JPH06235995A - Photosensitive material - Google Patents

Abstract

PURPOSE:To provide a high-sensitivity silver halide photosensitive material attaining high sensitivity without increasing the coating quantity of a silver halide emulsion and without deteriorating granularity, having little deterioration of granularity due to natural radiation, having little performance change when preserved in the high-temperature, high-humidity environment, and excellent in the preservation property. CONSTITUTION:A color negative photosensitive material is provided at least one layer of a silver halide emulsion layer on a base. A color-sensitive silver halide emulsion spectrally sensitized by a sensitizing pigment and a color- nonsensitive silver halide emulsion practically having no sensitivity in the photosensitive wavelength area of the color-sensitive silver halide grains, having the solubility lower than that of pure silver bromide, containing silver iodide of 0.1mol.% or above, and having the grain size of 0.1mum or above are mixed to form the silver halide emulsion layer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having high sensitivity and excellent storage stability, and a method for producing the same.

[0002]

2. Description of the Related Art In the photographic industry, various studies have been made for high sensitivity and high image quality. However, in view of recent demands for diversification of shooting conditions and use conditions, sufficient performance is still required. Not achieved. As a method for achieving high sensitivity and high image quality, there is a method of increasing the sensitivity granularity ratio of a silver halide emulsion for photography. Various studies have been conducted to increase the sensitivity of emulsions. Regarding grain formation, for example, as disclosed in JP-A No. 2-943, a method of selecting grain formation conditions and devising a halogen structure of silver halide can be mentioned. Regarding the chemical sensitization method, in addition to the usual gold sulfur sensitization, a reduction sensitization method described in JP-A-2-222939, JP-A-3-168632, etc., is used. −
No. 185330 attempts to devise a selenium sensitization method. However, even if such a method is used, the enhancement of sensitivity is still insufficient, and it is necessary to further enhance the sensitivity of silver halide grains.

Further, a method of using a tabular silver halide emulsion can be mentioned as a method of increasing the sharpness. The tabular silver halide grain is a grain effective in improving the sharpness because it has less light scattering due to its shape. However, in order to increase the sensitivity of silver halide photographic light-sensitive materials, it is inevitable to coarsen silver halide grains, which deteriorates granularity, and high-sensitivity photographic light-sensitive materials We were only able to provide products with inferior image quality compared to photosensitive materials. Further, as a method for providing a substantially high-sensitivity light-sensitive material with a minimum deterioration of granularity, various properties such as desilvering property during bleach-fixing processing are required in order to increase the number of development starting points as much as possible. There is a method of increasing the coating amount of silver halide emulsion grains within the allowable range.
However, the silver halide photographic light-sensitive material prepared by this method has a drawback that if it is stored for a long period of 6 months or more, the granularity is deteriorated due to the influence of natural radioactivity. Further, there is a drawback that the sharpness deteriorates when the amount of coated silver is increased.

Further, the usage forms of silver halide photographic light-sensitive materials have become more and more diversified in recent years, and the cases in which they are stored or used in a severe environment of high temperature and high humidity are increasing. In such a harsh environment, the performance of conventional light-sensitive materials is largely changed, and improvements have been desired, but the objectives have not been sufficiently achieved. In a silver halide photographic light-sensitive material, a color-sensitive silver halide emulsion and a silver halide emulsion substantially non-color-sensitive in the light-sensitive wavelength range of the silver halide emulsion are formed in the same layer for the purpose of increasing the sensitivity. The coating technique is described in US Pat.
No. 6,122, JP-A-4-276737 and the like. The technique disclosed in these patents was that non-color-sensitive silver halide grains were coated with regular grains having high solubility in the same layer or were mixed immediately before coating. However, there is no example in which such a technique is applied to a color negative, and it is conventionally known about a change in photographic property when a non-color-sensitive silver halide emulsion having a low solubility is mixed in the presence of a sensitizing dye. Absent.

[0005]

The object of the present invention is to achieve high sensitivity without increasing the coating amount of a silver halide emulsion and without deteriorating the granularity, and further to improve the granularity due to natural radiation. It is an object of the present invention to provide a high-sensitivity silver halide photographic light-sensitive material which is less deteriorated, has little change in performance even when stored in an environment of high temperature and high humidity, and has excellent storage stability.

[0006]

The object of the present invention can be achieved by the method described below. (1) In at least one silver halide emulsion layer provided on a support, a color-sensitive silver halide emulsion spectrally sensitized with a sensitizing dye and having a solubility lower than that of pure silver bromide,
It contains 0.1 mol% or more of silver iodide, contains silver halide grains having a grain size of 0.1 μm or more, and has substantially sensitivity in a wavelength region spectrally sensitized by the sensitizing dye. A photographic light-sensitive material containing a non-color-sensitive emulsion which does not exist, (2) a photographic light-sensitive material according to item (1) which is a color negative photographic light-sensitive material, and (3) the non-color-sensitive halogenated material The photographic light-sensitive material according to item (1), wherein the silver halide grains of the silver emulsion are tabular grains having an average aspect ratio of 2 or more, and (4) the color-sensitive silver halide emulsion is red-sensitive. (1), (2) or (3), wherein the photosensitive material has
(5) The silver halide grains contained in the color-sensitive silver halide emulsion account for 50% of the projected area of all silver halide grains.
The above is the aspect ratio of 12 or more, and the ratio of the length of the side having the maximum length to the length of the side having the minimum length is 2 or more.
The following hexagons are occupied by tabular grains having a silver iodide content of 2 mol% or more, and the variation coefficient of grain size of all silver halide grains is 20% or less (1 ), (2), (3) or (4), the photographic light-sensitive material, (6) a color-sensitive silver halide emulsion spectrally sensitized with a sensitizing dye, and a solubility lower than that of pure silver bromide.
It contains 0.1 mol% or more of silver iodide and contains silver halide grains having a grain size of 0.1 μm or more, and has substantially sensitivity in a wavelength region spectrally sensitized by the sensitizing dye. (7) A method for producing a photographic light-sensitive material, which comprises coating at least one silver halide emulsion layer on a support after mixing a non-color-sensitive silver halide emulsion. The method for producing a photographic light-sensitive material according to item (6), which is a color negative photographic light-sensitive material.

The present invention will be described in detail below. The present invention is
A silver halide emulsion spectrally sensitized with a sensitizing dye (color-sensitive silver halide emulsion), and a silver halide emulsion having substantially no sensitivity in the light-sensitive wavelength range of the color-sensitive silver halide emulsion ( It can be achieved by a silver halide photographic light-sensitive material containing a silver halide emulsion layer in which a non-color-sensitive silver halide emulsion is mixed. It is said that the non-color-sensitive silver emulsion as referred to herein has substantially no sensitivity in the light-sensitive wavelength range of the color-sensitive silver halide emulsion, at least at log E of 1.
It means that the sensitivity is 0 or more and low. For example, when the color-sensitive silver halide emulsion is spectrally sensitized to have sensitivity to red, a silver halide emulsion having substantially no sensitivity is 10 times or more when exposed to red. It means that the same density as that of the color-sensitive silver halide emulsion is not provided unless the red exposure amount is given. In order to achieve such a difference in sensitivity, for example, the sensitizing dye used in the color-sensitive silver halide emulsion is not added to the non-color-sensitive silver halide emulsion, or only a small amount is added. , And the like.

However, this is not the case after the mixing. That is, when the silver halide emulsion that was not color-sensitive before mixing was exposed in the color-sensitive wavelength range of the color-sensitive silver halide emulsion after mixing, the sensitivity was less than 1.0 in logE. A difference is preferred. That is, when a light-sensitive material containing a silver halide emulsion layer of the present invention is exposed to an amount 10 times as much as an exposure amount required for exposure of a color-sensitive silver halide, it is not color-sensitive before mixing It means that the existing silver halide emulsion is also exposed to light, and by performing development processing, the non-color-sensitive silver halide emulsion also contributes to image formation. Such a phenomenon is achieved by moving a part of the sensitizing dye of the color-sensitive silver halide emulsion to the non-color-sensitive silver halide emulsion and adsorbing it. When the non-color-sensitive silver halide emulsion is used in such a manner, it is necessary to optimally chemically sensitize the non-color-sensitive silver halide emulsion. Although the mechanism for increasing the sensitivity of the present invention is being studied intensively, the present inventors consider as follows. The amount of the sensitizing dye added to the color-sensitive silver halide emulsion is selected so as to maximize the sensitivity in the color sensitized region. However, in the manufacturing method in which the sensitizing dye is added before the start of chemical sensitization, the addition amount of the sensitizing dye also affects the chemical sensitization process, and the optimum amount of the sensitizing dye and the chemical sensitizing dye for spectral sensitization are used. It has been found that the optimum amounts of sensitizing dyes in the sensitizing process are usually not consistent. The purpose of adding the sensitizing dye before the start of the chemical sensitization step is to ripen it for a long time to strengthen the adsorption of the sensitizing dye, but another important purpose is to control the chemical sensitization. There is. When the sensitizing dye is used for such a purpose, the optimum amount of the sensitizing dye in the chemical sensitization step becomes larger than the optimum amount of the sensitizing dye for the spectral sensitization, and thus the optimum sensitizing dye is used. However, the excess sensitizing dye is added in the end even if the intended amount is selected. An excessive amount of sensitizing dye exhibits unfavorable adverse effects such as lowering the intrinsic sensitivity of the silver halide emulsion and suppressing development. When a non-sensitizing emulsion containing no sensitizing dye or containing only a small amount of sensitizing dye is added to such a color-sensitive emulsion containing an excess of sensitizing dye, The excess sensitizing dye that has been transferred migrates to the non-color-sensitive emulsion, and the color-sensitive emulsion is released from the adverse effect described on the left, thus increasing the sensitivity. Further, as described above, if the non-color-sensitive emulsion is also subjected to appropriate chemical sensitization, the sensitizing dye transferred from the color-sensitive emulsion is adsorbed to the non-color-sensitive emulsion and The color-sensitive emulsion also becomes color-sensitive and can contribute to image formation.

The effect of the present invention is also exhibited in a manufacturing method in which the sensitizing dye is not added before the start of chemical sensitization, that is, the sensitizing dye is added during the chemical sensitization step or after the chemical sensitization. That is, the adsorption enhancement of the sensitizing dye can be performed by adding the sensitizing dye in an amount larger than the optimum amount of the sensitizing dye for photographic sensitivity. Then, by adding the non-color-sensitive emulsion of the present invention, the strongly adsorbed sensitizing dye is left as it is, but not adsorbed, or adsorbed weakly to reduce the intrinsic sensitivity, or to suppress the development progress. Dyes such as those mentioned above can be removed from the color-sensitive emulsion. Further, the present invention has found an unexpected effect that deterioration of granularity due to natural radiation can be reduced.
The reason for this is considered to be that the sensitivity in the visible region (spectral sensitized region) can be increased without increasing the sensitivity to natural radiation, although the investigation is currently under way. The present invention can be achieved by using a silver halide emulsion having a solubility lower than that of silver bromide for the non-color-sensitive silver halide emulsion. U.S. Pat. No. 4,656,122,
JP-A-4-276737 discloses that high sensitivity can be achieved by mixing a non-color-sensitive silver halide emulsion having a higher solubility than a color-sensitive silver halide emulsion. Although the technical content of increasing the sensitivity in these patents is unknown, it is possible to provide only a light-sensitive material which is poor in production stability due to the use of a silver halide emulsion having a high solubility and has a large sensitivity change due to storage.

In the present invention, the above-mentioned problems are solved by using a non-color-sensitive silver halide emulsion having a solubility (solubility in an aqueous solution) lower than that of pure silver bromide, and further higher sensitivity is achieved. That is, by using the non-color-sensitive emulsion of the present invention, for example, even when the dissolution time before coating is several hours, the non-color-sensitive emulsion is dissolved and the photographic sensitivity is not changed, and stable production can be performed. You can Further, a color-sensitive and a non-color-sensitive silver halide emulsion are mixed just before coating.
Contrary to the method of No. 276737, it was found that sensitization and production stability were improved by performing aging at high temperature after mixing as described later. The non-color-sensitive silver halide of the present invention is preferably silver iodobromide.
The silver iodide content may be any value as long as it is 0.1 mol% or more. The higher the silver iodide content is, the more preferable, but the upper limit is the solid solution limit. Silver iodide content 1 mol%
The above is preferable, more preferably 5 mol% or more and 15 mol% or less, and particularly preferably 5 mol% or more and 10 mol% or less. It is also preferable to have a higher silver iodide content than the color-sensitive silver halide emulsion. Increasing the silver iodide content of the non-color-sensitive silver halide lowers the solubility and prevents the deposition of silver halide on the color-sensitive silver halide grains due to the dissolution of the non-color-sensitive silver halide grains. To prevent. Strengthens the adsorption of the sensitizing dye that has migrated from the color-sensitive silver halide grains when mixed with the color-sensitive silver halide emulsion.
It is considered that such effects can be obtained, and as a result, a silver halide emulsion having high production stability and storage stability and high sensitivity can be provided.

The ratio of the non-color-sensitive silver halide emulsion of the present invention to be used depends on the grain size and shape of the color-sensitive silver halide emulsion,
It depends on the amount of sensitizing dye, silver iodide content, etc., and the grain size, shape, and silver iodide content of the non-color-sensitive silver halide emulsion. 0.5% by weight or more based on the amount of silver of the basic silver halide emulsion 20
Weight% or less is preferable, more preferably 1.0% by weight
The above is to be used at 10% by weight or less. Any non-color-sensitive silver halide emulsion of the present invention may be used as long as it has a grain size of 0.1 μm or more (equivalent sphere diameter). In the present invention, fine particles having a size of 0.1 μm or less are not only highly sensitive, but also have high solubility and production stability,
It is not preferable because it deteriorates storage stability. In the present invention, it is most preferable to use tabular silver halide grains having an aspect ratio of 2 or more as the non-color-sensitive silver halide grains.

The tabular silver halide grains will be described below. Here, the tabular grains are a general term for grains having one twin plane or two or more parallel twin planes. In this case, the twin plane refers to the (111) plane when ions at all lattice points on both sides of the (111) plane have a mirror image relationship. In the tabular silver halide grains, the aspect ratio means the ratio of the diameter to the thickness of the 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 refers to the diameter of a circle having an area equal to the projected area of a grain when the silver halide emulsion is observed with a microscope or an electron microscope.
Therefore, the aspect ratio of 2 or more means that the diameter of this circle is twice or more the thickness of the particles. Further, the average aspect ratio is obtained by randomly extracting 1000 silver halide grains of the emulsion and measuring the individual aspect ratios thereof. Form grains are selected and the arithmetic mean of the aspect ratios of the individual grains of the tabular grain group is calculated to obtain the average aspect ratio. The arithmetic mean of the diameters or thicknesses of the individual grains of the tabular grain group used for calculating the average aspect ratio is taken as the average grain diameter or average grain thickness, respectively. As an example of the method of measuring the aspect ratio,
This is a method of taking a transmission electron microscope photograph by the replica method and determining the equivalent circle diameter and thickness of each particle. In this case, the thickness is calculated from the length of the shadow of the replica. The average aspect ratio of the non-color-sensitive tabular silver halide grains is preferably 2.0 or more. It is more preferably 3.0 or more and 10.0 or less, and particularly preferably 4.0 or more and 8.0 or less. The average particle diameter is preferably 0.15 μm or more and 3.0 μm or less. The average particle thickness is preferably 0.5 μm or less, more preferably 0.2 μm or less.

The method for preparing the non-color-sensitive tabular silver halide grains of the present invention will be described. In order to form tabular core grains, it is preferable that a water-soluble silver salt and a halide salt aqueous solution are simultaneously mixed in a reaction vessel in which an aqueous gelatin solution is present, and further aged. The silver salt added is preferably 0.1 mol or more, more preferably 0.1 mol or more and 0.5 mol or less, and particularly preferably 0.15 mol or more and 0.3 mol or less, relative to 1 liter of the aqueous gelatin solution. Is. The following are preferable conditions for forming tabular nuclei of the non-color-sensitive tabular grain of the present invention. 1) The gelatin concentration is preferably 0.8 to 20% by weight, particularly preferably 1.0 to 15% by weight. Ordinary photographic gelatin is used as the gelatin seed.
High concentration (1.6 to 20 wt%) gelatin solution is difficult to use because it is set at a temperature below ℃, so low molecular weight gelatin (molecular weight 2000 to 100,000) and modified gelatin such as phthalated gelatin, live in the cold sea. Gelatin taken from fish skin is particularly preferable. 2) U.S. Pat. No. 3,785,777 (1974) and German Pa are used as an additive mixing device for improving stirring.
A device for adding and mixing the reaction solution in the liquid as described in tent Application (OLS) No. 2,556,888 is preferable. 3) The addition rate of silver salt and halide salt is 6 × 10 ⁻⁴ mol / min per 1 liter of gelatin aqueous solution.
It is preferably 2.9 × 10 ^-1 mol / min. 4) Ordinary photographic gelatin is used as the gelatin to be added to the silver salt or halide salt aqueous solution to be added, but the gelatin can be added within a range such that the aqueous solution does not set, and usually 0.05 to 1.6 wt% However, if a heating device is attached to these liquids, it is possible to add even higher concentrations (about 20 wt%).

Further, in this case, low molecular weight gelatin (molecular weight 2000 to 100,000), modified gelatin, etc. are difficult to set as gelatin seeds, and are particularly preferable. When gelatin is added to the aqueous silver salt or halide salt solution to be added, the gelatin species, concentration and temperature should be the same as those in the reaction vessel. Is maintained, and more uniform nucleation can be performed, so that it is more preferable. 5) The Br ^- concentration in the reaction vessel is pBr 1.0-
2.5 can be used. 6) As the irrelevant salt concentration in the reaction solution, 1.0 × 10 ^-2
~ 1 mol / liter, more preferably 1 x 10 ^-1 to 1 m
The ol / liter region can be used.

A process for growing the tabular nucleus grains thus obtained is necessary. The amount of silver used in this grain growth process is preferably 2.0 or less, more preferably 1.0 or more and 2.0 or less, and particularly preferably 1 or less in terms of molar ratio with respect to silver used for nucleation. It is 0.5 or more and 2.0 or less. In the grain growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated. The size of the emulsion grains can be adjusted by controlling the temperature, selecting the kind and amount of the solvent, and controlling the addition rate of silver salt and halide used during grain formation. Further, a method of supplying a part or all of silver added in the grain growth process as fine grains of silver halide as described in JP-A-62-99751 can also be used. The non-color-sensitive tabular silver halide emulsion of the present invention can be prepared by referring to known methods for preparing tabular silver halide emulsions other than the above-mentioned methods. Examples of tabular silver halide emulsions include reports of Cugnac and Chateau, and "Photographic Emulsion Chemistry" (Focal) by Duffin.
Press, New York, 1966) pp. 66-72, and APH Trivelli, WF Smith, "Phot. Journal" 80 (1940) 285.
As described in Japanese Patent Application Laid-Open No. 58-113927,
The methods described in JP-A-58-113928 and JP-A-58-127921 can be referred to. In addition to these, for example, Cleeve's Theory and Practice of Photography (Cl
eve, Photography Theory and Practice (1930),
131 pages; Gatov, Photographic Science and Engineering (Gutoff, Photographic S
cience and Engineering), Volume 14, 248-257
P. (1970); U.S. Pat. No. 4,434,226,
4,414,310, 4,433,048, 4,439,520 and British Patent No. 2,112,15.
The method described in No. 7 can be referred to.

The silver halide grains used in the non-color-sensitive tabular silver halide emulsion are preferably subjected to chemical sensitization represented by sulfur sensitization and gold sensitization. The location of chemical sensitization varies depending on the composition, structure, and shape of emulsion grains and the intended use of the emulsion. In some cases, the chemically sensitized nuclei are embedded in the grain, at a shallow position from the grain surface, or in some cases the chemically sensitized nuclei are formed on the surface. The effect of the present invention is effective in any case, but particularly preferable is the case where a chemical sensitizing nucleus is formed near the surface. That is, the surface latent image type emulsion is more effective than the internal latent image type emulsion. Chemical sensitization is by James (TH James),
The Photographic Process, 4th Edition, published by Macmillan, 1977, (TH James, The Theory of t
he Photographic Process, 4 th ed, Macmillan, 1977
) 67-76 and using active gelatin, and Research Disclosure 120, April 1974, 12008; Research Disclosure, 34, June 1975, 1
3452, U.S. Pat. Nos. 2,642,361 and 3,2.
97,446, 3,772,031, 3,85
7,711, 3,901,714, 4,26
PA as described in 6,018 and 3,904,415, and British Patent 1,315,755.
It can be carried out using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers at g5-10, pH 5-8 and temperature 30-80 ° C.

The non-color-sensitive silver halide grains of the present invention may have any grain size, but as described above, the non-color-sensitive silver halide grains of 0.1 μm or more are used. The present invention is achieved by the following. Preferably 0.
It is 15 μm or more and 3.0 μm or less, more preferably 0.15 μm or more and 1.5 μm or less, and particularly preferably 0.15 μm or more and 1.0 μm or less. The non-color-sensitive silver halide emulsion of the present invention may be added to the color-sensitive silver halide emulsion at any time during the production process before coating, but the color-sensitive silver halide emulsion may be added with a sensitizing dye. The effect of the present invention cannot be exhibited unless a non-color-sensitive silver halide emulsion is added after the addition of. That is, it means that the effect of the present invention is not exhibited by the production method in which the sensitizing dye is mixed with the non-sensitizing emulsion before the sensitizing dye is added to the color-sensitive emulsion, and then the sensitizing dye is added. . Further, the color-sensitive silver halide emulsion of the present invention is preferably subjected to chemical sensitization after addition of a sensitizing dye. The specific method will be described later. When the non-color-sensitive silver halide emulsion of the present invention is added to the color-sensitive silver halide emulsion, the color-sensitive emulsion is preferably ripened at a high temperature of 50 ° C. or higher. Further, it is more preferable to perform aging for at least 10 minutes after the addition. By mixing at a high temperature and sufficiently ripening, the photographic sensitivity can be increased and the production stability can be improved. Japanese Patent Laid-Open No. Hei 4
The production method in which mixing and aging are not carried out immediately before coating as in No. 276737 is not preferable because not only the effects of the present invention are not exhibited but also the photographic performance after production is large.

The color-sensitive silver halide emulsion used in the present invention may be any emulsion, but is characterized in that it is spectrally sensitized with a sensitizing dye. The wavelength for spectral sensitization may be in any range, but is usually 400 to 500 nm for blue color sensitivity, 500 to 600 nm for green color sensitivity, and 600 to
Spectral sensitization is performed so as to have a red color sensitivity of 700 nm. It is generally known that a sensitizing dye has a larger adverse effect (such as intrinsic desensitization) on a silver halide emulsion as the wavelength range of spectral sensitization becomes longer. In terms of cyanine dyes, trimethine cyanine dyes have greater intrinsic desensitization than monomethine cyanine dyes, and thiacarbocyanine dyes have greater intrinsic desensitization than oxacarbocyanine dyes. In the present invention,
By adding a non-color-sensitive silver halide emulsion, the effect is manifested by removing the excess and sensitizing dye contained in the color-sensitive silver halide. The larger the value is, the larger the effect is, and it is preferable to use in a silver halide emulsion layer having a green color sensitivity rather than a blue color sensitivity and a red color sensitivity rather than a green color sensitivity.

The following is a color-sensitive silver halide emulsion which can be used in the silver halide light-sensitive material of the present invention and which is mixed with the non-color-sensitive silver halide emulsion of the present invention and a halogen used in other photosensitive layers. Explain the silver halide emulsion. Hereinafter, the silver halide emulsion or the silver halide grain of the present invention will be referred to as the silver halide emulsion or the grain thereof. The silver halide grains used in the present invention are silver bromide, silver chloride, silver iodide, silver chlorobromide, 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. When rapid development / desilvering (bleaching, fixing and bleach-fixing) steps are desired, silver halide grains having a high silver chloride content are desirable. Further, when the development is appropriately suppressed, it is preferable to contain silver iodide. In the color negative photographic light-sensitive material of the present invention, preferably 1 to 3
It is a silver halide containing 0 mol% of silver iodide, more preferably 5 to 20 mol%, particularly preferably 8 to 15 mol%. It is preferable that the silver iodobromide grains contain silver chloride in order to reduce lattice strain. The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in its grains. Typical examples thereof are JP-B-43-13162 and JP-A-61-21554.
No. 0, JP-A-60-222845, JP-A-60-14
It is a core-shell type or double structure type grain having a halogen composition in which the inside and the surface layer of the grain are different as disclosed in Japanese Patent No. 3331 and JP-A No. 61-75337. Further, it is not a simple double structure, but is disclosed in JP-A-60-2228.
It is possible to form a triple structure as disclosed in No. 44, or a multilayer structure of more than that, or to thin the silver halide having different composition on the surface of the core-shell double structure grain. . In order to give a structure to the inside of the particle, not only the wrapping structure as described above but also a so-called junction structure can be formed. Examples of these are JP-A-59-133540 and JP-A-58-10.
8526, European Patent 199,290A2, JP-B-58-24772, JP-A-59-16254 and the like. The crystal to be bonded can have a composition different from that of the crystal serving as the host and can be generated by bonding to the edge, corner, or surface of the host crystal. Such a junction crystal can be formed even if the host crystal has a uniform halogen composition or has a core-shell type structure.

In the case of a junction structure, it is naturally possible to combine silver halides with each other, but a silver salt compound not having a rock salt structure such as silver rhodanide and silver carbonate may be combined with silver halide to form a junction structure. In addition, a non-silver salt compound such as lead oxide may be used as long as a joint structure is possible. In the case of silver iodobromide grains having these structures, it is a preferred embodiment that the core portion has a higher silver iodobromide content than the shell portion. On the contrary, in some cases, grains having a low silver iodide content in the core part and a high shell part are preferable. Similarly, with respect to the grains having a junction structure, the grains having a high silver iodide content in the host crystal and having a relatively low silver iodide content in the junction crystal may be used, or vice versa. Further, the boundary portion having different halogen compositions of the particles having these structures may be a clear boundary or an unclear boundary. In addition, a positive embodiment in which the composition is positively and continuously changed is also a preferred embodiment. In the case of silver halide grains in which two or more silver halides exist as a mixed crystal or have 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. Increasing the silver iodide content in the vicinity of the surface or 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 attaches only to a part of the grain. For example, the halogen composition may be changed only on one surface of the tetrahedral grain composed of the (100) plane and the (111) plane, 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 that do not contain twin planes, are edited by The Photographic Society of Japan, Fundamentals of the Photographic Industry, Silver Salt Photography (Corona Publishing Co.), P.P. 163, eg, 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 and used from multiple twins and the like 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 case of normal crystal (10
A cube consisting of (0) faces, an octahedron consisting of (111) faces,
JP-B-55-42737, JP-A-60-222842
It is possible to use dodecahedron grains having a (110) plane disclosed in Japanese Patent No. In addition, the Journal of Imaging Sc
ience, Vol. 30, p. 247, (hl1) plane particles typified by (211) as reported in 1986,
(Hh1) plane particles typified by (331), (210)
The (hk0) plane particles typified by the 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 devise. (100) plane and (1
11) Tetrahedral grains in which the faces coexist in one grain, (10
Particles in which (0) plane and (110) plane coexist, or (11
Particles in which two planes or a large number of planes coexist, such as particles in which 1) planes and (110) planes coexist can be selected and used according to the purpose.

A value obtained by dividing a circle-equivalent diameter of a projected area by a grain thickness is called an aspect ratio, which defines the shape of tabular grains. Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. The tabular grains are described in Cleve, Photography Theory and Practice (19
30), p. 131; Gatov, Photographic Science and Engineering (Gutoff, Photog
raphic Science and Engineering), Volume 14, 248
~ 257 (1970); U.S. Pat. No. 4,434,2.
No. 26, No. 4,414, 310, No. 4,433, 04
No. 8, 4,439,520 and British Patent No. 2,11.
It can be prepared by the method described in No. 2,157. When tabular grains are used, the covering power increases,
The sensitizing dye has advantages such as an increase in color sensitization efficiency, which is described in detail in the above-cited US Pat. No. 4,434,226. The average aspect ratio of 80% or more of the total projected area of the grains is preferably 1 or more and less than 100. It is more preferably 2 or more and less than 20, and particularly preferably 3 or more and less than 10. The shape of tabular grains can be selected from triangles, hexagons, circles, and the like. A regular hexagon with approximately six sides of equal length, as described in U.S. Pat. No. 4,797,354, is a preferred form.

The diameter of the circle equivalent to the projected area is often used as the grain size of tabular grains.
The average diameter as described in No. 8,106 is 0.6
Particles of micron or smaller are preferable for improving image quality. An emulsion having a narrow grain size distribution as described in U.S. Pat. No. 4,775,617 is also preferable. It is preferable to increase the sharpness by limiting the grain thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. Further, grains described in JP-A-63-163451, in which the grain thickness and the interplanar distance between twin planes are defined, are also preferable.
In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select particles containing no dislocation lines, particles containing several dislocations or particles containing many dislocations according to the purpose. It is also possible to select a dislocation or a curved dislocation introduced linearly with respect to a specific direction of the crystal orientation of the particles, or to introduce the dislocations throughout the particles or only in a specific part of the particles, for example, The dislocation can be introduced only in the fringe portion of the grain. The introduction of dislocation lines is preferable not only in the case of tabular grains but also in the case of regular grains or amorphous grains typified by potato grains. In this case as well, it is a preferable form to limit the particles to specific portions such as vertices and edges.

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. , JP Sho 60
The surface may be modified as disclosed in No. 22130. A structure with a flat particle surface is common,
It is sometimes preferable to intentionally form the unevenness.
JP-A-58-106532, JP-A-60-22132
Part of the crystals described in US Pat. No. 0, for example, a method of drilling holes in the centers of vertices or planes, or US Pat.
Raffle particles described in 643,966 are examples. The grain size of the emulsion used in the present invention can be evaluated by the equivalent circle diameter of the projected area using an electron microscope, the equivalent spherical diameter of the particle volume calculated from the projected area and the grain thickness, or the equivalent spherical diameter of the volume determined by the Coulter counter method. It can be used by selecting from ultrafine particles having a sphere-equivalent diameter of 0.05 micron or less, and coarse particles having a sphere-equivalent diameter of more than 10 microns. Preferably, grains having a size of 0.1 micron or more and 3 microns or less are used as the photosensitive silver halide grains. The 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. As a scale representing the size distribution, the variation coefficient of the projected area circle diameter of particles or the sphere equivalent diameter of volume may be used. When using a monodisperse emulsion, the coefficient of variation is 25%
Or less, more preferably 20% or less, still more preferably 1
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. Further, two or more kinds of polydisperse silver halide emulsions or a combination of monodisperse emulsions and monodisperse emulsions can be mixed or laminated and used. The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by P.Glafki.
des, Chimie et Physique Photographique, Paul Monte
l, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Ch
emistry (Focal Press, 1966)), "Manufacturing and coating of photographic emulsions" by Zelikmann et al., published by Focal Press (VL Ze)
likman et al., Making and Coating Photographic Emu
lsion, Focal Press, 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.

The method of adding silver halide grains which have been preliminarily formed into a reaction vessel for preparing an emulsion is described in US Pat. Nos. 4,334,012, 4,301,241 and 4,150,994. Is more preferable. These can be used as seed crystals, and are effectively 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 may be selected from total addition at once, addition in plural 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 of converting most or a very small part of the halogen composition of silver halide grains by a halogen conversion method is described in US Pat. Nos. 3,477,852, 4,142,900, European Patents 273,429 and 273. , 430, West German Published Patent No. 3,819,241, etc.,
This is an effective particle formation method. A solution of soluble halogen or silver halide grains can be added to convert it to a more sparingly soluble silver salt. It is possible to select from a method such as conversion at once, conversion by dividing into plural times, or continuous conversion.

In addition to the method of adding soluble silver salt and halogen salt at a constant concentration and a constant flow rate for grain growth, British Patent No. 1,
469,480, U.S. Pat. No. 3,650,757,
The particle forming method in which the concentration is changed or the flow rate is changed as described in U.S. Pat. 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. Furthermore, 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 US Pat. Nos. 2,996,287, 3,342,605, 3,415,650 and 3,785,777. , West German Published Patents 2,556,885, 2,555,364
It can be used by selecting from the methods described in No. Silver halide solvents are useful for the purpose of promoting ripening. For example, it is known to have excess halogen ions present in the reactor to accelerate aging. Other ripening agents can also be used. The total amount of these ripening agents can be compounded in the dispersion medium in the reactor before adding silver and halide salts, and the halide salts, silver salts or peptizers can be added in the reactor as well. Can also be introduced. As another variation, the ripening agent can be introduced independently at the halide salt and silver salt addition stages.

Ammonia, thiocyanate (such as rhodan potassium and rhodan ammonium), organic thioether compound (for example, US Pat. Nos. 3,574,628 and 3,0).
No. 21,215, No. 3,057,724, No. 3,03
8,805, 4,276,374, 4,29
7,439, 3,704,130, 4,78
2,013, compounds described in JP-A-57-104926 and the like. ), A thione compound (for example, JP-A-53-82).
408, 55-77737, U.S. Pat. No. 4,22.
Growth of tetra-substituted thioureas described in 1,863, etc., compounds described in JP-A-53-144319), and silver halide grains described in JP-A-57-202531. Examples thereof include mercapto compounds, amine compounds (for example, JP-A No. 54-100717, etc.), etc. that can accelerate the reaction.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various kinds of synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. You can In addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan. No. 16.
The enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may 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 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 semitransparent membrane,
It can be selected and used from a centrifugal separation method, a coagulation sedimentation method, and an ion exchange method. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added at the time of grain formation, when the grains are modified, or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. 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, Pd, Bi
Etc. can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydrates, 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 (CN) ₆ ],
(NH ₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl ₆ ,
(NH ₄ ) ₃ RhCl ₆ , K ₄ Ru (CN) _{6 and the} like. The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, or may use two or more types in combination.

The metal compound is preferably added after being dissolved in water or a suitable solvent such as methanol or acetone.
Aqueous hydrogen halide solution (eg HC to stabilize the solution)
l, HBr, etc. or alkali halide (eg KC)
1, NaCl, KBr, NaBr, etc.) can be used. If necessary, acids and alkalis may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. It is also possible to add it to a water-soluble silver salt (eg AgNO ₃ ) or an aqueous alkali halide solution (eg NaCl, KBr, KI) and continuously add it during the formation of silver halide grains. Further, 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 chalcogenide compound as described in U.S. Pat. No. 3,772,031 during emulsion preparation may be useful. 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. You can It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized. A type in which chemically sensitized nuclei are embedded inside the grain, a type in which it is embedded at a shallow position from the grain surface,
Alternatively, there is a type that makes a chemically sensitized nucleus on the surface. In the emulsion of the present invention, the location of the chemically sensitized nucleus can be selected according to the purpose, but it is generally preferable that at least one type of chemically sensitized nucleus is formed near the surface.

One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogenide sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, 4th Edition, Published by Macmillan, 1
977 (TH James, The Theory of the Photogr
aphic Process, 4 th ed, Macmillan, 1977) 67-7
It can be carried out using activated gelatin as described on page 6, and also Research Disclosure 120.
Vol., Apr. 1974, 12008; Research Disclosure, Vol. 34, Jun. 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446.
No. 3,772,031, No. 3,857,711
Nos. 3,901,714, 4,266,018 and 3,904,415, and British Patent Nos. 1,3.
PAg5-10, p as described in No. 15,755.
Sulfur, selenium, at H5-8 and temperature 30-80 ° C
It can be tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers. 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 divalent or tetravalent palladium salt. Preferred palladium compounds are 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. 3,853.
7,711, 4,226,018 and 4,05
The sulfur-containing compounds described in 4,457 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 compounds known to suppress fog and increase sensitivity in the process of chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat. Nos. 2,131,038, 3,
411,914, 3,554,757, JP-A-5
No. 8-126526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, pp. 138-143. The emulsion of the present invention is preferably combined with gold sensitization. The preferred amount of gold sensitizer is 1 × 10 ⁻⁴ to 1 × per mol of silver halide.
It is 10 ^-7 mol, and more preferably 1 × 10 ^{-5 to} 5 mol.
× 10 ⁻⁷ mol. The preferable range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferable range of the thiocyan compound or the selenocyan compound is 5 × 10 5.
^{It is} from ^-2 to 1 x 10 ^-6 . The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is silver halide 1
It is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol per mol, and more preferably 1 × 10 ⁻⁵ to 5 × 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, etc.), selenoketone And selenium compounds such as selenoamides can be used. In some cases, selenium sensitization is preferably used in combination with sulfur sensitization, precious metal sensitization, or both. The silver halide emulsion of the present invention is preferably subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization. Here, the reduction sensitization is a method of adding a reduction sensitizer to a silver halide emulsion, a method of growing in a low pAg atmosphere of pAg 1 to 7, which is called silver ripening, or a method of ripening, a pH of 8 to 8 called high pH ripening. The method of growing or aging in 11 high pH atmosphere 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, or 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 is suitable per mol of silver halide. 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 it is preferable to add it at an appropriate time during grain growth. Further, the reduction sensitizer may be added in advance to the water solubility of the water-soluble silver salt or the water-soluble alkali halide, and the silver halide grains may be precipitated using these aqueous solutions. Further, it is also a preferable method to add the solution of the reduction sensitizer in several times as the grains grow, or to continuously add the solution for a long time.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. What is an oxidizing agent for silver?
It refers to a compound that acts on metallic silver to convert it into silver ions. Especially, the extremely fine silver particles produced as a by-product in the process of forming the silver halide grains and the chemical sensitization process,
Compounds that can be converted to silver ions are effective. The silver ions generated here may form a poorly soluble silver salt such as silver halide, silver sulfide and silver selenide, or may form a readily soluble silver salt such as silver nitrate. Good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Inorganic oxidants include ozone, hydrogen peroxide and its adducts (eg NaBO ₂ · H ₂ O ₂ · 3H ₂ O, 2NaC).
_{O 3 · 3H 2 O 2,} Na 4 P 2 O 7 · 2H 2 O 2, 2N
a ₂ SO ₄ .H ₂ O ₂ .2H ₂ O), peroxy acid salts (eg K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O)
₈ ), a peroxy complex compound (for example, K ₂ [Ti (O
₂ ) C ₂ O ₄ ] ・ 3H ₂ O, 4K ₂ SO ₄・ Ti (O
₂ ) OH ・ SO ₄・ 2H ₂ O, Na ₃ [VO (O ₂ )
_{(C 2 H 4) 2 ·} 6H 2 O ], permanganate (e.g., KMnO _4), chromates (e.g., K ₂ Cr ₂ O
₇ ) and other oxyacid salts, iodine and bromine and other halogen elements,
Perhalogenates (eg potassium periodate), salts of high valent metals (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). The preferred oxidant of the present invention is ozone,
Hydrogen peroxide and its adducts, halogen elements, inorganic oxidants for thiosulfonates, and organic oxidants for quinones. It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. The method can be selected from a method of using an oxidant and then reduction sensitization, the reverse method thereof, or a method of coexisting both of them. These methods can be selectively used in 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 fogging during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, thiazoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as tria Theindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,
3a, 7) Tetraazaindenes), pentaazaindenes and many other compounds known as antifoggants or stabilizers can be added. For example, US Pat. Nos. 3,954,474 and 3,982,947.
And those described in JP-B No. 52-28660 can be used. Japanese Patent Application No. Sho 62-
There are compounds described in 47225. Antifoggants and stabilizers can be used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to expressing the original antifoggant and stabilizing effects by adding during emulsion preparation, it controls the crystal habit of grains, reduces the grain size, reduces the solubility of grains, controls chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention has been spectrally sensitized with methine dyes and the like. 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 Nucleus of fused aromatic hydrocarbon ring, namely, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benz Imidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms. In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanin nucleus, A 5-6 membered heterocyclic nucleus, such as 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 2,977,2.
No. 29, No. 3,397,060, No. 3,522,05
No. 2, No. 3,527, 641, No. 3, 617, 293
No. 3,628,964, 3,666,480
Issue 3, Issue 3,672,898, Issue 3,679,428
No. 3,703,377, No. 3,769,301
Nos. 3,814,609 and 3,837,862
No. 4,026,707, British Patent No. 1,344.
No. 281, No. 1,507,803, Japanese Patent Publication No. 43-49
No. 36, No. 53-12375, JP-A No. 52-1106.
18 and 52-109925.

Along with the sensitizing dye, a dye that does not have a spectral sensitizing effect by itself or a substance that does not substantially absorb visible light and may be contained in an emulsion exhibiting supersensitization. The sensitizing dye may be added to the emulsion 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 as described in US Pat. Nos. 3,628,969 and 4,225,666, a chemical sensitizer is used. Spectral sensitization can be carried out simultaneously with chemical sensitization by adding at the same time, or prior to chemical sensitization as described in JP-A-58-113928, and silver halide grain precipitate formation. It is also possible to start the spectral sensitization by adding before completion of the above. Furthermore, US Pat. No. 4,225
It is also possible to add these said compounds separately, as taught in US Pat. No. 666, ie to add some of these compounds prior to chemical sensitization and the rest after chemical sensitization. And U.S. Pat. No. 4,183,756.
It can be at any time during the formation of silver halide grains including the method disclosed in No. However, it is preferable to add a sensitizing dye to the light-sensitive silver halide emulsion used in the emulsion layer of the present invention immediately before the chemical sensitization step. The addition amount is 4 × 10 ⁻⁶ to 8 × 10 ⁻³ per mol of silver halide.
Although it can be used in a molar amount, it is about 5 × 10 ^{−5 in} the case of a more preferable silver halide grain size of 0.2 to 1.2 μm.
˜2 × 10 ⁻³ mol is more effective.

The above-mentioned various additives are used in the light-sensitive material of the present technology, but various additives other than the above can be used depending on the purpose. These additives are
For more details, Research Disclosure Item 17
643 (December 1978), Item 18716 (1)
997 November) and Item 308119 (1989)
(December, 2012), and the relevant parts are summarized in the table of succession.

───────────────────────────────── Additive type RD17643 RD18716 RD308119 ───────── ───────────────────────── 1 Chemical sensitizer page 23 648 page right column page 996 2 Sensitivity enhancer Same as above 3 Spectral sensitizer, 23 ~ Page 24 page 648 right column ~ 996 right ~ 998 right supersensitizer page 649 right column 4 whitening agent page 24 998 right 5 antifoggant, page 24 ~ 25 page 649 right column 998 right ~ 1000 right and stable Agent 6 Light absorber, pages 25 to 26, page 649, right column to 1003 left to 1003 right Filter dye, page 650, left column UV absorber 7 stain inhibitor page 25, right column, page 650, left column to right column, 1002 right 8 Dye image stabilization Agent 25 pages 1002 right 9 Hardener 26 pages 651 left column 1004 right to 1005 left 10 Binder page 26 same as above 1003 right to 1004 right 11 plasticizers, lubricants page 27 650 right column 1006 left to 1006 right 12 coating aid Agents, pages 26-27 Same as above 1005 Left to 1006 Left Surfactant 13 Tatic 27 pages Same as above 1006 Right to 1007 Left Anti-agent 14 Matting agent 1008 Left to 1009 Left

The silver halide emulsions that can be generally used in the present invention have been described above. The color-sensitive silver halide emulsions used in the present invention are the monodisperse high aspect ratio tabular emulsions described below. Is also a preferred embodiment. 50% or more of the projected area of all silver halide grains is
A hexagon having an aspect ratio of 12 or more and 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 having a silver iodide content of 2 mol% or more. It is preferable to use, as a tabular grain, a silver halide emulsion characterized in that the variation coefficient of grain size of all silver halide grains is 20% or less, as the color-sensitive silver halide emulsion of the present invention. This emulsion is called a monodisperse high aspect ratio tabular emulsion. The monodisperse high aspect ratio tabular emulsion will be described below. The aspect ratio of the monodisperse high aspect ratio tabular emulsion of the present invention is 12 or more, preferably 15 or more, more preferably 18 or more. It is highly preferable that the higher the aspect ratio, the higher the sharpness and the larger the sensitization width when mixed with the non-color-sensitive silver halide emulsion of the present invention.

The coefficient of variation in grain size of the monodisperse high aspect ratio tabular emulsion of the present invention is 20% or less, preferably smaller, more preferably 15% or less. The monodisperse high aspect ratio tabular grain of the present invention has a hexagonal shape. The hexagonal shape means that the shape of the main plane of the tabular grain has an adjacent side ratio (maximum side length / minimum side length) of 2 or less. The adjacent side ratio is preferably 1.6 or less, and more preferably the adjacent side ratio is 1.2 or less. Especially in high aspect ratio grains, triangular tabular grains increase in tabular grains.
Triangular tabular grains appear when Ostwald ripening proceeds too much. Therefore, it is necessary to shorten the aging time as much as possible. For that purpose, it is necessary to devise to increase the ratio of tabular grains by nucleation. The variation coefficient of the grain size of the monodisperse high aspect ratio tabular grain of the present invention is 20% or less, preferably 17% or less, and 15% or less.
The following is more preferable. The monodisperse high aspect ratio tabular emulsion of the present invention is silver iodobromide or silver iodochlorobromide and has an average silver iodide content of 2% or more, preferably 3% or more, more preferably 4% or more. Further, silver chloride is preferably 10 mol% or less, more preferably 3 mol% or less, and particularly preferably not contained. The balance of silver iodide and silver chloride is silver bromide. The monodisperse high aspect ratio tabular grain may have at least two or more layered structures having substantially different halogen compositions or a uniform composition within the grains, but preferably has two or more layered structures. . The silver iodide content of the high silver iodide portion preferably has a portion of 6% or more, more preferably 8% or more. The iodine ion content in the high silver iodide portion in the grain can be measured by an analytical electron microscope using a transmission electron microscope. When an electron beam used in a transmission electron microscope enters a silver halide grain, the incident electron causes inelastic scattering in the sample to generate a characteristic X-ray. This characteristic X-ray is a value peculiar to the element and gives information on the composition of the element in the sample. When the silver iodide content increases, the intrinsic sensitivity increases with blue exposure. Also, when spectrally sensitized,
It is known that the adsorption power of the cyanine dye is increased and the coverage of the sensitizing dye is increased. In the developing process, it is known that the graininess is improved because I ⁻ released during development has a development inhibiting ability.

The monodisperse high aspect ratio tabular grains of the present invention are formed by the steps of nucleation, Ostwald ripening and growth. Any of these steps is important in suppressing the spread of the particle size distribution, but it is impossible to narrow the spread of the size distribution generated in the previous step in the subsequent step,
Care must be taken that the size distribution does not broaden during the initial nucleation process. An important point in the nucleation process is the relationship between the temperature of the reaction solution and the nucleation time during which silver ions and bromide ions are added to the reaction solution by the double jet method to cause precipitation. In JP-A-63-92942 by Saito, it is described that the temperature of the reaction solution during nucleation is preferably in the range of 20 to 45 ° C. in order to improve monodispersity. In addition, JP-A-2-
222940, the preferred temperature during nucleation is 60 ° C.
It is stated that: The time required for nucleation
It can be shown that the high aspect ratio tabular grains having high monodispersity can be formed at any temperature which is practically easy to be used, by defining by using the function of temperature. When an aqueous solution of silver nitrate and an aqueous solution of potassium bromide are added to the reaction solution, precipitation of silver halide occurs immediately. The number of fine silver halide grains produced increased during the addition of silver ions and bromide ions, but did not increase in proportion to the time, and the increase gradually slowed down to a constant value without any increase. Becomes the value of. The silver halide grains produced by precipitation start to grow immediately after formation. Nuclei that occur sooner grow more easily, and nuclei that occur later do not. If the size of the nuclei varies during the growth during each formation, the subsequent Ostwald ripening further amplifies the size variation. The broadening of the size distribution of nuclei that occurs during nucleation is determined by the nucleation time and the temperature of the reaction solution. The spread of the size distribution starts at 60 seconds when nucleated at 30 ° C. When nucleation is performed at 60 ° C., polydispersion occurs in 30 seconds, and when nucleation is performed at 75 ° C., polydispersion occurs in 15 seconds. The time until the spread of the size distribution begins depends on the temperature at the time of nucleation, and this is because it reflects the time until the minute silver halide grains are dissolved.

As a method of forming nuclei, there are known a so-called single jet method in which only an aqueous solution of silver nitrate is added to a solution of a halide salt, and a double jet method in which an aqueous solution of silver nitrate and an aqueous solution of halide salt are simultaneously added. A preferable nucleation condition for the monodisperse high aspect ratio tabular emulsion of the present invention is a double jet method in which the degree of supersaturation in the stirring and mixing apparatus is high and nucleation is likely to occur because it is necessary to have a high twin nucleus generation probability. . Nucleation can be performed at 20 ° C. to 60 ° C., but the twin nucleus is highly likely to occur, and it is preferably performed at 30 to 60 ° C. from the viewpoint of suitability in production. After the temperature is raised after nucleation, pAg is adjusted to 7.6 to 10.0, and grains other than tabular grains are extinguished with a silver halide solvent. After obtaining only the tabular grain group in this manner, desired tabular seed crystal grains are obtained by the grain growth process. It is desirable to add silver and halogen solutions so that new crystal nuclei are not generated in the grain growth process. The aspect ratio of the emulsion grains can be controlled by selecting the temperature during the grain growth process, pAg, the addition rate of the aqueous silver nitrate solution and the aqueous halide solution, and the like. Further, a method of supplying a part or all of silver added in the grain growth process as fine particles of silver halide as described in JP-A-62-99751 can be used.

The general silver halide light-sensitive material of the present invention will be described below. The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. The number of layers and the order of layers of the non-photosensitive layer are not particularly limited. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order from the support side.
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-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer has a layer of JP-A-61-43748.
No. 59-113438, No. 59-113440
Nos. 61-20037 and 61-20038, the couplers, the DIR compounds, etc. may be contained, and a color mixing inhibitor may be contained as usual.

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 constitution 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. Further, JP-A-57-112751, JP-A-62-20035.
No. 0, No. 62-206541, No. 62-206543
As described in the publications, etc., a low-sensitivity emulsion layer may be provided on the side remote from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH)
/ High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (G
L) / high-sensitivity red photosensitive layer (RH) / low-sensitivity red photosensitive layer (RL), or BH / BL / GL / GH / RH /
RL order or BH / BL / GH / GL / RL / RH
Can be installed in order. In addition, Japanese Examined Japanese Patent Publication 55-349
As described in Japanese Patent No. 32,32, it is also possible to arrange in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, JP-A-56-25738,
As described in the specification of No. 62-63936,
Blue-sensitive layer / GL / RL / G from the side farthest from the support
It is also possible to arrange them in the order of H / RH.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a low 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. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, they 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. Also, in the case of four or more layers, the arrangement may be changed as described above.

In order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add to the photographic material a compound capable of being immobilized by reacting with formaldehyde described in No. 87 and No. 4,435,503. The light-sensitive material of the present invention can be incorporated into U.S. Pat. Nos. 4,740,454 and 4,788,132.
JP-A-62-18539, JP-A-1-28355
It is preferable that the mercapto compound described in No. 1 is contained. A compound described in JP-A No. 1-106052, which releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof, to the light-sensitive material of the present invention, irrespective of the amount of developed silver produced by the development processing. Is preferably contained. In the light-sensitive material of the present invention, international publication WO88 / 04
No. 794, dyes dispersed by the method described in JP-A-1-502912 or EP317,308A, US Pat. No. 4,420,555, JP-A-1-259358.
It is preferable to include the dyes described in No.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure No. 17643, VII-C to G, and No.
307105, VII-C to G. Examples of yellow couplers include U.S. Pat. Nos. 3,933,501 and 4,022,620.
No. 4,326,024, No. 4,401,752
No. 4,248,961, Japanese Patent Publication No. 58-1073.
No. 9, British Patent Nos. 1,425,020 and 1,47
Preferred are those described in US Pat. No. 6,760, US Pat. Nos. 3,973,968, 4,314,023, 4,511,649, and European Patent 249,473A. As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat.
310,619, 4,351,897, EP 73,636, and US 3,061,432.
No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-6
0-33552, Research Disclosure No.
24230 (June 1984), JP-A-60-4365.
No. 9, No. 61-72238, No. 60-35730,
No. 55-118034, No. 60-185951, U.S. Pat. Nos. 4,500,630, and 4,540,65.
No. 4, No. 4,556,630, International Publication WO88 /
Those described in No. 04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 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, U.S. Patents 3,446,622, 4,333,999.
Issue No. 4,775,616, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable. Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,080,
No. 211, No. 4,367,282, No. 4,40
No. 9,320, No. 4,576,910, British Patent No. 2,102,137, European Patent No. 341,188A and the like.

As couplers in which the color forming dye has an appropriate diffusibility, US Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, West German Patent (Publication) No. 3 , 234,533 are preferred. Researched Disclosure No. 1 is a colored coupler for correcting unwanted absorption of color forming dyes.
7643, Item VII-G, No. 307105, Item VII-G
, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-3
9413, U.S. Pat. Nos. 4,004,929, 4,138,258, and British Patent 1,146,368.
Those described in No. 10 are preferable. Also, US Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in 4,181,
It is also preferable to use a coupler described in U.S. Pat. No. 4,777,120 having a dye precursor group capable of reacting with a developing agent to form a dye as a leaving group. Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers releasing a development inhibitor are disclosed in the above-mentioned RD17643, VII-F and No. 307105, VII-F patents, JP-A-57-151944 and 57-15423.
No. 4, No. 60-184248, No. 63-37346.
No. 63-37350, U.S. Pat. No. 4,248,9.
Those described in No. 62 and No. 4,782, 012 are preferable.

As a coupler capable of releasing a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,093
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-1-4940.
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 competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. Nos. 4,283,472, and 4,338,393.
No. 4,310,618 and the like, multiequivalent couplers, JP-A-60-185950 and JP-A-62-242.
52, etc., DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 31
No. 3,308A, a coupler that releases a dye that recovers color after separation, R.I. D. No. 11449, No. 24241, bleach accelerator releasing couplers described in JP-A No. 61-201247, ligand releasing couplers described in US Pat. No. 4,555,477, etc., and JP-A No. 63-75747. Leuco Dye-releasing Coupler, US Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 4,181.

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. 2,322,222.
No. 027 and the like. Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate,
Bis (1,1-diethylpropyl) phthalate), esters of phosphoric acid or phosphonic acid (eg triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl Phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2
-Ethylhexylphenylphosphonate), benzoic acid esters (for example, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate), amides (for example, N, N-diethyldodecane amide, N, N-diethyllaurylamide,
N-tetradecylpyrrolidone), alcohols or phenols (eg isostearyl alcohol, 2,4
-Di-t-amylphenol), aliphatic carboxylic acid esters (eg bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate), aniline derivatives (eg N, N-dibutyl-2-
Butoxy-5-tert-octylaniline), hydrocarbons (for example, paraffin, dodecylbenzene, diisopropylnaphthalene) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used, and typical examples thereof include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,36.
3, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.
In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248 are used.
1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-described in JP-A No. 1-80941.
Dimethylphenol, 2-phenoxyethanol, 2-
It is preferable to add various antiseptics or antifungal agents such as (4-thiazolyl) benzimidazole. The present invention can be applied to various color light-sensitive materials. Color negative film for general or movie, color reversal film for slide or TV, color paper,
Representative examples include a color positive film and a color reversal paper. Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643-2
No. 18716, page 647, right column to page 648, left column, and page 879, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less is more preferable, and 16 μm or less is particularly preferable. The film swelling speed T _1/2 is preferably 30 seconds or less,
20 seconds or less is more preferable. The film thickness is 25 ° C and relative humidity is 5
Mean film thickness measured under 5% humidity control (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, A Green (A. G
Reen) et al., Photographic Science and Engineering (Photogr. Sci. Eng.), 19
It can be measured by using a swellometer (swelling meter) of the type described in Vol. 2, No. 2, pp. 124-129, T _1/2
Is 90% of the maximum swollen film thickness reached when the film is processed with a color developer at 30 ° C. for 3 minutes and 15 seconds, and the saturated film thickness is defined as 1% of the saturated film thickness.
It is defined as the time to reach / 2. Membrane swelling speed T
_1/2 can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling rate is 150 to 400.
% Is preferred. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula: (maximum swollen film thickness-film thickness) / film thickness
Can be calculated according to. The photographic material of the present invention has a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer.
It is preferable to provide the hydrophilic colloid layer (referred to as a back layer). In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener,
It is preferable to contain a binder, a plasticizer, a lubricant, a coating aid, a surface active agent and the like. The swelling ratio of this back layer is preferably 150 to 500%.

The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pages 28-29, No. 18
Development can be carried out by a usual method described in 651, left column to right column, and No. 307105, pages 880 to 881. 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 a typical example thereof is 3-methyl-4-
Amino-N, N-diethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Examples thereof include amino-N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Of these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly preferable. Two or more of these compounds can be used in combination depending on the purpose.

The color developer may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It is common to contain a development inhibitor such as a bromide salt, an iodide salt, benzimidazoles, benzothiazoles or a mercapto compound, or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents. Agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclo Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--1,
1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-
Hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

The pH of these color developing solutions is generally 9-12. The replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 square meter of the light-sensitive material, and it is 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also do it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air.
The contact area between the photographic processing liquid and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio (cm ⁻¹ ) is preferably 0.1 or less, More preferably, it is 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing liquid in the processing tank, Japanese Patent Laid-Open No. Hei 1
The method using a movable lid described in JP-A-82033 and the slit development processing method described in JP-A-63-216050 can be mentioned. Reducing the aperture ratio is preferably applied not only in both the color development and black-and-white development steps but also in the subsequent steps, for example, all steps such as bleaching, bleach-fixing, fixing, washing and stabilizing. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developing solution.

The color development processing time is usually set between 2 and 5 minutes, but it is possible to further shorten the processing time by using a high temperature and high pH and using a high concentration of the color developing agent. it can. 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. In addition, processing with two continuous bleach-fixing baths, fixing before bleach-fixing,
Alternatively, the bleaching process may be performed after the bleach-fixing process according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are organic complex salts of iron (III), such as aminoamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid and glycol etherdiaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetate iron (III) complex salt are used from the viewpoint of rapid treatment and prevention of environmental pollution. preferable. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution containing these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8.0, but it should be processed at a lower pH in order to speed up the processing. You can also

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
-37418, 53-72623, 53-95.
No. 630, No. 53-95631, No. 53-10423.
No. 2, No. 53-124424, No. 53-141623.
No. 53-28426, Research Disclosure No. 17129 (July 1978) and the like, compounds having a mercapto group or a disulfide group; thiazolidine derivatives described in JP-A No. 50-140129; -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5.
Thiourea derivatives described in No. 61; West German Patent No. 1,12
No. 7,715, iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30; Japanese Patent Publication No. 4
Polyamine compounds described in JP-A-5-8836; Others, JP-A-49-40943, JP-A-49-59644 and JP-A-53-
94927, 54-35727, 55-265.
Compounds described in No. 06 and No. 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and in particular, US Pat.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid is a compound having an acid dissociation constant (pka) of 2 to 5, specifically, acetic acid,
Propionic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. Use of thiosulfates Is generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate with thiocyanate, thioether compound, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add 0.1 to 10 mol / liter of an imidazole such as methylimidazole. The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. The preferred time is 1 to 3 minutes, more preferably 1 to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to 4 ° C.
It is 5 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening stirring, a method of causing a jet stream of a processing solution to collide with an emulsion surface of a light-sensitive material described in JP-A-62-183460, or JP-A-62-183460.
A method of increasing the stirring effect using the rotating means of No. 183461, and further moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. How to improve,
There is a method of increasing the circulation flow rate of the entire processing liquid.
Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film and, as a result, increases the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. The automatic developing machine used for the light-sensitive material of the present invention preferably has the light-sensitive material conveying means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the deterioration of the performance of the treatment liquid.
Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. 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), the application, and the temperature of rinsing water, the number of rinsing tanks (number of stages), replenishment method such as countercurrent and forward flow, and various other conditions. 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 the Journal of the Society of Motion Pictur.
e and Television Engineers Volume 64, p. 248 ~
253 (May 1955 issue). According to the multistage countercurrent method described in the above document,
Although the amount of water to be washed can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and the resulting suspended matter adhering to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively. In addition, JP-A-57-
No. 8542, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, Sanitary Technology "Sterilization, sterilization, and antifungal technology of microorganisms" edited by the Society (1982) Industrial Technology Association, "Antibacterial and antifungal agent encyclopedia" edited by Japan Society for Antibacterial and Antifungal (1
It is also possible to use the fungicide described in 986).

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and the washing time can be set variously depending on the characteristics of the light-sensitive material, the use, etc., but generally 15 to 45 ° C. for 20 seconds to 10 minutes,
A range of 30 seconds to 5 minutes at 25 to 40 ° C is preferably selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, Japanese Patent Laid-Open No. 57-8543,
All known methods described in JP-A-58-14834 and JP-A-60-220345 can be used. In addition, following the water washing treatment, there is a case where further stabilization treatment is performed,
An example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow solution that accompanies the washing with water and / or the supplement of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
It is preferable to correct the concentration by adding water. 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. For example, indoaniline compounds described in US Pat. No. 3,342,597, No. 3,342,599, Research Disclosure No. 14850 and N.
Schiff base type compound described in No. 15159, No. 1
Aldol compounds described in 3924, US Pat. No. 3,7
Metal salt complexes described in JP-A-53-135.
The urethane compound described in No. 628 can be mentioned. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56-64339 and JP-A-57-144547.
No. 58-115438 and the like.
Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to. The silver halide photographic light-sensitive material of the present invention is disclosed in US Pat. No. 4,500,626,
JP-A-60-133449 and 59-218443.
No. 61-238056, European Patent 210,660.
It can also be applied to the photothermographic materials described in A2 and the like. The silver halide light-sensitive material of the present invention is described in JP-A 2-3
When applied to the film unit with a lens described in No. 2615, Jpn.

[0070]

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

Example 1 (Preparation of non-color-sensitive silver halide emulsion 1-A) An aqueous solution prepared by dissolving 6 g of an inert low molecular weight (average molecular weight of 50,000) gelatin and 2.5 g of potassium bromide in 1 liter of distilled water. 30 ° C
After stirring, the 1M aqueous solution of silver nitrate and the 1M aqueous solution of potassium bromide and potassium iodide (96/4 in molar ratio) were added thereto at a flow rate of 50 cc / min for 24 seconds, and then the pAg was increased to 10. After adding 20 g of inert gelatin and raising the temperature to 65 ° C., 50 g of ammonium nitrate and 100 cc of a 1M aqueous sodium hydroxide solution were added to 30 g.
It was aged for minutes to form plate nuclei. Subsequently, after adding 8 g of glacial acetic acid, 100 cc of a 1 M aqueous solution of silver nitrate and 1 M of potassium bromide.
An aqueous solution was added in equimolar amounts at an addition rate near the critical growth rate to grow a tabular emulsion. 135g total for growth
Used silver nitrate. The pH of the grown emulsion was adjusted by adding gelatin after the desalting step by the usual flocculation method.
It was adjusted to 6.6 and pAg 8.5. The temperature of this emulsion was raised to 56 ° C., sodium thiosulfate, chloroauric acid, potassium thiocyanate and N, N-dimethylselenourea were added,
Chemical sensitization was performed so that the sensitivity was highest for 1/100 second. Average aspect ratio 6.4, sphere equivalent diameter 0.24μ
Thus, tabular grains having m and a coefficient of variation of 23% were obtained.

(Production Method of Color Sensitive Silver Halide Emulsion 1-1 (Comparative Emulsion 1-1)) Tabular silver bromide 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 silver was dissolved in 1 liter of distilled water, and p
Ag was adjusted to 8.2 and pH was adjusted to 5, and the mixture was kept warm at 75 ° C. and vigorously stirred. Subsequently, particles were formed by the following procedure. 1) A silver nitrate (141 g) aqueous solution and a potassium bromide aqueous solution were added while keeping the pAg at 8.4. 2) The temperature was lowered to 55 ° C., and an aqueous potassium iodide (4 g) solution was added at a constant flow rate. 3) Add an aqueous solution of silver nitrate (63g) and an aqueous solution of potassium bromide.
Addition was carried out while maintaining Ag at 8.9. It was cooled to 35 ° C, washed with water by the usual flocculation method, added with 50 g of gelatin and redispersed to obtain pH 6.0 and pA.
It was adjusted to g 8.2. It was a tabular emulsion having an average equivalent spherical diameter of 1.10 μm and an average aspect ratio of 6.8. 6 this emulsion
The temperature was raised to 4 ° C., and the sensitizing dye ExS-1 described below was added to 2.4 × 1.
0 ⁻⁴ mol / mol Ag, ExS-2 1.0 × 10 ⁻⁵ mol / mol Ag, ExS-3 3.5 × 10 ⁻⁴ mol / mol A
After g was added and the mixture was aged for 20 minutes, sodium thiosulfate, chloroauric acid, potassium thiocyanate and N, N-dimethylselenourea were sequentially added and aged for 90 minutes for optimum chemical sensitization. "Optimally" here is 1/1
00 sec This is the condition that gives the highest sensitivity.

(Production Method of Color-Sensitive Silver Halide Emulsion 1-2 (Emulsion 1-2 of the Invention)) The same procedure as in Comparative Emulsion 1-1 was used. However, after aging for 90 minutes,
The non-color-sensitive silver halide emulsion 1-A was added so that the silver amount ratio was 5/95 with respect to the silver amount in the emulsion, followed by ripening for 20 minutes and cooling. It has been confirmed that no change in photographic performance is observed even after aging for a longer time. (Production Method of Color Sensitive Silver Halide Emulsion 1-3 (Comparative Emulsion 1
-3)) An aqueous solution (water 1200 m) containing gelatin having an average molecular weight of 15000 in a reaction vessel having a volume of 4 liters.
1, gelatin 7 g, KBr 4.5 g) were added, and the solution temperature was maintained at 30 ° C. with stirring by the double jet method.
A 9 M silver nitrate aqueous solution and a 1.9 M potassium bromide aqueous solution were simultaneously added for 10 seconds respectively. 350 ml of this emulsion
650 ml of inert gelatin (containing 20 g of gelatin and 1.2 g of potassium bromide) was added to this, and the temperature was raised to 75 ° C. and ripened for 80 minutes. Next, the pH of the emulsion was adjusted to 7.0 with nitric acid, 1 g of potassium bromide was added, and then 405 ml of a 1.9 M silver nitrate aqueous solution and a 1.9 M potassium bromide and potassium iodide (98/2 molar ratio) aqueous solution. Was added so that the pAg was kept at 8.3. After the temperature was lowered to 55 ° C., 40 ml of a 0.6 M silver nitrate aqueous solution and 40 ml of a 0.6 M silver iodide aqueous solution were added over 10 minutes. After adjusting the pAg to 8.9 by adding potassium bromide, 157 ml of a 1.9 silver nitrate aqueous solution and 157 ml of a 1.9 M potassium bromide aqueous solution were added over 26 minutes. Cool to 35 ° C., wash with normal flocculation method, add 50 g of gelatin and redisperse, pH 6.0, p
It was adjusted to Ag 8.2. This emulsion was a monodisperse high aspect ratio tabular emulsion having an average aspect ratio of 18, a sphere-equivalent diameter of 1.1 μm, and a grain size variation coefficient of 12%. Then, chemical sensitization was performed in the same manner as in Comparative Emulsion 1-1. At this time, the sensitizing dye is the comparative emulsion 1-
1 times the amount added.

(Production Method of Color-Sensitive Silver Halide Emulsion 1-4 (Emulsion 1-4 of the Invention)) The same procedure as in Comparative Emulsion 1-3 was used. However, after aging for 90 minutes,
The non-color-sensitive emulsion 1-A was added so that the silver amount ratio would be 5/95, ripened for 20 minutes, and then cooled. It has been confirmed that no change in photographic performance is observed even after aging for a longer time.

(Preparation of Multilayer Coated Sample) Each layer having the following composition was multilayer coated on an undercoated cellulose triacetate film support to prepare multi-layer color light-sensitive material Samples 1-1 to 1-4. Created. (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 in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 1.40 ExM-1 0.18 ExF-1 2.0 × 10 ⁻³ HBS-1 0.20 Second 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 -1 0.10 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 1.5 × 10 ⁻⁵ ExS-3 4 .5 × 10 ⁻⁴ ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.0050 ExC-7 0.0050 ExC-8 0.020 Cpd-2 0.025 HBS- 1 0.010 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 0.11 ExC-7 0.0010 ExC-8 0.025 Cpd-2 0.023 HBS-1 0.010 Gelatin 0.75

Fifth Layer (High Sensitivity Red Sensitive Emulsion Layer) Emulsion E Silver 1.40 ExS-1 2.28 × 10 ⁻⁴ ExS-2 9.5 × 10 ⁻⁶ ExS-3 3.33 × 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

Seventh Layer (Low-Sensitivity Green Sensitive Emulsion Layer) Emulsion A Silver 0.17 Emulsion B Silver 0.17 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 ( Mid-Sensitivity Green Sensitive Emulsion 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 -3 0.045 ExY-1 0.01 ExY-5 0.030 HBS-1 0.16 HBS-3 8.0x10 ^-3 gelatin 0.90

Ninth Layer (High Sensitivity Green Sensitive Emulsion Layer) Emulsion E Silver 1.25 ExS-4 3.7 × 10 ⁻⁵ ExS-5 8.1 × 10 ⁻⁵ ExS-6 3.2 × 10 ⁻⁴ ExC-1 0.010 ExM-1 0.015 ExM-4 0.040 ExM-5 0.019 Cpd-3 0.020 HBS-1 0.25 HBS-2 0.10 Gelatin 1.20 10th layer ( Yellow filter layer) Yellow colloidal silver 0.010 Cpd-1 0.16 HBS-1 0.60 Gelatin 0.60

Eleventh Layer (Low Sensitivity Blue Sensitive 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 F Silver 1.38 ExS-7 3.0x 10 ^-4 ExY-2 0.10 ExY-3 0.10 HBS-1 0.070 Gelatin 0.86

Thirteenth Layer (First Protective Layer) Emulsion G Silver 0.20 UV-4 0.11 UV-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 1.00 Fourteenth Layer (Second Layer) 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, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B are appropriately added. -6,
F-1 to F-17 and iron salt, lead salt, gold salt, platinum salt, iridium salt, palladium salt and rhodium salt are contained.

[0085]

[Table 1]

In Table 1, (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 gold-sensitized and sulfur-sensitized under the conditions shown in Table 3 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. And selenium sensitization is applied. (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.

[0087]

[Chemical 1]

[0088]

[Chemical 2]

[0089]

[Chemical 3]

[0090]

[Chemical 4]

[0091]

[Chemical 5]

[0092]

[Chemical 6]

[0093]

[Chemical 7]

[0094]

[Chemical 8]

[0095]

[Chemical 9]

[0096]

[Chemical 10]

[0097]

[Chemical 11]

[0098]

[Chemical 12]

[0099]

[Chemical 13]

[0100]

[Chemical 14]

[0101]

[Chemical 15]

However, the fifth and sixth layers were coated with the following composition. Sample 1-1 Emulsion E for the fifth layer and ExS-1, Comparative Emulsion 1-1 with the same silver coating amount except for the sensitizing dyes of 2 and 3
Coating was performed with the same composition except that was replaced with. Sample 1-2 The fifth layer of Sample 1-2 was reduced in coating amount of Comparative Emulsion 1-1 from 1.40 to 1.33 in terms of silver coating amount. The amount of sensitizing dye applied was correspondingly reduced. The sixth layer contained the non-photosensitive emulsion 1-A so that the silver coating amount was 0.07. Sample 1-3 The fifth layer was replaced with Sample 1-1, and the comparative emulsion 1-1 was replaced with the emulsion 1-2 of the present invention. The silver coating amount was set to be the same as that of Sample 1-1. Sample 1-4 The fifth layer was replaced with Sample 1-1, and Comparative emulsion 1-1 was replaced with Comparative emulsion 1-3. The silver coating amount was set to be the same as that of Sample 1-1. Sample 1-5 The fifth layer was replaced with Sample 1-1, and Comparative Emulsion 1-1 was replaced with Emulsion 1-4 of the present invention. The silver coating amount was set to be the same as that of Sample 1-1. Sample 1-6 When the fifth layer was coated, Comparative Emulsion 1-1 and Lippmann emulsion (particle size 0.08 μm) were mixed immediately before coating to perform multilayer coating. The silver coverage was 1.33 for the comparative emulsion,
The Lippmann emulsion was adjusted to 0.07 so that the total was the same as that of sample 1-1. Since the coating amount of the comparative emulsion was smaller than that of Sample 1-1, the coating amount of the sensitizing dye was also reduced.

(Processing) The sample prepared in this manner
After leaving for 16 hours at 0 ° C and 70% relative humidity,
It was exposed for 1/100 seconds through a continuous wedge, and color development processing was performed under the following conditions.

[0104]

Next, the composition of the treatment liquid is shown. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 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-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH (potassium hydroxide and sulfuric acid Adjusted by) 10.05

(Bleach) (Unit: g) Ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt 10.0 3-Mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Water was added to 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 6.0

(Fixer) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 0.5 Ammonium sulfite 20.0 Ammonium thiosulfate aqueous solution (700 g / liter) 295.0 ml Acetic acid (90%) 3.3 Add water 1. 0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 6.7

(Stabilizing Solution) (Unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added to 1.0 liter pH 8.5

The processed sample was subjected to density measurement with a red filter to evaluate the sensitivity. The sensitivity was determined by the reciprocal of the exposure amount that gives a density of fog + 0.2. Also, 0.8
Create a sample that has been uniformly exposed so that the
Graininess was also evaluated. Further, the granularity of the sample stored in the natural state for 6 months was also measured. The results are shown in Table 2. The sensitivity and granularity are shown as relative values with respect to Sample 1-1.
The granularity after storage for 6 months is shown as a relative value to the granularity of Sample 1-1 one day after application. The larger the value of the sensitivity, the higher the sensitivity, and the larger the value of the granularity, the finer the granularity.

[0110]

[Table 2]

Sample 1-3 of the present invention as compared with Sample 1-1
It can be seen that the sample has high sensitivity while having the same granularity without increasing the amount of coated silver. Also, for comparison sample 1
-2 indicates that the coating amount of the color-sensitive emulsion and the non-color-sensitive emulsion is Sample 1
-3, except that the non-color-sensitive emulsion was coated on the intermediate layer of another layer. Both the sensitivity and the granularity are worse than those of the comparative sample 1-1. That is,
It can be seen that the effect of the present invention is exhibited only when the color-sensitive emulsion and the non-color-sensitive emulsion are mixed and coated in the same layer as in Sample 1-3. Further, Sample 1-6 is disclosed in JP-A-4-276.
A sample obtained by mixing the Lippmann emulsion immediately before coating according to the example of No. 737 shows that the granularity is deteriorated and high sensitivity cannot be achieved at all. Also, sample 1
-4 and Sample 1-5 are samples using a monodisperse high aspect ratio monodisperse tabular emulsion as a color-sensitive emulsion. Sample 1-4
On the other hand, Sample 1-5 contained a non-color sensitive emulsion, but achieved high sensitivity in the same manner as when a conventional tabular grain emulsion 1-1 contained a non-color sensitive emulsion. However, the monodisperse high aspect ratio tabular emulsion has a larger sensitizing effect.
The use of such tabular emulsions is the preferred embodiment. Further, the granularity of Sample 1-1 after being stored for 6 months is significantly deteriorated. This is due to natural radiation. The samples of the present invention, 1-3 and 1-5, exhibit the excellent property that the deterioration of the granularity is very small. This is probably because the sensitivity to radiation in the visible region could be lowered relatively. As described above, the sample of the present invention can achieve markedly high sensitivity without increasing the amount of coated silver and without deteriorating the granularity, and also improve the deterioration of the granularity due to natural radiation. I was able to.

Example 2 (Production Method of Non-Photosensitive Emulsion 2-A to 2-E) Non-photosensitive Emulsion 2-A was prepared in the same manner as Non-Photosensitive Emulsion 1-A of Example 1.
~ 2-D was prepared. However, the non-photosensitive emulsion 2-A was pure silver bromide from which potassium iodide was removed during nucleation, and the non-photosensitive emulsion 2-B was completely the same as the non-photosensitive emulsion 1-A. -C, 2-D, and 2-E contain potassium iodide at the time of flat plate growth, and the average silver iodide content is 2-mol: 1 mol%, 2-D: 5 mol%, 2-E: 10 mol. It became to be%. (Production Method of Photosensitive Emulsion 2-1 to 2-5) Photosensitive Emulsion 2-1 to 2-by the same method as Photosensitive Emulsion 1-2 of Example 1.
5 was prepared. However, the non-photosensitive emulsion is the photosensitive emulsion 1
In place of the non-photosensitive emulsion 1-A used in the case of -2, the previously prepared non-photosensitive emulsions 2-A to 2-E were added at the time of preparation of the photosensitive emulsions 2-1 to 2-5. (Preparation of multilayer coating sample) Sample 2 was prepared according to the method of Example 1.
-1 to 2-5 were created. In addition, Sample 2-6 is the first embodiment.
A sample exactly the same as the sample 1-1 was prepared (only the comparative emulsion 1-1 was used in the fifth layer). Samples 2-1 to 2-
The emulsion of the fifth layer of No. 5 is photosensitive emulsions 2-1 to 2-
5 was used. Exposure, development by the same method as in Example 1,
Processing was performed to determine sensitivity and granularity. Further, the sample before exposure was stored for 1 month under the condition of 30 ° C. and 80% relative humidity, and then the sensitivity was determined by the same method. Further, as in Example 1, the granularity was determined by storing the sample in a natural environment for 6 months. The results are shown in Table 3.

[0113]

[Table 3]

From the results shown in Table 3, it can be seen that when the non-photosensitive silver halide emulsion was pure silver bromide, the sensitizing effect by mixing the emulsions was small and the sensitivity change after storage was large. By containing silver iodide in an amount of 0.1 mol or more as in the present invention, the sensitizing effect is remarkably increased and the change in sensitivity after storage can be made extremely small. It was unexpected that the presence of such a small amount of silver iodide would have a very dramatic effect. Further, the higher the silver iodide content of the non-photosensitive emulsion, the greater the sensitizing effect and the smaller the change in sensitivity after storage for one month. From this fact, it is assumed that the presence of silver iodide strengthens the adsorption of the sensitizing dye that has moved from the photosensitive silver halide emulsion, resulting in the effect of increasing the sensitizing effect and improving the storage stability. It seems that Regarding the granular deterioration due to natural radiation, the deterioration of the granularity of the sample of the present invention is very small as in the first embodiment. Further, the dependency of the non-color sensitive emulsion on the silver iodide content is small. The object of the present invention can be achieved by containing at least 0.1 mol% of silver iodide.

Example 3 A non-photosensitive silver halide emulsion as shown in Table 4 was prepared.

[0116]

[Table 4]

Emulsions having an aspect ratio of 1 are cubic grains, and grains having an aspect ratio of 2 or more are tabular grains. The silver iodide content was all 1 mol%. These non-photosensitive emulsions are optimally chemically sensitized and no sensitizing dye is added. These non-color-sensitive silver halide emulsions were added to the light-sensitive silver halide emulsion in the chemical sensitization step according to the method for producing the color-sensitive silver halide emulsion 1-2 used in Example 1, and then at 64 ° C. Aging for 20 minutes was carried out to prepare a light-sensitive silver halide emulsion in which a non-light-sensitive silver halide emulsion was mixed. The addition amount of the non-photosensitive silver halide emulsion was selected so that the sensitivity in the multilayer sample was the highest in each sample. The emulsion thus prepared was subjected to multi-layer coating according to the method of Example 1 to prepare samples 3-1A to 3-
8A was made. Further, the color-sensitive silver halide emulsion of Example 1 was prepared, and mixed with the non-color-sensitive silver halide emulsion shown in Table 4 just before coating according to the method of JP-A-4-276737 to perform multilayer coating. Samples 3-2B to 3-8B were prepared.

The above samples were exposed, developed, processed and measured according to the method of Example 1 to determine the sensitivity and granularity.
Further, the standard deviation of sensitivity was obtained by preparing the same sample 10 times. The average value of 10 samples was used for sensitivity and granularity. The results are shown in Table 4 above. The results of Table 4 will be described. When a fine-grained cube of less than 0.1 μm is used in the non-photosensitive emulsion, there is almost no sensitizing effect and the granularity deteriorates. By increasing the grain size, the sensitizing effect is exhibited and the deterioration of granularity is reduced. However,
When the non-photosensitive emulsion is replaced with tabular grains, the sensitizing effect is dramatically increased, and the deterioration of granularity can be further reduced. It can be seen that when tabular grains are used for the non-photosensitive emulsion, the dependence on grain size is relatively small, and tabular grains having any grain size of 0.1 μm or more may be used. The sample prepared by mixing the non-color-sensitive emulsion and the color-sensitive emulsion immediately before coating may be a tabular emulsion non-color-sensitive emulsion having a grain size of 0.1 μm or more or an aspect ratio of 2 or more. The sensitizing effect is very small. Further, there is a large variation in the manufacturing process, and comparing the standard deviations of sensitivity, Sample A in which the non-color-sensitive emulsion of the present invention was added and ripened at 64 ° C. for 20 minutes
Shows a variation of 1/5 or less with respect to the sample B, and it can be seen that stabilization of the manufacturing process can be achieved. From the above results, in order to exert the effect of the present invention, 0.1 μm
It is necessary to use a non-photosensitive emulsion of the above size,
Further, tabular grains having an aspect ratio of 2 or more are very excellent as a non-photosensitive emulsion, and in order to exhibit a sensitizing effect and stabilize the manufacturing process, high temperature ripening after addition of a non-sensitive emulsion is performed. Is effective.

Example 4 (Production Method of Color-Sensitive Silver Halide Emulsion 4-1A) A method similar to that of the color-sensitive silver halide emulsion 1-1 of Example 1 was prepared. However, the chemical sensitization was optimally performed without adding the sensitizing dye in the chemical sensitization step. A color-sensitive emulsion containing no sensitizing dye and showing spectral sensitivity only in the intrinsic range was obtained. (Production Method of Color-Sensitive Silver Halide Emulsion 4-1B) A color-sensitive silver halide emulsion 1-2 was prepared in the same manner as in the color-sensitive silver halide emulsion 1-2 of Example 1. However, the chemical sensitization was optimally performed without adding the sensitizing dye in the chemical sensitization step. The non-color-sensitive emulsion 1-A was added in the same manner as in the emulsion 1-2 so that the silver amount ratio was 5/95. A sensitizing dye containing no non-sensitizing emulsion was obtained which showed a spectral sensitivity only in the intrinsic range without containing a sensitizing dye. However, in this case, strictly speaking, since the photosensitive wavelengths of the color-sensitive emulsion and the non-color-sensitive emulsion are common, the names of the color-sensitive emulsion and the non-color-sensitive emulsion are not correct. The present emulsion was prepared as a comparative example, but for convenience sake, it is referred to as a color-sensitive emulsion mixed with a non-color-sensitive emulsion. (Production Method of Color-Sensitive Silver Halide Emulsion 4-2A) A method similar to that of the color-sensitive silver halide emulsion 1-1 of Example 1 was used. However, in the chemical sensitization process, the sensitizing dye is ExS.
After adding 4.4 × 10 ^-4 mol / mol Ag of -7, optimum chemical sensitization was performed. A color-sensitive emulsion having a spectral sensitivity in the blue region was obtained.

(Production Method of Color-Sensitive Silver Halide Emulsion 4-2B) A method similar to that of the color-sensitive silver halide emulsion 1-2 of Example 1 was used. However, in the chemical sensitization step, the sensitizing dye was optimally chemically sensitized after adding 4.4 × 10 ⁻⁴ mol / mol Ag of ExS-7. The non-color-sensitive emulsion 1-A was added in the same manner as in the emulsion 1-2 so that the silver amount ratio was 5/95. A color-sensitive emulsion having a spectral sensitivity in the blue region and containing a non-color-sensitive emulsion was obtained. (Production Method of Color-Sensitive Silver Halide Emulsion 4-3A) A method similar to that of the color-sensitive silver halide emulsion 1-1 of Example 1 was used. However, in the chemical sensitization process, the sensitizing dye is ExS.
-4 is 3.7 × 10 ⁻⁵ mol / mol Ag, ExS-5 is 8.1 × 10 ⁻⁵ mol / mol Ag, and ExS-6 is 3.2 ×.
Optimal chemical sensitization was performed after adding 10 ⁻⁴ mol / mol Ag. A color-sensitive emulsion having a spectral sensitivity in the green region was obtained. (Production Method of Color-Sensitive Silver Halide Emulsion 4-3B) A color-sensitive silver halide emulsion 1-2-3 was prepared in the same manner as in Example 1. However, in the chemical sensitization process, the sensitizing dye is ExS.
-4 is 3.7 × 10 ⁻⁵ mol / mol Ag, ExS-5 is 8.1 × 10 ⁻⁵ mol / mol Ag, and ExS-6 is 3.2 ×.
Optimal chemical sensitization was performed after adding 10 ⁻⁴ mol / mol Ag. The addition of the non-color sensitive emulsion 1-A was 5 in terms of silver amount ratio.
The same procedure as for Emulsion 1-2 was performed so that the ratio becomes / 95. A color-sensitive emulsion having a spectral sensitivity in the green region and containing a non-color-sensitive emulsion was obtained. (Production Method of Color-Sensitive Silver Halide Emulsion 4-4A) A color-sensitive silver halide emulsion 1-1 was prepared in the same manner as in Example 1. A color-sensitive emulsion having a spectral sensitivity in the red region was obtained. (Production Method of Color-Sensitive Silver Halide Emulsion 4-4B) A color-sensitive silver halide emulsion 1-2-4 was prepared in exactly the same manner as in Example 1. The non-color-sensitive emulsion 1-A was added in the same manner as in the emulsion 1-2 so that the silver amount ratio was 5/95. A color-sensitive emulsion having a spectral sensitivity in the red region and containing a non-color-sensitive emulsion was obtained.

(Preparation of multilayer coating sample) According to the method of Example 1, a multilayer coating sample was prepared. Samples 4-1A and 1B Samples 4-1A and 4-1B were prepared by incorporating the previously prepared color-sensitive silver halide emulsions 4-1A and 4-1B into the twelfth layer which is a high-sensitivity blue-sensitive emulsion layer. It was created. At this time,
The coated silver amount was set to be the same for 4-1A and 4-1B. Samples 4-2A and 2B Samples 4-2A and 4-2B in which the twelfth layer, which is a high-sensitivity blue-sensitive emulsion layer, contains the previously prepared color-sensitive silver halide emulsions 4-2A and 4-2B, respectively. It was created. At this time,
The coated silver amount was set to be the same for 4-2A and 4-2B. -Samples 4-3A and 3B Samples 4-3A and 4-3B were prepared by incorporating the previously prepared color-sensitive silver halide emulsions 4-3A and 4-3B into the ninth layer which is a high-sensitivity green-sensitive emulsion layer. It was created. At this time, the coated silver amount was set to be the same between 4-3A and 4-3B. -Samples 4-4A and 4B Samples 4-4A and 4-4B were prepared by incorporating the previously prepared color-sensitive silver halide emulsions 4-4A and 4-4B into the fifth layer which is a high-sensitivity red-sensitive emulsion layer. It was created. At this time, the coated silver amounts were set to be the same for 4-4A and 4-4B.

The sample prepared as described above was exposed, developed, processed and measured according to the method of Example 1 to determine the sensitivity. However, sample 4-1A, B, sample 4-2A, B, the sensitivity when measured with a blue filter, sample 4-3A,
B is the sensitivity when measured with a green filter, sample 4-4
A and B are sensitivities when measured with a red filter.
For each sample, the ratio of the sensitivity of the sample containing the non-photosensitive emulsion to the sample containing no non-photosensitive emulsion was determined.
The results are shown in Table 5.

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[Table 5]

As can be seen from Table 5, even when the non-sensitizing emulsion is contained in the color-sensitive emulsion containing no sensitizing dye, no sensitization is achieved. It can be seen that high sensitivity can be achieved only when the non-color-sensitive emulsion is contained in the spectrally sensitized color-sensitive emulsion. Further, it can be seen that the sensitization effect is larger when the non-color sensitive emulsion is contained in the color sensitive emulsion having the color sensitivity of green rather than blue and red rather than green. That is, the present invention shows that the effect is greatest when the red color-sensitive emulsion contains the non-color-sensitive emulsion.

[0125]

As described above, according to the present invention, it is possible to achieve high sensitivity without impairing the granularity, less deterioration of granularity due to natural radiation, good storage stability under high temperature and high humidity conditions, and It is possible to provide a silver halide color photographic light-sensitive material excellent in manufacturing stability.

Claims (7)

[Claims] 1. A color-sensitive silver halide emulsion spectrally sensitized by a sensitizing dye in at least one silver halide emulsion layer provided on a support, and having a solubility higher than that of pure silver bromide. Low, containing 0.1 mol% or more of silver iodide, containing silver halide grains having a grain size of 0.1 μm or more, and being substantially sensitive in a wavelength region spectrally sensitized by the sensitizing dye. A photographic light-sensitive material characterized by containing a non-color-sensitive emulsion having no. 2. A color negative photographic light-sensitive material.
The photographic light-sensitive material described. 3. The photographic light-sensitive material according to claim 1, wherein the silver halide grains of the non-color-sensitive silver halide emulsion are tabular grains having an average aspect ratio of 2 or more. 4. The photographic light-sensitive material according to claim 1, 2 or 3, wherein the color-sensitive silver halide emulsion has red color sensitivity. 5. The silver halide grains contained in the color-sensitive silver halide emulsion have an aspect ratio of 12 or more and a minimum length of 50% or more of the projected area of all the silver halide grains. Is a hexagon having a ratio of the side length having the maximum length to the length of 2 or less and a silver iodide content of 2
5. The photographic light-sensitive material according to claim 1, wherein the variation ratio of the grain size of all silver halide grains is 20% or less, which is occupied by tabular grains having a mol% or more. 6. A color-sensitive silver halide emulsion spectrally sensitized with a sensitizing dye and having a solubility lower than that of pure silver bromide and a density of 0.
It contains 1 mol% or more of silver iodide and has a grain size of 0.1.
After mixing a non-color-sensitive silver halide emulsion containing silver halide grains having a size of at least μm and having substantially no sensitivity in the wavelength region spectrally sensitized with the above-mentioned sensitizing dye, at least it is supported on a support. A method for producing a photographic light-sensitive material, which comprises coating as one silver halide emulsion layer. 7. The method for producing a photographic light-sensitive material according to claim 6, wherein the photographic light-sensitive material is a color negative photographic light-sensitive material.