5.0 μm. The average particle thickness is preferably 0.5 μm or less. A more preferable tabular grain has an average grain diameter of 0.3 μm.
5.0 μm or less, average grain thickness 0.5 μm or less, average aspect ratio 3.0 or more and 8.0 or less, and occupies 85% or more of the total projected area of silver halide grains in one emulsion layer. Is.

Further, more preferable results may be obtained by using monodisperse tabular grains. The structure and manufacturing method of monodisperse tabular grains are described in, for example, JP-A-63-151618.
However, 70% or more of the total projected area of a silver halide grain is the length of the side having the maximum length with respect to the length of the side having the minimum length. Of hexagons with a ratio of 2 or less and parallel 2
The hexagonal tabular silver halide grains are occupied by tabular silver halide having an outer surface as the outer surface, and the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains [variation in grain size represented by the circle equivalent diameter of the projected area]. (standard deviation)
Value divided by the average particle size] has a monodispersity of 20% or less.

The tabular grains used in the present invention are Cug
nac (Cunayak), Chateau (Chateau)
Report and Duffin's "Photog"
radical Evolution Chemistr
y "(Published by Local Press, New York
1966) 66-72, and A. P. H. Tri
velli, W. F. Smith edition, “Phot.Jounal” 80 (1940)
Year) page 285. In addition, JP-A-58-1
No. 13927, No. 58-113928, No. 58-12
It can be easily prepared by referring to the method described in No. 7921. For example, in an atmosphere having a relatively high pAg value of pBr of 1.3 or less, a seed crystal having 40% by weight or more of tabular grains is formed. Next, tabular grains are obtained by growing a seed crystal while maintaining the pBr value at the same level and simultaneously adding a silver and halogen solution. In such a grain growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated.

The tabular silver halide grains used in the present invention are silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver iodochloride,
Alternatively, silver iodochlorobromide may be used, but silver iodobromide, silver iodochloride or silver iodochlorobromide is preferable, and the average silver iodide content is 3.0 mol% or more, particularly 3. It is preferably 0 mol% or more and 30.0 mol% or less of silver iodobromide, silver iodochloride or silver iodochlorobromide.

The silver halide grain of the present invention has dislocations inside the grain. The dislocation of silver halide grains is described in, for example, J. F. Hamilton, Photo. Sci.
Eng. , 11 , 57, (1967) and T.W. Shioz
awa, J .; Soc. Photo. Sci. Japan.
35 , 213, (1972), and can be observed by a direct method using a transmission electron microscope at low temperature. In other words, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample is placed to prevent damage (printout etc.) due to electron beam. Observation is performed by a transmission method in a cooled state. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough.
It can be observed more clearly by using an electron microscope of 200 kV or more for particles having a thickness of μm.

The positions of dislocations in the tabular grains of the present invention occur in the major axis direction of the tabular grains from the distance X% of the length from the center to the side to the side, and the value of X is preferably. 10 ≦ X <100, more preferably 30 ≦
X <98, and more preferably 50 ≦ X <95. At this time, the shape formed by connecting the positions where the dislocations start is close to a particle shape, but may not be a perfect shape and may be distorted. The direction of the dislocation line is approximately from the center to the side, but it often meanders.

The number of dislocations in the tabular grains of the present invention is 1
It is preferable that 50% (number) or more of grains containing 0 or more dislocations are present. More preferably, 80% (number) or more of particles containing 10 or more dislocations are present, and particularly preferably 80% (number) or more of particles containing 20 or more dislocations.

The introduction of dislocations in the tabular grain of the present invention can be controlled by providing a specific high iodine phase inside the grain. Specifically, the substrate grain is prepared and then the high iodine phase is added. It can be obtained by covering the outside with a phase having a lower silver iodide content than the high iodide content. Proper selection of conditions is especially important.

As a result of intensive studies, the present inventors have found that the presence of a silver halide solvent at the time of introducing dislocations is very effective for the above purpose.

The silver halide solvent used in the present invention means water or a mixed solvent of water and an organic solvent (for example, water / methanol =
1/1, etc.) can dissolve silver chloride in a weight of more than twice the weight of silver chloride which can be dissolved at 60 ° C. in a silver halide solvent present at a concentration of 0.02 mol. ..

Specifically, (i) thiocyanate, (i
i) Thioether compounds, serenaether compounds, telluroether compounds (for example, US Pat. No. 2,521,926).
No. 3021215, No. 3038805, No. 3046232, No. 3574628, No. 42.
No. 76374, No. 3704130, No. 42974.
No. 39, No. 4752560, No. 4695534
No. 4,695,535, No. 4,713,322, No. 4,78,2013, Japanese Patent Publication No. 58-30571, JP-A No. 57-104926, No. 60-80840, No. 6
2-14646, 62-23035, 63-2
No. 59653, No. 63-26152, JP-A-1-12.
No. 1845, No. 1-1212846, No. 1-2184
No. 7, No. 1-209440, No. 1-210945,
1-216337, 1-236338, 1-
No. 217450, No. 2-118566), (iii) thiocarbonyl compound, selenocarbonyl compound (for example, Japanese Patent Publication Nos. 58-51252, 59-11892, and JP-A-55-77737). Tetrasubstituted thioureas described in U.S. Pat. Nos. 4,221,863 and 4,749,646, and JP-B-60-1134.
No. 1), (iv) a specific mercapto compound or mesoionic compound (for example, JP-B-63-29727).
, Compounds described in JP-A-60-163042),
(V) Sulfite, (vi) a compound having an imino group (for example, Japanese Patent Publication Nos. 62-2301 and 59-45135,
JP-A-57-82833, 57-188036,
57-196228 and 58-54333). Among these, (i) ~
The compound of (v) is preferred.

More specifically, the compound represented by the following general formula (I) is preferable as the compound (ii).

R ^1- (X ₂ -R ³ ) _m -X ₁ -R ² (I) In the formula, m represents 0 or an integer of 1 to 12.

X ₁ and X ₂ represent a sulfur atom, a selenium atom, a tellurium atom or an oxygen atom, but are always 1
Is a sulfur atom, a selenium atom, or a tellurium atom, and a sulfur atom is particularly preferable.

R ¹ and R ² may be the same or different and each represents a lower alkyl group (having 1 to 5 carbon atoms) or a substituted alkyl group (having 1 to 30 total carbon atoms).

Here, as the substituent, for example, —OH, —
COOM ¹ , -SO ₃ M ¹ , -NHR ⁴ , -NR
⁴ R ^4, -N ⁺ R ⁴ R ⁴ R ⁴ (where R ⁴ may be the same or ^{different), - OR 4, -CONHR 4} , -COOR
⁴ , a heterocycle and the like can be mentioned.

M ¹ represents a hydrogen atom or a cation.

R ⁴ may be a hydrogen atom, a lower alkyl group or a substituted alkyl group further substituted with the above-mentioned substituent.

Two or more substituents may be substituted, and they may be the same or different.

R ³ represents an alkylene group (preferably having 1 to 12 carbon atoms).

However, when m is 2 or more, m X ₂ and R ³
Can be the same or different.

Further, one or more groups such as --O--, --CONH--, --SO ₂ NH-- may be present in the middle of the alkylene chain, and the substitution described in R ¹ and R ² is possible. It may be substituted with a group.

Further, R ¹ and R ² may be bonded to each other to form a cyclic compound.

The synthesis of these compounds can be carried out by the methods described in the above-mentioned patent specifications or cited documents. In addition, some compounds are commercially available.

The compounds of the silver halide solvent used in the present invention are listed below (PTS represents paratoluene sulfonate).

[0043]

[Chemical 3]

[0044]

[Chemical 4]

[0045]

[Chemical 5]

[0046]

[Chemical 6]

[0047]

[Chemical 7]

[0048]

[Chemical 8]

[0049]

[Chemical 9] The preferred addition amount of the silver halide solvent used in the present invention is
The amount is in the range of 1 × 10 ^-5 mol to 1 × 10 ^-1 mol per mol of silver, and the more preferable addition amount is 1 × 10 ^-4 mol to 5 × 10 ^-2 mol. The most preferred range is 1 × 10 ⁻³ to 1 × 10 ⁻² mol per mol of silver.

The internal high iodine phase refers to a silver halide solid solution containing iodine. In this case, silver iodide, silver iodobromide and silver chloroiodobromide are preferable as the silver halide, but silver iodide or silver iodobromide (silver iodide content of 10 to 40 mol%) is preferable. More preferably, and particularly preferably silver iodide.

It is important that the internal high iodine phase is not uniformly deposited on the plane of the tabular grains of the substrate, but rather is localized. Such localization may occur on the main plane of the plate, on the side surface, on the side, or on the corner. Further, it may be selectively and epitaxially coordinated to such a site. As a method for this purpose, it is preferable to use a so-called conversion method in which an iodide salt is added alone.

The silver iodide content of the tabular grains of the substrate is lower than that in the high iodide phase, preferably 0 to 12 mol%, more preferably 0 to 10 mol%.

The outer phase which covers the high iodine phase is lower than the silver iodide content of the high iodine phase, preferably the silver iodide content is 0 to 12 mol%, more preferably 0 to 10 mol%. It is preferably 0 to 3 mol%.

The iodide content of the internal high iodide phase is higher than the average iodide content of silver bromide, silver iodobromide or silver chloroiodobromide present on the grain surface, and preferably 5 times or more. , Particularly preferably 20 times or more.

Further, the amount of silver halide forming the internal high iodine phase is 50 mol% or less, more preferably 10 mol% or less, and especially 5 mol% of the total silver amount of the grains. The following is preferable.

The following is a description of the emulsion of the present invention and the emulsion used in combination therewith.

The silver halide grains used in the present invention are silver bromide, silver chloride, silver iodide, silver chloroiodide, silver iodobromide and silver chloroiodobromide. Other silver salts such as silver rhodanide, silver sulfide, silver selenide, silver carbonate, silver phosphate, and silver organic acid may be contained as separate grains or as a part of silver halide grains.

In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or with a structure, it is important to control the halogen composition distribution between grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. A uniform halogen distribution between grains is a desirable property.
In particular, a highly uniform emulsion having a variation coefficient of 20% or less is preferable. Another preferred form is an emulsion where there is a correlation between grain size and halogen composition. For example, there is a correlation in which larger size particles have a higher iodine content, while smaller particles have a lower iodine content. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

It is important to control the halogen composition near the surface of the grain. Increase the content of silver iodide near the surface,
Alternatively, increasing the silver chloride content changes the adsorbability of the dye and the developing rate, and can be selected according to the purpose.
When changing the halogen composition in the vicinity of the surface, it is possible to select either a structure that encloses the entire grain or a structure that adheres only to a part of the grain. For example, (100) plane and (1
This is the case where the halogen composition is changed only on one surface of the tetrahedral grain 11), or on one of the main plane and the side surface of the tabular grain.

The silver halide grains used in the present invention, even if they are normal crystals not containing twin planes, are edited by The Photographic Society of Japan, Fundamentals of The Photographic Industry, Silver Salt Photographs (Corona Publishing Co.), P.P. 163, for example, single twin containing one twin plane, parallel multiple twin containing two or more parallel twin planes, non-parallel containing two or more non-parallel twin planes. It can be selected from multiple twins and the like and used according to the purpose. An example of mixing particles having different shapes is disclosed in US Pat. No. 4,865,964, but this method can be selected as necessary.
In the case of normal crystal, a cube consisting of (100) plane, (11
An octahedron composed of 1) planes is disclosed in JP-B-55-42737 and JP-A-60-222842 (110).
A dodecahedral grain composed of planes can be used. In addition, the Journal of Imaging Scene
30: p. 247 (h11) plane particles typified by (211), (hh1) plane particles typified by (331), (21) as reported in 1986.
The (hk0) plane particles typified by the (0) plane and the (hk1) plane particles typified by the (321) plane may be selected and used according to the purpose although the preparation method requires some contrivance. A tetrahedral grain in which the (100) plane and the (111) plane coexist in one grain,
Depending on the purpose, particles having two or many surfaces such as particles having both (100) surface and (110) surface or particles having both (111) surface and (110) surface may be selected and used according to the purpose. You can

The silver halide emulsion used in the present invention is a treatment for rounding grains as disclosed in European Patent Nos. 96,727B1 and 64412B1 or West German Patent No. 2,306,447C2. No., JP-A-6
The surface may be modified as disclosed in 0-221320.

A structure having a flat particle surface is generally used.
It is sometimes preferable to intentionally form the unevenness.
JP-A-58-106532, JP-A-60-22132
US Pat.
The grain size of the emulsion used in the present invention in which the ruffle grain described in No. 643,966 is an example is the circle equivalent diameter of the projected area using an electron microscope, and the sphere equivalent of the grain volume calculated from the projected area and the grain thickness. It can be evaluated by the diameter or the equivalent diameter of a sphere of the volume by the Coulter counter method. It can be used by selecting from ultrafine particles having a sphere-equivalent diameter of 0.05 μm or less, and coarse particles having a diameter of more than 10 μm. It is preferable to use grains having a size of 0.1 μm or more and 3 μm or less as photosensitive silver halide grains.

The normal crystal emulsion used in the present invention may be a so-called polydisperse emulsion having a wide grain size distribution, or a monodisperse emulsion having a narrow size distribution, and can be selected and used according to the purpose. The coefficient of variation of the projected area circle equivalent diameter of a particle or the sphere equivalent diameter of a volume may be used as a scale representing the size distribution. Coefficient of variation is 25% when using monodisperse emulsion
Or less, more preferably 20% or less, further preferably 1% or less.
It is preferable to use an emulsion having a size distribution of 5% or less.

In some cases, the monodisperse emulsion is defined as a grain size distribution such that 80% or more of all grains fall within ± 30% of the average grain size in terms of grain number or weight. In order to satisfy the target gradation of the light-sensitive material, the emulsion layers having substantially the same color sensitivity have different grain sizes.
One or more kinds of monodisperse silver halide emulsions can be mixed in the same layer or multi-layered in different layers. Furthermore, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and polydisperse emulsions can be mixed or laminated and used.

The emulsion of the present invention and the photographic emulsion used in combination with it are described in "Physics and Chemistry of Photography" by Graphide, published by P. Montefel (P. Glafkides, Chemie e.
tPhisque Photographie,
Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duf).
fin, Photographic Emulsion
Chemistry (Focal Press, 19
66)), "Production and Coating of Photographic Emulsions" by Zelikmann et al.,
Published by Focal Press, Inc. (VL Zelikman e
t al. , Making and Coating
Photographic Emulsion (Foc
al Press, 1964)) and the like. That is, any of an acidic method, a neutral method, an ammonia method, etc. may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used.
According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

A method of adding pre-precipitated silver halide grains to a reaction vessel for emulsion preparation, US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. The method described in 1. is optionally preferred. These can be used as seed crystals,
It is also effective when supplied as silver halide for growth. In the latter case, it is preferable to add an emulsion having a small grain size, and the addition method can be selected from total addition at once, divided addition in a plurality of times or continuous addition. It is also effective in some cases to add particles having various halogen compositions in order to modify the surface.

A method for converting most or only a part of the halogen composition of silver halide grains by the halogen conversion method is described in US Pat. Nos. 3,477,852 and 4,1.
42,900, European Patents 273,429 and 27
No. 3,430, West German Laid-Open Patent No. 3,819,241, etc., and is an effective particle forming method. A solution of soluble halogen or silver halide grains can be added to convert it to a less soluble silver salt. It is possible to select from a method such as converting at once, dividing into plural times, converting, or converting continuously.

As a method of grain growth, in addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate, British Patent 1,469,480 and US Pat.
A particle forming method in which the concentration is changed or the flow rate is changed as described in No. 0,757 and No. 4,242,445 is a preferable method. By increasing the concentration or increasing the flow rate, the amount of silver halide supplied can be changed by a linear function, a quadratic function, or a more complicated function of the addition time. It is also preferable in some cases to reduce the amount of silver halide supplied, if necessary. Further, when adding a plurality of soluble silver salts having different solution compositions, or when adding a plurality of soluble halogen salts having different solution compositions, an addition method in which one is increased and the other is decreased is also an effective method. Is.

A mixer for reacting a solution of a soluble silver salt and a soluble halogen salt is described in US Pat. No. 2,996,287.
No. 3,342,605, No. 3,415,65
No. 0, No. 3,785,777, West German Published Patent No. 2,
It can be selected and used from the methods described in Nos. 556,885 and 2,555,364.

Gelatin is advantageously used as the protective colloid used in the preparation of the emulsion of the present invention and as the binder of the 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 and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives. A variety of synthetic hydrophilic polymer substances such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. 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-processed 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 of washing with water can be selected according to the purpose, but it is preferably selected in 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,
The method can be selected from the centrifugal separation method, coagulation sedimentation method and 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 the metal ion salt to be present before coating, depending on the purpose. When the grains are doped, it is preferably added during grain formation, after grain formation, or before chemical sensitization, when modifying the grain surface or when used as a chemical sensitizer. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Mg, Ca, Sr, Ba, Al, S
c, Y, La, Cr, Mn, Fe, Co, Ni, Cu,
Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. 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, CdB
_{r 2, CdCl 2, Cd (} NO 3) 2, Pb (NO 3)
₂ , Pb (CH ₃ COO) ₂ , K ₃ [Fe (C
N) ₆ ], (NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ Ir
Cl ₆ , (NH ₄ ) ₃ RhCl ₆ , K ₄ Ru (CN) ₆
And so on. Halo as a ligand for a coordination compound,
It can be selected from aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may use two types or a combination of three or more types.

The metal compound is preferably added after being dissolved in water or a suitable solvent such as methanol or acetone.
In order to stabilize the solution, a method of adding a hydrogen halide aqueous solution (eg, HCl, HBr) or an alkali halide (eg, KCl, NaCl, KBr, NaBr) can be used. If necessary, acid or alkali may be added. The metal compound may be added to the reaction vessel before grain formation or may be added during grain formation. Further, a water-soluble silver salt (eg AgNO ₃ ) or an aqueous alkali halide solution (eg NaCl, KBr,
Kl) and continuously added during the formation of silver halide grains. Furthermore, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods.

The method of adding a chalcogen compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful in some cases. In addition to S, Se and Te, cyanate, thiocyanate, selenocyanate, carbonate, phosphate and acetate may be present.

The silver halide grain of the present invention is subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization, noble metal sensitization and reduction sensitization at any step of the silver halide emulsion production process. Can be applied with. It is preferable to combine two or more sensitizing 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 in the 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 nuclei can be selected according to the purpose, but it is generally preferable that at least one chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, alone or in combination, by TH James, The Photographic Process, 4th. Edition, published by Macmillan, 1
977 (TH James, The Theor
y of the Photographic Pro
cess, 4th ed, Macmillan, 197
7) It can be carried out using active gelatin as described on pages 67-76, and Research Disclosure, Vol. 120, April 1974, 12008; Research Disclosure, Vol. 34, June 1975,
13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, and 4 , 266,018 and 3,904,41
5, and pAg 5-10, pH 5-8 and temperature 30 as described in British Patent 1,315,755.
It can be sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers at -80 ° C. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. 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 palladium compound means a palladium divalent salt or a tetravalent salt. A preferred palladium compound is
It is represented by R ₂ PdX ₆ or R ₂ 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, K ₂ PdCl ₄ , (NH ₄ )
₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂
PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with thiocyanate or selenocyanate.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
711, 4,266,018 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 sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine,
A compound known to suppress fog and increase sensitivity in the process of chemical sensitization is used. 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 aforementioned 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 preferable range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . 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, and more preferably 1
It is ^{x10 -5 to} 5 x 10 ^-7 mol.

Selenium sensitization is a preferred sensitizing method for the emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea), selenoketones are used. , Selenoamides and the like can be used. In some cases, selenium sensitization is preferably used in combination with sulfur sensitization, precious metal sensitization, or both.

During grain formation of the silver halide emulsion of the present invention,
It is preferable to carry out reduction sensitization 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 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, and two or more kinds of compounds can be used in combination. As reduction sensitizers, stannous chloride, thiourea dioxide, 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 per 1 mol of silver halide is suitable.

The reduction sensitizer is dissolved in water or a 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 a method of adding it at an appropriate time during grain growth is preferred. 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. In addition, it is also a preferable method to add the solution of the reduction sensitizer in several times with the grain growth or to continuously add the solution for a long time.

Acid for silver during the manufacturing process of the emulsion of the present invention.
It is preferable to use an agent. What is an oxidizing agent for silver?
Has the effect of acting on metallic silver and converting it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very small silver particles by-produced during the chemical sensitization process
Compounds that convert the above into silver ions are effective. here
The silver ions generated in are silver halide, silver sulfide, and selenium.
It may form a sparingly soluble silver salt such as silver halide, or silver nitrate.
A silver salt that is easily soluble in water may be formed. Oxidation for silver
The agent may be an inorganic substance or an organic substance. inorganic
Ozone, hydrogen peroxide and its addition as oxidizing agents
Thing (eg NaBO₂・ H₂O₂・ 3H ₂O, 2Na
CO₃・ 3H₂O₂, Na_FourP₂O₇・ 2H₂O₂Two
Na₂SO_Four・ H₂O₂・ 2H₂O), peroxy acid salt
(Eg K₂S₂O₈, K₂C₂O₆, K₂P
₂O₈), Peroxy complex compounds (eg, K₂[Ti
(O₂) C₂O_Four] ・ 3H₂O, 4K₂SO_Four・ Ti
(O₂) OH / SO_Four・ 2H₂O, Na₃[VO
(O₂) (C₂H_Four)₂] ・ 6H₂O, permanganate
(For example, KMnO_Four), Chromate (eg, K₂C
r₂O₇) Such as oxyacid salts, halogens such as iodine and bromine
Element, perhalogenate (eg potassium periodate) Plateau
Valency metal salts (eg, potassium hexacyanoferrate)
) And thiosulfonate.

Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide and 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 quinones of organic oxidizing agents.
It is a preferred embodiment that the reduction sensitization and the oxidizing agent for silver are used in combination. The method 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 selected and used in both the grain forming step and the chemical sensitization step.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, thiazoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, For example, triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) tetraazaindenes), pentaazaindenes, etc. can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,98.
Nos. 2,947 and 52-28660 can be used. One of the preferred compounds is the compound described in JP-A-63-212932.
Antifoggants and stabilizers are used before particle formation, during particle formation,
After grain formation, washing step, dispersion after washing, before chemical sensitization,
It can be added during the chemical sensitization, after the chemical sensitization, and at various times before coating according to the purpose. Addition during emulsion preparation to exert the original antifoggant and stabilizing effects, as well as controlling the crystal wall of grains, reducing grain size,
It can be used for various purposes such as decreasing the solubility of grains, controlling chemical sensitization, controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. 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, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, an indolenine nucleus, a benzoindolenine nucleus, an indole nucleus, a benzoxador nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus and the like can be applied. These nuclei may have a substituent on a carbon atom.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
A 5- or 6-membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, or a thiobarbituric acid nucleus can be applied.

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 and 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
7,803, Japanese Patent Publication Nos. 43-4936, 53-12
375, JP-A Nos. 52-110618 and 52-10.
No. 9925.

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

The timing of adding the sensitizing dye to the emulsion may be at any stage in the emulsion preparation which has heretofore been known to be useful. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but it is described in US Pat. No. 3,62.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-58-11.
It can be carried out prior to chemical sensitization as described in US Pat. No. 3,928, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. Furthermore, it is possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, ie to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It can be added after the sensation, and can be added at any time during the formation of silver halide grains including the method disclosed in US 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 about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm. Is.

The light-sensitive material produced by using the silver halide emulsion obtained in the present invention comprises a silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer on a support. It suffices that at least one layer is provided, and there is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer. As a typical example, a silver halide photographic light-sensitive material having at least one color-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. The photosensitive layer is a unit photosensitive layer having a color sensitivity to any of blue light, green light, and red light. In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layer is generally used. Is arranged in order from the support side, the red color-sensitive layer,
The green-sensitive layer and the blue-sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

For the intermediate layer, JP-A-61-43748 is used.
No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, a coupler as described in the specification, a DIR compound may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are a high sensitivity emulsion layer and a low sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of emulsion layers can be preferably used. Usually, it is preferable that the layers are arranged so that the sensitivities are gradually lowered toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also,
JP-A-57-112751, JP-A-62-200350
Nos. 62-206541 and 62-206543, a low-sensitivity emulsion layer may be provided on the side farther from the support and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
For example, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL) / high sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / R
H / RL order or BH / BL / GH / GL / RL /
It can be installed in the order of RH.

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Also, JP-A-56-25738 and 62-6393.
As described in the specification No. 6, it is also possible to provide the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Further, as described in JP-B-49-15495, the uppermost layer is a silver halide emulsion layer having the highest photosensitivity, the middle layer is a silver halide emulsion layer having a lower photosensitivity, and the lower layer is a lower photosensitivity layer than the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. It may be arranged in the order of layer / high-speed emulsion layer / low-speed emulsion layer.

In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.

In the case of four layers or more, the arrangement may be changed as described above.

As described above, various layer structures and arrangements can be selected according to the purpose of each light-sensitive material.

The above-mentioned various additives are used in the light-sensitive material of the present invention, 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 (1978).
December 18), Item 18716 (1 January 1979)
January) and Item 308119 (November 1989), and the relevant parts are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23 648 page right column 996 page 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, page 23 to page 648 right column to 996 right to 998 right intensity sensitizer Agent 649 right column 4 whitening agent page 24 647 right column 998 right 5 antifoggant, pages 24 to 25 page 649 right column 998 right to 1000 right and stabilizer 6 light absorber, page 25 to 26 page 649 right Column-1003 Left-1003 Right Filter dye, page 650 Left column UV absorber 7 Anti-stain agent Page 25 Right column 650 Left-right column 8 Dye image stabilizer Page 25 9 Hardener 26 pages 651 Left column 1004 Right- 1005 left 10 binder 26 pages same as above 1003 right to 1004 right 11 plasticizers and lubricants page 27 650 right column 1006 left to 1006 right 12 coating aid, pages 26 to 27 same as above 1005 left to 1006 left surfactant 13 static 27 Page Same as above 1006 Right to 1007 Left Inhibitor Also, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,987 Reacts with formaldehyde as described in Nos. 4,435,503, it is preferable to add a compound capable of immobilizing the photosensitive material.

Various color couplers can be used in the present invention. Specific examples thereof include Research Disclosure No. 17643, VII-CG, and the same No. 307105, VII-C to G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
Issue No. 4,326,024, No. 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107.
39, British Patent Nos. 1,425,020 and 1,4
76,760, U.S. Pat. Nos. 3,973,968, 4,314,023, 4,511,649,
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
1,432, 3,725,067, Research
Disclosure No. 24220 (June 1984)
Mon.), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238 and 60.
-35730, 55-118034, 60-1
Those described in U.S. Pat. No. 8,5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and International Publication W088 / 04795 are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
52,212, 4,146,396, and 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, 249,453A, US Patents 3,446,622 and 4,333,999.
No. 4,775,616, No. 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212 and 4,296,4
Those described in JP-A No. 199, JP-A-61-42658 and the like are preferable.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,08.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, European Patent 341,188A.
No. etc.

Examples of couplers in which the color forming dye has a suitable diffusibility include US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are available from Research Disclosure N.
o. 17643, Item VII-G, ibid. Of 307105
Section VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929.
No. 4,138,258, British Patent No. 1,14.
Those described in No. 6,368 are preferable. Further, a coupler described in US Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released upon coupling, and a reaction with a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
The DIR coupler that releases the development inhibitor is the above-mentioned RD coupler.
No. 17643, Item VII-F and No. 30710
5, patents described in paragraph VII-F, JP-A-57-151
944, 57-154234, 60-1842.
No. 48, No. 63-37346, No. 63-37350
U.S. Pat. Nos. 4,248,962 and 4,783.
Those described in No. 2,012 are preferable.

As a coupler capable of releasing a nucleating agent or a development accelerator in an image form during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59.
Those described in Nos. 157638 and 59-170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 and JP-A-1
Compounds releasing a fog agent, a development accelerator, a silver halide solvent and the like by an oxidation-reduction reaction with an oxidized product of a developing agent described in JP-A-45687 are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
Couplers described in U.S. Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
No. 618 and the like, multiequivalent couplers, JP-A-60-18.
5950, DI described in JP-A-62-24252, etc.
R redox compound-releasing coupler, DIR coupler-releasing coupler, DIR coupler-releasing redox compound or DIR redox-releasing redox compound. , RD. No.
11449, No. 24241, JP-A-61-201
No. 247, etc., bleach accelerator releasing couplers, US Pat. No. 4,555,477, etc., ligand releasing couplers, JP-A-63-75747, leuco dye releasing couplers, US Pat. , 774,181, and the like, which release a fluorescent dye.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, ibid.
18716, 651 left column to right column, and the same No. 307
Development processing can be carried out by a usual method described on page 880-881.

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.

The silver halide light-sensitive material of the present invention, when applied to a film unit with a lens described in JP-B-2-32615, JP-B-3-39784 and the like,
It is effective because the effect can be more easily expressed.

[0126]

The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. Example 1 (1) Preparation of Emulsion Preparation of Emulsion 1-A (Comparative Emulsion) Silver bromide tabular grains having a thickness of 0.1 μm and a circle-equivalent diameter of 0.7 μm were prepared as seed crystals. A seed crystal containing 6 g of Ag was dissolved in 1.0 liter of distilled water, and pAg was adjusted to 8.2, p
The H was adjusted to 5, the temperature was kept at 75 ° C, and the mixture was vigorously stirred. Subsequently, particles were formed by the following procedure.

(I) AgNO ₃ (141 g) aqueous solution and K
The Br aqueous solution was added while keeping the pAg at 8.4.

(Ii) The temperature was lowered to 55 ° C., and KI (4 g) aqueous solution was added at a constant flow rate.

(Iii) AgNO ₃ (63 g) aqueous solution and KB
The aqueous r solution was added while keeping the pAg at 8.9.

The mixture was cooled to 35 ° C., washed with water by a conventional flocculation method, 50 g of gelatin was added, pH 6.0, p
Prepared to Ag 8.2. Preparation of Emulsion 2-A (Emulsion of the present invention) Same as Emulsion 1-A except that 2 × 10 ⁻³ mol of the compound represented by the chemical formula (1) was present in the grain forming step (ii) of Emulsion 1-A. And particles were formed. Preparation of Emulsion 2-B (Emulsion of the present invention) Same as Emulsion 1-A except that 2 × 10 ⁻³ mol of the compound represented by the chemical formula (5) was present in the grain forming step (ii) of Emulsion 1-A. And particles were formed.

Emulsions 1-A, 2-A, and 2-B had a mean equivalent spherical diameter of 1.1 μm and contained tabular grains having an aspect ratio of 3.0 or more at 70% of the total projected area.

Emulsions 1-A, 2-A and 2-B were subjected to gold-sulfur-selenium sensitization as follows.

The emulsion was heated to 64 ° C. and the sensitizing dye E described below was added.
xS-1 is 2.4 × 10 ⁻⁴ mol / mol Ag, ExS-2
1.0 × 10 ⁻⁵ mol / mol Ag and ExS-3 3.5.
× 10 ^-4 mol / mol Ag, sodium thiosulfate 7.4 ×
10 ^-6 mol / mol Ag, chloroauric acid 1.9 × 10 ^-6 mol /
Molar Ag, potassium thiocyanate 1.9 × 10 ⁻³ mol /
Molar Ag, N, N-dimethylselenourea 1.5 × 10
^-6 mol / mol Ag was added for optimum chemical sensitization. (2) Preparation of coating sample and its evaluation The coating sample was prepared by coating the emulsion and the protective layer on the cellulose triacetate film support provided with the undercoat layer at the coating amounts shown in the following "Table-1". did.

Table-1 Emulsion coating conditions (1) Emulsion layer-Emulsion ... Various emulsions (silver 3.6 × 10 ^-2 mol / m ² )
² ) ・ Coupler shown in the following "Chemical Formula 10" (1.5 × 10 ^-3 mol / m ² )

[0135]

[Chemical 10] -Tricresyl phosphate (1.10 g / m < ² >)-Gelatin (2.30 g / m < ² >) (2) Protective layer-2,4-dichloro-6-hydroxy-s-triazine sodium salt (0.08 g /) m ² ) ・ Gelatine (1.80 g / m ² ) These samples were placed under the conditions of 40 ° C. and 70% relative humidity for 14
After leaving for a while, the film was exposed through a continuous wedge for 1/100 second, and color development shown in the following "Table-2" was performed.

The processed sample was measured for density with a green filter.

Table-2 Process Processing time Processing temperature Color development 2 minutes 00 seconds 40 ° C Bleach fixing 3 minutes 00 seconds 40 ° C Water washing (1) 20 seconds 35 ° C Water washing (2) 20 seconds 35 ° C Stability 20 seconds 35 ° C Drying 50 seconds 65 ° C. Next, the composition of the treatment liquid is described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 2.0 1-Hydroxyethylidene-3.0 1,1-Diphosphonic acid Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg Hydroxylamine sulfate 2.4 4- [N-ethyl-N-β-4.5 hydroxyethylamino] -2-methylaniline sulfate Add water 1.0 liter pH 10.05 (bleach-fixer) (Unit: g) Ethylenediaminetetraacetic acid Ferric acid 90.0 Ammonium dihydrate Ethylenediaminetetraacetic acid 5.0 Disodium salt Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution 260.0 ml (70%) Acetic acid (98%) 5.0 ml Bleach accelerator shown in "Chemical formula 11": 0.01 mol

[0138]

[Chemical 11] 1.0 liter pH 6.0 (water washing liquid) was added with water, and tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas).
And OH type anion exchange resin (the same Amberlite IR-
400) was passed through a mixed bed type column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then sodium isocyanurate dichloride 2 was added.
0 mg / liter and 1.5 g / liter of sodium sulphate sulfate were added.

The pH of this liquid is in the range of 6.5-7.5. (Stabilizing liquid) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-0.3 monononylphenyl ether (Average degree of polymerization: 10) Ethylenediaminetetraacetic acid 0.05 Disodium salt water was added to add 1. 0 liter pH 5.0-8.0 Sensitivity was expressed as the relative value of the logarithm of the reciprocal of the exposure amount expressed in lux · sec which gives a density of 0.2 on the fog.

Regarding the pressure characteristics, the pressure characteristics were tested by the sample method A. Then, exposure for sensitometry was given and color development shown in Table 2 was performed. Test method A After placing in an atmosphere with a relative humidity of 55% for 3 hours or more, a load of 4 g was applied with a 0.1 mmφ needle in the same atmosphere, and the emulsion surface was scratched at a speed of 1 cm / sec. .

The developed sample was measured with a measuring slit of 5 μm × 1 mm to measure the densities of the pressed portion and the unpressed portion. Pressure fog occurred in the unexposed area and pressure desensitization occurred in the highly exposed area. The results of sensitivity and pressure characteristics are shown in Table-3.

[0142]

[Table 1] From Table 3, it is clear that the emulsion according to the present invention has high sensitivity but little fog and is excellent in pressure characteristics. Example 2 The emulsions 1-A, 2-A and 2-B prepared in Example 1 were sensitized with gold-sulfur-selenium as follows.

The emulsion was heated to 64 ° C. and the sensitizing dye E described below was added.
xS-4 was 4.7 × 10 ⁻⁵ mol / mol Ag, ExS-5
1.1 × 10 ⁻⁴ mol / mol Ag and ExS-6 4.0
× 10 ^-4 mol / mol Ag, sodium thiosulfate 7.4 ×
10 ^-6 mol / mol Ag, potassium thiocyanate 1.9 ×
10 ^-3 mol / mol Ag, chloroauric acid 1.9 × 10 ^-6 mol /
Molar Ag, N, N-dimethylceriurea 2.3 × 10 ⁻⁶
Mol / mol Ag was added for optimum chemical sensitization.

On the undercoated cellulose triacetate film support, each layer having the composition shown below was coated in multiple layers to prepare samples 101 to 103 as multilayer color light-sensitive materials. (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 g / m ² , and for silver halide, the coating amount converted to 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) 1st layer (antihalation layer) Black colloidal silver 0.18 gelatin 1.40 ExM-1 0.18 ExF-1 2.0x10 ^-3 HBS-1 0.20 2nd layer (intermediate) Layer) Emulsion G Silver 0.065 2,5-di-t-pentadecylhydroquinone 0.18 ExC-2 0.020 UV-1 0.060 UV-2 0.080 UV-3 0.10 HBS-10 .10 HBS-2 0.020 gelatin 1.04 Third layer (low-sensitivity red-sensitive emulsion layer) Emulsion A Silver 0.25 Emulsion C Silver 0.25 ExS-1 4.5 × 10 ^-4 ExS-2 1. 5x10 ^-5 ExS-3 4.5x10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.005 ExC-7 0.0050 ExC-8 0. 020 Cpd-2 0.025 HBS- 0.10 Gelatin 0.87 Fourth Layer (medium-sensitivity red-sensitive emulsion layer) Emulsion D silver ^{0.80 ExS-1 3.0 × 10 -4} ExS-2 1.2 × 10 -5 ExS-3 4.0 × 10 ^-4 ExC-1 0.15 ExC-2 0.060 ExC-4 0.011 ExC-7 0.0010 ExC-8 0.0025 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75 Fifth layer (high-sensitivity red-sensitive emulsion layer) Emulsion E Silver 1.40 ExS-1 2.0 × 10 ⁻⁴ ExS-2 1.0 × 10 ⁻⁵ ExS-3 3.0 × 10 ⁻⁴ ExC-1 0.095 ExC-3 0.040 ExC-6 0.020 ExC-8 0.007 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.10 Gelatin 1.20 6th layer (intermediate layer) Cpd-1 0.10 HBS-1 0.50 gelatin 1.10 7th layer (low-sensitivity green-sensitive emulsion layer) Emulsion A Silver 0.2 Emulsion B Silver 0.2 ExS-4 4.0 × 10 ⁻⁵ ExS-5 1.8 × 10 ⁻⁴ ExS-6 6.5 × 10 ^-4 ExM-1 0.010 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) Emulsion-sensitive layer) Emulsion D Silver 0.80 ExS-4 2.0 × 10 ^-5 ExS-5 1.4 × 10 ^-4 ExS-6 5.4 × 10 ^-4 ExM-2 0.16 ExM-30 0.045 ExY-1 0.01 ExY-5 0.030 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 gelatin 0.90 9th layer (high-sensitivity green-sensitive emulsion layer) Emulsion 1-A, One of 2-A and 2-B Silver 1.25 ExS-4 4.7 × 10 ^-5 ExS-5 1.1 × 10 ^-4 ExS-6 4.0 × 1 ^{0 -4 ExC-1 0.010 ExM-} 1 0.015 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.20 The 10 layers (yellow filter layer) yellow colloidal silver 0.010 Cpd-1 0.16 HBS-1 0.60 gelatin 0.60 11th layer (low-sensitivity blue emulsion layer) emulsion C silver 0.25 emulsion D silver 0.40 ExS-7 8.0 × 10 ⁻⁴ ExY-1 0.030 ExY-2 0.55 ExY-3 0.25 ExY-4 0.020 ExC-7 0.01 HBS-1 0.35 Gelatin 1.30 12th layer (high-sensitivity blue-sensitive emulsion layer) Emulsion E Silver 1.38 ExS-7 3.0 × 10 ⁻⁴ ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0 .86 13th layer (1st protection Layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00 14th layer (second protective layer) H-1 0.40 B -1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.10 B-3 0.10 S-1 0.20 gelatin 1.20 Further, each layer is appropriately stored. Resistance, processability, pressure resistance, mildew resistance
W-1 to improve antibacterial properties, antistatic properties and coating properties
To W-3, B-4 to B-6, F-1 to F-
17 and iron salt, lead salt, gold salt, platinum salt, iridium salt,
Contains rhodium salt.

Table 4 summarizes the characteristics of the grains in Emulsions A to G.

[0146]

[Table 2] In Table 4, (1) Emulsions A to F were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) Emulsions A to F were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate according to the examples of JP-A-3-237450. Has been done. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope.

[0147]

[Chemical formula 12]

[0148]

[Chemical 13]

[0149]

[Chemical 14]

[0150]

[Chemical 15]

[0151]

[Chemical 16]

[0152]

[Chemical 17]

[0153]

[Chemical 18]

[0154]

[Chemical 19]

[0155]

[Chemical 20]

[0156]

[Chemical 21]

[0157]

[Chemical formula 22]

[0158]

[Chemical formula 23]

[0159]

[Chemical formula 24]

[0160]

[Chemical 25]

[0161]

[Chemical formula 26]

[0162]

[Chemical 27] The color negative sensitivity of the green-sensitive layer was estimated based on the relative exposure amount of 0.1 greater than the minimum density of magenta. Further, a pressure characteristic test was conducted according to Test Method A.

Compared with the comparative sample, the sample according to the present invention had a low fog despite having a high sensitivity, and both the pressure fog and the pressure desensitization were small, and the effect of the present invention was remarkable. Example 3 An emulsion according to the present invention was prepared in the same manner as in Example 2 except that the fifth layer, the ninth layer and the first layer were used.
Optimum spectral sensitization and chemical sensitization for 2 layers,
Used for each layer. This photographic light-sensitive material was applied to a film unit with a lens, that is, a light-sensitive material packaging unit provided with an exposure function, as described in JP-B-2-32615 and JP-B-3-39784. By using the light-sensitive material according to the present invention, better photographs were obtained indoors, and the effect of the present invention was remarkable.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
It is characterized in that tabular silver halide grains having an aspect ratio of 3.0 or more introduced with dislocations in the presence of a silver halide solvent are contained in an amount of 50% or more of the total projected area of silver halide grains in the emulsion layer. Silver halide photographic light-sensitive material. 2. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
Tabular silver halide grains having an aspect ratio of 3.0 or more in which dislocations are introduced in the presence of the following general formula (I) are contained in an amount of 50% or more of the total projected area of silver halide grains in the emulsion layer. And a silver halide photographic light-sensitive material. [Chemical 1] In the formula, m represents 0 or an integer of 1 to 12, and X ₁ and X
₂ represents a sulfur atom, a selenium atom, a tellurium atom or an oxygen atom.