JPH0222640A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material superior in sensitivity, graininess, and sensitization development performance by specifying the silver halide grains of a silver halide emulsion. CONSTITUTION:At least one of emulsion layers contains >=2 kinds of silver halide emulsions having a ratio of each average particle diameter ratio of 1.1-1.6 and these emulsions are chemically sensitized so as to have at least one of maximum values of the latent image distribution of silver halide grains of each emulsion in the inside of the grain in the depth of <=0.01mum from the surface of the grain, thus permitting the obtained silver halide photographic sensitive material to be superior in sensitivity and graininess, and small in change of gradation, and superior also in sensitization development performance even if the development time is extended.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a halogenated trowel photosensitive material with improved graininess and suitable for sensitization.

(Prior Art) There are various performances required of silver halide photographic materials, but it is particularly important to achieve both high sensitivity and good image quality. In order to increase sensitivity, we improve the light absorption and quantum yield of the silver halide emulsion itself, and
For practical purposes, measures such as extending the development time are often used.

However, for example, extending the development time is often accompanied by an increase in fog, deterioration of graininess, and changes in gradation, so in order to achieve sufficient performance even outside of the optimized standard processing, the photosensitive material itself must be expensive. Technology needs to be introduced.

As a photographic emulsion technology that achieves both high sensitivity and good graininess, for example, U.S. Pat. The inherent desensitization of the silver halide emulsion is significantly smaller than that of silver halide emulsions of equal grain size that are chemically sensitized only on the surface.
It is disclosed that color sensitization sensitivity can be effectively improved by using a large amount of sensitizing dye.

Similarly, Journal of Photographic Science Vol. 13 at p.
/74L), Volume 25, page 1 (/977), Volume 3
Volume 7, page 1 (2007), Photographic Science and Engineering, volume 1, page 333 (
/ri 7 layer year), U.S. Patent No. 031. / Done! No. 3. ? ! 0,! , No. 37, Berichte der Bunsen Gesellschaft Führer Fuisijikalitssie Chemi vol. 6f p. 3j6 (1963) also states that high sensitivity can be obtained by emulsions that form latent images inside the grains. is listed. However, the internal latent image type emulsion used here has most of the radiation-sensitive areas (or latent image forming areas) inside the grains, and the ratio of surface sensitivity to total sensitivity is less than 10%. , the radiation sensitive portion is located at a depth of 0.01 μm or more from the surface. In this way, emulsions that form latent images well inside the grains will not develop sufficiently even if they are developed with the developing solutions of black-and-white, color negative, and color reversal light-sensitive materials, which are practically used, and the sensitivity will be substantially impaired. Become. Further, even if high sensitivity can be achieved by elongating the phenomenon time, fogging may be high, and gradation changes may become large depending on the phenomenon time.

Furthermore, US patent tube 3. No. 7, No. 7 discloses an emulsion in which the latent image is located in a cavity opening toward the grain surface and is developable with a surface developing liquid.

However, an emulsion that can develop a sensitivity equal to or higher than that of a surface latent image emulsion of the same size by processing with a surface phenomenon liquid cannot be called an internal latent image emulsion, and the advantages of an internal latent image emulsion described in Reference A However, color sensitization cannot be fully utilized. As mentioned above, for the processing liquids used in practical use, there has been no study as to what kind of latent distribution from the surface to the inside is preferable in order to achieve good sensitivity and image quality.

On the other hand, US patent 2. ? Yt, J1.2, 3°/71
, No. 212 describes a method for forming negative archives that increases speed and contrast by incorporating both silver halide grains that can form a surface latent image when exposed to light and silver halide grains that have internal fogging nuclei in an emulsion layer. Sexual photographic elements are described. In this photographic element, when the phenomenon is carried out after exposure, the silver halide grains with a surface latent image release a reaction product depending on the exposure amount, which creates cracks in the silver halide grains with internal fogging nuclei and enables the phenomenon. It is something that makes you familiar.

(Problems to be Solved by the Invention) The above elements are attracting attention as they allow two emulsions to achieve a balance between surface and internal sensitivity, which could not be achieved with a single emulsion. Because of this, it takes a long time for the phenomenon to occur, and has the drawbacks of increased fogging and large changes in gradation. Also, Tokukai Akihiro Tarcono! The 710 silver germide grains disclosed in No. λ have fogging nuclei inside them.
The same applies to the method of incorporating a silver halide emulsion into a light-sensitive emulsion layer and/or its adjacent layer to improve suitability for sensitization processing, and the technique disclosed in JP-A-KOKAI No. SHOTA-IO≠θ. There are drawbacks.

Therefore, it has been desired to have a photographic material that has high sensitivity and good graininess when subjected to standard phenomenon processing, and also exhibits small changes in gradation and fog during sensitization processing.

Therefore, an object of the present invention is to provide a silver halide photographic material having excellent sensitivity, graininess, and sensitization phenomenon.

(Means for Solving the Problem) The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, in which at least seven of the emulsion layers each have average grains. It contains two or more types of silver halide emulsions with a size ratio of 10 pairs// or more, and seven or more local maxima of the latent distribution of each of the silver halide grains are present inside the grains, and This is achieved by using a silver halide photographic light-sensitive material which is chemically sensitized so that the position of the maximum value is at a depth of less than 0.0 μm from the grain surface.

Here, the storage distribution is defined as the depth of the latent image from the particle surface (
X μm), and the latent number (y) is plotted on the vertical axis, where X is S: Silver halide emulsion average grain size (μm)Ag1: Residual silver after performing the following treatment on an unexposed emulsion coated sample Quantity Ago: The amount of coated silver before treatment, and the reciprocal of the exposure amount that gives a density of 10,000 mm when the following treatment is performed after white exposure for yrai/loo seconds. The processing conditions for obtaining the above latent image distribution are N-methyl-p-aminophenol sulfate, jg sodium L-ascorbate, 10g sodium metaborate, jjg potassium bromide.
Add 7g water
Anhydrous sodium sulfite was added in an amount of 0 to iog/l to a treatment solution having a pH of 1/1 (pH i), and the mixture was treated at 2!0C for 5 minutes.

By changing the amount of anhydrous sodium sulfite from θ to 10 g/l, the depth from the surface of the latent image in the silver halide grains developed during processing changes, and the latent friction number in the depth direction changes. You can know the changes in

The content of the present invention will be explained in detail below.

If the maximum value of the friction increase distribution determined as described above exists at a depth of 0.0/μm or more from the surface, black and white,
Even if the phenomenon occurs using a phenomenon liquid practically used for color negative or color reversal light-sensitive materials, the phenomenon is insufficient and the sensitivity is substantially impaired.

Internal latent image emulsion that has been reported so far! According to the 4 manufacturing method, controlling the thickness of the shell resulted in changing the ratio of surface sensitivity to internal sensitivity. However, the results of this study revealed that in order to achieve optimal sensitivity for a given process, it is necessary to control the particle formation conditions and the mode of latent image distribution.

On the other hand, the conventional internal latent image type silver halide grain design standard, which focuses only on the difference between the sensitivity when surface development is carried out and the sensitivity when internal phenomena are carried out, is also difficult to achieve optimum sensitivity.
is insufficient.

In other words, the maximum of the latent image distribution is 0.0! If the particle exists at a depth of .mu.m or more, the potential optimum sensitivity of the particle cannot be brought out due to insufficient phenomena depending on practical processing.

As described above, it has become clear that in order to develop optimal sensitivity, internal latent image type silver halide grains must be designed in consideration of the position where the maximum latent image distribution exists.

The above-mentioned practical processing solution refers to a processing solution in which the silver halide solvent is removed with the intention of producing only the surface latent image, or a processing solution containing a large amount of silver halide solvent with the intention of producing the internal latent image. It is not a phenomenon liquid that contains it.

In the former case, the sensitivity of the internal dispersion type emulsion of the present invention cannot be optimally expressed with the liquid, and in the latter case, the silver halide may dissolve too much during processing or the grain quality may deteriorate due to the contagion phenomenon. let Specifically, it is preferable that the developer contains 100 mg/l or less of potassium iodide or ioog/l or less of sodium sulfite or potassium sulfite as a silver halide solvent. In addition, potassium thiocyanate or the like can be used as a silver halide solvent in the phenomenon liquid.

The silver halogenide emulsion with the latent image distribution as described above exhibits high sensitivity and good graininess.
Although it is described in 3θ Bu0co No. 2, when it is contained alone in one color-sensitive layer or one emulsion layer,
Changes in photographic gradation occur with changes in phenomenon time. That is, when the development time is short, emulsion grains that have formed latent layers near the surface are not able to develop, giving a hard gradation due to the contagion phenomenon that induces the phenomenon of particles in the vicinity of the grains. on the other hand,
If the development time is long, the emulsion grains that have formed a latent image inside the grain will also be developed based on their own activity, resulting in a soft gradation that depends on the size distribution of the emulsion grains. It will be given.

As a result of examining methods to reduce such gradation changes that occur during the phenomenon time, we found that the maximum value of the latent distribution was reduced to 0 from the particle surface.
．． An emulsion having an average grain size of less than 0/μm, /, /
or more/A or less, preferably 1.73 or more and 1. It has become clear that the above object can be achieved by using a mixture of two or more types of silver halide emulsions that differ in a ratio of μ or less.

A technique for mixing two or more types of silver halide grains having different average grain sizes in a commonly used surface latent image type emulsion is described, for example, in JP-A-7-71-3. However, for the emulsion having the device distribution of the present invention, different sizes of λ
It was unexpected that the suitability for sensitization could be improved by mixing more than one species.

Mixing two or more types of emulsions with different sizes is useful in improving the gradation and sensitization development suitability of internal reservoir emulsions that exist at positions where the maximum value of the latent chamber distribution is less than 0,0/pm. However, in the latent distribution of the emulsion to be mixed,
It is preferable that the grain surface also have a latent image number of 1/1 or more and less than 1 times the maximum value in order to enhance the phenomenon activity of the emulsion layer and improve the sensitivity.

In addition, in the present invention, if the grain size ratio is larger than /, J, the gradation specific to each emulsion will separate, making it impossible to obtain a constant gradation over a wide exposure range. , i, and the average grain size of each emulsion approaches each other, the effect of mixing the two emulsions will not be sufficiently expressed, which is undesirable.

In the present invention, the average grain size refers to the diameter in the case of spherical silver halide grains, or the average value of the diameter when the projection field is converted into a circle with the same area in the case of grains with shapes other than cubic or spherical. , the individual grain size is rl, and the number is n
When l, the average particle diameter r is defined by the following formula.

The emulsions of the present invention can be color sensitized by methods well known in the art. The amount of sensitizing dye should be the amount that gives the highest negative blue sensitivity, but this amount is about the same as the amount that gives the highest negative blue sensitivity in surface latent emulsions. It is not preferable to add a very large amount of dye because it inhibits the development of the particles.

Further, the amount of the sensitizing dye is preferably varied depending on the size of each emulsion grain, and the larger the grain size is, the smaller the amount added is. Therefore, it is preferable to add the sensitizing dye before mixing the emulsion, for example, during grain formation, physical ripening, or chemical ripening.

The emulsion of the present invention can also be used without color sensitization. In this case, the effect on color sensitization described in Document A cannot be expected, but the effect on storage stability can be seen.

The silver halide photographic emulsion used in the present invention may contain any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride.

The preferred silver halide is silver iodobromide or silver iodochlorobromide containing less than about 30 moles of silver iodide.

Particularly preferred is silver iodobromide containing from about 0.1 moles to about 7 j moles, more preferably from /,j to j moles. Further, the halogen composition of each emulsion may be the same or different.

The maximum value of the silver iodide distribution within the grain may be one or more. Further, the silver iodide content at the maximum value is preferably at least twice the average silver iodide content of the entire grain, more preferably at least twice the average silver iodide content, and most preferably silver iodide itself. The position of the above maximum value may be anywhere below the internal chemical sensitizing part. It is preferable that the change gradient of the silver iodide composition to reach the maximum value is as large as possible, and in extreme cases, an epitaxial junction may be provided.

The crystal structure other than the region forming the maximum value of silver iodide distribution is -
It may be of a different type, or it may be of a different halogen composition, or it may have a layered structure.

These emulsion grains are described in British Patent No. 7,027. /μz issue, US Patent No. 3,! Or, O41, same≠.

Hiroqμ, t77 and special request Akira! T-2 Hiro "Disclosed in Heri issue etc.

Further, the grains of the present invention may themselves be joined to silver halide having a different composition by epitaxial joining, or may be joined to a compound other than silver halide, such as silver rhodan or lead oxide.

These emulsion grains are covered by US patent no. ,09≠,6ry
No., same, / Kuko, Po0 No., same gu, 1ge.

! jJ, British Patent No. 031.7 Octopus, US Patent No. 7,3≠2. t2λ issue, same number, 3rd! .

1A71r, same 'I, '73! , 10/No. 44.
! J! , No. 017, same j, 4tJ, PJ,! No. 3゜112,067, JP-A-ShojP-/12! l/-0
Disclosed in the issue etc.

Silver halide grains may be so-called regular grains having regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or may have irregular crystal shapes such as tabular, spherical, etc., and twin grains. Although particles having crystal defects such as planes or a composite form thereof may be used, regular particles are preferable in terms of controlling the latent image distribution. Also, mixtures of various crystal forms may be used.

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

The grain size of the silver halide may be fine grains of about 0.17 microns or less or dog-sized grains with a projected area diameter of up to about 10 microns, and may be an emulsion with a narrow distribution or a monodisperse emulsion with a wide distribution. However, a monodispersed emulsion is preferable in terms of improving graininess.

A typical monodispersed emulsion is an emulsion in which at least 3% by weight of the emulsion is within 4% of the average grain diameter. The average particle diameter is o, or ~3 microns;
Emulsions containing at least 5% by weight of silver halide grains or at least j% (by number of grains) of silver halide grains having an average grain diameter within the range of ±20e4 can be used in the present invention. A method for producing such an emulsion is described in U.S. Patent No. 3. j7≠, tsr issue,
3.43-j, J Rihiro and British Patent No. 1. ≠73
゜7≠? listed in the number. Also, Tokukai Sho≠za-t60
No. 0, No. j/-32027, No. j/-30'? No. 7, No. 3-/37/33, No. 7, No. 3-/37/33, No. 7, No. 7, No. 7, No. 3-/37/33, No. riμ/ri issue, same jlr-37t3! issue, same jr
- Monodisperse emulsions such as those described in Kotata No. 31r can also be preferably used in the present invention.

The method for preparing the internal latent image type emulsion of the present invention is described in US Pat. Ri7! P, No. 273, 3. ri44゜≠76,
No. 3,204,313, No. 3. It is possible to use the methods described in Japanese Patent Publication Akihiro 3-2 Tag Oj, Japanese Patent Publication Akihiro J-/3232, etc.; In order to obtain an emulsion with a latent image distribution of , it is necessary to adjust the chemical sensitization method, the amount of silver halide precipitated after chemical sensitization, and the precipitation conditions.

Specifically, U.S. Patent No. 3. No. 7, No. 213, an internal latent image type emulsion is prepared by precipitating silver halide again by a controlled double jet method on emulsion grains whose surfaces have been chemically sensitized. Precipitating silver halide onto the grains in the amounts practiced in this patent results in a surface sensitivity to total sensitivity ratio of less than 70 minutes. Therefore, in order to obtain the latent image distribution of the present invention, the amount of silver halide to be precipitated after chemical sensitization is determined according to US Pat. 7, and should be less than what is implemented in Core No. 3.

Also, U.S. Patent No. 3. AA, No. 4 (No. 7A) also employs a method in which silver halide is precipitated on emulsion grains after chemical sensitization by a controlled double jet method. When precipitated by a method such as that described above, it is not possible to embed the photosensitive nuclei inside the grains.Therefore, the emulsion implemented in the above-mentioned patent has a surface phenomenon that reduces the original surface at least as much as the chemically sensitized emulsion. The sensitivity increases by 0.021 ogE or more.For this reason, in order to obtain the latent image distribution of the present invention, the amount of silver halide to be precipitated after chemical sensitization must be set according to U.S. Pat. It is necessary to control the precipitation conditions (for example, the solubility of silver halide in the precipitation and the rate of addition of soluble silver salt and soluble halide salt) to a greater degree than what is practiced in No. 1.

In order to accelerate grain growth during production of the tabular grains of the present invention,
A method of increasing the addition rate, amount, and concentration of the silver salt solution (for example, AgNO3 aqueous solution) and halide solution (for example, KBr aqueous solution) to be added is preferably used.

These methods are described, for example, in British Patent No. 1.33! ,
octopus! No. 3, U.S. Patent No. 3. t7ko, riO0, same No.J
, No. 160.737, No. ≠, λ Hiroko, No. 1, Tokukai Sho! ! -l≠ko32ri, same j! -7ta 1r/21t, etc. can be referred to.

The properties of silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitation formation process. Such compounds may be initially present in the reactor or may be added in accordance with conventional methods and/or with the addition of one or more salts. US Patent No. 2.
≠<z, r, otO issue, same co, Otsu it, /47 issue,
same! , No. 737゜373, No. 3,772,037, and Research Disclosure /3'A%, /7/June, 13≠j-2, copper, iridium, lead, bismuth , cadmium, zinc (sulfur, chalcogen compounds such as selenium and tellurium), gold and
The properties of silver halide can be controlled by the presence of compounds such as compounds of noble metals in the silver halide precipitation process.

Silver halide emulsions undergo precipitation formation as described in Special Publication No. 1F-/U10, by Moisar et al., Journal of Photographic Science, Vol. 2, p. 77, p. 27. In the process, the inside of the particle can be reduced-sensitized.

Chemical sensitization is described in The Theory of Photographic Processes, by James T.
ames, The Theory of theP
photographic Process, p th
ad.

It can be carried out using activated gelatin as described in Macmillan, / 77), pp. 7-74, and also in Research Disclosure, Vol. Volume, /ri7/Year to Month, 73μ! λ, U.S. Patent No. A+2,3T/No. 3.2 7. Hiro≠ issue, 3,772,03/issue, same J, lr! 7, 7// issue, same 3. 0/, 7/≠ issue, same a, stt, oir issue, and same! , 'f'0≠, ≠/! No. 1, as well as British Patent No. 1.
316, 7ta! pAg7-10 as described in No.
S pH3~! and sulfur, selenium, tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers at temperatures of 3o-ro 0c. Chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound and as described in U.S. Pat.
// Issue, Dopi, No. 216.0II and Dohiro, 0j41
．． It is carried out in the presence of a sulfur-containing compound such as a sulfur-containing compound described in No. 1117 or a sulfur-containing compound such as hypo, a thiourea compound, or a rhodanine compound. Chemical sensitization can also be carried out in the presence of chemical sensitization aids. Chemical sensitization aids used include:
Compounds known to suppress capri and increase sensitivity are used in the process of chemical sensitization, such as azaindene, azapyridazine, azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Patent No. 2,/3/, 031
Same issue! , 41//, No. P/4, 3. j! ≠, 7j
No. 7, Tokukai Showa 3j-/Kotsu! JJ and the aforementioned "Photographic Emulsion Chemistry" by Duffin, pp./31r-/Ko.3. In addition to or in place of chemical sensitization, US Pat. ri/.

1 and 3. For example, reduction sensitization can be carried out using hydrogen, as described in the R♂μ, Kohiro issue,
U.S. Patent No. 1! /r, l, ri♂ issue, same 2,7μ3. /
12 and 2.7 Hiro 3.7t3, using reducing agents such as stannous chloride, thiourea dioxide, polyamines, and/or low pAg (e.g. less than 5) and/or high pH Can be reduced sensitized by treatment (for example! more dogs). Also, U.S. Patent No. 3. ri/7. Hiro? ! No. and 3. The color sensitization can also be improved by the chemical sensitization method described in Aj, ≠76.

Also, Tokugan Shojter 12 Kota R/issue and the same! tar/2 kota r
A sensitization method using an oxidizing agent as described in Kogo can also be applied.

The emulsion of the present invention is chemically sensitized so as to have a maximum value of the latent force distribution at a grain surface depth of less than 0/μm, and then shelled with silver halide. The distance from the particle surface is preferably o, oos to o
, oorpm.

The internal latent image type emulsion of the present invention is preferably chemically sensitized in its grain surface region, and the number of reservoirs is preferably 7/5 or more and less than 1 times the maximum value inside the grain. preferable. This is because the maximum value of the latent image distribution is 0.
Even if it is less than 0.01 μm, if the latent one-dimensional distribution on the surface exceeds the above maximum value, the color sensitization efficiency may become insufficient,
Furthermore, if the temperature is 5 minutes or less of the above-mentioned maximum value, the phenomenon may be insufficient in a practical phenomenon liquid.

Ordinary silver halide photographic emulsions different from the above-mentioned emulsions that can be used in the present invention can be produced by known methods, such as those described in Research Disclosure/71. Volume, A/71, 1
73 (/P7r 7λ month), pp. 22-23 @■,
Emulsion Preparation
and Types)” and volume 7, &/r
You can follow the method described in 7/Otsu (197 year l/month), page 64tt.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chimie et Phys
fquePhotographique Paul M
7), "Photographic Emulsion Chemistry" by Duffin, published by Cal Press (G, F, Duffin)
, Photographic Emulsion Ch.
emistry (Focal Press.

19tt), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
, published by Focal Press (V, L.

Zeltkrnan et al, Makfng a
nd Coating Photographic Em
ulsion, FocalPress, /Pl
x u ), etc. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Also known silver halide solvents (eg ammonia, rhodankali or US Pat. No. 3.27/).

/j7 issue, Tokukai Sho! /-/Ko340, Tokukai Akira! 3-Otsuji or issue, Tokukaisho! 3-/Hiroshi≠37th issue, Tokukai Shoj≠-
Physical ripening can also be carried out in the presence of thioethers and thione compounds described in JP-A No. 1001/7 or JP-A-1001/16121.

The silver halide emulsion consisting of regular grains used in the present invention can be obtained by controlling pAg and pH during grain formation. For more information, please see, for example, 7 Otographic Science and Engineering (Photogr.
aphic 5science and Engineer
ing) Volume 2, l! ri~16ta (/ri4J); Journal of Photographic Science (Jour
nal of Photographic Science
ce) / Volume 2, 2172-2! /page (/yAμ)
, U.S. Patent No. 3.63! , Jri≠ issue and British patent no.
．． It is described in Hiroshi/No. 3, 74#.

Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff, Ph.
otographic 5science andEng
ineering) Volume 1≠, pages 24# to 217 (l
70 years); U.S. Patent No. ≠, Ko 3≠, Koko wo, Do Hiro,
Hiro/Hiro, No. 310, same ≠, Hiro 33.0≠, same μ, <
432. ! No. 120 and British Patent No. 2. //2,13
It can be easily prepared by the method described in No. 7, etc. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, which are described in detail in the previously cited U.S. Pat. It is being

Details of the structure and manufacturing method of the monodispersed hexagonal tabular grains referred to in the present invention are disclosed in the patent application filed in 1973. iP/! According to the description in No. j, briefly stated, the emulsion is a silver halide emulsion consisting of a dispersion medium and silver halide grains, and 70 inches or more of the total projected area of the silver halide grains has a minimum A hexagonal shape in which the ratio of the length of the longest side to the length of the longest side is less than or equal to 0, and is occupied by tabular silver halide having two parallel surfaces as outer surfaces. Furthermore, the coefficient of variation of the grain size distribution of the hexagonal tabular silver halide grains [the value obtained by dividing the variation (standard deviation) of the grain size expressed by the circular diameter of its projected area by the average grain size. ] has a monodispersity of 20% or less, and the ascent ratio is ko,! Above, the particle size Fio,
rμm or more.

The silver halide grains can be produced through nucleation-Ostwald ripening and grain growth,
For details, please see Tokugan Shoj/-Kotata/j! Follow the instructions in the issue.

The properties of silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitation formation process. Such compounds may be initially present in the reactor or may be added along with one or more salts in accordance with conventional methods. U.S. Patent Tsutsuko,
μ≠r, otO issue, same co, tco I, /67 issue, same 3,7
37゜3/3 issue, 3,772,03/issue, and Research Disclosure /3 Hiromaki, /ri7j June, 73≠! Copper, iridium, lead, as described in 2.
The properties of silver halide can be controlled by the presence of compounds such as bismuth, cadmium, zinc (chalcogen compounds such as sulfur, selenium, and tellurium), gold, and compounds of Group I noble metals during the silver halide precipitation process.

Tokusho rr-ipto issue, Moiser et al., The Journal of Photographic Science, No. As described in Volume 1 to Core Pages (/277), monodisperse hexagonal tabular grains can be sensitized by internal reduction during the precipitation formation process.

The monodisperse hexagonal tabular grains used in the present invention can be wrapped in a sheath to form a core-sheath emulsion using techniques well known in the art. The method for forming this silver salt sheath is described in U.S. Patent No. 3. No. Jt7.77, No. J, No. 206.3IJ,
Same No. 3, 3/7, 322, Same No. J, Y/7. ≠rz issue, and the same number.

72≠, the description in No. 171r can be referred to.

In order to remove soluble silver salts from the emulsion before and after physical ripening, Nudel water washing, flocculation sedimentation method, ultrafiltration method, etc. are used.

The additives used in the chemical ripening and spectral sensitization of the emulsion used in the present invention are described in the above-mentioned Research Disclosure 'f'.
-A/7J! J (15'7r/J month) and &/
17/l (/P7?/January), and the relevant parts are summarized in the table below.

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

The spectral sensitizing dye, antifogging agent, and stabilizer can be used in any step of the photographic emulsion production process, or can be present at any stage after production up to just before coating. Examples of the former include a silver halide grain formation process, a physical ripening process, and a chemical ripening process.

That is, in addition to their original functions, spectral sensitizing dyes, antifoggants, and stabilizers are used to limit the formation positions of chemical sensitizing nuclei by utilizing other properties such as strong adsorption to emulsions. It is also used to stop excessive halogen conversion when obtaining bonded structure particles with a halogen composition, and to maintain the bonded structure of different types of halogens. Regarding these, JP-A No. 3J-2TJR, JP-A No. 31-///R-3J, Tr-AR'Y3R, JP-A 6.2-70A
No. o, U.S. Patent Tube J, t2r, No. 91,0, No. 1
t, 223. You can refer to the description in No. tJJ.

If some or all of the spectral sensitizing dyes, antifoggants, and stabilizers to be added are added before adding the chemical sensitizer, and then the chemical sensitizer is added and chemical ripening is performed, the chemical sensitization The positions where sensitive nuclei are formed on silver halide grains are limited to areas where sensitizing dyes, antifoggants and stabilizers are not adsorbed, thus preventing latent image dispersion and improving photographic properties. Therefore, it is particularly preferable. In particular, silver halide grains (//
/) When adding sensitizing dyes, antifoggants, and stabilizers that selectively adsorb to the surfaces, chemical sensitizing nuclei are formed only at the edges when hexagonal tabular grains are used, so preferable.

Generally, the above-mentioned additives are preferentially adsorbed on the crystal surfaces forming the main surfaces of the tabular grains, so that chemical sensitization nuclei are generated on different crystal surfaces of the tabular grains.

It is also effective to carry out chemical sensitization in the presence of a silver halide solvent. The types of silver halide solvents used are thiocyanate and Tokugan Sho t/- Kotata/! ! The solvents listed in No. 2 can be used.

The concentration of the solvent used is preferably 10-5 to 10-1 moJ/l.

In combination with either or both of the above techniques,
or independently as a third technique, silver salts such as silver thiocyanate, silver phosphate, silver carbonate, etc., which can form precipitates on the particle surface immediately before or during chemical sensitization. , and soluble silver salts such as silver acetate, silver trifluoroacetate, and silver nitrate, as well as finely divided silver halides (i.e., silver bromide, silver bromide,
Silver iodide and/or silver chloride) particles can be introduced. For example, Lippmann emulsions can be introduced during the chemical sensitization process.

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

Regarding spectral sensitization using antenna dyes, see patent application Sho J/-
! /396 issue, 4/-Jr4tJ7/ issue, A/-2
The description in No. 1827λ can be referred to.

Additive types/Chemical sensitizers Sensitivity enhancers Brighteners 7 Anti-stinting agents! Dye image stabilizer hardener io binder // plasticizer, lubricant RD776113 RD/17/l 3 pages ttir page right column same as above μ page colo page right column co! Page 2z Page 2 to page 27 tzo Page left to right column tri page left column Same as above page 630 right column Fi Various color couplers can be used in the present invention, and specific examples are given in the Research Disclosure (R
D) Described in the patent described in A/76 Ko 3, ■-C, C.

Examples of yellow couplers include U.S. Patent Tube J, ?
! ! , 60/issue, same issue! , No. 022.620, No. 1f, JJ&, No. 02'l-, No. 44. uO/.

7! λ, special public Akira! r-70132, British Patent No. 1
, +t, 2 j, 0ko 0, same No. 1. @74.7
Those described in No. AO, etc. are preferred.

As a magenta coupler! -Pyrazoline and pyrazoloazole compounds are preferred;
o, ti No.2, same No.g, JJ-/.

tri No. 7, European Patent Tube 7J, 636, U.S. Patent Tube J
, oti, p3.2, same no. 3,72! , No. 047, Research Disclosure I6 Ko Hirokoko 0 (iy
(June, 1986), JP-A-60-333-12, Research Disclosure A241230 (June, 2013), JP-A-1436!2, US Patent Application No. ≠,! 0
0, t30 issue, same issue ≠,! Particularly preferable are those described in gu o, tr≠, etc.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent No. μ.

0!2. JA? , No. 2.22, No. 2. tO/, No. 171,
Same No. 2,772,162, Same J, rPj, r24,
Same No. 3.77J, No. 002, Same No. J, 711r,
No. 301, No. u, 3341°0//, No. ≠, 3 core, No. 173, West German patent application No. 3, 3, 2, 7 Kota, European Patent No. 1 Ko/.

JtJ-1, U.S. Patent No. J, 4<! J, J Coco issue, same Daihiro, 333. Tatata-go, Dodai-Hiroshi, ≠! /, jj issue,
Same No. ≠, ≠ Core, No. 747, European Patent No. 1t/, 626
Those described in No. A etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are available from Research Disclosure/71. ■-G term of ≠3, U.S. Patent No. ≠, /l,! .

No. 70, Special Publication Show JR7-39μ73, U.S. Patent No. F
, 0OIA, No. 929, No. p, tJlr, No. 21, British Patent No. 1. /ltl, No. 361 is preferred.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Pat.
,! No. 70, European Patent No. 26. ! No. 70, West German Patent Publication No. 3,23μ, j33 are preferred.

Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. ≠! /, rcoO issue, same number ≠, oro, 2ii issue, same number 41. Jt 7,212, British Patent No. 2,10, 773, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the phenomenon suppressor has the aforementioned RD/7j≠3,
■-The patent described in Section F, JP-A-Sho J-7-/! IP≠
Hiro issue, 67-/j≠23μ issue, same to-it<-≠r
No. 1, U.S. Patent No.

2≠l, those described in Ri No. 42 are preferred.

Couplers that release a nucleating agent or a phenomenon accelerator in an imagewise manner include British Patent No. x, oP7, /≠θ,
Same 2nd. /3/, /r♂ issue, Tokukai Akira! Turf 17431
No. JP-/701410 is preferred.

In addition, examples of couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.

213, F7J No. 11-,! 31. ! No. 23,
Hiroshi Dodai, 310. Multi-equivalent couplers described in No. t/I etc.,
Examples include DIR redox compound-releasing couplers described in JP-A-40-111210 and the like, and couplers that release dyes that recover color after separation as described in European Patent No. 17J and JO2A.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat.

The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat.

No. 363, West German Patent Application (OLS) No. 2. ! Hiroshi.

Core No. 1/- and Core No. 2. ! 4'/, No. 230, etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, A/74≠3 cor page, and wholesaler/17/l t
It is written in the right column of Ko 7 to the left column of page 6≠1.

The color development solution used in the color development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color development agent as a main component. Aminophenol compounds are also useful as the main agent for this coloring phenomenon, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-≠-amino-N, N-diethylaniline, 3-methyl -≠-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-7-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-Hiro-ami/-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides, Fip-)luenesulfonates, and the like. Two or more of these metal compounds can be used in combination depending on the purpose.

The coloring stock solution contains pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
It is common to include inhibitors or anticapri agents such as benzimidazoles, benzothiazoles or mercapto compounds. In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethylamine, catecholsulfonic acids, triethylenediamine (72 μm diazabicyclo[co]) may be added.

various preservatives such as 2:l octane), organic solvents such as ethylene glycol, diethylene glycol, phenomenon promoters such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, Competitive couplers Coupling agents such as sodium boron hydride, auxiliary developing agents such as phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarmenic acids, aminopolyphosphonic acids, alkylphosphonic acids,
Various chelating agents such as phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid,
diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethyrythene-/,/-diphosphonic acid, nitrilo-N,
N,N-trimethylenephosphonic acid, ethylenediamine-
N, N, N/.

Typical examples include N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid) and their salts.

Furthermore, when reversal processing is performed, color development usually occurs after black and white development. This black-and-white developer contains known black-and-white phenomenon main agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as /-phenyl-3-pyrazolidone, and amine phenols such as #iN-methyl-p-aminephenol. Alternatively, they can be used in combination.

The pH of these color developer stock solutions and black-and-white phenomenon solutions is generally 2 to 1/2. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but is generally less than 31 per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, r o
It can also be less than 0 ml. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

After the color development phenomenon, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■) and cobalt (II).
Compounds of polyvalent metals such as I), chromium (■), and copper (If), peracids, quinones, and nitro compounds are used.

Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or copal) (I[[), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, Aminopolycarboxylic acids such as 3-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.:
Persulfates; bromates; permanganates; nitrobenzenes and the like can be used. Among these, aminopolycarboxylic acid iron(III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron(III) complex salts, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions.

The pH of the bleach solution or bleach-fix solution using these aminopolycarboxylic acid iron(I[I) complex salts is usually j, j~! However, to speed up the process, it is also possible to process at an even lower pH.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, and ammonium thiosulfate is the most commonly used. Can be used widely. As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (the number of stages), the replenishment method such as countercurrent or forward flow, and other conditions. can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of
MotionPicture and Te1evis
ion Engineers Volume t≠, P, Ko4t♂-
It can be determined by the method described in 263 (/P3-j year! month issue).

The pH of the washing water in the processing of the photosensitive material of the present invention is
and preferably Fit=? It is. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc.
In general, /! A range of 20 seconds to 10 minutes is selected for -≠z'C, preferably 30 seconds to 5 minutes for coj-≠o'C. Furthermore, instead of washing with water, the photosensitive material of the present invention can be directly processed with a stabilizing solution. In such a stabilization process, Japanese Patent Application Laid-Open No. 77-1. J Hiroshi No. 3! ♂－
/ Hiro, 13 Hiro, 1,0-. 220. jda! All known methods described in this issue can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid used for washing with water and/or replenishing the stabilizing liquid can be reused in step 17]f of the desilvering process, etc.

Various processing liquids in the present invention are used in io'C-tooC. Normally, the standard temperature is J3°C to Jr0C, but it is often possible to use high-temperature pressure to accelerate processing and shorten processing time, or conversely to lower the temperature to improve image quality and stability of the processing solution. can be achieved.

On the other hand, in order to effect the black and white light-sensitive material in the present invention, various known agents for effecting the effect can be used. i.e. polyhydroxybenzenes, such as hydroquinone, λ-chlorohydroquinone, -monomethylhydroquinone, catechol, pyrogallol, etc.; aminophenols, such as p-aminophenol, N-methyl-p
-aminophenol, 2.4t-diaminophenol, etc.: 3-pyrazolidones, such as /-phenyl-3-pyrazolidones, l-phenyl-hiro, μ'-dimethyl-3
-pyrazolidone, l-phenyl-≠-methyl-≠-hydroxymethyl-3-pyrazolidone,! , j-dimethyl-/-phenyl-3-pyrazolidone, etc.: Ascorbic acids, etc., can be used alone or in combination. Further, the phenomenon liquid described in Japanese Patent Application Laid-Open No. 2003-120002 can also be used.

For detailed examples of developers, preservatives, buffers, and development methods for black-and-white photosensitive materials, please refer to "
Research Disclosure” magazine 4/7j4tJ (1
5'7. Published in February 2013)

(Example) The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

Example 1 Silver iodobromide emulsions of 1offl as shown in Table 1 were
Manufactured. The method for preparing the emulsion is described below.

(Emulsion/) Aqueous gelatin solution kept at 72°C (o, <7J7%)
Maintain silver potential (SCE) +fomV inside, from 2 to /! A silver thinitrate aqueous solution and an aqueous solution containing KBr and KI were added by double jet over 53 minutes to prepare a monodisperse emulsion (edge length, 30 μm) having a crystal habit of 100). Next, sodium thiosulfate and sodium chloroaurate were added to this core emulsion as chemical sensitizers, and chemical ripening was performed for 11 minutes. After that, Ko! Reduce the temperature to zo 0c over a period of minutes and then l
By adding an aqueous silver nitrate solution and an aqueous solution containing KBr and KI over 3 minutes, the shishiel was precipitated to a final size of 0. J/μm average iodized steel content Komolti. Soluble silver salts were removed from this by a conventional 70° curation sedimentation method to obtain emulsion 1.

(Emulsion λ~t) Increase the silver nitrate addition rate at the initial stage of core grain formation (for example, in Emulsion 2, increase the addition time to μ minutes), reduce the core size,
In addition, emulsions λ to B were prepared in the same manner as emulsion / except that the amount of chemical sensitizer added was increased in inverse proportion to the core size (that is, in proportion to the surface area).

(Emulsion 7.r) Emulsion/,!, except that the shell precipitation time was changed from 3 minutes to 1 minute! Emulsion 7. I got t. By increasing the degree of supersaturation when precipitating the shell, the surface latent image distribution can be reduced as shown in the bottom note of Table 1.

(Emulsion, IO) The amount of silver nitrate added in core grain formation was reduced by 30 grams,
On the other hand, by using the same amount of silver nitrate as the amount of silver nitrate that was reduced in the precipitation of the shell, is it possible to create an emulsion? , got 10.

(Emulsion/l, /co) The silver nitrate and KBrSKI aqueous solution used for shell precipitation are added together at the time of core formation, and the chemical sensitizer is added after the soluble silver salt is removed by flocculation precipitation. /, /co were prepared. The amount of sodium thiosulfate to be added at this time is determined to be the optimum amount for the emulsion to obtain sensitivity.

! /, twice the amount was added.

(Emulsion 13 to -〇) Except for using monodisperse hexagonal tabular grains as the core grains, emulsion/,! , //, /λ Emulsion lJ,! ≠, /!
, /1, and emulsions /7°/I, /I, and Q were prepared by using monodisperse octahedral grains as core grains.

Next, an emulsion layer having the composition shown below was coated on the cellulose 93-acetate film support after being undercoated, and the silver iodobromide shown in Table 1 was sequentially added to the first red-sensitive emulsion layer. /~
/J/ (Table 2).

1st layer: antihalation layer black colloidal silver O, Coj g/m2
Ultraviolet absorber U-to, i g/m2
Ultraviolet absorber U-λ O,/g/m2 High boiling point organic solvent 0il-/0. /cc/m2 gelatin
l・rig/m 2nd λ layer: Intermediate layer-7 Cpd-D 10mg/m2 High boiling point organic solvent 0il-j aOmg/m2 Gelatin
0.1Ltg/m2 Third layer: Intermediate layer -
Cosilver iodobromide emulsion (average grain size o, iμm, AgI content 0, t
mole, %) 0.1g7m2 gelatin
O0≠g/m20μ layer: first red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-i and S-2 (average grain size 0.3μ, AgI content 5 tilt dispersed cubes) Silver amount o, 4μg/rn2 Coupler C-/0, J g/m2
C-20, Ojg/m2 High boiling point organic solvent Oi 1-/0, / cc/
m2 gelatin 0. Ig/m2 number!
Layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-/ and S-1 (monodispersed cubic emulsion with average grain size O0jμ and Agl content μm) Silver amount 0. Hiroshi g/m2 coupler C-to, ag/m2C-3o
, 4g/m2 C-10, OJ-g/m2 High boiling point organic solvent Oi 1-/0, /cc/
m2 gelatin 0. Ig/rn2 6th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-/ and S-1 (average grain size o, tμ, AgI content content 2 tilt dispersed cubes) Silver amount Q, g/m2 Turnip 5- C-J O,7ilm2 Gelatin /, /g/m2 7th layer: 7th
Eyebrows: Medium dye D-/0.0.2ilm2
gelachi 7 0. Ag/m2 Layer: Intermediate layer-μ Silver iodobromide emulsion (average grain size o, otμ, AgI content 1 mol%) Compound Cp d-A I, 2 g/m
2 Gelatin /, Og/m2 2nd
Layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-J and S-≠ (average grain size O9λμ, AgI content 5 tilt dispersed cube) Silver amount 0.1g7m2 Coupler C -4t o, 3g/rn2 compound Cpd-BO, 03g7m2 gelatin
0.1ilm2 1st of @: 2nd
Green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and S-a (
Emulsion layer is listed in Table λ) Silver amount O11g/m2 Coupler C-4! 0. jg/m2 Compound Cpd-B O, 03g7m2 Gelatin
0.6ilm2 11th layer: 3rd green-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-3 and 5-tx (Average grain size θ, tμ, Ascto ratio! AgI content Content 2tilt) Plate emulsion) Silver amount 0.1ilm2 Coupler C-g 0. rg/m2 compound
Cpd-B O, 01g7m2 gelatin
/, 0g7m2 12th layer: Intermediate layer -j Dye D-, 20,0μg/m2 Gelatin 0.4g7m2 13th layer: Yellow filter layer Yellow colloidal silver θ, /g/m2 Compound
Cpd-Ao, 01g7m2 Gelatin /, /g/m2 1st ≠ layer gelatin 0.7g/m2 1st! Layer: First blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-z and S-1 (
Average particle size 0. Jμ, monodisperse cubic emulsion with AgI content of 3 molt) Silver content 0. Ag/m2 coupler C-j O, 6g/m2 gelatin 0. rg/m2 16th layer: second blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-z and S-+ (
Average particle size 0.2μ, aspect ratio 7, AgI content 2
Tilt plate emulsion) Silver amount 0. Hiroshi g/m2 Coupler C-to, J g/m2
C-60, 3g/m2 Gelatin 0. ? g/m2 Seventeenth layer: Third blue-sensitive emulsion layer Silver iodobromide emulsion containing sensitizing dyes S-t and S-1 (
Average particle size i, oμ, ascto ratio 7 AgI content content 2
Tilt plate emulsion) Silver amount 0.4'g/m2 Coupler C-go, 7g/rn2 Gelatin 1.2g/m2 7th r
Layer: 1st protective layer UV absorber U-/0.011-g/m2U
-3o, o3g/m2 U-Hiro o, ozg/m2 U-j O,0μg/m2 U-A O,01g7m2 Compound Cpd-CO,1g7m2 Dye D-1o, ozg/rn2 Gelatin 0.7g/m2 1st Protective layer: Silver iodobromide emulsion (average grain size 0./μm, AgI content 0.j
Molch) Q, /g/m2 Polymethyl methacrylate (average particle size /, Jμ) o, tg/m2 Copolymer of methyl methacrylate and acrylic acid≠:t (average particle size i, tμ) 0.1g7m2Cpd
E O, OJg/m2 Fluorine-containing surfactant W-/jmg/m2 Gelatin
0. Jrg/m2 In addition to the above composition, a gelatin hardener H-/ and a surfactant were added to each layer.

The structural formula of the compound used in this example is shown below.

C-/ C-≠ C-1 Qil-/ Dibutyl phthalate 1l-2 Tricresyl phosphate 1l-J (1:pdA U-/ -j -J pdB pac pdD pdE C15H31COOC1,H33 -i S-j S-≠ H-/ CH2=CH502CH2CONI (CH2=CH2=cHsO2CH2CONHcH2-t-r D-/ Each of the above samples was exposed to white wedge light and subjected to the following development process. The results are shown in Table 2.

* th-current tIR 6 minutes zroc First wash ≠! Seconds 3rI Reversal! Second 31 1 Color development stock 6 minutes 3tI Bleach White 2 minutes 3 Bleach fixing Hirobu 31s Second washing (1) 7 minutes 3r Second wash (2) 1 minute 3 In the evaluation of suitability for water sensitization, processing for t minutes was also performed.

The composition of each treatment liquid was as follows.

- Developer solution NitriloN, N, N-) rimethylenephosphonic acid! Sodium salt -,og Sodium sulfite Jag Hydroquinone・
Potassium monosulfonate Potassium carbonate/-Phenyldermethyl-G Hydroxymethyl-3 Pyrazolidone Potassium bromide Potassium thiocyanate Potassium iodide Og 33g Co, Qg λ, 3g Ha4g Co, Omg pH Not adjusted Methylenephosphonic acid 3. Sodium salt stannous chloride cohydrate p-aminophenol sodium hydroxide glacial acetic acid J, Og /, Ogo, ig rg 11ml pH2,t.

pH was adjusted with hydrochloric acid or potassium hydroxide.

First washing liquid PH4,00 pH was adjusted with hydrochloric acid or sodium hydroxide.

Ethylenediamine tetramethylene Renphosphonic acid Conodium phosphate 2.Og s,og pH7.00 9H was prepared with hydrochloric acid or sodium hydroxide.

Methylenephosphonic acid! Na thorium salt sodium sulfite Trisodium phosphate water salt potassium bromide −,0g 7.0g 3bug HaOg potassium iodide Sodium hydroxide Citrazic acid N-ethyl-N-(β-meta (sulfonamide ethyl) -3-methyl-≠-amino Aniline sulfate 3.6-cythiaoctane/.

t-diol Ta Omg J,Og /, 3g 11g /, 0g pH//, rO pH was adjusted with hydrochloric acid or potassium hydroxide.

Sodium salt/water salt Ethylenediamine fluoroacetic acid/ Fe (m)/Ammonium ・λ water salt ammonium bromide ammonium nitrate 10, Og 120g 00g 0g bleach accelerator o, oz mole pH4, JO The pH was adjusted with hydrochloric acid or aqueous ammonia.

Fe(III)/Ammonium ・Komizu salt Ethylenediamine≠acetic acid/co Sodium salt sodium thiosulfate sodium sulfite og z,og Og /λ　,0g pHA, A.

The pH was adjusted with hydrochloric acid or aqueous ammonia.

A mixed-bed column filled with the second washing liquid tap water and an H-type strongly acidic cation exchange resin (Amberlite IR-/20B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-4t00) Water was passed through the solution to reduce the concentration of calcium and magnesium ions to below Jmg/l, and then 20mg/l of sodium incyanurate dichloride and zg/l of sodium sulfate were added. The pH of this solution is 6.
3-7. It is in the range of j.

Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization IO) ml pH Not adjusted (Note 1) Relative sensitivity is the relative value of the logarithm of the exposure amount required to give a color density that is higher than the minimum density by θ. expressed.

(Note 2) Graininess was expressed as RMS value at concentration/0. The RMS value is described in "Theory of Photographic Process" by James, 1st edition (1977), P, 4/R.

(Note 3) Gradation is indicated using CO and S values.

CO,S means Dmin+1. The logarithm value of the density of Jo and the amount of exposure that gives the density -〇.

! The characteristic value is given by the following equation, where ΔD is the difference in density in the exposure amount.

CO,S = ΔD10, z In the table, sample/QrFi, which is an embodiment of the present invention,
It can be seen that by mixing emulsion 1, which has the same graininess as Sample 102 but has a larger grain size, o, o, o high sensitivity can be obtained, and the change in gradation with respect to change in development time is small, which is preferable.

Similarly, when we look at samples 10j and 101 with respect to sample ///, they have the same grain size as K and 0.0! , 0.0μ higher sensitivity can be obtained, but it can be seen that better results can be obtained by using a size ratio and a mixing ratio like that of toy.

Furthermore, using an emulsion with a latent image distribution such as 10% l//2 results in low sensitivity, and mixing emulsions can result in a sensitivity that is intermediate between large-sized and smaller-sized emulsions. It can be seen that only granular particles are obtained.

The effectiveness of the present invention was also obtained for tabular and octahedral emulsions such as Samples/CoJ and X21.

In this example, only the data regarding the green-sensitive layer were listed, but similar results were obtained when the data were used for the growing-sensing layer and the green-sensitive layer.

Example 1 An emulsion layer having the following composition was coated, and samples 0/2 were coated.
0 pieces were made. For silver halides and colloidal silver, the amount expressed in g/m2 of the silver; for couplers, additives and gelatins, the amount expressed in g/m2; and for sensitizing dyes, the amount in the same layer. It is expressed as the number of moles per mole of silver halide.

1st layer (antihalation layer) Black colloidal silver...0.2 Gelatin...7.3 Colored coupler〇-7...o, it UV absorber U-1...
o, i Same as above U-7... O1λ Dispersion oil 0il-/... 0.0/ Same as above 0
i1-2...o, oi λth layer (intermediate layer) Fine grain silver bromide (average grain size 0.01μ) ・ ・ ・ 0. /j Gelatin...i,.

Colored coupler〇-r...0.02Dispersed oil 0il-2...θ,/3rd layer (first red-sensitive emulsion layer) Sample 10r for sample OIK, sample 10r for sample OI Emulsion of 1st O layer... Silver O6≠ Gelatin sensitizing dye S-y Sensitizing dye s-r Sensitizing dye S-tacoupler C-2 Coupler Ci.

Coupler C-// Coupler C- Dispersion oil 0il-1 Same as above 0il-μ μth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide! morch, jμ) Sensitizing dye S-7 Sensitizing dye S-r Sensitizing dye S-y Coupler C-ta Coupler~C-t.

Coupler C-ti Coupler cr-r ・ ・ ・ / ・ ・ ・ 3 Average particle size O0 ・ ・ 0.7 /X10-4 X10-4 /X10-5 ・ ・ 0, λ μ ・ ・ O, +2 G O, OtI ・ ・ O, Oa ・ ・ 0.6 . 0 OJ ・ ・ 0.03 ・ ・ 0.0/2 Dispersion oil 01l-2... 0. /j Same as above 0il-μ
...0.02 Third layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (iodide@jmalti, average diameter l.

7 μm1 As is a tabular grain with a high contrast ratio)... Silver/
, 0 gelatin... /, 0 sensitizing dye S-7... /×/θ-4 sensitizing dye S-r
...! X10-4 sensitizing dye S-2...
/X10-5 coupler C-/co...0
．． Oj coupler C-/3...0. /Dispersion oil 011-co...0. O7 same as above 01l
-/...0.02 6th layer (middle layer) Gelatin.../, 0 Compound C
pd-F...0.03 dispersion oil 01
1-2...0. Or 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide≠malti, average grain size 0°3μ)
...Silver 0. JO sensitizing dye 5-7o
... jXlo-4 sensitizing dye S-tλ ...
0.3×10-4 sensitizing dye S-/l...CoX10-4 gelatin.../,
0 coupler C-1t...0. Co-coupler C-// ... 0.03 coupler ~ C-
7... 0. OJ Dispersion oil 01l-ko ... o, z 1st layer (
First green-sensitive emulsion layer) Silver iodobromide emulsion (Silver iodide! Morch, average grain size θ.

! μ) ... Silver θ, G sensitizing dye 5-
to ---zxto-4 sensitizing dye 5-t-...
2X10-4 sensitizing dye 5-ti-・-0,J
X/ to l-4 coupler C-7z...0
．． +2j coupler C-7... 0.0! Coupler C-tA...0.0/! Coupler C-// ... 0.0t dispersion oil 01l
-2... 0.2 second layer (@J green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide! morch, average diameter 7° 7 μm,
The ass is the best! tabular grains)...silver 0. rj gelatin ... /, 0 sensitizing dye S-/J ---3, rxto-4 sensitizing dye 5-
lu --・t, axlo-4 coupler C-/7
・--o, oi coupler C-/l
... 0. OJ coupler C-/P...
・0. Co coupler C-7... 0.0 Co coupler C-λ/... 0.02 Dispersion oil 0f1-Co... 0.20 Same as above 0il-/
-o, or 10th layer (yellow filter layer) Gelatin... 1. Co-yellow colloidal silver...silver o,ol compound Cpd-
G...0. /Dispersed oil 0i1-λ
... 0. J 1st/layer (first back-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide μmolar, average grain size (7,
Jμ) ... Silver 0. Hiro Gelatin
・・l／、.

Sensitizing dye 5-tz ... λX10-4 coupler C-1o ... 0.2 coupler C-
// ... 0.01 dispersion oil 0il-
2... 0.2 First co-layer (first back-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide j morch, average diameter 7°7 μm1
(Tabular grains with acetate ratio)... Silver 0.1 ・ ・ ・ O, Δ ・ ・ ・ / /! Coupler C-CoO Dispersion oil 0il-Co 73rd layer (first protective layer) Gelatin ultraviolet absorber U-1 Same as above U-7 Dispersion oil 01l-,2 Q,t Ool O,Coo,oi Dispersion oil 0il- / ... 0.0 / First Hiro layer (No. 1 protective layer) Fine particle bromide # (average particle size 0.01 μ) Silver 0.1 Gelatin ... 0. lIj polymethyl methacrylate particles (diameter/, !μ) ... 0. J Hardener H
-t...Q, Hiroformaldehyde scavenger Cpd-)I...0. jr formaldehyde scavenger Cpd-I... o,! In addition to the above components, a surfactant was added to each layer as a coating aid.

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

x/y=7/3 (weight ratio) Oil-Pi Bisphthalate (coethylhexyl) C-ta C-/.

C-／　／ C-/jr C-/& mol, wt.

Approximately 20,000 C-/C-/J C-/ ≠ C-/7 C-/r CH2 C(CH3)3 C-/RiC-20 S-! C-ko / α pdG -tt S-t Ko(niMz)sbs3N&H3 H S-73 cpa-H cpa-I S-t ≠ S-Jlr A tungsten light source is used for this photographic element, and the color temperature is adjusted with a filter. After applying the exposure of CojCMS adjusted to ≠t000K, a phenomenon treatment was performed with Jlr''C according to the following processing steps.

Color phenomenon 3 minutes it second Bleach White 6 minutes 30 seconds Wash with water for 10 seconds Fixed arrival time: 0 seconds Water Wash 3 minutes is seconds Safe, fixed, 1 minute 0! seconds The composition of the treatment liquid used in each step was as follows.

Color current solution diethylenetriaminepentaacetic acid i,og/-hydroxyethylidene- /,/-diphosphonic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxylamine sulfate ≠-(N-ethyl-N-β- hydroxyethylamino) Add monocomethylaniline sulfate solution and bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt Ethylenediaminetetraacetic acid disodium Ammonium bromide Ammonium nitrate H 2.0g 11.0g 3o, og l, reference g /, Jmg 2.4! g ≠ , jg /, 01 10.0 100.0f1 10, Og /! rO,0g 10,Og Add water /,O1! pHt
, 0 fixer ethylenediaminetetraacetic acid disodium salt /, 0g sodium sulfite μ, og ammonium thiosulfate aqueous solution (717%) i7z, om1 sodium bisulfite ke, add 4g water
7.01 pH 4.6 Stabilizing liquid formalin (4!0) λ, Oml polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add 0.3 g water 1.011 The combination of the emulsion of the present invention It was confirmed that sample 20/ used had higher sensitivity and improved graininess than sample 02 using comparative emulsion -/r.

(Effects of the Invention) According to the present invention, a silver halide photographic material having excellent sensitivity and graininess can be obtained. Moreover, the above-mentioned light-sensitive material exhibits little change in gradation even when the development time is extended, that is, it has excellent sensitization developability, which is a great practical advantage.

Claims (1)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the emulsion layers has an average grain size ratio of 1.1 or more to 1.
．． containing two or more types of silver halide emulsions of 6 or less,
Chemically sensitized so that one or more of the maximum values of the latent image distribution of each of the silver halide grains is present inside the grain, and the position of the maximum value is at a depth of less than 0.01 μm from the grain surface. A silver halide photographic material characterized by: