JPH0778599B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material having improved graininess and suitable for sensitized development.

(Prior Art) There are various performances required for a silver halide photographic light-sensitive material, but it is important to achieve both high sensitivity and good image quality. Here, as a means for increasing the sensitivity, it is often practically practiced to improve the light absorption and quantum yield of the silver halide emulsion itself and to obtain a high sensitivity by means of prolonging the development time. However, for example, the extension of the developing time is often accompanied by an increase in fog, deterioration of graininess, and a change in gradation, and in order to develop sufficient performance other than the standard developing process which is optimized there, the photographic exposure It is necessary to introduce more advanced technology into the material itself.

As an emulsion technique for achieving both high sensitivity and good graininess, for example, US Pat. No. 3,979,213 (hereinafter referred to as Document A) discloses that internal desensitization at the time of color sensitization of an internal latent image type silver halide emulsion is It is disclosed that it is significantly smaller than the chemically sensitized silver halide emulsion of equal grain size, and as a result, the color sensitization sensitivity can be effectively improved by using a large amount of sensitizing dye.

Similarly, Journal of Photographic Science Vol. 13, p. 48 (1965), vol. 22, p. 174 (1974), p. 2
Volume 5, page 19 (1977), Volume 31, page 41 (1986), Photographic Science and Engineering,
Volume 19, p. 333 (1975), U.S. Patent Nos. 4,035,185 and 3,
No. 850,637, Berichte der Bunsen Geselsyaft Fuya, Fuiji Ikaritsushie Chemie, Vol. 67, p. 356 (1963) also states that high sensitivity can be obtained by emulsions forming latent images inside grains. Has been done.

(Problems to be Solved by the Invention) However, the internal latent image type emulsion used here has most of the radiation sensitive part (or latent image forming part) inside the grain, and the ratio of surface sensitivity to total sensitivity is It is less than 10%, or the radiation sensitive part is deeper than 0.01 μm from the surface. As described above, an emulsion which forms a latent image sufficiently inside the grain causes insufficient development even when developed with a developer of a practical black-and-white / color negative / color reversal light-sensitive material, which substantially impairs sensitivity. It will be. In addition, even if high sensitivity can be exhibited due to the extension of the developing time, the fog will be high,
Gradation change may be caused depending on the development time.

Further, U.S. Pat. No. 3,966,476 discloses emulsions in which the latent image is placed in cavities which open towards the grain surface and which can be developed with a surface developer. However, an emulsion capable of exhibiting a sensitivity equal to or higher than that of a surface latent image type emulsion of the same size by treatment with a surface developing solution cannot be said to be an internal latent image type emulsion. The excellent color sensitizing property of No. 1 cannot be fully utilized. As described above, what kind of latent image distribution from the surface to the inside is preferable for developing a practical developer in order to develop good sensitivity and image quality has not been sufficiently studied.

On the other hand, U.S. Pat.Nos. 2,996,382 and 3,178,282 disclose that both silver halide grains capable of forming a surface latent image upon exposure and silver halide grains having an internal fog nucleus are placed in an emulsion layer to improve speed and contrast. Elevated negative imageable photographic elements are described. In this photographic element, when development is performed after exposure, silver halide grains having a surface latent image release a reaction product depending on the exposure amount, which makes cracks in the silver halide grains having an internal fog nucleus to enable development. It is something that can be done. This element is noted as one that realizes a balance of surface and internal sensitivity that could not be achieved by a single emulsion by two kinds of emulsions, but one of them has a fog nucleus, so that the development time is prolonged. It has the drawback that the fog rises and the gradation changes significantly. In addition, JP-A-59-214852
And a method for improving suitability for sensitization by incorporating a silver halide emulsion having a fog nucleus inside a silver halide grain in a light-sensitive emulsion layer and / or an adjacent layer thereof. 56-1040 has the same drawbacks as above.

Therefore, there has been a demand for a photographic light-sensitive material which has high sensitivity and good graininess at the time of standard development processing and has a small change in gradation and fog at the time of sensitization processing.

Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material having excellent sensitivity and granularity ratio and excellent sensitizing and developing suitability.

(Means for Solving the Problems) The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the emulsion layer comprising silver halide grain surface iodide. It contains two or more kinds of silver halide emulsions having different silver contents of 1 mol% or more and 15 mol% or less, and the latent image distribution from the surface of each silver halide grain to the inner depth direction is at least 1 maximum. Has a value inside the particle, and the position where the maximum value exists is from the surface
A silver halide photographic light-sensitive material characterized by being chemically sensitized to have a depth of less than 0.01 μm.

Here, the latent image distribution is the depth of the latent image from the particle surface (x μm) on the horizontal axis and the number of latent images (y) on the vertical axis, where x is S: Silver halide emulsion average grain size (μm) Ag ₁ : Residual silver amount after performing the following treatment on an unexposed emulsion-coated sample Ag ₀ : Amount of coated silver before treatment, and y is 1 / It is the reciprocal of the exposure amount that gives a density of fog +0.2 when the following processing is performed after performing white exposure for 100 seconds. The processing conditions for obtaining the latent image distribution are as follows: N-methyl-p-aminophenol sulfate 2.5g L-sodium ascorbate 10g sodium metaborate 35g potassium bromide 1g Water (1) (pH 9.6) Add anhydrous sodium sulfite 0-10g / l to 2
It is treated at 5 ° C. for 5 minutes. Here, by changing the amount of anhydrous sodium sulfite to 0-10 g / l,
The depth from the surface of the latent image in the silver halide grains developed during processing changes, and the change in the number of latent images in the depth direction can be known.

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

When the maximum value of the latent image distribution obtained as described above exists at a deep position of 0.01 μm or more from the surface, the latent image distribution is developed with a developer practically used for black-and-white, color negative or color reversal light-sensitive materials. However, the development becomes insufficient and the sensitivity is substantially impaired.

According to the method of preparing an internal latent image type emulsion which has been reported so far, controlling the shell thickness results in changing the ratio of surface sensitivity to internal sensitivity.

However, conventional internal latent image type silver halide grains, which focus on only the difference between the sensitivity when surface development is performed and the sensitivity when internal development is performed, are not sufficient to achieve optimum sensitivity. is there.

That is, even if the ratio of the surface sensitivity and the internal sensitivity is the same (for example, the surface sensitivity is ½ of the internal sensitivity), it is practical when the maximum of the latent image distribution exists at a deep position of 0.01 μm or more. It has been found that processing can lead to underdevelopment and less than the potential optimum sensitivity of the grains.

The above-mentioned practical processing solution means a large amount of silver halide solvent intended to develop only the surface latent image and intentionally develop the developing solution excluding the silver halide solvent and the internal latent image. It is not a developer that contains it.

In the former developer, the sensitivity of the internal latent image type emulsion of the present invention cannot be optimally expressed, and in the latter case, the silver halide is excessively dissolved during processing, or graininess is generated by infectious development. make worse. Specifically, 100 mg / l or less potassium iodide or 100 mg / l as a silver halide solvent in a developing solution is used.
It is preferred to contain g / l or less of sodium sulfite or potassium sulfite. Besides, potassium thiocyanate or the like can be used as a silver halide solvent in the developing solution.

Japanese Patent Application No. 61-30602 discloses that a silver halide emulsion having a latent image distribution as described above exhibits high sensitivity and good graininess.
Although described in 9, this is a single color-sensitive layer,
Alternatively, when it is contained in one emulsion layer, the gradation tends to change with the development time. This is because when the developing time is short, the emulsion grains having a latent image formed near the surface thereof can be developed, and due to infectious development that induces the development of grains in the vicinity of the grains, the tone becomes high. On the other hand, when the development time is long, the emulsion grains having a latent image formed therein are also developed based on the development activity of the emulsion grains themselves, so that the soft tone depends on the size distribution of the emulsion grains. I can understand.

As a result of investigating a method of reducing the gradation change with the development time, the grain surface silver iodide content is 1 mol% to 15 mol%, more preferably 2 mol% to 8 mol%.
It has been clarified that the above object can be achieved by mixing two or more kinds of silver halide emulsion grains having a latent image distribution different from each other by mol% or less. Further, it is more preferable that not only the surface but also the average silver iodide content of each grain is separated by 1 mol or more, preferably 2 mol% or more and 8 mol% or less. A technique for mixing two or more kinds of silver halide emulsions having different halogen compositions in a normal surface latent image type emulsion is disclosed in, for example, JP-A-56-78831. It was unexpected to improve the sensitizing and developing suitability by mixing two or more kinds of emulsions having different halogen compositions.

Mixing two or more emulsions having different halogen compositions is useful for improving the gradation and sensitized development suitability of the internal latent image type emulsion where the maximum of latent image distribution is less than 0.01 μm. However, in the latent image distribution of the emulsion to be mixed, the number of latent images in the grain surface is not less than ⅕ of the maximum maximum value and less than 1 time, which enhances the developing activity of the emulsion layer and increases the sensitivity. It is preferable because it is improved.

Further, in the present invention, if the difference in silver iodide content becomes too large, the gradation peculiar to each emulsion is separated, and a constant gradation cannot be obtained for a wide exposure amount, which is not preferable.

Further, when the difference in silver iodide content is small, the effect of mixing two kinds of emulsions is not sufficiently exhibited, which is not preferable.

The emulsion of the present invention can be sensitized by a method well known in the art. The amount of the sensitizing dye should be the amount that gives the maximum negative blue sensitivity, but this amount is about the same as the amount that the maximum negative blue sensitivity is obtained in the surface latent image type emulsion, and is much larger than that amount. Addition of a large amount of dye is not preferable because it suppresses development of particles.

The emulsion of the present invention can also be used without being subjected to color sensitization. In this case, the effect on color sensitization described in Document A cannot be expected, but the effect on latent image storability is observed.

For the silver halide photographic emulsion used in the present invention, any of silver iodobromide, silver iodochlorobromide and silver chloroiodobromide may be used. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing from about 0.5 mol% to about 15 mol% and more preferably from 1.5 to 5 mol% silver iodide.

The maximum value of the silver iodide distribution in the grain may be one or plural. The silver iodide content at the maximum value is preferably at least twice the average silver iodide content of the entire grain, more preferably at least four times, and most preferably silver iodide itself. The larger the gradient of change in the silver iodide composition up to the maximum value, the more preferable, and in an extreme case, an epitaxial junction may be provided.

The crystal structure other than the site forming the maximum value of the silver iodide distribution may be uniform, may have a different halogen composition, or may have a layered structure. These emulsion grains, British Patent No. 1,027,146, U.S. Patent No. 3,505,068,
No. 4,444,877 and Japanese Patent Application No. 58-248469.

Surface silver iodide content of grains is determined by X-ray photoelectron spectroscopy (XPS)
The silver iodide content up to a depth of about several tens of angstroms can be determined by these methods. The average silver iodide content of each grain can be determined by performing the above measurement after annealing at 250 ° C. for 3 hours to make the silver iodide distribution in the grain uniform.

Further, the grain of the present invention itself may be bonded to silver halide having a different composition by epitaxial bonding, or may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide. These emulsion grains, U.S. Patent Nos. 4,094,684, 4,142,900, 4,459,353, British Patent 2,038,792, U.S. Patents 4,349,622, 4,395,
478, 4,433,501, 4,463,087, 3,656,962
No. 3,852,067, JP-A-59-162540 and the like.

The silver halide grains may be so-called Regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having irregular crystal shapes such as tabular and spherical grains. However, the regular particles are preferable in controlling the latent image distribution. Also, a mixture of various crystal forms may be used.

Tabular grains having an aspect ratio of 5 or more are also preferably used in the present invention.

The grain size of silver halide may be fine grains of about 0.1 micron or less, large grains having a projected area diameter of up to about 10 microns, a monodisperse emulsion having a narrow distribution, or an emulsion having a wide distribution. A monodisperse emulsion is preferred for improving graininess.

A typical monodisperse emulsion is an emulsion in which at least 95% by weight is within ± 40% of the average grain diameter.
The average particle diameter is 0.05-3 microns and is at least 95
Emulsions in which at least 95% by weight or (number of grains) of silver halide grains are within the range of average grain diameter ± 20% can be used in the present invention. Methods for producing such emulsions are described in U.S. Pat.Nos. 3,574,628 and 3,655,394 and British Patent No.
No. 1,413,748. In addition, JP-A-48-8600,
51-39027, 51-83097, 53-137133, 54-48
Monodisperse emulsions such as those described in No. 521, No. 54-99419, No. 58-37635, No. 58-49938 can also be preferably used in the present invention.

Two or more kinds of emulsions contained in the same layer constituting the present invention may have the same or different grain size. When the grain sizes are different, the one having a higher silver iodide content may be a large size or a small size, but the smaller size brings the developing activity of each emulsion grain closer and is smooth. It is preferable in constructing gradation.

The average grain size referred to in the present invention is the diameter of a spherical silver halide grain, or the diameter of a cubic image or a grain of a shape other than spherical when the projected image is converted into a circular image of the same area. When the average value and the individual particle size thereof are r _i and the number thereof is n _i , the average particle size is defined by the following formula.

When the emulsions to be mixed have different average grain sizes and a sensitizing dye is added to them, the amount should be changed according to the size of each emulsion grain, and the larger the grain size, the smaller the addition amount. Is preferred. Therefore, the sensitizing dye is preferably added before mixing the emulsion, for example, during grain formation, physical ripening, or chemical ripening.

The mixing ratio of the emulsion of the present invention can be appropriately changed depending on the surface silver iodide content or the purpose of use.

For example, when mixing two kinds of emulsions, the weight ratio is 3: 97-
It can be used in the range of 97: 3.

The method of preparing the internal latent image type emulsion of the present invention is described in US Pat.
979,213, 3,966,476, 3,206,313, 3,917,4
The methods described in JP-B-85, JP-B-43-29405, JP-B-45-13259 and the like can be used. In any method, an emulsion having a latent image distribution of the present invention can be obtained. ,
The chemical sensitization method, the amount of silver halide precipitated after chemical sensitization, and the precipitation conditions must be adjusted.

Specifically, in U.S. Pat.No. 3,979,213, an internal latent image type emulsion is prepared by re-precipitating silver halide by a control double jet method on emulsion grains whose surface is chemically sensitized. . If the amount of silver halide practiced here is precipitated on the grains, the ratio of surface sensitivity to total sensitivity will be less than one tenth. Therefore, in order to obtain the latent image distribution of the present invention, the amount of silver halide precipitated after chemical sensitization is controlled by the method of US
It must be less than what is implemented in 3,979,213.

Also in U.S. Pat. No. 3,966,476, a method of precipitating silver halide on emulsion grains after chemical sensitization by a control double jet method is carried out. However, when chemically sensitized silver halide is precipitated by the method as practiced in this patent, the photosensitive nuclei cannot be embedded inside the grain. Therefore, the emulsions embodied in the above patents are at least 0.02 log E more sensitive than surface-chemically sensitized emulsions by surface development. Therefore, in order to obtain the latent image distribution of the present invention, the amount of silver halide precipitated after chemical sensitization is higher than that carried out in U.S. Pat. It is necessary to control the solubility of the silver halide and the rate of adding the soluble silver salt and the soluble halogen salt) to less than 0.01 μm.

In order to accelerate grain growth during production of the tabular grains of the present invention,
A method of increasing the addition rate, the addition amount, and the addition concentration of the silver salt solution (for example, AgNO ₃ aqueous solution) and the halide solution (for example, KBr aqueous solution) to be added are preferably used.

For these methods see, for example, British Patent No. 1,335,925.
U.S. Pat.Nos. 3,672,900, 3,650,757, and 4,
Reference can be made to the descriptions of 242,445, JP-A-55-142329 and JP-A-55-15812.

The properties of silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor, or they may be added along with one or more salts according to conventional methods. US Patent 2,44
No. 8,060, No. 2,628,167, No. 3,737,313, No. 3,772,031
And Research Disclosure, 134, 197
June 1993, as described in 13452, copper, iridium,
The presence of compounds such as lead, bismuth, cadmium, zinc (chalcogen compounds such as sulfur, selenium and tellurium), gold and compounds of Group VII noble metals during the silver halide precipitation formation process contributes to the characteristics of silver halide. Can be controlled. Japanese Examined Japanese Patent Publication No. 58-1410, Moisar
Et al., Journal of Photographic Science, Vol. 25, 1977, pp. 19-27, silver halide emulsions can reduce and sensitize the inside of grains during the precipitation formation process.

Chemical sensitization is described by TH James, The Theory of Photographic Process, 4th Edition,
Published by Macmillan, 1977, (THJames, The Theory of
the Photographic Process, 4 th ed, Macmillan, 1977) 6
It can be carried out using activated gelatin as described on pages 7-76, and also Research Disclosure 12
Volume 0, April 1974, 12008; Research Disclosure, Volume 34, June 1975, 13452, U.S. Pat. No. 2,642,361.
No. 3, 3,297,446, 3,772,031, 3,857,711,
No. 3,901,714, No. 4,266,018, and No. 3,904,415
And British Patent No. 1,315,755, p.
It can be carried out using Ag, 5 to 10, pH 5 to 8 and temperature of 30 to 80 ° C., with sulfur, selenium, tillu, gold, platinum, palladium, iridium or a combination of these sensitizers. Chemical sensitization is optimally carried out in the presence of gold and thiocyanate compounds and also in U.S. Pat. Nos. 3,857,711 and 4,26.
It is carried out in the presence of a sulfur-containing compound described in 6,018 and 4,054,457 or a sulfur-containing compound such as hypo, thiourea compound, and rhodanine compound. Chemical sensitization can also be performed in the presence of a chemical sensitization aid. As the chemical sensitization aid used, compounds such as azaindene, azapyridazine, and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used.
Examples of chemical sensitization aid modifiers include U.S. Patent No. 2,131,038,
No. 3,411,914, No. 3,554,757, JP-A-58-126526 and the above-mentioned Daphine's "Photographic Emulsion Chemistry", pages 138-143. In addition to, or as an alternative to chemical sensitization, reduction sensitization can be performed using, for example, hydrogen as described in U.S. Pat.Nos. 3,891,446 and 3,984,249, and U.S. Pat.Nos. 2,518,698 and 2,743,182. Issue 2 and 2,
Using stannous chloride, thiourea dioxide, polyamines and such reducing agents as described in 743,183,
Alternatively, reduction sensitization can be achieved by treatment with pAg (eg less than 5) and / or high pH (eg greater than 8). Further, the color sensitization can be improved by the chemical sensitization method described in US Pat. Nos. 3,917,485 and 3,966,476.

Further, the sensitizing method using an oxidizing agent described in Japanese Patent Application Nos. 59-122981 and 59-122984 can also be applied.

When the surface of the silver halide emulsion grain of the present invention is chemically sensitized, the number of latent images formed is 1/5 or more and less than 1 time the maximum value of latent image distribution formed inside the grain of less than 0.01 μm. Is preferred.

In order to remove the soluble silver salt from the emulsion before and after physical ripening, it is accompanied by a Nudel washing, a flocculation precipitation method or an ultraleakage method.

The additives used in the chemical ripening and spectral sensitization of the emulsion used in the present invention are the above-mentioned Research Disclosure N.
o.17643 (Dec. 1978) and No. 18716 (Dec. 1978)
Month), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two Research Disclosures, and the locations described in the table below are shown.

The spectral sensitizing dye, the antifoggant and the stabilizer can be used by being present in any step of the photographic emulsion production process, or can be present in any stage after production until immediately before coating. Examples of the former include a silver halide grain forming step, a physical ripening step and a chemical ripening step.
That is, the spectral sensitizing dyes, antifoggants and stabilizers are used to limit the formation position of chemical sensitized nuclei or to use different halogens by utilizing other properties such as strong adsorption to the emulsion in addition to their original functions. It is also used for the purpose of stopping excessive halogen conversion at the time of obtaining a junction structure particle having a composition and maintaining a junction structure of different halogens. Regarding these, JP-A-55-26589, JP-A-58-111935, and JP-A-58-28738
No. 6, JP-A-62-7040, U.S. Patent Nos. 3,628,960 and 4,
The description in No. 225,666 can be referred to.

If some or all of the spectral sensitizing dyes, antifoggants and stabilizers to be added are added before the chemical sensitizer is added, and then the chemical sensitizer is added for chemical ripening, The position where the sensitized nuclei are formed on the silver halide grains is limited to the place where the sensitizing dye, antifoggant and stabilizer are not adsorbed, so latent image dispersion is prevented and photographic characteristics are improved. Therefore, it is particularly preferable. Especially for silver halide grains (11
1) When adding a sensitizing dye that selectively adsorbs to a surface, an antifoggant and a stabilizer, the chemical sensitizing nuclei are formed especially when the hexagonal tabular grains are used because they are formed only in the edge part. preferable.

In general, the additives are preferentially adsorbed on the crystal surfaces forming the major surface of the tabular grains, so that chemical sensitization nuclei occur on different crystal surfaces of the tabular grains.

It is also effective to carry out chemical sensitization in the presence of a silver halide solvent. As the type of silver halide solvent used, thiocyanate and the solvents described in Japanese Patent Application No. 61-299155 can be used. The concentration of solvent used is 10 ^-5 to 10 ^-1 mol / l
Is preferred.

In combination with either or both of the above techniques,
Alternatively, as a third technique independently of these, a silver salt such as silver thiocyanate, silver phosphate, silver carbonate or the like capable of producing precipitation on the grain surface immediately before or during the chemical sensitization. , And soluble silver salts such as silver acetate, silver trifluoroacetate and silver nitrate, and fine silver halide (ie silver bromide, which can be Ostwald ripened on the tabular grain surface).
Silver iodide and / or silver chloride) grains can be introduced. For example, a Lipman emulsion can be introduced in the process of chemical sensitization.

Further, the silver halide emulsion used in the present invention may be a system which is spectrally sensitized with an antenna dye.

Regarding spectral sensitization with an antenna dye, Japanese Patent Application No. 61-513
The descriptions of No. 96, No. 61-284271, No. 61-284272 can be referred to.

The ordinary silver halide photographic emulsion used in the present invention in addition to the above emulsions can be produced by a known method, for example, Research Disclosure, Volume 176, No. 17643 (1978 12
Mon., pp. 22-23, "I. Emulsion Preparation
and Types) ”and 187, No. 18716 (November 1979)
Mon), page 648.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides.Chemie e.
t Physique Photographique Paul Montel.1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press, Inc. (GF
Duffin Photographic Emulsion Chemistry (Focal Pres
s, 1966), "Production and Application of Photographic Emulsion" by Zelikmann et al.,
Published by Forcal Press (VL Zelikman et al, Making an
d Coating Photographic Emulsion, Focal Perss, 1964)
And the like.
That is, any of an acidic method, a neutral method, an ammonia method and the like 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.

Further, known silver halide solvents (for example, ammonia, rodan potassium or U.S. Pat. No. 3,271,157, JP-A-51-1236).
0, JP-A-53-82408, JP-A-53-144319, JP-A-54
Physical aging can be carried out in the presence of thioethers and thione compounds described in JP-A No. -100717 or JP-A No. 54-155828.

The silver halide emulsion composed of regular grains used in the present invention can be obtained by controlling pAg and pH during grain formation. For more information, see, for example, Photographic Scien
ce and Engineering) 6, 159-165 (1962); Journal of Photographic Science (Jour)
nal of Photographic Science) Volume 12, pp. 242-251 (196
4), U.S. Patent No. 3,655,394 and British Patent No. 1,413,74
It is described in No. 8.

Tabular grains are described by Gaft, Photographic Science and Engineering (Gutoff, Photographic
Science and Engineering) Volume 14, pp. 248-257 (1970
Year); U.S. Pat. Nos. 4,434,226, 4,414,310, and 4,43
It can be easily prepared by the method described in 3,048, 4,439,520 and British Patent 2,112,157.
The use of tabular grains has advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, which is described in detail in US Pat. No. 4,434,226 cited above.

The details of the structure and manufacturing method of the monodisperse hexagonal tabular grain according to the present invention are described in Japanese Patent Application No. 61-299155. Briefly, the emulsion is a silver halide comprising a dispersion medium and silver halide grains. A hexagon in which 70% or more of the total projected area of the silver halide grain has a ratio of the length of the side having the maximum length to the length of the side having the minimum length of 2 or less And hexagonal tabular silver halide grains having two parallel surfaces as outer surfaces, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains [the circle of the projected area Value obtained by dividing the variation (standard deviation) of the particle size represented by the converted diameter by the average particle size]
Has a monodispersity of 20% or less, an aspect ratio of 2.5 or more, and a particle size of 0.2 μm or more.

The silver halide grains can be prepared by undergoing the formation-Ostwald ripening and grain growth.
The details are as described in Japanese Patent Application No. 61-299155.

The properties of silver halide grains can be controlled by allowing various compounds to be present in the silver halide precipitation forming process. Such compounds may be initially present in the reactor, or they may be added along with one or more salts in a conventional manner. US Patent 2,44
No. 8,060, No. 2,628,167, No. 3,737,313, No. 3,772,031
And Research Disclosure, 134, 197
June 1993, as described in 13452, copper, iridium,
The characteristics of silver halides by the presence of compounds such as lead, bismuth, cadmium, zinc (chalcogen compounds such as sulfur, selenium and tellurium), gold and compounds of Group VII noble metals during the silver halide precipitation formation process. Can be controlled. Japanese Patent Publication 58-1410, Moise
r) etc., The Journal of Photographs
As described in Science, Vol. 25, pp. 19-27 (1977), monodisperse hexagonal tabular grains can undergo internal reduction sensitization in the precipitation formation process.

The monodisperse hexagonal tabular grains used in the present invention can be sheathed by a technique well known in the art to give a core-sheath emulsion. Regarding the method of forming this silver salt sheath, US Pat.
Reference can be made to the descriptions of 3,367,776, 3,206,313, 3,317,322, 3,917,485, and 4,164,878.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure (R) mentioned above.
D) No. 17643, VII-C to G.

Yellow couplers include, for example, U.S. Pat.
No. 1, No. 4,022,620, No. 4,326,024, No. 4,401,7
Those described in No. 52, Japanese Examined Patent Publication No. 58-10739, British Patent Nos. 1,425,020, 1,476,760 and the like are preferable.

As the magenta coupler, 5-pyrazoline-based and pyrazoloazole-based compounds are preferable, and US Pat. No. 4,310,61
9, No. 4,351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552.
Issue, Research Disclosure No. 24230 (6 June 1984)
JP-A-60-43659, U.S. Pat. Nos. 4,500,630, 4,540,654 and the like are particularly preferable.

Examples of cyan couplers include phenol type and naphthol type couplers, and U.S. Pat. No. 4,052,212;
4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162,
No. 2,895,826, No. 3,772,002, No. 3,758,308,
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,
329,729, European Patent 121,365A, U.S. Patent 3,446,6
No. 22, No. 4,333,999, No. 4,451,559, No. 4,427,
Those described in 767, European Patent No. 161,626A and the like are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are Research Disclosure No. 17643 VII-
Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No. 1,
Those described in Nos. 146 and 368 are preferable.

As the coupler in which the color forming dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

A coupler which releases a photographically useful residue upon coupling is also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the above-mentioned RD17643, VII-F patents, JP-A-57-151944 and 57-154234.
Nos. 60-184248 and US Pat. No. 4,248,962 are preferred.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,13.
Those described in 1,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP-A-60-18
DIR redox compound releasing coupler described in No. 5950,
Examples thereof include couplers that release a dye that restores color after separation described in EP 173,302A.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

The steps of the latex dispersion method, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

Suitable supports that can be used in the present invention include, for example, the aforementioned R
Page 28 of D.No.17643, and 648 from the right column of 647 of the same No.18716
It is described in the left column of the page.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3 -Methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

The pH of these color developers is preferably 9 to 13.

The present invention is particularly preferably applied to a color reversal photographic light-sensitive material.

When the reversal process is performed, black and white development is usually performed and then color development is performed. This black-and-white developer contains dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or N-methyl-p.
Known black-and-white developing agents such as aminophenols such as aminophenol can be used alone or in combination.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further processing with two continuous bleach-fix baths,
The fixing treatment before the bleach-fixing treatment or the bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.
The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment system such as countercurrent and forward flow, and various other conditions. Therefore, it can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in Jour.
nal of the Society of Motion Picture and televisio
n Engineers, Volume 64, p248-253 (May 1955 issue).

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents.

On the other hand, in the present invention, various known developing agents can be used for developing the black-and-white light-sensitive material. That is, polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol and pyrogallol; aminophenols such as p-aminophenol and N-methyl-p.
-Aminophenol, 2,4-diaminophenol, etc .; 3
-Pyrazolidones, for example 1-phenyl-3-pyrazolidones, 1-phenyl-4,4'-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5,5- Dimethyl-1-phenyl-3-pyrazolidone and the like; ascorbic acids and the like can be used alone or in combination. Also, JP-A-58-559
The developer described in No. 28 can also be used.

For detailed examples of developing agents, preservatives, buffers, and developing methods for black and white light-sensitive materials and their usage, see "Research Disclosure," No. 17643 (1978).
Published in December) XIX to XXI, etc.

〔Example〕

Hereinafter, the present invention will be specifically described with reference to examples. The invention is not limited to these examples only.

Example 1 Twenty-four kinds of silver iodobromide emulsions as shown in Table 1 were prepared.
The method for preparing the emulsion will be described below.

(Emulsion 1) 15% silver nitrate aqueous solution and KBr while keeping pH8 silver potential (SCE) +80 mV in gelatin aqueous solution (0.037%) kept at 72 ° C.
A KI-containing aqueous solution was added with a double jet over 50 minutes to prepare a monodisperse emulsion having a (100) crystal habit (edge length 0.61 μm). Next, to this core emulsion, sodium thiosulfate and sodium chloroaurate were added as chemical sensitizers, pH 6.7,
Chemical ripening was performed at +80 mV for 55 minutes. After that, a 15% silver nitrate aqueous solution and an aqueous solution containing KBr and KI are added again to pH 6.0+ over 5 minutes.
The shells were precipitated by addition at 10 mV to a final size of 0.31 μm average silver iodide content of 2 mol%. Emulsion 1 was obtained by removing the soluble silver salt from this by a conventional flocculation precipitation method.

(Emulsions 2 to 8) Emulsion 2 was prepared by adjusting the concentrations of KI and KBr in the alkali halide aqueous solution during grain formation and shell precipitation.
~ 8 were prepared. Here, the higher the silver iodide content, the higher the silver potential kept constant during precipitation, and the more the amount of chemical sensitizer.

(Emulsions 9 and 10) In Emulsions 1 and 3, emulsions 9 and 10 were prepared by decreasing the addition rate of silver nitrate at the time of core grain formation, setting the addition time to 53 minutes, and increasing the grain size. The amount of chemical sensitizer was 0.9 times each.

(Emulsions 11 and 12) Emulsions 11 and 12 were obtained in the same manner as the emulsions 1 and 3 except that the time for precipitating the shell was changed from 5 minutes to 1 minute. By increasing the degree of supersaturation when precipitating the shell, the surface latent image distribution can be reduced as shown in the bottom note of Table 1.

(Emulsions 13 and 14) Reduce the amount of silver nitrate added to form core particles by 30%,
On the contrary, Emulsions 13 and 14 were obtained by using the same amount of silver nitrate as that which was reduced for precipitation of Ciel.

(Emulsions 15 and 16) Add silver nitrate used for precipitation of shell and KBr, KI aqueous solution at the time of core formation, and add chemical sensitizer after removing soluble silver salt by flocculation precipitation. To prepare emulsions 15 and 16. The amount of sodium thiosulfate added at this time was 1.2 times that of emulsions 1 and 3 in order to obtain the optimum fog / sensitivity ratio.

(Emulsions 17 to 20) Emulsions 17 and 18 were prepared by using silver iodobromide having a silver iodide content of 3.4 and 4.8 mol% as the core grains and hexagonal monodisperse tabular grains having an aspect ratio of 5. Here, the silver potentials in the steps of grain formation, chemical ripening, and shell precipitation were set to -20 mV, +30 mV, and -20 mV, respectively. The amount of the chemical sensitizer was set to 1 / 3.5 with respect to the emulsions 4 and 8.

Further, emulsions 19 and 20 were obtained by performing chemical ripening after removing the soluble silver salt as in emulsions 15 and 16.

(Emulsions 21 to 24) Emulsions 21 to 24 were prepared by using octahedral monodisperse particles as core particles.

The performance of these emulsions 1-24 is shown in Table 1.

Samples 101 to 132 were prepared by coating an emulsion layer having the following composition on a subbed cellulose triacetate film support and sequentially adding silver iodobromide shown in Table 1 to the second green sensitive emulsion layer. Created (Table 2).

1st layer: Anti-halation layer Black colloidal silver 0.25g / m ² UV absorber U-1 0.1 g / m ² UV absorber U-2 0.1 g / m ² High boiling point organic solvent Oil-1 0.1 cc / m ² Gelatin 1.9 g / m ² second layer: intermediate layer -1 Cpd-D 10 mg / m 2 high-boiling organic solvent Oil-3 40 mg / m ² gelatin 0.4 g / m ² layer 3: intermediate layer-2 iodobromide Silver emulsion (average grain size 0.1 μm AgI content 0.5 mol%) 0.1
g / m ² gelatin 0.4 g / m ² 4th layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.6 μm, AgI content 5 mol% monodisperse cube) silver amount 0.4 g / m ² coupler C-1 0.2 g / m ² C-2 0.05 g / m ² high boiling point organic solvent Oil-1 0.1 cc / m ² gelatin 0.8 g / m ² Fifth layer: Second red-sensitive emulsion layer Spectral-sensitized silver iodobromide emulsions of sensitizing dyes S-1 and S-2 (monomer having an average grain size of 1.0 µm, 4 mol% monodisperse cubic emulsion) Silver amount 0.4 g / m ² coupler C-1 0.2 g / m ² C-3 0.2 g / m ² C-2 0.05 g / m ² high boiling organic solvent Oil-1 0.1 cc / m ² gelatin 0.8 g / m ² 6th Layer: Third red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (monodisperse spherical grains having an average grain size of 1.3 µ and AgI content of 2 mol%) Silver amount 0.4 g / m ² coupler C-3 0.7 g / m ² gelatin 1.1 g / m ² 7th layer: intermediate layer -3 dye D-1 0.02g / m ² Ze Chin 0.6 g / m ² Eighth Layer: interlayer -4 iodobromide emulsion (average grain size 0.06Myu AgI content 1 mol%) Compound Cpd-A 0.2 g / m ² Gelatin 1.0 g / m ² 9th Layer: First green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and S-4 (monodisperse cube having an average grain size of 0.4 μm and an AgI content of 5 mol%) Silver amount: 0.5 g / m ² coupler C-4 0.3 g / m ² compound Cpd-B 0.03 g / m ² gelatin 0.5 g / m ² 10th layer: second green emulsion layer Iodine odor containing sensitizing dyes S-3 and S-4 Silver halide emulsion (emulsion name is listed in Table 2) Silver amount 0.4 g / m ² coupler C-4 0.3 g / m ² compound Cpd-B 0.03 g / m ² gelatin 0.6 g / m ² 11th layer: 3rd green Emulsion-sensitive layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-4 (tabular emulsion with average grain size 1.3 μm, aspect ratio 5 and AgI content 2 mol%) Silver amount 0.5 g / m ² coupler C-4 0.8 g / m ² compound Cpd-B 0.08g / m ² gelatin 1.0 g / m ² 12th layer: intermediate layer 5 Dye ^D-2 0.05g / m 2 gelatin 0.6 g / m ² 13th Layer: Yellow filter layer Yellow colloidal silver 0.1 g / m ² Compound Cpd-A 0.01g / m ² gelatin 1.1 g / m ² 14th Layer: Gelatin 0.7 g / m ² Fifteenth layer: First blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (monodisperse cube having an average grain size of 0.65 μm and an AgI content of 3 mol%). Emulsion) Silver amount 0.6 g / m ² coupler C-5 0.6 g / m ² gelatin 0.8 g / m ² 16th layer: 2nd blue-sensitive emulsion layer Iodobromide containing sensitizing dyes S-5 and S-6 Silver emulsion (tabular emulsion with average grain size 1.0μ, aspect ratio 7, AgI content 2 mol%) Silver amount 0.4 g / m ² coupler C-5 0.3 g / m ² C-6 0.3 g / m ² gelatin 0.9 g / m ² 17th layer: 3rd blue emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-5 and S-6 (average grain size 1.8 µ, aspect ratio 7 tabular with AgI content 2 mol%) Emulsion) Silver amount 0.4 g / m ² coupler C-6 0.7 g / m ² gelatin 1.2 g / m ² 18th layer: 1st protective layer UV absorber U-1 0.04g / m ² 〃 U-3 0.03g / m ² 〃 U-4 0.03g / m ² 〃 U-5 0.05g / m ² 〃 U-6 0.05g / m ² compound Cpd-C 0.8 g / m ² dye D-3 0.05g / m ² gelatin 0.7 g / m ² 19 layer: second protective layer silver iodobromide emulsion (average grain size 1.0 μm, AgI content 0.5 mol%)
0.1 g / m ² Polymethylmethacrylate (average particle size 1.5μ) 0.1 g / m ² Methyl methacrylate / acrylic acid 4: 6 copolymer (average particle size 1.5μ) 0.1 g / m ² Cpd E 0.03g / m ² Fluorine-containing surfactant W-1 3 mg / m ² gelatin 0.8 g / m ^{2 In} each layer, a gelatin hardener H-1 and a surfactant were added in addition to the above composition.

Each of the above-mentioned samples was exposed to white wedges and subjected to the above-mentioned development processing. The results are shown in Table 2. Processing process time Temperature 1st development 6 minutes * 38 ° C 1st water wash 45 seconds 38〃 Reversal 45〃 38〃 Color development 6 minutes 38〃 Bleach 2〃 38〃 Bleach fixing 4〃 38〃 Second water wash (1 ) 1〃 38〃 2nd water washing (2) 1〃 38〃 stability 1〃 25〃 * In the evaluation of sensitized development suitability, 8 minutes processing was also performed.

The composition of each treatment liquid was as follows.

Second washing solution Tap water is passed through a mixed bed column filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). Water was added to control the concentration of calcium and magnesium ions to 3 mg / l or less, and subsequently 20 mg / l of sodium isocyanurate dichloride and 1.5 g / l of sodium sulfate were added.
The pH of this solution is in the range 6.5-7.5.

(Note 1) Relative sensitivity is expressed as the relative value of the logarithm of the exposure amount required to give a color density 1.0 higher than the minimum density.

(Note 2) The graininess is expressed by the RMS value at a density of 1.0.

The RMS value is described in “Theory of Photographic Process”, 4th Edition (1977), P.619, by T. J. Geems.

(Note 3) The gradation is shown using the value of G _0.5 .

G _0.5 is a characteristic value given by the following equation, where ΔD is the difference between the density of D _min +0.20 and the density of the exposure amount giving the density −0.5.

G _0.5 = ΔD / 0.5 In Table 2, Sample 109, which is an embodiment of the present invention, is Sample 1
It can be seen that, although the sensitivity and the graininess are the same as those of 02, the gradation change with respect to the change of the development time in which the emulsions having different silver iodide contents are mixed is small, which is preferable.

Using an emulsion having a latent image distribution like Emulsions 15 and 16 has low sensitivity and emulsions 13 and 14 have poor graininess,
It can be seen that the mixing of the emulsions only gives the intermediate sensitivity and graininess of the larger and smaller emulsions.

The effectiveness of the present invention was also obtained for tabular octahedral emulsions such as samples 127 and 131.

Although only data relating to the green-sensitive layer are shown in this example, similar results were obtained when used for the blue-sensitive layer and the green-sensitive layer.

(Example 2) Samples 201 and 202 were prepared by coating an emulsion layer having the following composition. For silver halides and colloidal silver, the amount of silver expressed in g / m ² units, for couplers, additives, and gelatin, the amount expressed in g / m ² units, and for sensitizing dyes, the same layer. It is shown in the number of moles per mole of silver halide.

1st layer (anti-halation layer) Black colloidal silver ...... 0.2 Gelatin …… 1.3 Colored coupler C-7 …… 0.16 UV absorber U-6 …… 0.1 Same as above U-7 …… 0.2 Dispersion oil Oil-1 …… 0.01 Same as above Oil-2 …… 0.01 Second layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ) …… 0.15 Gelatin …… 1.0 Colored coupler C-8 …… 0.02 Dispersion oil Oil-2 …… 0.1 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 2 mol% average grain size 0.3 µ) ...... Silver 0.4 gelatin ...... 0.6 Sensitizing dye S-7 ...... 1.0 × 10 ^-4 Sensitizing dye S-8: 3.0 × 10 ^-4 Sensitizing dye S-9: 1 × 10 ^-5 Coupler C-9: 0.06 Coupler C-10: 0.06 Coupler C-11: 0.04 Coupler C- 8 …… 0.03 Dispersed oil Oil-2 …… 0.03 Same as Oil-4 …… 0.012 4th layer (second red sensitive emulsion layer) Silver iodobromide emulsion (Sample 109 for sample 201, Fee emulsion tenth layer of sample 102 for 202) .... 0.7 Sensitizing dye S-7 ... 1 × 10 sensitization ^-4 dye S-8 ...... 3 × 10 ^-4 Sensitizing dye S-9 ... 1 × 10 ^-5 Coupler C-9 …… 0.24 Coupler C-10 …… 0.24 Coupler C-11 …… 0.04 Coupler C-8 …… 0.04 Dispersed oil Oil-2 …… 0.15 Same as above Oil-4 …… 0.02 No. Five layers (third red-sensitive emulsion layer) Silver iodobromide emulsion (5 mol% silver iodide, tabular grains having an average diameter of 1.7 μm and an aspect ratio of 6) ...... Silver 1.0 Gelatin ...... 1.0 Sensitizing dye S-7 …… 1 × 10 ^-4 Sensitizing dye S-8 …… 3 × 10 ^-4 Sensitizing dye S-9 …… 1 × 10 ^-5 Coupler C-12 …… 0.05 Coupler C-13 …… 0.1 Dispersion oil Oil -2 ... 0.01 Same as above Oil-1 ... 0.05 6th layer (intermediate layer) Gelatin ... 1.0 Compound Cpd-F ... 0.03 Dispersion oil Oil-2 ... 0.05 7th layer (1st green emulsion layer) Silver iodobromide emulsion (4 mol% silver iodide, Hitoshitsubu径 0.3μ) ......
Silver 0.30 Sensitizing dye S-10 ...... 5 × 10 ^-4 Sensitizing dye S-12 ・ ・ ・ 0.3 × 10 ^-4 Sensitizing dye S-11 ・ ・ ・ 2 × 10 ^-4 Gelatin ・ ・ ・ 1.0 Coupler C-15 ・ ・ ・... 0.2 Coupler C-11 ... 0.03 Coupler C-7 ... 0.03 Dispersion oil Oil-2 ... 0.5 Eighth layer (second green emulsion layer) Silver iodobromide emulsion (5 mol% silver iodide, average grain size) Diameter 0.5μ) ……
Silver 0.4 Sensitizing dye S-10 ...... 5 × 10 ^-4 Sensitizing dye S-12 ・ ・ ・ 2 × 10 ^-4 Sensitizing dye S-11 ・ ・ ・ 0.3 × 10 ^-4 Coupler C-15 ・ ・ ・ 0.25 Coupler C −7 …… 0.03 Coupler C−16 …… 0.015 Coupler C−11 …… 0.01 Dispersion oil Oil-2 …… 0.2 9th layer (3rd green emulsion layer) Silver iodobromide emulsion (5 mol% silver iodide) , Tabular grains having an average diameter of 1.7μ and an aspect ratio of 5) ...... Silver 0.85 gelatin ...... 1.0 Sensitizing dye S-13 …… 3.5 × 10 ^-4 Sensitizing dye S-14 …… 1.4 × 10 ^-4 Coupler C −17 …… 0.01 Coupler C-18 …… 0.03 Coupler C-19 …… 0.20 Coupler C-7 …… 0.02 Coupler C-21 …… 0.02 Dispersed oil Oil-2 …… 0.20 Same as above Oil-1 …… 0.05 No. 10 layers (yellow filter layer) Gelatin …… 1.2 Yellow colloidal silver …… Silver 0.08 Compound Cpd-G …… 0.1 Dispersion oil Oil-2 …… 0.3 Eleventh layer (first blue sensitive emulsion layer) Monodisperse silver iodobromide Agent ( 4 mol% silver iodide, average grain size 0.3μ)
…… Silver 0.4 Gelatin …… 1.0 Sensitizing dye S-15 …… 2 × 10 ^-4 Coupler C-20 …… 0.9 Coupler C-11 …… 0.07 Dispersion oil Oil-2 …… 0.2 12th layer (2nd blue) sensitive emulsion layer) silver iodobromide agent (silver iodide 5 mol%, mean diameter of 1.7 [mu] m, an aspect ratio of 6 tabular grain) ...... silver 0.5 gelatin .... 0.6 sensitizing dye S-15 ...... 1 × 10 the ^{- 4} Coupler C-20 ...... 0.25 Dispersion oil Oil-2 ...... 0.07 13th layer (1st protective layer) Gelatin ...... 0.8 UV absorber U-6 ...... 0.1 Same as above U-7 ...... 0.2 Dispersion oil Oil- 2 …… 0.01 Dispersed oil Oil-1 …… 0.01 14th layer (2nd protective layer) Fine silver bromide (average particle size 0.07μ) …… Silver 0.5 gelatin …… 0.45 Polymethylmethacrylate particles (diameter 1.5μ) ...... 0.2 Hardener H-1 ...... 0.4 Formaldehyde scavenger Cpd-H ...... 0.5 Formaldehyde scavenger Cpd-I ...... 0.5 Each The in addition to the above components, a surfactant is added as a coating aid.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

Oil-4 Bis (2-ethylhexyl) phthalate The photographic element was exposed to 25 CMS with a tungsten light source and a filter adjusted to a color temperature of 4800 ° K and then developed at 38 ° C according to the processing steps described below.

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The composition of the treatment solution used in each process is as follows. It was

Color developer Diethylenetriaminepentaacetic acid 1.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0g Sodium sulfite 4.0g Potassium carbonate 30.0g Potassium bromide 1.4g Potassium iodide 1.3mg Hydroxylamine sulfate 2.4g 4- (N- Ethyl-N-β-hydroxyethylamino)
2-Methylaniline sulfate 4.5g Water added 1.0l pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium 10.0g Ammonium bromide 150.0g Ammonium nitrate 10.0g Water added 1.0l pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 175.0 ml Sodium bisulfite 4.6 g Add water 1.0 l pH 6.6 Stabilizer formalin (40%) 2.0 ml Polyoxyethylene -P-monononylphenyl ether (average degree of polymerization: 10) 0.3 g Water 201 was added 1.0 l Sample 201 using the emulsion combination of the present invention is the result shown in Example 1 with respect to the comparative sample 202. It was confirmed that the sensitivity was high and the graininess was improved similarly to.

(Effect of the Invention) According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and good graininess can be obtained. Moreover, the above-mentioned light-sensitive material exhibits stable photographic performance even by the sensitized development processing, and has a great merit in practical use.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the emulsion layer has a silver iodide content of 1 mol% to 15 mol on the surface of silver halide grains. %, The latent image distribution from the surface of each silver halide grain toward the inner depth has a maximum value of at least 1 inside the grain. The location of the local maximum is from the surface
A silver halide photographic light-sensitive material, which is chemically sensitized to have a depth of less than 0.01 μm.