JPS61260236A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enable graininess to be improved while maintaining proper gradation by using the first photosensitive silver halide emulsion contg. silver iodide, the second internally fogged silver halide emulsion, and the third substantially nonphotosensitive nonfogged silver halide emulsion. CONSTITUTION:The same or separate silver halide emulsion layers contain the first photosensitive silver halide emulsion contg. silver iodide, the second internally fogged silver halide emulsion having an average grain diameter of <=0.6mum, and the third substantially nonphotosensitive nonfogged silver halide emulsion having an average grain diameter of <=0.6mum, thus permitting graininess to be greatly improved without changing proper gradation.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide photographic material (hereinafter referred to as a "photosensitive material"), and in particular to a silver halide photographic material with improved graininess and gradation. This invention relates to a photographic material with high sensitivity and high covering power.

[Conventional technology]

The covering power of silver halide emulsions is of great interest to emulsion manufacturers. This is because the use of high covering power emulsions saves on the amount of silver needed to maintain a constant optical density. In order to increase the covering power of silver halide emulsions (U.S. Pat. 2. To me.

No. 322, No. 3,77F, No. 2Fλ, No. 3゜327
,? / No. 7, No. 3. Otsu 07.2';##, British patent/
, 4t, 2. p, No. 277, etc.

[Problems to be solved by the present invention]

In the combination of this high-iodine surface-sensitive emulsion and an emulsion consisting of small-sized internally fogged grains, iodine ions are released from the former emulsion grains during development in proportion to the exposure amount, and these ions are absorbed by the internal fogging. It is believed that it is based on the principle that causes the development of fine-grain emulsions. Therefore, it is expected that this effect will occur in the exposure image quiz of photosensitive emulsions. However, in reality, there is a dark value in the amount of iodine ions that causes this effect, giving a characteristic curve that is sharper than expected from the imagewise format. Furthermore, because of the high iodine content of the surface-sensitive emulsion grains, contagious development occurs between the light-sensitive emulsion grains, particularly when processed with a developer containing glutaraldehyde, resulting in an even higher contrast characteristic curve. As a result, it is inevitable that the graininess also deteriorates. We have proposed a special technology to prevent this latter contagious development effect! No. 2-2.26λ/ discloses a technique for the combined effect of a menion triazolium compound and a certain type of polyethylene oxide compound. Special application 1973-/73
-7'I discloses the combined effect of a mesoionic triazolium compound and a monomethine cyanine dye. However, with these techniques, it is not possible to control the developability of internally fogged fine particles by iodide ions. Furthermore, when these additives are added in large amounts, they have the disadvantage that they retard the progress of development when processed with a so-called low-activity developer containing a small amount of developing agent or having a low pH.

An object of the present invention is to eliminate the above-mentioned drawbacks of the prior art, and in particular to provide a high-sensitivity silver halide photosensitive material which has improved graininess while maintaining appropriate gradation and has a high covering power for developed silver.

[Means for solving problems]

As a result of extensive research, the present inventors have found that the above object can be achieved by the present invention described below.

That is, on at least one side of the support, at least 7
In a silver halide photographic light-sensitive material having a silver halide emulsion layer, the silver halide photographic emulsion layer is a photosensitive silver halide emulsion (first emulsion) containing silver iodide and an average grain size of O, In addition to the silver halide emulsion (second emulsion) with internal grains of Sμ or less, the average grain size is 0.
．． To provide a silver halide photographic light-sensitive material characterized by containing a substantially non-fogged silver halide emulsion (third emulsion) of 6μ or less (
From the second point, the above purpose can be achieved.

As mentioned above, as the third emulsion, the average grain size is 0.6.
Substantial ζ with no fogging of less than μ: Using a non-light-sensitive silver halide emulsion ζ: Therefore, it was completely unexpected that graininess could be greatly improved while maintaining appropriate gradation. be.

In the photographic material of the present invention, the seventh emulsion, the first emulsion, and the third emulsion are in the same emulsion layer (there may be two emulsion layers,
Alternatively, each may be in a separate emulsion layer.

The second and third emulsions used in the present invention are preferably substantially non-photosensitive to the first emulsion. Also,
As mentioned above, the λ-th emulsion is an emulsion that contributes to an increase in image density during the development of a photosensitive emulsion (=development is caused), but the third emulsion is not developed and therefore increases image density. 1: is preferably an emulsion that does not contribute.

In the present invention, "photosensitive" means that the sensitivity of the photosensitive silver halide emulsion (first emulsion) is higher than the sensitivity of the second emulsion or the third emulsion. More specific (
= means that the sensitivity is 70 times or more, more preferably 100 times or more the sensitivity of the internal fogged silver halide emulsion.

The sensitivity here is defined in the same way as the sensitivity shown below.

Next, three types of emulsions used in the present invention will be explained.

As the photosensitive silver halide emulsion, a conventional silver halide emulsion such as a surface latent image type emulsion is used.

Here, the surface latent image type silver halide emulsion is 7 to 171
After 00 seconds of exposure, when developing using the surface development (A) method and internal development (B) method shown below, the sensitivity obtained with surface development (A) is higher than the sensitivity obtained with internal development (B). The sensitivity of the former is preferably one or more times that of the latter. Here, sensitivity is defined as follows:

S is sensitivity, Bh is maximum density (Dmax) and minimum density (D
min)
pmin).

[Surface development (A)]

Develop for 10 minutes at a temperature of 20°C in a developer with the following formulation.

N-Methyl-p-aminophenol (hemisulfate) 2.3g Ascorbic acid 10g Sodium metaborate tetrasalt 3j'g Potassium bromide
Add 7g water
/l [Internal development (B)] Red blood salt 3g/! and phenosafranin 0.0/2tg/l
20° C. for 70 minutes, then washed with water for 70 minutes, and developed in a developer having the following formulation at 20° C. for 70 minutes.

N-methyl-p-aminophenol (hemisulfate) 2.3-g ascorbic acid 10g sodium metabolate tetrahydrate 33g potassium bromide
7g Sodium Thiosulfate
Add 3g water
/1 As the photosensitive silver halide, specifically, silver chloroiodide, silver iodobromide, and silver chloroiodobromide can be used.

Silver iodobromide is preferably used. The content of silver iodide here is preferably in the range from 2 to 30 molty, particularly from Z to 10 molty.

Further, as for the halogen composition of the first emulsion, it is preferable that the silver iodide content thereof is equal to or higher than the silver iodide content of the first emulsion and the third emulsion.

The average grain size is preferably larger than that of a silver halide emulsion having internal fog nuclei (internally fogged silver halide emulsion), particularly preferably 0.1 μm or more. The particle size distribution may be narrow or wide. The silver halide grains in the emulsion may have regular crystal shapes such as cubic or octahedral, or irregular crystal shapes such as spherical or plate-like.
It may have a crystalline form (ular) or a composite form of these crystalline forms. It may also consist of a mixture of particles of various crystalline forms. Also, the particle diameter is 1 of the particle thickness.
Tabular grains that are more than twice as large are preferably used in the present invention.

Such tabular grains are described in 1 U.S. Patent No. g.

4tj4t, 226th issue, same issue, 4tj4t, Cocoa issue, Tokukai Sho! It is described in detail in the specifications such as ♂-/22ri No. 2/.

The photosensitive) 10-genide silver emulsion used in the present invention is k'
=f57 Chimi Photography (p, Qlafkides)
e et physics photograph
ique) J (Po/I/ ・% 7tel paul
Published by Monte 1, / 1967), by G. F. Duffin
ic Emulsion Chemistry) J (The Focal Press'l'he li'ocal
Press, 1979 Otsu 6), V, L, Zelikman et al.
) Author: Making and Coating Photographic Emulsion
atingphotographic Emulsio
n) J (focal pvx 'l'he Fo
It can be prepared using the method described in, for example, published by Cal Press, 2003.

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

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 type of the simultaneous mixing method, a method of keeping the pAg in the liquid phase in which silver chloride is produced constant, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion with a regular crystal shape and a uniform grain size (nearly 2) can be obtained.

Two or more types of 710 silver germide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a 11"diu" salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

As the photosensitive silver halide emulsion, a so-called primitive emulsion which is not chemically sensitized can be used, but it is usually chemically sensitized.

For chemical sensitization, for example, H.
H, Fr1eser) ed.
Der Fotograftsien Prozetse Mituto Zilbel Halogennieden (1)ieGrundlag
en der photography
ozesse mit silver-haloge
Niden) J (Akademische verlagsgesell)
schaft.

/Rigo♂ Annual) t7! The method described on pages 734 to 734 can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof can be found in US Pat. 74t, 4t
No. 4, 2.4t/θ16? ri number, 2.27F, ri 4t
No. 7, Ko, '72/, JTR No. 3, 636, Tata! No., g, θ3ko, ri2t, g, 067.74tθ
listed in the number. As a reduction sensitizer, stannous salt,
Amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used, and specific examples thereof can be found in U.S. Patent No. 2,4t♂2. ? ! Q, 2.4t/
No. 9,974, 2. j/? , No. 49F, 2,9L! r
No. 3,409, No. 2,973, No. 1.10, Ko, J9g,
No. 637, 3. 30. rgo No. 7, ri, θttit, t
It is described in the tr issue.

For noble metal sensitization, in addition to total complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used; specific examples thereof are given in the US patent.

It is described in 3 Tata, 0t3, same, ttr, θ6θ, British patents tir, oti, etc.

Various compounds can be added to the above-mentioned photosensitive silver halide emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the photosensitive material. Those compounds are guhydroxy-6-methyl-7,3,3a,
7-Chitrazaindene, 3-methyl-benzothiazole, /-phenyl-! -A large number of compounds have been known for a long time, including mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts.

An example of a compound that can be used is K, Mies (Me 9
), “The Theory of the Photographic
Process x ('l'he Theory of th
ephotographic process) (
In addition to listing the original literature in 3rd edition, 79g6), JP-A No. 27029, Sho Geta, same! θ-g30g,
same! No. 0-/412, U.S. Patent No. J, ? 60
.

Any of the antifoggants listed in Otsu No. 3 can be used.

Next, as the interior (silver halide emulsion having difoggable nuclei (silver halide emulsion with fogged interior)) used in the light-sensitive material of the present invention, a transparent support is prepared such that the amount of silver in copying is 2 g/m2, for example. Top (= D-/ without exposing the coated test piece)
3t'
C,, when developed for 2 minutes, it gave a transmission fog density of o, r or less (excluding the density of the support itself), and the same test piece was not exposed (21/2 potassium iodide θ, jg An emulsion that gives a transmission fog density of 0 or more (excluding the density of the support itself) when developed for 3t'C, J minutes with a developer added to /11 is used.

Silver halide emulsions having fog nuclei inside can be prepared by various known methods. For example, US Patent No. 1! Octopus...2! U.S. Pat. A core emulsion having fog nuclei can be prepared by the method described in the specification of No. 2 or by first fogging under conditions of low pAg and high pH, or by chemically fogging with a reducing agent, a gold compound, a sulfur-containing compound, etc. and then depositing a shell emulsion around this core emulsion (US Pat. No. 31.206.3/3).
(Refer to the core-shell emulsion technique described in the specification), JP-A-Sho! ? -, 2/1. The method described in the specification of g4t No. 7,
There is a method in which the interior and surface of silver halide grains are covered together, and then the fog nuclei on the surface are bleached with a red blood salt solution or the like.

The silver halide emulsion having fog nuclei inside has an average grain size smaller than that of a surface latent image type silver halide emulsion, and preferably has an average grain size of 0, or to 01μ, and preferably 0.3μ. More preferably, those having an average particle size of below 06.2 μm are particularly preferred and give good results.

In the present invention, the grain size of silver halide is expressed by the grain diameter in the case of spherical or approximately spherical grains, and in the case of grains of other shapes (for example, cubes, flat plates, etc.), it is the diameter of a sphere with the same volume. I will express it.

Silver halides used in the internally fogged silver halide emulsion include silver bromide, silver iodobromide, silver iodochlorobromide,
Any of silver chlorobromide, silver chloride, etc. may be used. Silver iodochlorobromide and silver chlorobromide are preferred.

By adsorbing a beta compound having a mercapto group on the surface of the internally covered silver halide emulsion of the present invention, fogging and uneven staining during development can be suppressed or prevented.
This is preferable in that it does not impair photographic properties over time. As such mercapto compounds, those represented by the following general formula (N) are particularly preferred.

General formula (1) (wherein, X represents 10-1-Nu- or -S-.R
1s R2, R3 and R4 represent hydrogen or a group capable of substituting hydrogen, and at least one of R1, R2, R3 and R4 has a substituted or unsubstituted carbon number / ~/3 alkyl group or aryl group. ) For specific examples of the compound represented by general formula (I), please see the patent application! Tar/70177 Specification Pages 1 to 7? These items can be used effectively.

The compound represented by the general formula (I) of the present invention is used per mole of internally fogged silver halide grains from /x/θ-5 to /x7
It can be used in the range of 0-1 mol, preferably /×
It is preferable to add it in a proportion of 10-4 to 10-2 mol. Most preferably, the amount added is close to the saturated adsorption amount on the surface of the internal fogging particles. As for the addition method, it may be directly dispersed in a hydrophilic colloid, or it may be added after being dissolved in an organic solvent such as methanol or ethylene glycol.

In addition, internal fog silver halide emulsion cylinder 3 is added to the same emulsion layer.
When there is an emulsion and a light-sensitive silver halide emulsion,
It is preferable to add the compound of general formula (1) to the internal fogging silver halide emulsion in advance and allow it to be adsorbed before mixing the two.

Specifically, silver chloroiodide, silver iodobromide, silver chloroiodobromide, silver chloride, silver chlorobromide, and silver bromide are used as the substantially non-light-sensitive unfogged silver halide emulsion. be able to. Preferably,! Silver chlorobromide and silver bromide containing less than 1 mole of chloride, and silver iodobromide containing less than 2 mole of iodine are used. The average grain size is the same as that of an internally covered silver halide emulsion, and θ is 01 to 0. ! μ is preferable, 0°3μ or less is more preferable, and θ1.2μ or less is particularly preferable. It is preferable that the particle size distribution is narrow.

The silver halide grains in the emulsion may have regular crystal shapes such as cubic or octahedral, or irregular crystal shapes such as spherical or plate-like.
ar) may have a crystalline form. It may also consist of a mixture of particles of various crystalline forms.

This third emulsion contains the aforementioned P, Gerafkides, G, F,
It can be prepared using the method described in Dufyn, V.L., Zerichman et al.

Also, US Patent No. 2. j? , 2.23-0 is also suitable.

Furthermore, a core-shell type emulsion in which the halogen compositions of the core and shell portions are different may also be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

In any case, the third silver halide emulsion is usually not chemically sensitized on the surface or inside of its grains.

The light-sensitive silver halide emulsion (first emulsion), the internally fogged silver halide emulsion (first emulsion), and the substantially non-light-sensitive unfogged halogen of the silver halide photographic light-sensitive material of the present invention The content ratio with the silver oxide emulsion (third emulsion) is
It can be changed depending on the emulsion type used (for example, halogen composition), the type or purpose of the photosensitive material used, the contrast of the emulsion used, etc. ) is the preferred silver content ratio? ri:/ to λθ:♂θ, and particularly preferably wo;/ to 4t:6. Further, the silver ratio of the third emulsion to the first emulsion is preferably from :/ to 3=2, particularly preferably from r:2 to j:! It is. Further, the total amount of coated silver is preferably o, r~7 g/m2 per one side, particularly 0.7 g/m2.
~jg/m2 is preferred.

Several embodiments are possible regarding the layer structure of the photographic material according to the invention.

■ On the support: Two layers, an emulsion layer consisting of a mixture of the first emulsion, the first emulsion, and the third emulsion, and a protective layer (auxiliary layer) are provided in order. ■ An emulsion layer consisting of a first emulsion is further provided between the support layer (auxiliary layer) ■ An emulsion layer consisting of a mixture of the first emulsion and the third emulsion , an emulsion layer consisting of the first emulsion, a protective layer (
Examples include those in which auxiliary layers) are sequentially provided.

Moreover, these structures may be provided not only on one side but also on both sides of the support.

Note that the auxiliary layer according to the present invention may be provided separately from the protective layer.

The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used is one described above.

Further, the protective layer may be a single layer or a multilayer.

A matting agent and/or a smoothing agent may preferably be added to the emulsion layer or protective layer of the silver halide photographic material of the present invention. An example of a matting agent is water such as polymethyl methacrylate with a suitable particle size (preferably a particle size of 0.j to !μ or a particle size of at least twice the thickness of the protective layer, especially at least twice the thickness of the protective layer). Organic compounds such as dispersible vinyl polymers or inorganic compounds such as silver halide, barium strontium sulfate, etc. are preferably used. Smoothing agents help prevent adhesion failure similar to matting agents, and are particularly effective in improving frictional properties related to camera compatibility during shooting or projection of motion picture films. Moraffin, waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or their derivatives, silicones such as polyalkylpolysiloxanes, polyarylpolysiloxanes, polyalkylarylpolysiloxanes, or their alkylene oxide addition derivatives. etc. are preferably used.

The silver halide photographic material of the present invention may also be provided with an antihalation layer, an intermediate layer, a filter layer, etc., if necessary.

Various hydrophilic colloids can be used as binders in the photographic material of the present invention.

Examples of colloids used for this purpose are f-t
'Latin, colloidal albumin, polysaccharide,
Examples include hydrophilic colloids generally used in the photographic field, such as cellulose derivatives, synthetic resins, polyvinyl compounds including polyvinyl alcohol derivatives, and acrylamide polymers. Along with the hydrophilic colloids, hydrophobic colloids can be included, such as dispersed polymeric vinyl compounds, especially those which increase the dimensional stability of the photographic material. Suitable compounds of this type include water-insoluble polymers made by polymerizing vinylic monomers such as alkyl acrylates or alkyl methacrylates, acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates.

In the photographic material of the present invention, the photographic silver halide emulsion layer and other hydrophilic colloid layers can be hardened with any suitable hardener. These hardeners include JP-A-Sho J-3.
-7602j, J3-7go026 and jj-77
Vinylsulfonyl compounds such as those described in No. 6/9: hardeners having active halogens, nidioxane derivatives, oxypolysaccharides such as nioxy starch, and the like.

Other additives may be added to the photographic silver halide emulsion layer, particularly those useful in photographic emulsions, such as lubricants, sensitizers, light-absorbing dyes, plasticizers, and the like.

The photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful.

In the photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

The photosensitive material of the present invention may also contain a surfactant for other purposes. Depending on the purpose, any of nonionic, ionic and amphoteric surfactants can be used, such as /IJ oxyalkylene derivatives and amphoteric amino acids (including sulfobetaines). Such surfactants are disclosed in U.S. Pat. No. 6θo, tr3/, U.S. Pat.
,．． 27J-.

No. 727, U.S. Wf2, No. 7♂7.604, U.S. Patent No. 2. r/6,920, U.S. Patent J, 739°t
No. 7 and Belgian patent! λ, described in J'12.

In the light-sensitive material of the present invention, the emulsion, particularly the first emulsion, may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used in ordinary negative-working silver halide emulsions. especially,
It is advantageous to use dye concentrations that do not substantially reduce the inherent sensitivity of the silver halide emulsion. of sensitizing dye per mole of silver halide to about 〇X/θ-5 to about! X10-4 mole, especially about 41X1 of sensitizing dye per mole of silver halide
It is preferred to use a concentration of 0-5 to 2X10-4 molar.

In the photographic material of the present invention, the emulsion layer and other layers are coated on one or both sides of a flexible support commonly used in photographic materials. Useful as flexible supports are films of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene, polyethylene terephthalate, baryta layers or alpha-olefin polymers (e.g. evaporated polyethylene, polypropylene, ethylene/butene copolymers). ) etc. are coated or laminated.

In the photographic material of the present invention, the emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various known coating methods. For application, dip application method,
A roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

The present invention can be used with any photographic material that requires high sensitivity or high contrast. For example, it is used in X-ray photographic materials, lithographic photographic materials, black and white negative photographic materials, color negative photographic materials, color <-ze-photosensitive materials, and the like.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure (ReSearChl) isclos
ure) / No. 71 No. 2t5” ~ 30 pages (RD-
77g4t3), any of the known methods and known treatment liquids can be applied. This photographic processing may be either photographic processing for forming a recorded image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing), depending on the purpose. Processing temperature is normal/TOC! It is selected between θ0C, but /
Temperature lower than 10C or! The temperature may exceed 0°C.

As the developer used in the present invention, in addition to a high-activity developer, a low-activity developer with a lower developing agent concentration or lowered pH can also be used.

For example, developers used in black-and-white photographic processing can include known developing agents.

As developing agents, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. /-
phenyl-3-pyrazolidone), aminophenols (
For example, N-methyl-p-aminephenol), etc.
They can be used alone or in combination. Further, a developer containing a hardening agent such as gel tar aldehyde is also preferably used. For photographic processing of the light-sensitive material of the present invention, JP-A-37-7♂! 3! It is also possible to process with a developer containing imidazoles as a silver halide solvent as described in No. Further, processing can be carried out using a developer containing a silver halide solvent and an additive such as indazole or triazole as described in JP-A-J-J'-j764t3. The developing solution generally contains other known preservatives, alkaline agents, pH buffers, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants,
It may also contain antifoaming agents, water softeners, viscosity imparting agents, and the like.

As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, a method may be used in which the photosensitive material is included in the emulsion layer and the photosensitive material is processed in an alkaline aqueous solution to perform development. Among the developing agents, hydrophobic ones are subject to Research Disclosure/
Otori-go (RD-/Otako♂), U.S. Patent No. 2.739,
No. 790, British Patent No. J'/J', 2! They can be incorporated into the emulsion layer by various methods such as those described in Patent No. J or West German Patent No. 1 J-4T 7.76.3. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

(Example) Next, the present invention will be specifically explained based on examples.

Examples / (1) Preparation of surface-sensitive silver halide emulsion (first emulsion): In a container containing an aqueous solution consisting of potassium bromide, potassium iodide, and gelatin, add an aqueous solution of silver nitrate and bromide using the usual ammonia method. A silver iodobromide emulsion (Agl = pmolti) having a plate-like shape with an average grain size of 7.0 μm was prepared by simultaneously adding an aqueous solution consisting of potassium and potassium iodide, and then mixed with a conventional agglomeration method. Desalted, gold-sulfur sensitized using chloroauric acid and sodium thiosulfate, and added as a stabilizer hydroxy-6-mether' + j r j
A-7-chitrazaindene was added to obtain a photosensitive silver iodobromide emulsion (2).

(2) Preparation of internal fog fine grain emulsion (first emulsion): 2
Weight% gelatin aqueous solution! ! While stirring at 0C, a silver nitrate aqueous solution and a mixed aqueous solution of potassium bromide and sodium chloride were simultaneously added to prepare a core cryo. Temperature 7!
The temperature was raised to 0C, and appropriate amounts of sodium dioxide and silver nitrate were added and aged for 1 minute to form fog nuclei on the core particles.

Temperature! ! Lower the temperature to 0C and add acetic acid and potassium bromide to adjust the pH.
After returning the pAg and pAg to 1, a silver nitrate aqueous solution and a mixed aqueous solution of potassium bromide and sodium chloride were added simultaneously, desalted by a normal flocculation method, redispersed in a gelatin aqueous solution C2, and then, 0.2 by applying a mercapto compound of the following formula to the eyes! A silver chloroiodobromide emulsion of μ was prepared.

(3) Preparation of non-photosensitive fine grain emulsion (third emulsion): 2% by weight gelatin aqueous solution containing a minute amount of potassium bromide!
! After adding a small amount of ammonia water while stirring at 0C,
Pure silver bromide particles are formed by simultaneously adding a silver nitrate aqueous solution and a potassium bromide aqueous solution while controlling the potential at a constant potential, desalted by a normal agglomeration method, redispersed in a gelatin aqueous solution, and then mixed with a 0.0% aqueous solution of potassium bromide. /J
−μ pure silver bromide emulsion ◎−/(no chemical sensitization)
was prepared.

(4) Preparation of emulsion coating solution: Emulsion ■, jgAg/m2 and emulsion ■-/0, jg
Ag/m2 and emulsion ■-/ After mixing the three emulsions in various amounts shown in Table/, monomethyl-7,! , 3a,7-titrazaindene, coating aid dodecyl, nzensul heptaonic acid salt, thickener polypotassium p-vinyl, nzensulfonate compound, and the following menion triazolium compound A were added.

Compound A (5) Preparation of coating solution for surface protective layer: Gelatin, thickener polyethylene sodium sulfonate, matting agent polymethyl methacrylate fine particles (average particle size 3.0 μm), hardener N, N'-ethylene bis −
(Vinyl sulfonylacetamide) A coating solution was prepared comprising a coating aid t-octerphenoxyethoxyethane/sodium sulfonate and a polyoxyethylene surfactant.

(6) Preparation of coating sample 2 The above-mentioned emulsion coating solution was coated on both sides of a polyethylene terephthalate support.The amount of silver was 2.3 g/m2 per side, and the gelatin from the emulsion coating solution was applied per side.

, < J g/m 2 , and gelatin from the surface protective layer coating solution was coated in an amount of 11 g/m 2 per side. Therefore, the total gelatin coating amount for any sample is 2.7 per side.
It was applied so that it was 9g/(H2).

(Kasensitometry 12) While keeping these samples at a temperature and humidity of aj'C,t°!%RH, each sample was measured at 340~g?θμm with an intensity peak at 7/μm after coating. After exposure to blue light through a continuous wedge, development was performed for 2 seconds at the standard development temperature of 3!0C using the following processing solution.
Fixed, washed with water, and dried.

Developer potassium hydroxide Kota, /4tg4
? Acid 10.96g Potassium sulfite 4t4t, 2□g Sodium bicarbonate? , 60g boric acid
/ , 00g diethylene glycol
2? , 26g ethylenediaminetetraacetic acid /
, 47g! -Methyl is nsotriazole □, ot
g! -Nitroimidazole θ, ,2? g Hydroquinone 3θ, oog/-phenyl-3-pyranzidone /
, 60g glutaraldehyde, 9
Add 3g sodium metabisulfite/1, 2.4□g potassium bromide 7,00g water to make up to 1/l.

(Adjust the pH to 70.2j.) Fixer Ammonium thiosulfate 200g Sodium sulfite (anhydrous) 20g Boric acid
2g Disodium ethylenediaminetetraacetate θ, /g aluminum sulfate /! g sulfuric acid
2g glacial acetic acid Add 2-g water to bring the total volume to /! Make it.

(p) (adjust to 2) The processed photographic material was subjected to sensitometry and the results are shown in Table/. In the same table, the sensitivity value is Cub I) + 0
．． The sensitivity of sample A/ in table / was calculated as the common logarithm of the reciprocal of the exposure amount required to obtain the transmitted light blackening density of 3, and was expressed as a relative value as / and θθ.

Also, the gamma value in the table is fog +0.2 on the above characteristic curve.
It is expressed as a slope between points giving a transmitted light blackening density of +2.0. Furthermore, graininess was evaluated and expressed as follows. A sample was prepared that was uniformly exposed to the same light source used for normal sensitometry so that the transmitted light blackening density was /, θ when developed under standard development conditions (3t 'C, xt seconds). . Measure the concentration of this sample.
It was measured using a microdensitometer with a char diameter of 2 Zμ, the root mean square (RMS) of the measurement was calculated, and the value was used as a measure of granularity. In other words, root nodules with a large value appear rough. RMS value is 0.01 or more /, 0.04t
4 or more and less than 0.0, 2, O, θ, θ, 04tt
Less than 3.0.0jr or more and less than 0゜041t2 is 4t,
A value of less than 0.037 was evaluated as good.

Table 1 shows that samples containing the non-light-sensitive emulsion of the present invention (2 to 2) maintain an appropriate gamma value (2,! or I23°0) while significantly improving graininess. On the other hand, sample (6) in which the internal fogging emulsion was reduced and no non-light-sensitive emulsion was added had a large desensitization and a large decrease in Dmax, a high tone of C2, and coarse graininess, and it is clear that it is not as good as the sample of the present invention. be.

(Example 2) (1) Preparation of emulsion The surface-sensitive silver halide emulsion used was exactly the same as in Example 1, but the internal fog fine grain emulsion was used in US Pat. By the method described in Tako, No. 2jθ, grains are formed so as to have a sensitivity of //100 or less from the above-mentioned surface-sensitive emulsion, and after desalting and redispersion, fog is caused inside the grains with light, and then ( By subsequently bleaching the same mercapto compound as in Example/■-/emulsion, the average grain size was 0.22μ.
A pure silver chloride emulsion (iodocomorti, chloride 1 mol %) -2 was obtained.

Substantially light-insensitive silver halide fine grain emulsion ■-2 is also disclosed in the above-mentioned US Pat. No. 2.39-2. - Perform particle formation, desalting, and redispersion by changing only the particle formation temperature from ■-2 with the method described in issue 26g. Prepared (
θ,/! Particles with the same halogen composition as ■−λ at μ).

(2) Preparation of emulsion coating solution An emulsion coating solution was prepared in the same manner as in Example/, but for comparison, the amount of the menion triazolium compound used in Example/ below was increased, and An additional sample to which methinecyanine dye was newly added was also prepared.

Dye B (3) Sensitometry In addition to performing the same sensitometry as in Example//, the following tests were also added. That is, in order to examine the photographic properties when processed at low temperature with a low-activity developer, hydroquinone was reduced to 11 g (2,/-phenyl-3-pyrazolidone was reduced to 0.2 jg) from the developer composition of Example/, and the pH was adjusted. 70.2
At 310C, use a developer with reduced potassium hydroxide so that j becomes 10.0! Table 21 also shows the sensitivity and gamma value (measured in the same manner as in Example) when second development was performed. In this case, the sensitivity of sample A at the standard temperature (3!0C) using the standard solution was 7. Expressed as a relative value (common logarithm) with θ.

Table λ: Similar to Table C/, the sample (-~3) to which the third emulsion of the present invention was added has a gamma value of an appropriate value (2,j~3).
3.0 range), the graininess was significantly improved, and the gradation and graininess were significantly improved compared to the samples (+t~ri) in which a large amount of mesoionic triazolium compound A and monomethine cyanine dye B were added. It is clear that this method is superior in that the improvement effect is large and the decrease in sensitivity is very small. Furthermore, photographic properties (sensitivity, gamma value) in low-temperature processing with low activity developer
However, the samples of the present invention are shown to clearly outperform the comparative samples.

(Example 3) The experiment was carried out in the same manner as in Example 3, except that Emulsion 1 of Example 2 was used in place of Emulsion 2 of Example 3. Much like that obtained in Example 1, the sample with the addition of the third emulsion of the invention was shown to give adequate gradation and good graininess.

(Example 4t) In Example 3, the third emulsion is O-/emulsion (θ.

/! When preparing the coating solution, in place of O/3μ silver iodobromide emulsion 0-3 (no chemical sensitization) containing 1 mole of iodine (pure silver bromide emulsion) J4tjn
A sample was prepared exactly the same as in Example 3, except that the following cyanine-based sensitizing dye C having green light sensitivity and having a J-band absorption peak was added. The experiment was carried out using filtered green light with a peak of
Similar results were obtained.

Dye C (Effect of the invention) Photosensitive silver halide emulsion containing silver iodide (first emulsion) and internally covered silver halide emulsion (first emulsion)
By simultaneously using a substantially non-light-sensitive unfogged silver halide emulsion as a third emulsion, it was possible to significantly improve graininess while maintaining appropriate gradation.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on at least one side of a support, a light-sensitive silver halide emulsion in which the silver halide photographic emulsion layer contains silver iodide; It is characterized by containing an internally fogged silver halide emulsion with an average grain size of 0.6μ or less and an unfogged, substantially non-photosensitive silver halide emulsion with an average grain size of 0.6μ or less. A silver halide photographic light-sensitive material.