JPS6271946A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having an improved development activity at a low temp. treatment by incorporating a photosensitive silver halide emulsion and a silver halide emulsion having a fog in the inside thereof to the titled material, and by using a silver halide particle which contains a larger amount of a silver iodide than the specific average content of a silver iodide and has either a uniform distribution of the silver iodide or a larger amount of the silver iodide in the inside of the silver halide particle than that of the surface thereof. CONSTITUTION:The titled material comprises the photosensitive silver halide emulsion and the silver halide emulsion having the fog in the inside thereof. The average content of the silver iodide contd. in the silver halide particle of the photosensitive silver halide emulsion is preferably 3-6mol%, and the distribution of the silver iodide contd. in said particle is uniform or the distribution is the larger amount of the silver halide in the inside of said particle than that of the surface of said particle. The workings that the content of the silver iodide contd. in the inner side of the silver halide particle is larger than that of the surface of said particle, mean that said content is 50-100wt%, preferably 50-75wt% on the weight basis of the total silver iodide content in the center part of said particle. Whereas, said content is 0-50wt%, preferably 25-50wt% in the surface part of said particle in a case that the vol. ratio of the surface part and the center part of said particle is 1:1.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention has high sensitivity and high concentration! The present invention also relates to a silver halide photographic material that is less dependent on processing.

(Prior Art) Regarding photographic images made of silver, the ratio of the optical density of the image to the amount of silver per unit area constituting the image is generally called covering power.
It is used as a measure of the optical efficiency of the silver that makes up the image. Generally, the covering power of a silver halide photographic light-sensitive layer increases as the silver halide grain size decreases, and decreases as the grain size increases. On the other hand, the sensitivity of the silver halide emulsion layer generally increases as the size of the silver halide grains increases, so silver halide emulsions with large grain sizes are used in highly sensitive photographic materials. Therefore, high-sensitivity photographic materials require a certain amount of silver per unit area to obtain a constant image density. In other words, more silver salt must be contained per unit area on the photographic material in order to obtain both high sensitivity and the required maximum image density. This is the reality of conventional high-sensitivity photographic materials! there were.

As an attempt to improve covering power while maintaining high sensitivity, a technique of adding various polymers to high-sensitivity coarse-grained silver halide emulsions was published in British Patent Nos. 1.048,057 and 1,039,471. No. 3,043,69, U.S. Pat.
No. 7 and No. 3,446,618. All of these have the effect of increasing the covering power to some extent, but are not sufficient, and may weaken the strength of the coating film, which is not desirable. On the other hand, U.S. Pat. No. 2,996,382 and U.S. Pat. 1
No. 78,282 discloses the use of a silver halide photographic light-sensitive material in which surface latent image type silver halide coarse grains and non-rodanide fine grains having capri nuclei inside are supported in the same layer or in an adjoining layer. It is described that photographic images with high sensitivity, high contrast, and high covering power can be obtained using the method.

However, in order to obtain sufficient high sensitivity, high density, and high contrast, method 1 requires a long development time in normal low-temperature processing, and especially in high-temperature rapid processing containing dialdehyde-based hardeners, the contrast It has the disadvantage that the value becomes too high and processing dependence becomes large.

In order to improve the development activity in low-temperature processing, attempts have been made to introduce various additives such as rhodan, imidazoles, and thioethers into sensitive materials and processing solutions. (For example, U.S. Patent No. 2,996.382;
It is described in the specifications of No.-78535 and No. 57-89749. ) In addition, attempts have been made to reduce processing dependence by adding additives such as nitrone salts, menion triazolium compounds, nonionic surfactants with norioxyethylene chains, and sensitizing dyes to the sensitive materials. . However, even if four new additives are added, it is clear that it would be more preferable if there were a means to improve the above-mentioned drawbacks.

(Object of the Invention) Therefore, the object of the present invention is to provide a light-sensitive silver halide emulsion and an internally fogged silver halide emulsion, wherein the silver iodide content of the light-sensitive silver halide emulsion is greater than 3 mol. It is an object of the present invention to provide a silver halide photographic light-sensitive material which has high development activity after low-temperature processing, high sensitivity, high density, and excellent processing dependence.

(Structure of the Invention) A silver halide photographic light-sensitive material having at least one layer of silver halide emulsion layer on a support and a light-sensitive silver halide emulsion layer and the inside thereof. containing a silver halide emulsion, and the average silver iodide content of the silver halide grains of the light-sensitive silver halide emulsion is more than 3 mol%,
The above object can be achieved by using a silver halide photographic material characterized in that the distribution of silver iodide within the grains is uniform, or is concentrated on the surface of the grains and inside the grains.

In general, it is desirable to increase the iodine content in silver halide photographic materials in order to increase daytime sensitivity.

For example, in regular type medical X-ray films, silver iodobromide emulsions containing about 2 mol of iodine are often used, which do not provide spectral sensitization.

However, if the iodine content of the emulsion could be increased, the absorption of blue light would increase, so that the emulsion could be made more sensitive to light. In addition, by making the highly sensitive component into fine particles, it can be used to increase the optical density (so-called covering) of developed silver. Furthermore, the blue light emitted by the fluorescent intensifying screen due to X-rays is transmitted not only to the emulsion side in contact with each phosphor of a film coated with a photosensitive emulsion on both sides of the support, but also to the other side beyond the support. The so-called cross-over light effect that sensitizes the emulsion surface can also be reduced by increasing the iodine content of the emulsion, thereby achieving high sharpness. In particular, in Japanese Patent Publication No. 41-2,068, the internal caplase fine grains are developed by the iodine released by the photosensitive silver halide grains during development, and the covering of visual silver is improved.
U.S. Patent 2,996,382, U.S. Patent 3,178,2
82, Special Publication No. 44-27,065, Special Publication No. 47-8.7
High iodine content is highly desirable in order to sufficiently bring about the effects described in No. 38 and US Pat. No. 1,426,277.

However, despite these numerous benefits, increasing iodine content also has some major drawbacks. For example, a high temperature rapid developer containing a glutaraldehyde hardener! When processed, photographic materials containing high iodosilver halide emulsions result in increased fog, increased contrast, deterioration of graininess, and deterioration of processing dependence. It has been considered to add a nitrone salt, a menion triazolium compound, a nonionic surfactant having a polyoxyethylene chain, and a sensitizing dye to the sensitive material for the purpose of improving the deterioration of processing dependence.

However, the addition of compounds such as thoron salts to such methods eliminates a significant portion of the increase in sensitivity obtained by increasing the silver iodide content. However, as in the present invention, the above-mentioned problems could be solved by making the distribution of silver iodide in the grains of a photosensitive silver halide emulsion uniform, or by making the distribution of silver iodide more concentrated inside the grains than on the grain surfaces.

In the present invention, "photosensitive" means that the sensitivity of the light-sensitive silver Rodanide emulsion is higher than the sensitivity of the internal fogged Silver Rodanide emulsion. More specifically, it means having a sensitivity that is 10 times or more, more preferably 100 times or more, the sensitivity of the internal fogged silver halide emulsion.

Sensitivity here is defined similarly to the sensitivity shown below.

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 1 to 1/1
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). An emulsion suitable for dogs, preferably an emulsion in which the sensitivity of the former is more than twice that of the latter. Here, sensitivity is defined as follows.

S is the sensitivity, and Eh is the maximum density (Dmax) and minimum density (
Dmin) intermediate density Σ(Drr+ax +Dm
indicates the amount of exposure required to obtain (in).

[Surface development (A)]

Develop in the following developer solution 1 at a temperature of 20° C. for 10 minutes.

N-Methyl-p-aminophenol (hemisulfate) 2.5g Ascorbic acid 10g Sodium metaborate tetrasalt 35,9 Potassium bromide
Add 1g water
16 [Internal development (B)] Red blood salt 3 j! /l and fuenosafunino 0.0126 i
The sample was treated in a bleaching solution containing 100 ml of 100% chloride at about 20° C. for 10 minutes, washed with water for 10 minutes, and then developed in a developer having the following formulation at 20° C. for 10 minutes.

N-Methyl-p-aminophenol (hemisulfate) 2.5g Ascorbic acid 109 Sodium metabolate tetrahydrate 35g Potassium bromide
1g sodium thiosulfate
Add 3g water
11 In the present invention, the term "uniform silver iodide distribution in a photosensitive silver halide emulsion" means that silver halide grains are divided into minute parts (for example, divided into parts of the same volume from the center to the surface).
In this case, it means that the iodide content of any minute portion is equal to the average silver iodide content of the entire grain. More specifically, it is preferably within ±10%, particularly within ±5%, of the average silver iodide content of the entire grain.

Furthermore, in the present invention, a grain in which silver iodide in the silver halide grain is more in the interior than in the surface means that when the grain is temporarily divided into the center and the surface at a volume ratio of 1:1, This means that 100% of the total silver iodide content is present in areas exceeding 50 parts, and less than 50 parts of silver iodide is present in the surface part.

Preferably, 95 inches from more than 50% of the groove in the center, 5 to 50 inches on the surface, more preferably 75 inches from more than 50 inches on the center, and 25% to 50 inches on the surface. less than

Regarding the intragrain silver oxide distribution of the silver halide grains of the present invention, see, for example, T., M., Kelly, M.;

G., Mason, “Glofile of Halogen Composition in Silver Halide Microcrystals,” Journal of Applied Physics, Vol. 47, (11)
), p. 4721 (1976), which combines ion etching and X-ray photoelectron spectroscopy (ESCA). Silver chloride and silver iodochlorobromide can be used. The content of silver iodide is preferably in the range of 3 to 15 molti, particularly 3 to 6 molti based on the entire grain. The average particle size is 0.
The range is more preferably 0.2 μm to 2 μm than 1 μm to 3 μm.

Further, the silver halide of the present invention may have a regular crystal shape such as a cube or an octahedron, or an irregular crystal shape such as a spherical shape or a plate shape.
Those having a crystalline form (ular) are also good.

In addition, the diameter of the particles is at least 3 times the thickness, preferably 5 times the thickness.
-20 times larger tabular grains may be used (here, the grain diameter is the diameter of a circle with an area equal to the projected area, and the grain thickness is the distance between two parallel planes). At this time, it is also possible to use an emulsion in which the tabular grains occupy 50 inches or more of the total projected area. For more information, see U.S. Patent 4
．． No. 434,226, No. 4,439,520, European Patent No. 84,637A2, Guto [Photographic Science and Engineering]
ff * Photographic 5science
andEngineering), Volume 14, 24
pp. 8-257 (1970) Research Disclosure (RESEARCH DISCLO8URE) No. 2
Volume 25, A22534 (January 1983) P, 2.0~
It is described in P. 58, etc.

The grains of the present invention in which the distribution of silver iodide in the grains is uniform or more in the interior than on the surface can be prepared by various known methods.

i.e. p, (Glafkides)
Written by Chim
ie at Physique Photography
ique (, Ball Mantel) (Paul Mon
tel ) Publishing, 1967, by G. F. Duffin (Photographic Emulsion Chemistry) PhotographicEhul
aion Chemistry (The Focal Press, 1966)
,” t' (Zelikman et al.) Zelikman
et al (Making and Coating Photographic Emulsion) Makir, g and
Coating Photographic Emuls
ion ((The Focal Press) The Foca
1Press, 1964). 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 under an excess of silver ions (so-called back-mixing method).

As one form of the simultaneous mixing method, a method in which PAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondral 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.

In these methods, iodides (e.g. potassium iodide,
A method in which IJum) is introduced into a mixing vessel before the start of precipitation formation, a method in which it is introduced into a halide solution such as a simultaneous mixing method, and a third aqueous iodide solution is further added at any stage of grain formation. You can use methods such as Wear.

As another preferred method of preparation, a method of preparing a core/shell emulsion can be used. According to this method,
A shell (coating layer) having a halogen composition having the same or lower iodine content can be deposited on a core particle (inner core particle) having an arbitrary halogen composition. If the halogen compositions of the core and shell are different, it may be difficult for the shell to deposit, so it is necessary to consider changes in the degree of critical supersaturation. However, it is preferable to take into account the pAgt reaction temperature, the type and amount of silver rodanide solvent, etc., and to prevent re-nucleation so as to allow rapid growth within a range that does not exceed the critical supersaturation level. It is also preferable to increase the number of moles added per unit time as the total surface area of the particles increases. In addition, in the case where the shell is silver bromide, in the presence of core particles containing bromide and silver iodide in advance,
A method of adding a silver nitrate water bath solution (one-sided mixing method) can also be used. For more information, see U.S. No. 3,935,014,
JP-A No. 50-38525, JP-A No. 53-22408, JP-A No. 43-13162, (Journal Photo Science) J, Photo, Sci, 2
4.198 (1976), U.S. Patent 4,242,445
No., JP-A-55-158124, etc.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a lead 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.

...Silver rhodanide emulsions are usually chemically sensitized.

For chemical sensitization, for example Il, (freezer) Fr
Die Grundlagen der Photo
ographishenprozesse mit S
ilberhalogeniden
cheVerlagsgesellschaft, 1
968), pages 675 to 734, can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, logenins); Kuramoto sensitization method using tin salts, amines, hydrazine conductors, formaminone sulfinic acid, 7-ranium compound): Noble metal compounds (e.g. total complex salts, Pt, Ir, PTIYZ, etc. in the periodic table) A noble metal sensitization method using complex salts of metals of the above group can be used alone or in combination.

These specific N are described in U.S. Patent No. 1 for sulfur sensitization
, No. 574,944, No. 2,410,689, No. 2,278,947, No. 2,728,668, No. 3,656,955, etc., regarding the reduction sensitization method in the United States. Patent No. 2,983,609, Patent No. 2.419,974
U.S. Pat. No. 2,399,083 and U.S. Pat. No. 2.448 regarding noble metal sensitization methods
, 060 and British Patent No. 618,061.

Next, the silver halide emulsion having capri nuclei inside to be used in the light-sensitive material of the present invention has a content of, for example, 2 g/silver in terms of silver content.
Transmission of 0.5 or less when a test piece coated on a transparent support so as to have a transparency of Kabu IJ 11!4 degrees (excluding the concentration of the support itself)
When the same test piece was developed without exposure at 35°C for 2 minutes with a developer containing D-19 with 0.51/l of potassium iodide added, the transmission fog IJ m degree (support An emulsion is used that gives the same concentration (excluding the concentration of the body itself).

Silver halide emulsions having capri cores inside can be prepared by various known methods. For example, the highly internally sensitive emulsion described in U.S. Pat. No. 2,592,250 is fogged by light irradiation, as described in U.S. Pat. No. 2,996,382 v: First, a core emulsion with capri cores is prepared by fogging under low pAg, high pAg conditions or chemically fogging with a reducing agent, a gold compound, or a sulfur-containing compound, and then the core emulsion is coated with a capri core. JP-A-58-2006, such as depositing a shell emulsion around the periphery (see core-shell emulsion technique described in U.S. Pat. No. 3,206,313).
There is a method described in Japanese Patent No. 215,647, and 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.

The silver halide emulsion having an internal capri nucleus 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 1.0 to 0.05 μm. Those having an average particle size of .6 to 0.1 .mu.m are most preferred, and those with an average particle size of 0.5 .mu.m or less are particularly preferred and give good results.

In the present invention, the grain size of silver halide is expressed by the particle diameter 1 in the case of spherical or approximately spherical particles, and by the diameter of a sphere with the same volume in the case of particles of other shapes (for example, cubes, etc.). shall be.

In the case of tabular grains, the above-mentioned method will be used.

The internally fogged silver halide emulsion may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride, and the like.

The content ratio of the photosensitive silver rodanide and the internally fogged silver halide in the silver halide photographic light-sensitive material of the present invention is determined by the emulsion type (for example) used, the rodan composition used, and the photosensitive material used. It can be changed depending on the type or purpose of the material, the contrast of the emulsion used, etc., but it is preferably 100:1 to 1:100-'Q, especially 10:1.
to 1:10 is preferred. Further, the total amount of coated silver is preferably 0.5 to 10 g/.

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

■ An emulsion layer consisting of a photosensitive silver rhodanide and an internal silver halide and a protective layer are sequentially provided on a support. A type in which an emulsion layer made of silver is sequentially provided ■ A type in which an internally covered emulsion layer made of silver rodanide, an emulsion layer made of photosensitive silver halide, and a protective layer are provided in this order on a support. Things can go up.

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

The retention layer of the silver halide photographic light-sensitive material of the present invention includes 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.

The silver halide photographic light-sensitive material of the present invention may further include an antihalation layer, an intermediate layer, a filter layer,
etc. can be provided.

Various compounds can be contained in the photographic material of the present invention for the purpose of preventing capri during the manufacturing process, storage, or photographic processing, or for stabilizing the photographic performance.

Namely, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercazotopenzothiazoles, Mercaptobenzimidazoles, mercaptotetrazoles, mercaptotetrazoles (% 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as carxyl group or sulfone group : Thioketo compounds such as oxazolinthione; Azaindenes such as tetraazaindene C, especially 4-hydroxy substituted (
Many compounds known as anti-capri agents or stabilizers can be added, such as 1+3*3a, 7) tetraazaindenes): benzenethiosulfonic acids: benzenesulfinic acid: etc.

For more detailed examples of these and how to use them, see, for example, U.S. Pat. No. 3,954,474;
Please refer to the specifications of 98λ947 and 4,021,248 or Japanese Patent Publication No. 52-28,660!
Wear.

The photographic light-sensitive material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination, or these and acrylic acid, It is possible to use a polymer containing a combination of methacrylic acid, α,β-unsaturated dicarzenic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component.

For example, U.S. Patent Nos. 2,376,005 and 2,73
No. 9,137, No. 2,853,457, No. 3,062
, No. 674, No. 3,411,911, No. 3,488,
No. 708, No. 3,607,290, No. 3,635,7
No. 15, No. 3.645,740, No. 3,525,62
No. 0, British Patent No. 1,186,699, British Patent No. 1,307,
You can use the one described in No. 373! Wear.

The photographic emulsions of this invention may be spectrally sensitized with methine dyes and others. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization.

Useful sensitizing dyes, supersensitizing dye combinations, and supersensitizing substances are available from Research Disclosure (Re5e).
Arch Disclosure ) Volume 176 176
43 (published December 1978), page 23, section 1.

The photographic emulsion ji of the photographic light-sensitive material of the present invention has increased sensitivity,
For the purpose of increasing contrast or accelerating development, for example, polyalkylene oxide or its ether, ester,
It may also contain U34 forms such as amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imiguzole derivatives, 3-pyrazolidones, and the like. For example, U.S. Patent 2,400,5
No. 32, No. 2,423,549, No. 2,716,06
No. 2, No. 3.617,280, No. 3,772,021
No. 3.808,003, British Patent No. 1,488,9
Those described in No. 91 etc. can be used.

As binders or protective colloids in photographic emulsions, it is advantageous to use gelatin (e.g. lime-processed gelatin, acid-processed gelatin, derivative gelatin, gelatin graft polymers, etc.), but other hydrophilic colloids (e.g. hydroxyl (ethylcellulose, phorhinylic alcohol, phylynylimidazole, etc.) can be used.

The photographic emulsion layer or other hydrophilic colloid layer of the photographic light-sensitive material of the present invention includes coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization). Various surfactants may be included for various purposes.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol 1.t?l
J ethylene glycol/polyderopylene IJ coal condensates, polyethylene glycol alkyl or alkylaryl ethers, ethers, polyethylene glycol, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, silicone polyethylene oxide nonionic surfactants such as adducts), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of tang: alkylamine salts, alkylsulfonates, Alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxyethylene Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphoric ester groups, such as alkyl phosphates; amino surfactants, aminoalkylsulfonic acids, aminoalkyl sulfates, Amphoteric surfactants such as phosphoric acid esters, alkyl betaines, and amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and aliphatic Alternatively, cationic surfactants such as phosphonium or sulfonium salts containing heterocycles can be used.

Specific examples of the fluorosurfactant include the compounds listed below.

As a fluorine-based low molecular compound, U.S. Patent No. 3.775
, No. 126, No. 3,589,906, No. 3.798,
No. 265, No. 3,779,768, No. 4.407,9
Specification No. 37, West German Patent No. 1,293,189, British Patent No. 1,259,398, British Patent Application No. 58,431, West German Patent No. 1,330,356,
No. 1,417,915, Japanese Unexamined Patent Publication No. 1987-87826,
No. 49-10722, No. 49-46733, No. 50
-16525, 50-113221, 50-1
No. 61236, No. 50-99525, No. 51-791
No. 7, No. 51-32322, No. 51-106419, No. 51-151124, No. 51-151125,
No. 51-151126, No. 51-151127, No. 51-129229, No. 52-127974, No. 5
No. 3-84712, No. 53-146622, No. 54-
No. 14224, No. 54-48520, No. 55-776
No. 2, No. 56-114'944, No. 58-16233
No. 59-23344, Special Publication No. 48-4313
No. 0, Publication No. 52-16073, Research Disclosure Shop 16630, No. 17341. 17611
etc. are described.

As a fluorine-based polymer compound, U.S. Patent No. 4,
No. 175,969, No. 4,087,394, No. 4.0
No. 16,125, No. 3,676,123, No. 3.67
9,411, 4,304,852, JP-A-52-129520, 54-158222, 55
-57842, 57-11342, 57-19
No. 735, No. 57-179837, “Chemistry Review/
"L27, New Fluorine Chemistry" (edited by the Chemical Society of Japan, 1980)
), Riyo, "Functional Fluorine-Containing Polymers" (Nikkan Kogyo Shimbun, 1982), etc.

Various other additives may be used in the photographic material of the present invention, if necessary. For example, dyes, hardeners,
There are fluorescent brighteners, etc. Specifically, Research Disclosure (RESEARCHDISCLO8U匪)
No. 176, pages 28-30 (RD-17643, 1978
2008) can be used.

In the photographic light-sensitive material of the present invention, the silver halide emulsion layer may be provided not only on one side but also on both sides of the support.

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 0.3 to 5 μm or a particle size of at least 2 times, especially 4 times or more, 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 the frictional properties of video films related to camera compatibility during shooting or projection. Waxes such as rough-in, esters of higher fatty acids, polyfluorinated hydrocarbons or derivatives thereof, polyalkylpolysiloxanes, polyarylpolysiloxanes, polyalkylarylpolysiloxanes, or their alkylene oxyP addition derivatives. Silicones and the like 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.

Photographic materials to which the present invention can be used include X-ray photographic materials, lithographic photographic materials, black-and-white photographic films, and various other photographic materials.

For the processing of the photosensitive material of the present invention, for example, Research Disclosure (Research Disclosure) may be used.
e) Any of the known methods and known treatment liquids as described in No. 176, pages 28-30 (RD-17643) can be applied. Depending on the purpose, this photographic processing may be either photographic processing that forms a silver image (black and white photographic processing) or photographic processing that forms a dye image (color photographic processing). The processing temperature is usually selected between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used.

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

As developing agents, dihydroxybenzenes (for example, hydroquinone), 3-pinzolidones (for example, 1-
phenyl-3-pyrazolidone), amine phenols (
For example, N-methyl-p-aminophenol) can be used alone or in combination.

In addition, the developing solution generally contains known preservatives, alkaline agents, pH buffering agents, antifoggants (benzotriazoles such as methylbenzotriazole and nitroindazole,
benzothiazoles, indazoles, tetrazoles, thiazoles, etc.), as well as solubilizers, color toning agents, development accelerators, surfactants, antifoaming agents, water softeners, hardeners, and viscosity agents, as required. It may also contain an imparting agent.

The μ of the developer is 9 to 11, especially 9.5 to 10.
5 is preferred.

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 fixer contains water-soluble aluminum salt as a hardening agent↑
Good too.

(Example) Next, specific examples used in the present invention will be shown. However, the present invention is not limited to these specific examples.

Example-1 ■ Preparation of a silver iodobromide emulsion (4.0 molt AgI) uniformly containing silver iodide.
While maintaining pAg at 8.9, an aqueous silver nitrate solution (1.18 mol) and a mixed aqueous solution of potassium bromide and potassium iodide were simultaneously added to an aqueous solution kept at ℃ to obtain an average particle size of 1.2.
μ octahedral silver iodobromide grains (4.0 mol% AgI) were prepared, desalted by a conventional precipitation method, redispersed in gelatin solution, and treated with total sulfur using chloroauric acid and logenine sulfur sensitizers. A silver iodobromide emulsion (4.0 mol %, AgI) (2) uniformly containing silver iodide was prepared by chemical sensitization by a sensitization method.

■ Silver iodobromide emulsion (4,
Preparation of octahedron by simultaneously adding silver nitrate aqueous solution (0.59 mol) and a mixed aqueous solution of potassium bromide and potassium iodide to the same gelatin aqueous solution as in ① while keeping PAg at 8.6. Silver iodobromide core particles (8.0 mol% Ag1) were prepared, and then P
While maintaining Ag at 9.0, silver nitrate aqueous solution q[(0.59 mol) and potassium bromide aqueous solution were simultaneously added to deposit a shell on the core to form octahedral iodobromide with an average particle size of 1.2μ. A silver iodobromide emulsion (4.0 mol %AgI) was prepared, followed by desalting, redispersion, and chemical sensitization in the same manner as in ①. AgI) :■
was prepared.

■ Silver iodobromide emulsion (4,
Preparation of octahedral silver bromide core particles by simultaneously adding a silver nitrate aqueous solution (0.59 mol) and a potassium bromide aqueous solution while keeping PAg at 9.0 in the same gelatin aqueous solution as in ①. Next M
While maintaining pAg at 8.6, add silver nitrate aqueous solution (0.59
mol) and a mixed aqueous solution of potassium bromide and potassium iodide were simultaneously added to deposit a lumpy shell on the core to form an octahedral silver iodobromide emulsion (4.0 mol%
) was desalted, redispersed, and chemically sensitized by the same method as in ■ to prepare a silver iodobromide emulsion (4.0 mole AgI) with a large amount of silver iodide distributed on the surface.

Incidentally, only silver halide grains were taken out from the silver iodobromide emulsions ①, ② and 0 thus obtained, and each was subjected to ion etching, F, and SCA to remove iodine from the grain surface to the center of the grain. The silver oxide distribution, that is, the ratio of the silver iodide peak to the silver bromide peak was determined.

As a result, it was confirmed that the silver iodide distribution of the emulsion was uniform from the grain surface to the center, with emulsion ■Cj1 having more silver iodide in the center, and emulsion ◎ having more silver iodide in the surface.

■ Preparation of silver halide emulsion with internal fogging Silver chlorobromide emulsion tJiJ with internal light sensitivity and average grain size of 02 μm by the same method as in Example I in the specification of US Pat.
The interior of the emulsion was covered by light irradiation to obtain emulsion (2) to which 5-alkylamide-2mercazotobenzimidazole was added as a fog 9 inhibitor.

■ Preparation of coated samples and evaluation of photographic performance Emulsion C was applied to emulsions ■ and ■, and the Ag amount was 3.0 g/m2, respectively.
．． 0.59/m", dodecylbenzenesulfonate as a coating aid and p-vinylbenzenesulfonate as a thickener, and 4-hydroxy-6methyl-1.3. 3a, 7-
After adding citrazaindene, samples 1 to 2 were coated on a polyethylene terephthalate support at the same time as a surface protective layer and dried, and nitrone was added to emulsions 1 and 2 at 0.4 mrnot and 0.8 mmoj/Ag, respectively.
Samples @ and ■ with mot added were prepared. At this time, the amount of binder applied in the surface protective layer and emulsion layer was 1.597, respectively.
m2.2, Ofi 7m”, and 20% of the binder was polyacrylamide.Also, a vinyl sulfone compound was used as a hardening agent, and a polyoxyethylene nonionic surfactant and a soft-containing material were used as a static resistant material. A base sulfonic acid surfactant, polymethyl methacrylate (PMMA) as a matting agent, and Snowtex C (manufactured by Nichichi Kagaku) as a film quality improving agent were added.

After keeping the above sample at a temperature and humidity of 25°C and 65% R)l for 7 days, it was
Wedge exposure (1/20 second) was performed using nm blue light, and processing was performed for 25 seconds at 31°C, 35°C, and 37°C using an automatic processor (Fuji Photo Film ■, Teru-4ooo).

At this time, the developer composition was as follows.

l-phenyl-3-pyrazolidone 1.5g hydroquino/30 I5-nitroindazole 0.25J anhydrous sodium sulfite so-g boric acid 10I KBr 10 9 KI 5 w9 glutaraldehyde 5g Add water
11PH10.2 After development, fixing, washing with water, and drying were performed.

Further, the graininess was measured at a density of D # 0.6.

Table 1 summarizes the sensitivity, maximum density, granularity, and processing temperature dependence of samples ① to ②.

As is clear from 8-1, 9 coating samples ■ using photosensitive emulsions ■ and ■ in which silver iodide distribution is uniform or small on the grain surface
, @ have lower relative sensitivity than samples with high silver iodide content on the grain surface, but development temperature dependence, graininess, and maximum degree are higher.

In addition, sangur@, which is a photosensitive emulsion ◎ with nitrone added, ■
The development temperature dependence is small and it is comparable to samples ① and ＠, but the maximum density and relative sensitivity are low.

Claims (1)

[Claims] A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support contains a light-sensitive silver halide emulsion and an internally fogged silver halide emulsion; A silver halide photographic sensitizer, characterized in that the average silver iodide content in the silver halide grains of the emulsion is more than 3 mol %, and the silver iodide distribution within the grains is uniform, or more in the interior of the grains than on the grain surfaces. material.