CN1299162C - Silver halide emulsion and silver halide photographic photosensitive material - Google Patents

Abstract

The present invention provides a silver halide emulsion which does not cause low sensitivity and soft tone even with digital exposure such as laser scanning exposure and obtains hard tone gradation with high sensitivity, and a silver halide photographic light-sensitive material using the same. Further, a silver halide emulsion is provided which has high sensitivity, low fogging, excellent reciprocity law characteristics under high illumination, and small sensitivity fluctuation and small gradation fluctuation accompanying the time fluctuation of post-exposure treatment. The silver halide emulsion is formed by silver halide particles with a silver chloride content of 90 mol% or more, and is characterized in that the maximum content of silver iodide in the corner parts of the silver halide particles is higher than the content of silver iodide in the main surface parts of the particles, and the silver halide particles contain at least 1H or more₂O, OH, O, OCN, thiazole or substituted thiazole as a ligand, and a 6-coordinate complex of Cl, Br or I as the remaining ligands and Ir as a central metal.

Description

Silver halide emulsion and silver halide photographic photosensitive material

technical field

The present invention relates to a silver halide emulsion and a silver halide photographic photosensitive material. Specifically, it relates to a silver halide emulsion capable of obtaining a hard-tone gradation with high sensitivity even in digital exposure such as laser scanning exposure, and a silver halide using the silver halide emulsion Photographic photosensitive materials. Furthermore, it relates to a silver halide emulsion which has high sensitivity but is not excessively sensitive, has excellent reciprocity law characteristics at high illuminance, and has little change in sensitivity change and gradation change with time until post-exposure processing, its production method and Use its silver halide color photographic photosensitive material.

Background technique

In recent years, in the field of color printing using color printing paper, the penetration of digitalization is amazing. For example, the digital exposure method using laser scanning exposure is directly processed by the processed color negative film with a color printing machine that has been practiced for many years. Compared with the analog exposure method of printing plate, it shows the popularity rate of rapid development. The characteristic of this digital exposure method is that high-quality images can be obtained during image processing, and it has played a great role in improving the quality of color printing using color printing paper. With the rapid spread of digital cameras, it is an important element to easily obtain high-quality color photos from these electronic recording media, and it is considered that these will lead to a further leap in popularity.

On the other hand, as a color printing method, technologies such as inkjet printing method, sublimation method, and color electrophotographic copying are each developing, and the photographic quality is praised as a color printing method. Among these, the digital exposure method using color printing paper is characterized by high picture quality, high productivity, and also high image fastness, but it is also desired to further improve these and provide more in a simpler and cheaper way. High quality photography.

For silver halide emulsions used in color printing paper, fast processability is mainly required in order to improve productivity, so silver halide emulsions with a high silver chloride content are used. Such silver halide emulsions with a high silver chloride content generally tend to cause low-sensitivity soft tone due to high-illuminance exposure of laser scanning exposure, so various technologies have been developed to improve this point.

In order to improve the misalignment of silver chloride emulsions to high illuminance, doping with iridium is known. However, it is also known that the silver chloride emulsion doped with iridium will produce latent image sensitization in a short time after exposure. The local phase with a high content rate and doped with iridium solves the problem of latent image sensitization. The silver halide emulsion prepared by this method can obtain high sensitivity and hard tone even if it is exposed at a relatively high illuminance of 1/100 second, and there is no problem of latent image sensitization. Up to the ultra-high-illumination exposure of 1 μ second obtained by the digital exposure method of laser scanning exposure, it is still necessary to maintain high sensitivity, but the problem of difficulty in obtaining hard grayscale is also obvious. U.S. Patent No. 5,691,119 discloses a method for hardening high-illuminance gradation by using a method for preparing an emulsion having a partial phase having a high silver bromide content. However, there are still shortcomings of insufficient effect and unstable performance under repeated modulation.

In US Pat. Nos. 5,783,373 and 5,783,378, a method of using at least three dopants to reduce high-illuminance irregularities and form a hard tone is disclosed. However, in order to obtain a hard tone gradation, a dopant having a desensitizing hard tone effect is used, which is incompatible with high sensitivity in principle.

In U.S. Patent No. 5,726,005 and No. 5,736,310, it is disclosed that an emulsion with a very large concentration of I on the subsurface of a high silver chloride emulsion is used to obtain an emulsion with a small high-illuminance irregularity at high sensitivity. Based on this, it can be seen that the higher the illumination exposure, the higher the sensitivity can be obtained. As for the gray scale, it is soft, which is not suitable for digital exposure where the amount of light is only limited to the dynamic range.

In Japanese Patent Application No. 58-95736, No. 58-108533, No. 60-222844, No. 60-222845, No. 62-253143, No. 62-253144, No. 62-253166, No. 62-254139 , U.S. Patent No. 63-46440, U.S. Patent No. 63-46441, U.S. Patent No. 63-89840, U.S. Patent No. 4820624, No. 4865962, No. 5399475, No. 5284743, etc., disclose emulsions with high silver chloride content Among them, in various forms, a phase with a high silver bromide content is partially contained, thereby obtaining high sensitivity. However, the use of an emulsion containing a silver bromide-containing phase and a silver iodide-containing phase, which has a special hardening effect in ultrahigh light exposure like laser scanning exposure, is not disclosed.

In US Pat. No. 5,049,485, it is disclosed that Au(I) compounds coordinated by mesoions are used for chemical sensitization, thereby obtaining high-sensitivity hardening. US Patent No. 5,945,270 discloses chemical sensitization using an Au(I) compound coordinated by a meso-ion containing a water-soluble group, thereby obtaining high-sensitivity hardening. Although these are known to be relatively stable Au(I) compounds, the use of emulsions containing silver bromide-containing phases and silver iodide-containing phases to have special hardening effects in high-illuminance exposure is not disclosed.

On the other hand, in recent years, for color printing paper, performance requirements such as higher sensitivity, stable processing, higher image quality, and faster development process have become more and more intense. To increase the sensitivity of silver chloride emulsions, the method of including bromide ions in emulsion particles has been mainly studied so far. For example, the method disclosed in the specification of European Patent No. 0295439 is a method of containing bromide ions on the surface of the particle, and in the specification of U.S. Patent No. 5252454, it is disclosed that the bromide concentration is formed on the surface of the particle by directional growth to at least 20 mol%. The local phase method disclosed in U.S. Patent No. 5,252,456 is to make a fine particle emulsion cooperate with a larger high silver chloride host particle emulsion, and form a bromide-rich compound on the surface of the particle by Ostwald ripening phase method. On the other hand, iodide ions may be contained in the silver chloride emulsion particles to increase the sensitivity. However, until now, there have been few cases where high sensitivity was targeted, and the examples containing iodide ions represented by the above cited patents generally allow low concentrations or avoid this problem.

List several examples of high sensitivity to iodide ions in high silver chloride emulsions. The technical feature disclosed in US Patent No. 5264337, No. 5292632 and No. 5314798 specifications is to make the inside of the particles contain band-shaped iodide in the later stage of forming high chloride silver {100} plate particles. US Patent No. 5,275,930 shows an example of combining bromide ions and iodide ions at a low ratio to epitaxially grow at the corners of flat-shaped particles. The technical features disclosed in the specification of JP-P8-220681, JP-8-234340, JP-8-220684, JP-8-240879 and JP-8-234345 have in common that the host is hyperchlorinated. The method of containing iodide ions in the silver oxide emulsion particles has been contrived to form a high chloride layer on the subsurface of the emulsion particles which has the maximum concentration of iodide ions, but no iodide is intended to be contained on the iodide-containing layer.

When iodide ions and silver chloride form mixed crystals, the interlattice silver ions inside the particles increase significantly. Therefore, it was found that the high sensitivity formed by iodide ions promotes the formation of photosensitive nuclei due to the increase of interlattice silver ions. In the above-cited patents, there is no iodide-containing layer on the surface, or since it is limited to the corner portion, the effect of increasing the sensitivity cannot be induced to the maximum. On the other hand, when the iodide ion is contained on the outermost surface of the particle, after the particle is formed, the iodide ion adsorbed on the outermost surface forms an unstable component in the subsequent chemical sensitization and other treatments and enters into the silver chloride. In the layer, it is easy to form image blur, which is not suitable for high sensitivity.

Contents of the invention

The first problem to be solved by the present invention is to provide a silver halide emulsion and a silver halide photographic photosensitive material using it, which do not cause low sensitivity and soft tone even in digital exposure like laser scanning exposure, and thus High sensitivity obtains hard tone grayscale.

The second problem to be solved by the present invention is to provide a silver halide emulsion excellent in latent image preservation and dependence on exposure temperature and humidity, and a silver halide photographic photosensitive material using the same. Furthermore, the third subject of the present invention is to provide a silver halide emulsion and its production method, and a silver halide color photographic photosensitive material using it. Although the silver halide emulsion has high sensitivity, the image is clear, and the reciprocity under high illuminance is high. The law characteristics are very good, and the sensitivity change and gray scale change caused by the change of post-exposure processing time are very small at any time.

Solution to the problem

The method for solving the above-mentioned problems is as follows, that is,

<1> A silver halide emulsion formed of silver halide grains having a silver chloride content of 90 mol % or more, wherein the maximum silver iodide content in the corners of the silver halide grains is higher than that in the main surface of the grains. content rate, and the silver halide particles contain at least one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as a ligand, the remaining ligands are formed by Cl, Br or I, and Ir is the central metal 6 coordination complexes.

(Hereafter, the above-mentioned silver halide particles are referred to as "specific silver halide particles")

<2> A silver halide emulsion characterized by forming a silver bromide-containing phase and a silver iodide-containing phase in a layered form, and containing silver halide grains with a silver chloride content of 90 mol % or more.

<3> The silver halide emulsion described in the above <2>, wherein the silver bromide-containing phase is formed on the inside of the grains more than the silver iodide-containing phase.

<4> The silver halide emulsion according to the above <2> or <3>, wherein the silver bromide-containing phase and the silver iodide-containing phase are formed adjacent to each other.

<5> The silver halide emulsion according to any one of the above <1> to <4>, wherein the silver halide grains are cubic or tetrahedral grains.

<6> The silver halide emulsion according to any one of the above <1> to <5>, wherein the electron emission time of the silver halide grains is 10 ^-5 seconds to 10 seconds.

<7> The silver halide emulsion according to any one of the above <1> to <6>, wherein the silver halide grains contain Cl, Br, or I as a ligand and Ir as a center metal in a six-coordinate complex body.

<8> The silver halide emulsion described in the above <7>, characterized in that the above-mentioned hexacoordinate complex is contained in the silver bromide-containing phase.

<9> The silver halide emulsion according to any one of the above <1> to <8>, wherein the latent image oxidation potential of the above silver halide emulsion is higher than 70 mV.

<10> The silver halide emulsion according to any one of the above <1> to <9>, wherein the silver halide emulsion is gold-sensitized.

<11> The silver halide emulsion described in the above <10> is characterized in that the above silver halide emulsion is gold-treated with colloidal gold sulfide or a gold sensitizer whose complex stability constant logB ₂ of gold is 21 or more and 35 or less. Sensitized.

<12> A silver halide photographic photosensitive material characterized by comprising the silver halide emulsion described in any one of the above <1> to <11>.

<13> A silver halide emulsion comprising silver halide grains with a silver chloride content of 90 mol% or more, wherein the maximum silver iodide content at the corners of the silver halide grains is higher than the silver iodide content at the main surface of the grains.

<14> The silver halide emulsion according to any one of the above <1> to <13>, wherein the main surface of the silver halide grains is composed of a (100) plane.

<15> The silver halide emulsion described in <13> or <14>, wherein the iodide ion content is 0.06 mol% or more relative to the total silver content of the total emulsion grains.

<16> The silver halide emulsion according to any one of the above <13> to <15>, wherein the iodide ion content is 0.1 mol% or more relative to the total silver content of the total emulsion grains.

<17> The silver halide emulsion according to any one of the above <1> to <16>, which is characterized in that it is spectrally sensitized by trimethadione cyanine.

<18> The silver halide emulsion according to any one of the above <13> to <17>, wherein the silver halide grains contain one or more transition metal complexes.

<19> The silver halide emulsion described in the above <18>, wherein the central metal of at least one transition metal complex in the above-mentioned overplating metal complex is ruthenium, rhodium or osmium.

<20> The silver halide emulsion according to any one of the above <1> to <19>, wherein the bromide ion concentration in the layered silver bromide-containing phase has a maximum concentration inside the silver halide grains, And the iodide ions in the silver iodide-containing phase have a very large concentration on the surface of the silver halide particles.

<21> A silver halide photosensitive material for color photography, which has at least one layer of blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red-sensitive silver halide emulsion layer on a support, and is characterized in that the blue-sensitive halide At least one of the silver emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer contains the silver halide emulsion described in any one of the above <1> to <20>.

Detailed ways

The present invention will be described in detail below.

The silver halide emulsion of the present invention contains specific silver halide grains. The particle shape of the particles is not particularly limited, and it is preferably composed of cubic or tetradecahedron crystal particles (the vertices of these particles are spherical and may have higher-order faces) or octahedral crystal particles, or It is formed by flat-shaped particles with an aspect ratio of 2 or more formed from a {100} plane or a {111} plane with more than 50% of the total projected area. The so-called aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the particle thickness. In the present invention, cubic or tetradecahedral particles are more preferable.

As the silver halide emulsion of the present invention, an emulsion containing specific silver halide grains is used. The silver chloride content must be at least 90 mol%, and from the viewpoint of quick handling, the silver chloride content is preferably at least 93 mol%, more preferably at least 95 mol%.

The specific silver halide grains in the silver halide emulsion of the present invention are any one of the following 1) and 2).

1) A silver bromide-containing phase and a silver iodide-containing phase each form a layer (hereinafter referred to as constitution 1).

2) The maximum silver iodide content in the corner portion is higher than the silver iodide content in the main surface portion of the particle (hereinafter referred to as constitution 2).

In the above, either one of 1) or 2) may be satisfied, and both may be satisfied.

In the present invention, the aforementioned silver halide grains are referred to as specific silver halide grains, and the silver halide emulsion containing the silver halide grains is referred to as the silver halide emulsion of the present invention. When it is only any one, it is called the silver halide grain of composition 1, or the silver halide grain of constitution 2.

The silver halide particles of the constitution 1 will be described below.

From the viewpoint of hard tuning and excellent latent image stability, the silver bromide content is preferably 0.1-7 mol%, more preferably 0.5-5 mol%. Considering high-illuminance exposure, high sensitivity, and hard tone, the silver iodide content is preferably 0.02-1 mol%, more preferably 0.05-0.50 mol%, especially preferably 0.07-0.40 mol%. The following describes the silver halide particles constituting 2. The silver iodide content is preferably at least 0.1 mol%, more preferably 0.1-0.8 mol%, particularly preferably 0.25-0.60 mol%.

The silver halide particles constituting 1 of the present invention are preferably silver iodobromochloride particles, more preferably silver iodobromochloride particles composed of the above-mentioned halogen.

Configuration 1 of the present invention has silver halide grains having a silver bromide-containing phase and a silver iodide-containing phase. The term "silver bromide-containing phase or silver iodide-containing phase" as used herein refers to a portion having a higher concentration than the surrounding silver bromide or silver iodide. The halogen composition of the silver bromide-containing phase or silver iodide-containing phase and its surroundings can also be changed continuously or abruptly. Such a silver bromide-containing phase or a silver iodide-containing phase may form a concentration layer with a certain range in a certain part of the particle, or may be a maximum point that does not expand. The partial silver bromide content in the silver bromide-containing phase is preferably at least 5 mol%, more preferably 10 to 80 mol%, particularly preferably 15 to 50 mol%. The partial silver iodide content in the silver iodide-containing phase is preferably at least 0.3 mol %, more preferably 0.5 to 8 mol %, particularly preferably 1 to 5 mol %. Such a silver bromide-containing phase or a silver iodide-containing phase may have several layers in each particle, and the content ratio of each silver bromide or silver iodide may be different, but must have at least one phase.

The present invention constitutes 1 that the silver bromide-containing phase and the silver iodide-containing phase in the silver halide grains have, most importantly, a layered shape surrounding each grain. A best form of forming a layered silver bromide-containing phase or silver iodide-containing phase around the particles is that each phase has a uniform concentration distribution in the direction around the particles. However, in the silver bromide-containing phase or silver iodide-containing phase that exists in a layered form around the particles, the maximum or minimum point of the concentration of silver bromide or silver iodide exists in the direction around the particles, and may have a concentration distribution. For example, when there is a layered silver bromide phase or a silver iodide-containing phase surrounding the particle near the surface of the particle, the concentration of silver bromide or silver iodide at the corner or edge of the particle may be different from that on the main surface. Unlike the layered silver bromide-containing phase and silver iodide-containing phase surrounding the particle, it exists completely isolated on a specific part of the particle surface, or it may be a silver bromide-containing phase or a silver iodide-containing phase that does not surround the particle.

Such a silver-bromide-containing phase or a silver-iodide-containing phase, from the consideration of improving the local concentration with less amount of silver-containing bromide or silver iodide, the particle volume is preferably composed of 3-30% silver content, more preferably 3-30%. 15% silver volume composition.

The silver bromide-containing phase and the silver iodide-containing phase constituting the silver halide particles of the present invention may exist in the same part of the particle or in different parts. From the point of view of being easy to control the formation of particles, it is preferable to exist in different parts. parts. Silver iodide may be contained in the silver bromide-containing phase, and conversely, silver bromide may also be contained in the silver iodide-containing phase. In general, in the formation of high-chloride silver particles, since the added iodide penetrates the particle surface more easily than bromide, the silver iodide-containing phase is easily formed near the particle surface. Therefore, when the silver bromide-containing phase and the silver iodide-containing phase exist in different parts of the particle, it is preferable to form the silver bromide-containing phase inside the silver iodide-containing phase. In such a case, another silver bromide-containing phase may be provided on the outer side of the silver iodide-containing phase near the particle surface.

In order to achieve the effects of high sensitivity and hard adjustment of the present invention, the silver bromide content or the silver iodide content required to form the silver bromide-containing phase or the silver iodide-containing phase inside the particle is increased, but there is such a danger that, that is, Reducing the silver chloride content more than necessary impairs rapid processability. Therefore, it is desirable to have the silver bromide-containing phase adjacent to the silver iodide-containing phase in order to concentrate these functions of controlling the photographic effect near the surface within the particle. From these aspects, measured from the inside, it is better to form a silver bromide-containing phase anywhere from 50% to 100% of the particle volume, and to form a silver iodide-containing phase anywhere from 85% to 100% of the particle volume. . More preferably, the silver bromide-containing phase is formed anywhere from 70% to 95% of the particle volume, and the silver iodide-containing phase is formed anywhere from 90% to 100% of the particle volume.

The silver halide grains of configuration 2 of the present invention will be described.

The corner portion specified in Configuration 2 refers to a polygonal pyramid-shaped portion formed by separating from the apex of the particle by one-fifth of the length of the side (the length of the ridge line connecting the apexes). When the vertex of the particle is rounded, the ridgeline is extended and determined by extrapolation from the estimated vertex.

The content of iodide ions contained in the silver halide particles is preferably at least 0.01 mol %, more preferably at least 0.06 mol %, most preferably at least 0.1 mol %, per mol of total silver. Good silver iodide chloride phase particles containing 0.06-1.0 mol %, more preferably 0.1-0.8 mol %, most preferably 0.25-0.60 mol of iodide ions can obtain high sensitivity and have excellent high-illuminance exposure adaptability. The silver iodobromide particles of the present invention may have a core-shell structure. At this time, the ion content of iodide in the shell part is 0.01 to 8.0 mole % per mole of silver in the shell part, more preferably 0.05 to 6.0 mole %, most preferably 0.25 to 4.0 mole %, and the iodide content in the core part is The ion content is preferably one-tenth or less of the value of the shell portion. On the surface of the silver halide particles, it is particularly preferable to have a localized silver bromide phase of 0.2 to 5 mol %, more preferably 0.5 to 3 mol %, per mol of total silver, because high sensitivity can be obtained and photographic performance is stable.

The silver iodide content in the corners of silver halide emulsion grains can be studied using an electron analysis microscope. By analyzing a predetermined part of the particle with an electron analysis microscope, spot analysis can be performed by reducing the light spot to 2nm or less, and the silver iodide content can be measured. The same measurement is carried out on silver halide particles whose content is known, and the detection curve is drawn. Based on the ratio of Ag intensity and I intensity obtained in advance, the silver iodide content can be obtained. As the analysis line source of the electron analysis microscope, it is suitable for the radiation type electron gun in the field with higher electron density than thermionic electrons, which can reduce the spot size to less than 2nm, and can easily analyze the halogen composition of a small part. The determination of the silver iodide content in the corners is carried out by tilting the electromagnetism sample and only contacting the specified part with the electron beam. When making a sample, this method can also be used to pour the emulsion particles on the copper screen with the support film opened. Use the analytical electric display to survey and map the larger silver iodide content rate in the whole, and after narrowing the maximum area in the specified part, perform the above-mentioned point analysis in the specified area, measure a few points to dozens of points, and find the maximum value.

Using the ESCA method, the silver iodide content in the main surface portion of the silver halide emulsion grains was determined as the surface iodine content. In the present invention, the maximum silver iodide content in the corner portion is preferably 1 to 100 times, more preferably 1.1 to 50 times, most preferably 1.2 to 20 times the maximum silver iodide content in the main surface portion.

When the silver halide grains of the configuration 2 of the present invention contain a localized silver bromide phase, it is preferable to epitaxially grow the localized silver bromide phase having a silver bromide content of at least 10 mol % or more on the particle surface. The silver bromide content of the silver bromide partial phase is preferably from 10 to 60 mol%, more preferably from 20 to 50 mol%. The silver bromide localized phase is composed of 0.1 to 5 mol% of silver, more preferably 0.3 to 4 mol% of silver, based on the total amount of silver constituting the silver halide particles in the present invention. In the local phase of silver bromide, it is preferable to contain iridium(III) chloride, iridium(III) bromide, iridium(IV) chloride, sodium hexachloroiridate(III), hexachloroiridium(IV) Group (VIII) metal complex ions such as potassium hexaamine iridium (IV) salt, iridium (III) trioxalate salt, and iridium (IV) trioxalate salt. The amount of these compounds to be added can be selected in a wide range depending on the purpose, but it is preferably 10 ^-9 to 10 ^-2 mol relative to 1 mol of silver halide. These Group VIII metal complex ions will be described in detail later.

When preparing the specific silver halide grains of the present invention (that is, silver halide grains satisfying at least one of constitutions 1 and 2), in order to contain silver bromide or silver iodide introduced bromide or iodide, a bromide salt can be added alone or iodide salt solution, alternatively, add bromide salt or iodide salt solution together with silver salt solution and perchloride salt solution. In the latter case, the bromide salt or iodide salt solution and the perchloride salt solution are added individually, or as a mixed solution of bromide salt or iodide salt and perchloride salt. Bromide salts or iodide salts may be added in the form of soluble salts such as alkali or alkaline earth bromide salts or iodide salts. Or, as described in US Pat. No. 5,389,508, bromide ions or iodide ions split from organic molecules are introduced. As an additional source of bromide or iodide ions, fine silver bromide particles or fine silver iodide particles can also be used.

The bromide salt or iodide salt solution may be added collectively at the moment of particle formation, or may be added over a certain period of time. The position where iodide ions are introduced into the high chloride emulsion is limited in terms of obtaining a high-sensitivity, low-oversensitization emulsion. The more the iodide ions are introduced into the interior of the emulsion particles, the smaller the increase in sensitivity. Therefore, it is better to add the iodide salt solution from more than 50% of the particle volume, more preferably from 70% and most preferably from 85%. It is better to add the iodide salt solution from 98% more inside of the particle volume, better to end the addition from 96% more inside. The addition of iodide salt solution, from the surface of the particle, ends slightly inward to obtain a higher sensitivity, low transition sensitivity emulsion.

On the other hand, the addition of the bromide salt solution is preferably carried out from more than 50% of the particle volume, more preferably from more than 70% of the particle volume.

The concentration distribution of bromide or iodide ions in the depth direction of the particle can be determined by etching/TOF-SIMS (Time of Flight-Secondary lon Mass Spectrometry), for example, using TRIFT II TOF-SIMS manufactured by Phi Erans Determination. The TOF-SIMS method is specifically described in "Secondary Ion Mass Analysis Method Selected by Surface Analysis Technology" edited by the Japanese Society for Surface Science (issued in 1999) by Maruzen Co., Ltd. When analyzing emulsion particles using the etching/TOF-SIMS method, even if the addition of iodide salt solution ends inside the particles, it can be analyzed that iodide ions permeate to the particle surface. The emulsion of the present invention is analyzed by the etching/TOF-SIMS method. It is preferable that the iodide ion has a maximum concentration on the particle surface, and the iodide ion concentration gradually decreases towards the inside, while the bromide ion preferably has a maximum concentration inside the particle. . The local concentration of silver bromide, if the silver bromide content is high enough, can also be determined by X-ray refraction.

The electron emission time of the silver halide emulsion of the present invention is preferably from 10 ^-5 seconds to 10 seconds. The electron release time referred to here is the time from when the silver halide emulsion is exposed to light, the photoelectrons generated in the silver halide crystal are captured by the electron traps existing in the crystal until they are released again. When the electron release time is shorter than 10 ^-6 seconds, it is difficult to obtain high-illuminance exposure, high sensitivity, and hard-tone grayscale. When it is longer than 10 seconds, the problem of latent image sensitization will occur during the short-time processing period after exposure. The electron release time is preferably between 10 ^-4 and 10 seconds, most preferably between 10 ^-3 and 1 second.

The electron release time can be measured by double-pulse photoconduction method. Using the microwave photoconduction method or the radiation wave photoconduction method, a short exposure time is given once triggered. Then, after a certain period of time, two trigger short-time exposures were given. In the first trigger exposure, the electron traps in the silver halide crystal capture electrons, and then when the second trigger exposure is given, the photoconduction signal of the second trigger becomes larger due to the blockage of the electron traps. The interval between the two exposures was set at ten minutes. Under the first trigger exposure, when the electrons captured by the electron trap had been released, the photoconduction signal of the second trigger roughly returned to its original size. For example, if the interval between two exposures is changed, the exposure interval dependence of the intensity of the light transmission signal triggered at the second time is collected, and the decrease of the intensity of the light transmission signal triggered at the second time is measured along with the exposure interval. This represents the release time of photoelectrons from electron traps. Electron release may continue for a certain period of time after exposure, but it is better to observe gradual release within 10 ^-5 to 10 seconds. It is more preferable to observe the release between 10 ^-4 and 10 seconds, and it is more preferable to observe the gradual release between 10 ^-3 and 1 second.

The specific silver halide grains in the silver halide emulsion of the present invention preferably contain iridium. As a compound of iridium, it is best to have a 6-coordinate complex with 6 ligands and iridium as the central metal; since it enters into the silver halide crystal uniformly, it is the most ideal. As a best form of iridium used in the present invention, it is better to have Cl, Br or I as a ligand, with Ir as the central metal's 6-coordinate complex, more preferably all 6 ligands Formed from Cl, Br or I, with Ir as the central metal, a 6-coordinate complex. At this time, in the 6-coordinate complex, Cl, Br or I may exist in admixture. The 6-coordinate complex with Cl, Br or I as the ligand and Ir as the central metal is preferably included in the silver bromide-containing phase in order to obtain high-illuminance exposure and hard gray tone.

Examples of six-coordinate complexes in which all six ligands are formed of Cl, Br or I and Ir is the central metal are listed below, and iridium in the present invention is not limited to these.

[IrCl ₆ ] ^2-

[IrCl ₆ ] ^3-

[IrBr ₆ ] ^2-

[IrBr ₆ ] ^3-

[IrI ₆ ] ^3-

As different optimal forms of iridium used in the present invention, it is better to have at least one non-halogen as a ligand and a hexa-coordinate complex with Ir as the central metal, and it is better to have H ₂ O, OH , O, OCN, thiazole or substituted thiazole as the ligand, and a 6-coordinate complex with Ir as the central metal, preferably with at least one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as the The ligand and the rest of the ligand are formed by Cl, Br or I, and a 6-coordinate complex with Ir as the central metal. The best is a 6-coordinate complex with one or two 5-methylthiazoles as ligands and the rest of the ligands being Cl, Br or I, with Ir as the central metal.

The following list has at least one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as a ligand, and the rest of the ligands are formed by Cl, Br or I, with Ir as the central metal. specific examples, but iridium in the present invention is not limited to these.

[Ir(H ₂ O)Cl ₅ ] ^2-

[Ir(H ₂ O) ₂ Cl ₄ ] ^-

[Ir(H ₂ O)Br ₅ ] ^2-

[Ir(H ₂ O) ₂ Br ₄ ] ^-

[Ir(OH)Cl ₅ ] ^3-

[Ir(OH) ₂ Cl ₄ ] ^3-

[Ir(OH)Br ₅ ] ^3-

[Ir(OH) ₂ Br ₄ ] ^3-

[Ir(O)Cl ₅ ] ^4-

[Ir(O) ₂ Cl ₄ ] ^5-

[Ir(O)Br ₅ ] ^4-

[Ir(O) ₂ Br ₄ ] ^3-

[Ir(OCN)Cl ₅ ] ^3-

[Ir(OCN)Br ₅ ] ^3-

[Ir(thiazole)Cl ₅ ] ^2-

[Ir(thiazole) ₂ Cl ₄ ] ^-

[Ir(thiazole)Br ₅ ] ^2-

[Ir(thiazole) ₂ Br ₄ ] ^-

[Ir(5-methylthiazole)Cl ₅ ] ^2-

[Ir(5-methylthiazole) ₂ Cl ₄ ] ^-

[Ir(5-methylthiazole)Br ₅ ] ^2-

[Ir(5-methylthiazole) ₂ Br ₄ ] ^-

As long as any one of the following is used alone, the subject of the present invention can be accomplished, that is, a 6-coordinate complex with Ir as the central metal having all 6 ligands formed by Cl, Br or I, or having at least A 6-coordinate complex with one H ₂ O, OH, O, OCN, thiazole or substituted thiazole as a ligand, the rest of the ligands are formed by Cl, Br or I, and Ir is the central metal. However, in order to further improve the effect of the present invention, it is best to use a 6-coordinate complex with all 6 ligands formed by Cl, Br or I and Ir as the central metal, and at least one H ₂ O, OH , O, OCN, thiazole or substituted thiazole as the ligand, and the rest of the ligands are formed by Cl, Br or I and Ir is the 6-coordinate complex of the central metal. Furthermore, a 6-coordination complex with at least one _H2O , OH, O, OCN, thiazole or substituted thiazole as a ligand, the rest of the ligands are formed by Cl, Br or I, and Ir is the central metal , it is best to use a complex composed of two kinds of ligands (one of H ₂ O, OH, O, OCN, thiazole or substituted thiazole, and one of Cl, Br or I).

The metal complexes listed above are anions, and when forming salts with cations, it is preferable that the counter cations are easily soluble in water. Specifically, alkali metal ions such as sodium ions, potassium ions, rubidium ions, cesium ions, and lithium ions, ammonia ions, and alkylammonium ions are preferable. These metal complexes can be dissolved in a mixed solvent of an appropriate organic solvent (for example, alcohols, ethers, glycols, ketones, esters, amides, etc.) mixed with water in addition to water. . These iridium complexes are preferably added in a range of 1×10 ^-10 mol to 1×10 ^-3 mol, more preferably 1×10 ^-8 mol to 1×10 ^-5 mol, per mol of silver during particle formation.

In the present invention, the above-mentioned iridium complex is directly added to the reaction solution when forming silver halide particles, or added to the halide aqueous solution forming silver halide particles, or added to other solutions, and formed by adding to the particles. In the reaction solution, it can well enter into the silver halide particles. Physical aging is carried out with microparticles in which iridium complexes are preliminarily incorporated into the particles, and the silver halide complexes can also be well incorporated into the silver halide particles. Furthermore, a combination of these methods can also be included in the silver halide particles.

When these complexes enter the silver halide particles, they can also be uniformly present inside the particles, but in the forms disclosed in JP-A-4-208936, JP-A-2-125245, and JP-A-3-188437, only the surface of the particles can be present. layer, a complex body exists only inside the particle and a layer not containing the complex body may be added on the surface of the particle. US Pat. No. 5,252,451 and No. 5,256,530 disclose physical aging of microparticles in which complexes enter the interior of the particles to modify the surface phase of the particles. This combination of methods can also be used to combine several complexes into one silver halide particle. The halogen composition of the above-mentioned complex position is not particularly limited. It is best to make all 6 ligands formed by Cl, Br or I and the 6-coordinate complex with Ir as the central metal exists at a concentration of silver bromide Huge portion.

In the present invention, metal ions other than iridium may be doped inside and/or on the surface of the silver halide particles. The metal ions used are preferably transition metal ions. Among them, iron, ruthenium, osmium, lead, cadmium, or zinc is preferable. It is better to use a 6-coordinate octahedral type complex formed by these metal ions accompanied by ligands. When using inorganic compounds as ligands, it is best to use cyanide ions, halide ions, cyanogen sulfide, hydroxide ions, peroxide ions, azide ions, nitrite ions, water, ammonia, nitrous Acyl ions, or thionitrosyl ions, preferably use any metal ion in the above-mentioned iron, ruthenium, osmium, lead, cadmium, or zinc for coordination, and several kinds of coordination can also be used in one complex molecule. seat. Organic compounds can also be used as ligands. As good organic compounds, there are chain compounds with main chain carbon number below 5 and/or heterocyclic compounds with 5-membered or 6-membered rings. Good organic compounds are intramolecular A compound having a nitrogen atom, a phosphorus atom, an oxygen atom or a sulfur atom as a coordination atom to a metal, preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole, imidazole, pyrazole, triazole, Basilane, Cholechromane, Pyridine, Pyridazine, Pyrimidine, Pyrazine. More preferably, these compounds are used as a skeleton and a substituent is introduced into them.

A good combination of metal ions and ligands is a combination of iron ions, ruthenium ions, and cyanide ions. In the present invention, iridium and these compounds can also be used in combination. In these compounds, cyanide ions preferably occupy more than half of the coordination numbers to the central metal iron or ruthenium, and the remaining coordination parts are preferably composed of cyanogen sulfide, ammonia, water, nitrosyl ions, and dimethyl sulfide. Occupied by sulfone, pyridine, pyrazine, or 4,4'-dipyridine. Preferably, the six coordination parts of the central metal are all occupied by cyanide, which can form a hexacyanoferric complex or a hexacyanoruthenium complex. For these complexes using cyanide ions as ligands, in the formation of particles, it is preferable to add 1×10 ^-8 to 1×10 ^-2 moles per 1 mole of silver, preferably 1×10 ^-6 to 5 ×10 ^-4 mol. When ruthenium and osmium are used as the central metal, it is preferable to use nitrosyl ions, thionitrosyl ions, or water molecules and chloride ions together as ligands. More preferably, a pentachloronitrosyl complex, a pentachlorothionitrosyl complex, or a pentachlorohydro complex is formed, and a hexachloro complex may also be formed. These complexes are preferably added in an amount of 1×10 ^-10 to 1×10 -6 mol, more preferably 1×10 ^-9 to 1× ^{10 -6} mol, per 1 mol of silver during particle formation.

In the silver halide emulsion of the present invention, several kinds of transition metal complexes are used in combination to obtain an emulsion with higher sensitivity, hard gray tone at low concentration, and excellent reciprocity law characteristics under high illuminance. When the transition metal complex used is aimed at high sensitivity, hard adjustment, and reciprocity law improvement, it is better to use at least three or more complexes. In order to obtain an excellent emulsion with wider reciprocity law characteristics, it is better Four or more transition metal complexes are used. In order to harden the gradation of the low-concentration portion, at least one complex is used, preferably a transition metal complex with ruthenium or osmium as the central metal, and is most suitable for constituting two silver halide particles.

The average particle size of the silver halide grains contained in the silver halide emulsion of the present invention (the diameter of a circle equivalent to the projected surface of the grains is taken as the grain size, and the average number) is preferably 0.1-2 μm. These particle size distributions are preferably so-called dispersed with a coefficient of variation (divided by the average particle size by the standard deviation of the particle size distribution) of 20% or less, preferably 15% or less, more preferably 10% or less. In this case, for the purpose of obtaining a wider latitude, the above-mentioned monodisperse emulsions are mixed and used in the same layer, and double-layer coating can also be performed.

The silver halide emulsion of the present invention may contain other silver halide grains in addition to the silver halide grains contained in the silver halide emulsion defined in the present invention (that is, specific silver halide grains). However, for the silver halide grains contained in the silver halide emulsion defined in the present invention, the projected area of the total silver halide grains in the silver halide emulsion is preferably 50% or more, more preferably 80% or more.

The latent image oxidation potential of the silver halide emulsion of the present invention is preferably higher than 70mV, more preferably higher than 100mV. The so-called latent image oxidation potential higher than 70mV means that the latent image has relatively strong oxidation resistance. The oxidation potential of the latent image can be measured by a method recorded in known materials such as photography and photosensitivity (Photographic Sensitivity Oxford University Press, Tadaaki Tani 1995) 103 pages. Specifically, 0.1-second grayscale exposure was given to the coated silver halide emulsion, and the potential at which the latent image was bleached was studied by immersing it in a redox bath of various potentials before image development.

The silver halide emulsion of the present invention is usually chemically sensitized. For the chemical sensitization method, sulfur sensitization represented by the addition of unstable sulfur compounds, noble metal sensitization represented by gold sensitization, or reduction sensitization can be used alone or in combination. As the compound used for chemical sensitization, it is preferable to use the compounds described in the lower right column on page 18 to the upper right column on page 22 of JP-A-62-215272. Among these, it is preferable to implement gold sensitization. The reason for the gold sensitization is that the variation in photographic performance can be further reduced during scanning exposure with laser light or the like.

For gold sensitization of the silver halide emulsion of the present invention, various inorganic gold compounds and gold (I) complexes having inorganic ligands, and gold (I) compounds having organic ligands can be used. As an inorganic gold compound, for example, gold chloride or its salt can be used, and as a gold (I) complex having an inorganic ligand, for example, a gold disulfide cyanate compound such as gold (I) potassium disulfide cyanate can be used. And dithiosulfate gold (I) 3 sodium and other compounds such as gold dithiosulfate compounds.

The silver halide emulsion of the present invention is preferably gold-sensitized using colloidal gold sulfide or a gold sensitizer whose complex stability constant _logβ2 of gold is 21-35. The production method of colloidal gold sulfide is described in Research, Open (Reserch Disclosure, 37154), Ionized Solid State (Solid State lonics) Vol. 79, pp. 60-66, 1995, Compt.Rend.Hebt.Seances Acad.Sci .Sect.B Volume 263, Page 1328, 1966, etc. As the colloidal gold sulfide, those having various sizes can be used, and those having a particle diameter of 50 nm or less can be used. The amount of addition can be changed in a wide range according to the situation. As gold atoms, per 1 mole of silver halide, it is 5×10 ^-7 ~ 5×10 ^-3 moles, preferably 5×10 ^-6 ~ 5×10 ^-4 moles . In the present invention, gold sensitization can also be combined with other sensitization methods, for example, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or sensitization using noble metals other than gold compounds.

A gold sensitizer having a gold complex stability constant _logβ2 of 21 to 35 will be described below.

For the determination of the complex stability constant _logβ2 of gold, the determination methods recorded in the following documents can be applied, such as comprehensive coordination chemistry (Comprehenslve Coordination Chemistry, chapter 55, page 864, 1987), Encyclopedia of Element Electrochemistry (Encyclopedia of Electrochemistry of the Elements, Chapter IV-3, 1975), Journal of the Royal Netherlands Chemical Society (Journal of the Royal Netherlands Chemical Society Vol. 101, p. 164, 1982), and their references. The measurement temperature was 25°C, the pH was adjusted to 6.0 with potassium dihydrogen phosphate and disodium hydrogen phosphate buffer solution, and the ionic strength was obtained by calculating the value of _logβ2 from the gold potential value obtained under the condition of 0.1M (KBr). In this assay method, the value of _logβ2 of sulfocyanate ion is 20.5, which is very close to the value of 20 recorded in the literature (Comprehensive Coordination Chemistry (Comprehensive Coordination Chemistry 1987, Chapter 55, Page 864, Table 2)). close value.

In the present invention, the gold sensitizer whose complex stability constant _logβ2 of gold is 21-35 is preferably represented by the following general formula (I).

General formula (I){(L ¹ ) _x (Au) _y (L ² ) _z Q _q } _p

In formula (I), L ¹ and L ² represent compounds whose logβ ₂ value is between 21 and 35. Preferable is the compound between 22-31, more preferably the compound between 24-28.

For example, L ¹ and L ² represent compounds containing at least one unstable sulfur group that can react with silver halide to generate silver sulfide, Z-lactoin compounds, thioether compounds, mesoionic compounds, -SR', heterocyclic compounds, Phosphine compounds, amino acid derivatives, sugar derivatives, and thiocyano groups may be the same or different. wherein R' represents aliphatic hydrocarbon, aryl, heterocyclic, acyl, carbamoyl, thiocarbamoyl, or sulfonyl.

Q represents a counter anion or a counter cation required to neutralize the charge of a compound, X and Z represent an integer of 0 to 4, y and p represent 1 or 2, and q represents a value of 0 to 1 including decimals. However, neither X nor Z can be 0.

As a good compound represented by the general formula (I), ^L1 and ^L2 represent compounds containing at least one unstable sulfur group that can react with silver halide to form silver sulfide, hydantoin compounds, thioether compounds, mesoionic compounds , -SR', a heterocyclic compound, or a phosphine compound, x, y, and z represent 1, respectively.

As a compound represented by the general formula (I), better L ^{and L} represent at least one compound, mesoionic compound or -SR' containing at least one unstable sulfur group that can react with silver halide to generate silver sulfide, x, y and z represents 1, respectively.

The gold compound represented by the general formula (I) will be described in more detail below.

As the compound represented by ^L1 and ^L2 in general formula (I) having an unstable sulfur group that can react with silver halide to generate silver sulfide, in thioketones (for example, thioureas, sulfamides, or thiocyanate class, etc.), phosphorothioate, thiosulfuric acid.

As the most preferable compounds containing at least one unstable sulfur group that can react with silver halide to form silver sulfide, there are thiones (preferably thioureas, sulfamides, etc.), and thiosulfuric acids.

Hereinafter, as the hydantoin compounds represented by ^L1 and ^L2 in the general formula (I), for example, hydantoin and N-methylhydantoin with or without replacement; as the thioether compound, there are Containing 1-8 thio groups, substituted or unsubstituted linear or branched alkylene groups (for example, ethylene, triethylene, etc.), or chain or cyclic thioethers linked by phenylene groups ( For example, bishydroxyethyl sulfide, 3,6-dithio-1,8-octanediol, 1,4,8,11-tetrathiocyclotetradecane, etc.); as mesoionic compounds, there are Ionic-3-mercapto-1,2,4-triazoles (for example, meso-1,4,5-trimethyl-3-mercapto-1,2,4-triazole, etc.) and the like.

When ^L1 and ^L2 in the general formula (I) represent -SR', the aliphatic hydrocarbon group represented by R' has 1-30 carbon atoms substituted or unsubstituted linear or branched alkyl (for example, Methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 1,5-Dimethylhexyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, hydroxyethyl, hydroxypropyl, 2,3-hydroxypropyl , carboxymethyl, carboxyethyl, sodium sulfoethyl, diethylethylamine, diethylpropylammonia, butoxypropyl, ethoxyethoxyethyl, n-hexyloxypropyl, etc.), 3 - Substitution or non-substitution cyclic alkyl group of 18 carbon atoms (for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, adamantium, cyclododecyl, etc.), 2-16 carbon atoms Alkenyl (for example, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl of 2-10 carbon atoms (for example, propyne, 3-pentyne, etc.), 6-16 Aralkyl groups of 6-20 carbon atoms (for example, benzyl, etc.); as aryl, there are substituted or unsubstituted phenyl and naphthyl groups of 6-20 carbon atoms (for example, unsubstituted phenyl, unsubstituted naphthyl, 3,5-dimethylphenyl, 4-butoxyphenyl, 4-dimethylaminophenyl, 2-carboxyphenyl, etc.); as the heterocyclic group, for example, substituted or unsubstituted aza Ring 5-membered ring (for example, imidazolyl, 1,2,4-triazolyl, tetrazolyl, oxadiazolyl, thiadiazolyl, benzimidazolyl, purinyl, etc.), substituted or unsubstituted nitrogen-containing Hetero 6-membered ring (for example, pyridyl, piperidyl, 1,3,5-triazinyl, 4,6-dimercapto-1,3,5-triazinyl, etc.), furyl, or thienyl; As the acyl group, there are, for example, acetyl, benzoyl, etc.; as the carbamoyl group, for example, there are dimethylcarbamoyl groups, etc.; as the thiocarbamoyl group, there are, for example, diethylthiocarbamoyl groups, etc.; 1-10 carbon atom substituted or non-substituted alkylsulfonyl (such as methanesulfonyl, ethanesulfonyl, etc.), 6-16 carbon atoms substituted or non-substituted phenylsulfonyl (such as phenylsulfonyl acyl, etc.).

As -SR' represented by ^L1 and ^L2 , a good R' is an aryl or heterocyclic group, more preferably a heterocyclic group, especially a 5-membered or 6-membered nitrogen-containing heterocyclic group, preferably a water-soluble A nitrogen-containing heterocyclic group substituted with a neutral group (for example, a sulfo group, a carboxyl group, a hydroxyl group, an amino group, etc.).

As the heterocyclic compound represented by ^L1 and ^L2 in the general formula (I), substituted or unsubstituted nitrogen-containing 5-membered heterocyclic rings (for example, pyrroles, imidazoles, pyrazoles, 1,2,3 - Triazoles, 1,2,4-triazoles, tetrazoles, oxazoles, isoxazoles, isothiazoles, oxadiazoles, thiadiazoles, pyrrolidines, pyrrolines, imidazolidines, imidazolines, pyrazolidines, pyrazolines, hydantoins, etc.), and heterocycles containing the 5-membered ring (indole, isoindole, indole , indazoles, benzoimidazoles, purines, benzotriazoles, carbazoles, tetraacrines, benzothiazoles, indolines, etc.), substituted or unsubstituted nitrogen-containing 6-membered heterocyclic rings (for example, pyridines, pyrazines, pyrimidines, pyridazines, triazines, thiadiazines, piperidines, piperazines, morpholines, etc.), and heterocycles containing the 6-membered ring (for example, Quinolines, isoquinolines, phthalazines, naphthyridines, quinozines, quinazolines, pteridines, phenanthridines, acridines, non-ortholines, phenazines, etc.), replacement Or unsubstituted furans, substituted or unsubstituted thiophenes, benzothiazolium salts, etc.

The heterocyclic compounds represented by ^L1 and ^L2 are preferably unsaturated nitrogen-containing 5-membered or 6-membered heterocycles, or heterocycles containing them, for example, pyrroles, imidazoles, pyrazoles, 1,2,4-triazoles, oxadiazoles, thiadiazoles, imidazolines, indoles, indidines, indazoles, benzimidazoles, purines, benzotriazoles, carbazoles Classes, tetraacrines, benzothiazoles, pyridines, pyrazines, pyrimidines, pyridazines, triazines, quinolines, isoquinolines, phthalazines, etc. Foggants, most preferably known heterocyclic compounds (for example, indazoles, benzymidazoles, benzotriazoles, tetraacrines, etc.).

As the phosphine compound represented by ^L1 and ^L2 in the general formula (I), it represents an aliphatic hydrocarbon group of 1-30 carbon atoms, an aryl group of 6-20 carbon atoms, a heterocyclic group (for example, pyridyl) , substituted or unsubstituted amino (for example, dimethylamino, etc.), and/or phosphines substituted with alkyloxy (for example, methoxy, ethoxy, etc.), preferably composed of 1-10 phosphines substituted with alkyl groups of 6-12 carbon atoms or aryl groups of 6-12 carbon atoms (for example, triphenylphosphine, triethylphosphine, etc.).

Furthermore, in the mesoionic compounds represented by ^L1 and ^L2 above, -SR', and, heterocyclic compounds, it is preferable to react with silver halide to generate silver sulfide unstable sulfur group (for example, thioureido group) etc.) replaced.

The compounds represented by L ¹ and L ² in the general formula (I) above may also have definable substituents, such as halogen atoms (such as fluorine atoms, chlorine atoms, bromine atoms, etc.), aliphatic Alkenyl (for example, methyl, ethyl, isopropyl, n-propyl, t-butyl, n-octyl, cyclopentyl, cyclohexyl, etc.), alkenyl (for example, allyl, 2 -butenyl, 3-pentenyl, etc.), alkynyl (e.g., propynyl, 3-pentynyl, etc.), aralkyl (e.g., benzyl, phenethyl, etc.), aryl (e.g., benzene base, naphthyl, 4-tolyl, etc.), heterocyclyl (e.g., pyridyl, furyl, imidazolyl, piperidinyl, morpholinyl, etc.), alkyloxy (e.g., methoxy, ethoxy butoxy, 2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy, etc.), aryloxy (e.g., phenoxy, 2-naphthyloxy, etc.), amino (e.g., Unsubstituted amino group, dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, ethylamino group, dibenzylamino group, anilino group, etc.), amido group (for example, acetylamino group, benzylamino group, etc.), ureido group (such as , non-substituted ureido, N-methylureido, N-phenylureido, etc.), thiourea (for example, non-substituted thiourea, N-methylthiourea, N-phenylthiourea, etc. ), selenourea group (for example, non-substituted selenouride group, etc.), phosphine selenide group (such as diphenylphosphine selenide, etc.), telluride group (for example, non-substituted telluride group, etc.), urine Alkyl (for example, methoxycarbonylamino, phenoxycarbonylamino, etc.), sulfonamide (for example, methylsulfonamide, phenylsulfonamide, etc.), sulfamoyl (for example, non-substituted sulfamoyl, N, N -Dimethylsulfamoyl, N-phenylsulfamoyl, etc.), carbamoyl (for example, non-substituted carbamoyl, N,N-diethylcarbamoyl, N-phenylcarbamoyl, etc.) , sulfonyl (for example, methanesulfonyl, P-toluenesulfonyl, etc.), sulfinyl (for example, methylsulfinyl, phenylsulfinyl, etc.), alkoxycarbonyl (for example, methoxycarbonyl, ethoxy carbonyl, etc.), aryloxycarbonyl (e.g., phenoxycarbonyl, etc.), acyl (e.g., acetyl, benzoyl, formyl, propionyl, etc.), acyloxy (e.g., acetoxy, benzoyloxy, etc.) , phosphoric acid amido group (for example, N, N-diethyl phosphoric acid amido, etc.), alkylthio (for example, methylthio, ethylthio, etc.), arylthio (for example, phenylthio, etc.), cyano, Sulfo group, sulfuric acid group, phosphine group, carboxyl group, hydroxyl group, mercapto group, carboxylidene group, nitro group, sulfinyl group, amino group (for example, trimethylamino group, etc.), phosphorus group, hydrazine group, thiazolyl group, siloxy group group (t-butyldimethylsilyloxy, t-butyldiphenylsilyloxy) and the like. When there are two or more substituents, they may be the same or different.

Q and q in the general formula (I) are explained below.

As the counter anion represented by Q in the general formula (I), there are halogen ions (for example, F ^- , Cl ^- , Br ^- , I ^- ), tetrafluoroborate ion (BF ₄ ^- ), hexafluorophosphate ion ( PF ₆ ^- ), sulfate ion (SO ₄ ^2- ), arylsulfonate ion (for example, P-toluenesulfonate ion, naphthalene-2,5-disulfonate ion, etc.), carboxyl ion (for example, Acetate ion, trifluoroacetate ion, bromate ion, benzoic acid ion, etc.); As the counter cation represented by Q, there are alkali metal ions (for example, lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, etc.), Alkaline earth metal ions (for example, magnesium ions, calcium ions, etc.), substituted or non-substituted ammonium ions (for example, non-substituted ammonium ions, triethylammonium ions, tetramethylammonium ions, etc.), substituted or non-substituted pyridinium ions ions (for example, non-substituted pyridinium ions, 4-phenylpyridinium ions, etc.) and the like. Then there are protons. q is the number of Q when the charge of the compound is neutralized, and represents a value of 0-1, and the value may be a decimal.

The counter anion represented by Q is preferably a halogen ion (for example, Cl ^- , Br ^- ), tetrafluoroborate ion, hexafluorophosphate ion, or sulfate ion. As the counter cation represented by Q, it is preferably an alkali metal ion (for example, sodium ion, potassium ion, rubidium ion, cesium ion, etc.), a replacement or no replacement ammonia ion (for example, no replacement ammonia ion, triethylammonium ion, tetramethylammonium ion, etc.), or protons.

Specific examples in which L ¹ or L ² represent compounds are shown below, but the present invention is not limited thereto, and the values in parentheses represent log β ₂ values.

【Chemical 1】

【Chemical 2】

The compound represented by the general formula (I) can be synthesized with reference to the known methods described below, for example, Inoganiteku. (Transition Met.Chem.1, 248 pages, 1976), Acta Crystal Crystal (Acta.Cryst.B32, 3321 pages, 1976), Japanese Patent Laid-Open No. 8-69075, Japanese Patent Publication No. 45-8831, European Patent No. 915371 A1, JP-6-11788, JP-6-501789, JP-4-267249, JP-9-118685, etc.

Specific examples of compounds represented by the general formula (I) are shown below, but the present invention is not limited thereto.

【Chemical 3】

【Chemical 4】

【Chemical 5】

The gold sensitization in the present invention is usually done by adding a gold sensitizer and stirring the emulsion for a certain period of time at high temperature (preferably above 40°C). The amount of the gold sensitizer to be added varies depending on various conditions, but as a standard, it is preferable to add 1×10 ^-7 to 1×10 ^-4 mol per 1 mol of silver halide.

As the gold sensitizer in the present invention, in addition to the above compounds, commonly used gold compounds (for example, auric acid chloride, potassium oleate chloride, oily (O- lic) trichloride, oily potassium thiocyanate, potassium iodide oleate, tetracyanooleic acid, oily ammonium thiocyanate, pyridyl gold trichloride, etc.).

In the silver halide emulsion of the present invention, in addition to gold sensitization, other chemical sensitization may be used in combination. As the combined chemical sensitization, sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization other than gold, or reduction sensitization can be used. As for the compound for chemical sensitization, it is preferable to use those described in the lower right column on page 18 to the upper right column on page 22 in JP-A-62-215272.

Various compounds or their precursors may be added to the silver halide emulsion of the present invention for the purpose of preventing fog in the production process, storage, or photographic processing of photosensitive materials, or for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72 of JP-A-62-215272 can be used, and 5-arylamino-1,2,3,4- Thiotriazole compound (the aryl residue has at least one electron-attracting group).

In the present invention, in order to improve the storage stability of the silver halide emulsion, compounds described in the following, that is, hydroxamic acid derivatives described in JP-A No. 11-109576 and hydroxamic acid derivatives described in JP-A No. 11-327094 can also be used. Adjacent to a carbonyl group, cyclic ketones with double bonds replaced by amino or hydroxyl groups at both ends (especially represented by general formula (S1), paragraph numbers 0036-0071 can be included in the specification of this application), JP-P-11-143011 The catechols and hydroquinones substituted with sulfo groups described in the gazette (for example, 4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, Sulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and its salts, etc.), The hydroxylamines represented by the general formula (A) in the US Patent No. 5,556,741 specification (recorded in the 56th line of the 4th column to the 22nd line of the 11th column in the US Patent No. 5,556,741, are also applicable to the present application, as the present invention A part of the description is included), and the water-soluble reducing agents represented by the general formulas (I) to (III) in JP-A-11-102045 can also be used in the present invention.

The silver halide emulsion of the present invention exhibits photosensitivity in the required light wavelength range, and may contain a spectrally sensitizing dye in order to impart so-called spectral sensitivity. As a spectrosensitizing pigment for spectroscopic sensitization in the blue, green, and red fields, it is recorded in Heterocyclic Compounds-Cyanine dyes and related Compounds by F.M.Harmer (John Wiley & Sons [New York, London], 1964). Specific compound examples and the spectroscopic sensitization method described in the upper right column on page 22 to page 38 of the aforementioned JP-A-62-215272 can be used. As a red photosensitivity spectrally sensitizing dye of silver halide emulsion particles having a high silver chloride content, the spectrally sensitizing dye described in JP-A No. 3-123340 has been studied in terms of stability, adsorption strength, dependence on exposure temperature, etc. In terms of consideration, it is the most ideal.

The spectral sensitizing dye in the green field is preferably a trimethine cyanine represented by the following general formula (T), more preferably a oxamethine cyanine or an oxazotrimethine cyanine.

General formula (T)

【Chemical 1A】

General formula (T)

In the formula, Z ₁₀₁ and Z ₁₀₂ respectively represent the atomic groups required to form a nitrogen-containing heterocyclic nucleus. The nitrogen-containing heterocyclic nucleus is preferably a 5- to 6-membered ring nucleus containing a nitrogen atom as a heteroatom and others, such as a sulfur atom, an oxygen atom, a selenium atom, or a tellurium atom. Condensed rings may also be bonded to these rings, and further substituents may be bonded. Specific examples of the above-mentioned nitrogen-containing heterocyclic nucleus include thiazole nucleus, benzothiazole nucleus, naphthiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthalene selenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthalene Azole nucleus, imidazole nucleus, benzoimidazole nucleus, naphthalene imidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus, phenylindolenine nucleus, indole nucleus, tellurazole nucleus , Benzene tellurazole nucleus, naphthalene tellurazole nucleus, etc. R ₁₀₁ and R ₁₀₂ respectively represent an alkyl group, an alkenyl group, an alkynyl group, or an aralkyl group. These groups and the groups described below are used in the meaning of including their substituents, respectively. For example, when referring to an alkyl group, it includes unsubstituted and substituted alkyl groups, which may be straight chain, branched chain, or cyclic. The number of carbon atoms in the alkyl group is preferably 1-8.

Examples of substituting groups that replace the alkyl group include halogen atoms (fluorine, chlorine, bromine, iodine, etc.), cyano groups, alkoxy groups, substituted or non-substituted amino groups, carboxylic acid groups, sulfonic acid groups, hydroxyl groups, etc. One or a combination of these can also be used for substitution. Specific examples of the alkenyl group include vinylmethyl groups. Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

m ₁₀₁ means 1. R ₁₀₃ represents a hydrogen atom, a lower alkyl group, an aralkyl group or an aryl group. Specific examples of the above-mentioned aryl group include substituted or unsubstituted phenyl groups. R ₁₀₄ represents a hydrogen atom. j ₁₀₁ and K ₁₀₁ represent 0 or 1, X ₁₀₁ ^- represents an acidic anion, and n ₁₀₁ represents 0 or 1.

Specific examples of the compound represented by the general formula (T) are listed below, but are not limited thereto.

【Chemical 3A】

【Chemical 4A】

The amount of these spectrally sensitizing pigments can be varied in a wide range depending on the circumstances, and can be added in the range of 0.5×10 ^-6 to 1.0×10 ^-2 mol per 1 mol of silver halide. More preferably, 1.0×10 ^-6 to 5.5×10 ^-3 mol is added.

The silver halide photographic photosensitive material of the present invention will be described below.

The silver halide photographic photosensitive material of the present invention may be black-and-white or colored, but it is preferable to use the silver halide emulsion of the present invention in a silver halide color photographic photosensitive material.

The silver halide color photographic photosensitive material using the silver halide emulsion of the present invention (hereinafter sometimes simply referred to as "photosensitive material") is a silver halide color photographic photosensitive material having at least one of the following layers formed on a support, that is, containing A silver halide emulsion layer of a yellow pigment coupler, a silver halide emulsion layer containing a deep red pigment-forming coupler, and a silver halide emulsion layer containing a cyanogen-forming coupler, wherein at least one of the above-mentioned silver halide emulsion layers contains the present Invented silver halide emulsions. In the present invention, the silver halide emulsion layer containing a yellow pigment-forming coupler functions as a yellow color-forming layer; the silver halide emulsion layer containing a magenta color-forming coupler functions as a magenta color-forming layer; and The silver halide emulsion layer containing a cyanogen-forming coupler functions as a cyanogenic layer. The silver halide emulsion contained in each of the yellow color-forming layer, magenta color-forming layer, and cyanochromic layer is optimal for light in mutually different wavelength ranges (for example, light in a blue range, a green range, and a red range). It is photosensitive.

The photosensitive material of the present invention may contain the following hydrophilic colloidal layer, antihalation layer, intermediate layer, and colored layer as required, in addition to the above-mentioned yellow color-forming layer, deep red color-forming layer, and cyanochromic layer.

In the photosensitive material of the present invention, conventionally known photographic materials and additives can be used.

For example, as a photographic support, a transmissive support and a reflective support can be used. As a permeable support, transparent films such as nitrocellulose films and polyethylene terephthalates are preferably used. Furthermore, polyesters of 2,6-naphthalene dicarboxylic acid (NDCA) and ethylene glycol (EG), polyesters of NDCA, terephthalic acid, and EG are provided with an information recording layer such as a magnetic layer. As the reflective support, it is preferable to form a laminate of several polyethylene layers and polyester layers, and at least one of the water-resistant resin layers (laminate) contains a white pigment such as titanium oxide.

As a more preferable reflective support in the present invention, there is also a polyolefin layer having fine pores on the paper substrate on the side where the silver halide emulsion layer is provided. The polyolefin layer can be formed by multiple layers. At this time, the polyolefin layer adjacent to the gelatin layer on the side of the silver halide emulsion layer does not have microscopic pores (for example, polypropylene, polyethylene), and is preferably formed on the side close to the paper substrate. It is formed of polyolefin (such as polypropylene, polyethylene) with tiny pores on it. The density of these multilayer or monolayer polyolefin layers located between the paper substrate and the photographic constituent layers is preferably 0.40 to 1.0 g/ml, more preferably 0.50 to 0.70 g/ml. The thickness of these multi-layer or one-layer polyolefin layers located between the paper substrate and the photographic constituent layers is preferably from 10 to 100 µm, more preferably from 15 to 70 µm. The thickness ratio between the polyolefin layer and the paper substrate is preferably 0.05-0.2, more preferably 0.1-0.15.

A polyolefin layer is provided on the opposite side (the back side) of the photographic constituent layer of the above-mentioned paper base body. From the consideration of improving the rigidity of the reflective support, it is the most ideal. At this time, the polyolefin layer on the back side is preferably a matte surface polyethylene or Polypropylene, more preferably polypropylene. The polyolefin layer on the back is preferably 5 to 50 μm, more preferably 10 to 30 μm, and preferably has a density of 0.7 to 1.1 g/ml. In the reflective support of the present invention, regarding the best form of the polyolefin layer on the paper substrate, such as JP-P-10-333277, No. 10-333278, No. 11-52513, No. 11-65024, Examples described in EP0880065 and EP0880066.

A fluorescent whitening agent may be contained in the said water-resistant resin layer. It is also possible to additionally form a dispersed hydrophilic colloidal layer containing a fluorescent whitening agent. As the above-mentioned fluorescent whitening agent, benzoxazole-based, coumarin-based, and pyrazoline-based fluorescent whitening agents are preferably used, and benzoxazolidine-based and benzoxazole-stilbene-based ones are more preferably used. The amount used is not particularly limited, but is preferably 1 to 100 mg/m ² . The mixing ratio at the time of mixing with the water-resistant resin is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass based on the resin.

As the reflective support, a hydrophilic colloidal layer containing a white pigment may be coated on a transmissive support or a reflective support as described above. The reflective support may also be a support having a specular reflective or second diffuse reflective metal surface.

As the support used in the photosensitive material of the present invention, a white polyester support for display, or a support having a silver halide emulsion layer side provided with a white pigment-containing layer can be used. To improve sharpness, an antihalation layer is preferably coated on the silver halide emulsion layer coated side or back of the support. The display can be viewed regardless of reflected light or transmitted light, and the transmission density of the support is preferably set in the range of 0.35 to 0.8.

In the photosensitive material of the present invention, for the purpose of improving the clarity of the image, etc., the dyes that can be decolorized by treatment (wherein the oxyalcohol system Dyes) to make the optical reflection concentration of the photosensitive material to 680nm reach more than 0.70, preferably contain more than 12 mass % (better more than 14 mass %) with 2-4 valent alcohols (for example, Trimethylolethane) and other surface-treated titanium oxide.

In the photosensitive material of the present invention, in order to prevent light seepage and halo, and improve the safety of the safety light, it is preferable to add the passage described in the 27th to 76th pages of the European Patent EPO 337490A2 specification to the hydrophilic colloidal layer. Treatment of decolorizable dyes (including oxyalcohol dyes, cyanine dyes). The dyestuffs recorded in the specification of European Patent EPO 819977 can also be added in the present invention. Of these water-soluble dyes, when the amount is increased, color separation and safelight safety are deteriorated. As dyes that do not deteriorate color separation, water-soluble dyes described in JP-A-5-127324, 5-127325, and 5-216185 are preferable.

In the present invention, instead of the water-soluble dye, a treatment-decolorable colored layer used in combination with the water-soluble dye is used. The coloring layer that can be treated to be decolorized can be directly connected to the emulsion layer, or can be arranged through an intermediate layer containing gelatin, hydroquinone and other treated anti-blending agents. This colored layer is preferably provided on the lower layer (support side) of the emulsion layer that develops the same primary color as the color to be colored. All the coloring layers corresponding to the respective primary colors are set separately, and only some of them can be arbitrarily selected and set. It is also possible to set coloring layers corresponding to coloring of several primary color gamuts. The optical reflection density of the colored layer, the optical density value in the wavelength range of the highest optical density in the wavelength range used for exposure (in the visible light range of 400 to 700 nm in normal printing exposure, and the wavelength of the scanning exposure light source used in scanning exposure) Preferably, it is 0.2-3.0, More preferably, it is 0.5-2.5, Especially preferably, it is 0.8-2.0.

In order to form the colored layer, a conventionally known method can be used. For example, there is the following method, like the dyes described in the upper right column on page 3 to page 8 of JP-A-2-282244, and the dyes described in the upper right column on page 3-page 11 of JP-A-3-7931, using a solid The state of microparticle dispersion, the method of being included in the hydrophilic colloidal layer, the method of mordant anionic pigment on the cationic polymer; the method of immobilizing the pigment in the layer adsorbing silver halide and other microparticles; JP-A-1 -A method using colloidal silver described in No. 239544, etc. As a method for dispersing the pigment fine powder in a solid state, for example, the method described in JP-A-2-308244, pages 4-13, is to contain at least water insoluble below pH6, but soluble at least above pH8. Water method of fine powder dye. For example, a method for mordanting an anionic dye on a cationic polymer is described on pages 18 to 26 of JP-A-2-84637. Regarding the preparation method of colloidal silver as a light absorbing agent, it is shown in US Pat. No. 2,688,601 and US Pat. No. 3,459,563. Among these methods, the method containing a fine powder dye, the method using colloidal silver, and the like are preferable.

The silver halide photosensitive material of the present invention can be used for color negative film, color positive film, color reversal film, color reversal printing paper, color printing paper, etc., but among them, it is preferably used as color printing paper. Color printing paper, preferably at least each of a yellow chromogenic silver halide emulsion layer, a deep red chromogenic silver halide emulsion layer and a cyanogenic chromogenic silver halide emulsion layer is formed, and these silver halide The emulsion layer is generally a yellow chromogenic silver halide emulsion layer, a dark red chromogenic silver halide emulsion layer, and a cyanogenic chromogenic silver halide emulsion layer in sequence from the proximity to the support.

However, a different layer configuration may also be adopted.

The silver halide emulsion layer containing yellow coupler can be arranged at any position on the support body. When the yellow coupler layer contains silver halide plate grains, it is better to be coated on the silver halide emulsion layer containing dark red coupler. At least one of the emulsion layer or the silver halide emulsion layer containing a cyanogen coupler is located away from the support. In terms of promoting color development, promoting desilvering, and reducing residual color caused by sensitizing pigments, the silver halide emulsion layer containing yellow coupler is preferably coated at a position farther from the support than other silver halide emulsion layers superior. Furthermore, from the aspect of reducing Blix fading, the silver halide emulsion layer containing cyano coupler is preferably the intermediate layer of other silver halide emulsion layers, and from the aspect of reducing light fading, the silver halide emulsion layer containing cyano coupler is preferably the last layer. lower level. Each color-forming layer of yellow, magenta, and cyan may be formed of two or three layers. For example, as described in JP-A-4-75055, No. 9-114035, No. 10-246940, U.S. Patent No. 5,576,159, etc., a coupler layer not containing a silver halide emulsion is provided adjacent to a silver halide emulsion layer, Forms a chromogenic layer.

As the silver halide emulsion and other materials (additives, etc.), photographic constituent layers (layer arrangement, etc.) used in the present invention, and the applicable processing method and processing additives for processing the photosensitive material, it is preferable to use JP-A-62-215272 , JP-2-33144, European Patent No. EPO 355660A2, it is better to use the one recorded in European Patent EPO 355660A2. Furthermore, it is also possible to use JP-A-5-34889, No. 4-359249, No. 4-313753, No. 4-270344, No. 5-66527, No. 4-34548, No. 4-145433, No. 2- Silver halide color photographic photosensitive materials and processing methods thereof described in No. 854, No. 1-158431, No. 2-90145, No. 3-194539, No. 2-93641, European Patent Publication No. 0520457A2, etc.

In the present invention, regarding the above-mentioned reflective support and silver halide emulsion, further, different metal ion species doped in silver halide particles, storage stabilizer or antifogging agent of silver halide emulsion, chemical sensitization method (sensitizer ), spectral sensitization method (spectral sensitizer), cyanide, deep red, yellow coupler and its emulsification dispersion method, color image preservation improver (anti-coloring agent and anti-fading agent), dye (coloring layer), gelatin For the type, layer structure of the photosensitive material, film pH of the photosensitive material, etc., it is preferable to use those described in various patents shown in Table 1 below.

elements Special Kaiping No. 7-104448 Special Kaiping No. 7-77775 Special Kaiping No. 7-301895 reflective support Column 7, line 12 ~ column 12, line 19 Column 35, line 43 to column 44, line 1 Line 40 in column 5 to line 26 in column 9 Silver halide emulsion Column 72, line 29 to column 74, line 18 Column 44, line 36 ~ column 46, line 29 Column 77, line 48 to column 80, line 28 Different types of metal ions Line 19 of column 74 ~ line 44 of the same column Column 46, line 30 to column 47, line 5 Column 80, line 29 to column 81, line 6 Preservation stabilizer or anti-fogging agent Column 75, line 9 ~ line 18 in the same column Line 20 in column 47 ~ line 29 in the same column Column 18, line 11 to column 31, line 37 (especially mercapto heterocyclic compounds) Chemical sensitization method (chemical sensitizer) Column 74, line 45 to column 75, line 6 Line 7 of column 47 ~ line 17 of the same column Column 81, line 9 ~ line 17 in the same column Spectral sensitization method (spectral sensitizer) Column 75, line 19 to column 76, line 45 Column 47, line 30 to column 49, line 6 Column 81, line 21 to column 82, line 48 Cyanogen coupler Column 12, line 20 ~ column 39, line 49 Column 62, line 50 to column 63, line 16 Column 88, line 49 ~ column 89, line 16 yellow coupler Column 87, line 40 to column 88, line 3 Column 63, line 17 ~ line 30 in the same column Column 89, line 17 ~ line 30 in the same column Crimson coupler Line 4 of column 88 ~ line 18 of the same column Column 63, line 3 to column 64, line 11 Line 34 in column 31 ~ line 44 in column 77 Line 32 in column 88 ~ line 46 in the same column Emulsification and dispersion method of encapsulation agent Column 71, line 3 to column 72, line 11 Line 36 in column 61 ~ line 49 in the same column Column 87, line 35 to line 48 Color image preservation improver (anti-colorant) Column 39, line 50 to column 70, line 9 Column 61, line 50 to column 62, line 49 Column 87, line 49 to column 88, line 48 Anti-fading agent Column 70, line 10 to column 71, line 2 Dyes (colorants) Column 77, line 42 to column 78, line 41 Column 7, line 14 to column 19, line 42, column 50, line 3 to column 51, line 14 Column 9, line 27 ~ column 18, line 10 Types of gelatin Line 42 of column 78 ~ line 48 of the same column Column 51, line 15 ~ line 20 in the same column Line 13 of column 83 ~ line 19 of the same column Layer composition of photosensitive materials Column 39, line 11 ~ line 26 in the same column Line 2 of column 44 ~ line 35 of the same column Column 31, line 38 ~ column 32, line 33 Film pH of photosensitive material Column 72, line 12 ~ line 28 in the same column scan exposure Column 76, line 6 ~ column 77, line 41 Column 49, line 7 to column 50, line 2 Column 82, line 49 to column 83, line 12 Preserving agent in imaging solution Column 88, line 19 ~ column 89, line 22

For the cyan, deep red and yellow couplers used in the present invention, other couplers described in the following can also be used, that is, the 4th line of the upper right column on page 91 to the upper left column 6 of page 121 in JP-A No. 62-215272 Line, line 14 in the upper right column on page 3-the last line in the upper left column on page 18 in No. 2-33144 and line 6 in the upper right column on page 30 to line 11 in the lower right column on page 35, and line 15 in page 4 in EPO355660A2 27 lines, 5 pages 30 lines to 28 last lines, 45 pages 29 lines to 31 lines, 47 pages 23 lines to 63 lines 50 lines.

In the present invention, it is preferable to add compounds represented by general formulas (II) and (III) in WO-98/33760 and general formula (D) in JP-A-10-221825.

The coupler (sometimes only referred to as "cyan coupler") that can be used in the present invention to form a cyanogen can use a pyrrolotriazole coupler, preferably the general formula (I) or Couplers represented by (II) and couplers represented by the general formula (I) in JP-A-6-347960, and exemplary couplers described in these patents. Phenol-based or naphthol-based cyan couplers can also be used, for example, cyan couplers represented by the general formula (ADF) described in JP-A-10-333297. As cyan couplers other than the above, pyrrozole-type cyan couplers described in European Patent No. EPO488248 and EPO491197A1, and 2,5-diacylaminophenol couplers described in U.S. Patent No. 5888716 can also be used. , U.S. Patent No. 4873183, the pyrazoline azole-type cyan color coupler with an electron-attracting group and a hydrogen bond group on the 6th position recorded in No. 4916051, JP-8-171185, and No. 8-311360 , and the pyrazolinazole-type cyan coupler having a carbamoyl group at the 6th position described in No. 8-339060.

In addition to the diphenylimidazole-based cyan coupler described in JP-A-2-33144, the 3-hydroxypyridine-based cyan coupler described in the specification of European Patent EPO333185A2 (wherein, as a specific example, The 4 equivalent couplers of the coupler (42) have a chlorine detachment group to form 2 equivalents, the couplers (6) and (9) are the best) and the cyclic active formazan described in the JP-A-64-32260 communique Fork-based cyan couplers (among them, coupler examples 3, 8, and 34 listed as specific examples are particularly preferred), pyrrole pyrazole-type cyan couplers described in European Patent No. EPO456226A1, and those described in European Patent No. EPO484909. Pyrromidazole-type cyan coupler.

Among these cyan couplers, particularly preferred are the pyrrole azole-based cyan couplers represented by the general formula (I) described in JP-A-11-282138, including the exemplary cyan couplers described in paragraphs 0012-0059 of this patent. Couplers (1) to (47) are applied to this application as they are, and therefore are included as a part of the description of this application.

As the magenta pigment-forming coupler (sometimes referred to as "magenta coupler") used in the present invention, 5-pyrrolidinone-based magenta couplers and pyrrolineazole-based magenta couplers described in the above-mentioned tables can be used. Coupler, wherein in terms of phase color and image stability, color development, etc., it is best to use the coupler recorded in the following documents, that is, the pyrroline triazole ring described in JP-A No. 61-65245 Pyrrolinetriazole coupler with 2nd or 3rd grade alkyl connected to the 2, 3 or 6 position, pyrrolinetriazole coupler with sulfonamide group in the molecule as described in JP-A-61-65246, JP-A-61-65246 No. 61-147254, the pyrroline azole coupler having an alkoxyphenyl sulfonamide carrying balance group, and the pyrrole having an alkoxy group and an aryloxy group at the 6-position described in European Patent No. 226849A and No. 294785A Linazole coupler. As a deep red color coupler, it is more preferably a pyrroline azole coupler represented by the general formula (M-1) described in JP-P-8-122984. Paragraphs 0009 to 0026 in this patent are also applicable to this application, as a description of this application Part of it is included. In addition, pyrrolineazole couplers having steric hindrance groups at both the 3-position and 6-position described in European Patent No. 854384 and European Patent No. 884640 can also be used.

As a yellow pigment-forming coupler (sometimes simply referred to as a "yellow coupler"), in addition to the compounds described in the above table, those described in the following documents, that is, those described in the specification of European Patent EPO447969A1 having 3 on the acyl group, can also be used. Acylacetamide-type yellow coupler with 5-membered ring structure, propanediphenylaniline-type yellow coupler with ring structure described in European Patent No. EPO482552A1 specification, European Laid-open Patent No. 953870A1, same as No. 953871A1 , Pyrrole-2 or 3-acyl or indole-2 or 3-acyl carbonyl acetate phenylaniline coupler described in No. 953872A1, No. 953873A1, No. 953874A1, No. 953875A1, etc., the United States An acylacetamide-type yellow coupler having a dioxane structure described in Patent No. 5118599. Among them, acetamide-type yellow couplers in which the acyl group is 1-alkylcyclopropane-1-carbonyl, and diphenylaniline-type yellow couplers in which one of the phenylanilines constitute an indoline ring are preferably used. These couplers can be used alone or in combination.

The coupler used in the present invention is preferably soaked with a thiocyanate-type latex polymer (such as U.S. Patent No. 4,203,716) in the presence (or absence) of the high-boiling organic solvents listed in the above table, or mixed with water-insoluble And the organic soluble polymers are dissolved together, and emulsified and dispersed in the hydrophilic colloidal aqueous solution. The most useful water-insoluble and organic solvent-soluble polymers include the monomers recorded in the 7th to 15th columns in the US Patent No. 4857449 specification and the 12th to 30th pages in the specification of International Publication WO88/00723 or copolymer. A methacrylate-based or an acrylamide-based polymer is more preferable, and an acrylamide-based polymer is more preferably used in consideration of color stability and the like.

In the present invention, known anti-mixture agents can be used, but among them, those described in the following patents are preferable.

For example, it is preferable to use the high molecular weight redox compounds described in JP-A-5-333501, phenidone and hydrazine-based compounds described in WO98/33760, U.S. Patent No. 4923787, etc., JP-A-5-249637, JP-A White color couplers described in Kaihei No. 10-282615 and German Patent No. 19629142A1. When increasing the pH of the developing solution to speed up the development, it is better to use the ones described in German Patent No. 19618786A1, European Patent No. 839623A1, European Patent No. 842975A1, German Patent No. 19806846A1, French Patent No. 2760460A1, etc. redox compounds.

In the present invention, it is preferable to use a compound having a triazine skeleton with a high molar absorption coefficient as the ultraviolet absorber, for example, compounds described in the following patents can be used. These are preferably added to the photosensitive layer or/and the non-photosensitive layer. For example, you can use JP-A-46-3335, JP-55-152776, JP-5-197014, JP-5-232630, JP-5-307232, JP-6-211813, JP-8-53427, JP-8 -234364, same 8-239368, same 9-31067, same 10-115898, same 10-147577, same 10-182621, German Patent No. 19739797A, European Patent No. 711804A and Special Table Flat 8 - Compounds described in No. 501291 and the like.

As the binder or protective colloid usable in the photosensitive material of the present invention, gelatin is conveniently used, and other hydrophilic colloids may be used alone or together with gelatin. As the best gelatin, the heavy metals contained in impurities such as iron, copper, zinc, manganese, etc. are preferably below 5ppm, more preferably below 3ppm. The amount of calcium contained in the photosensitive material is preferably below 20 mg/m ² , more preferably below 10 mg/m ² , most preferably below 5 mg/m ² .

In the present invention, in order to prevent various molds and bacteria from multiplying in the hydrocolloid layer to cause image deterioration, it is preferable to add an antibacterial and antifogging agent described in JP-A-63-271247. The film pH of the photosensitive material is preferably from 4.0 to 7.0, more preferably from 4.0 to 6.5.

In the present invention, a surfactant can be added to the photosensitive material in consideration of improving the coating stability of the photosensitive material, preventing static electricity, and adjusting the charge amount. Examples of surfactants include anionic surfactants, cationic surfactants, betaine-based surfactants, and nonionic surfactants, such as those described in JP-A-5-333492. Surfactants used in the present invention may be those containing fluorine atoms. It is better to use a surfactant containing fluorine atoms. These fluorine atom-containing surfactants may be used alone or in combination with other known surfactants, preferably in combination with other known surfactants. The amount of these surfactants added to the photosensitive material is not particularly limited, but usually 1×10 ^-5 to 1 g/m ² , preferably 1×10 ^-4 to 1×10 ^-1 g/m ² , More preferably, it is 1×10 ^-3 to 1×10 ^-2 g/m ² .

The photosensitive material of the present invention can form an image based on image information through an exposure process of irradiating light and a development process of developing the photosensitive material irradiated with light.

The photosensitive material of the present invention is suitable for a scanning exposure method using a cathode line (CRT) in addition to a printing system using a negative printing machine. Compared with the apparatus using laser, the cathode line tube exposure apparatus is more convenient, smaller in size, less expensive, and easy to adjust the optical axis and color tone. For cathode line tubes used in image exposure, various illuminants that emit light in the spectral range can be used as needed. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or two or more kinds thereof may be used in combination. The spectral range is not limited to the above-mentioned red, green, and blue, and phosphors that emit light in the yellow, orange, violet, or infrared ranges can also be used. Each time a cathode line tube is used that mixes these illuminants to form a white glow.

The photosensitive material has several photosensitive layers with different spectral sensitivity distributions. When the cathode tube has several kinds of luminescent phosphors in the spectral range, it can expose several colors at one time, that is, input the image signals of several colors into the cathode Inside the line pipe, the surface of the pipe emits light. It is also possible to input the image signals of various colors in sequence each time, and each color can emit light in sequence, and the method of exposing the colors other than the color through the filter (sequential surface exposure), generally, the sequential surface exposure method , because it can use high-resolution cathode line tubes to obtain high-quality images, so it is the most ideal.

The photosensitive material of the present invention preferably uses a digital scanning exposure method, which uses a gas laser, a light-emitting diode, a semiconductor laser, or a semiconductor laser or a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal. Combined second high-frequency light source (SHG) and other monochromatic high-density light. In terms of system miniaturization and low cost, it is preferable to use a semiconductor laser or a second high-frequency generating light source (SHG) that combines a nonlinear optical crystal with a semiconductor laser or a solid-state laser. In order to design a small, inexpensive, long-life, and highly stable device, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser for at least one of the exposure light sources.

When such a scanning exposure light source is used, the maximum spectral sensitivity wavelength of the photosensitive material of the present invention can be set arbitrarily according to the wavelength of the scanning exposure light source used. When a semiconductor laser is used as a solid-state laser to excite a light source or an SHG light source obtained by combining a semiconductor laser with a nonlinear optical crystal, the oscillation wavelength of the laser can be divided into half to obtain blue light and green light. Therefore, the maximum spectral sensitivity of the photosensitive material is It can be kept within the three wavelength ranges of blue, green and red. The exposure time of this scanning exposure is defined as the time for exposing the size of a pixel when the pixel density is 400 dpi, and the exposure time is preferably not more than 10 ^-4 seconds, more preferably not more than 10 ^-6 seconds.

The silver halide color photographic photosensitive material of the present invention is preferably combined with an exposure and development system described in the following known documents. Examples of the above-mentioned developing system include the automatic printing and developing system described in JP-A-10-333253, the photosensitive material input device described in JP-A 2000-10206, and the image-reading system described in JP-A-11-215312. The recording system of the device, the exposure system comprising the color image recording method described in JP-A-11-88619 and JP-A-10-202950, the digital optical printing system including the remote diagnosis method described in JP-A-10-210206 , Japanese Patent Application No. 10-159187, an optical printing system including an image recording device.

The scanning exposure method most suitable for this invention is described in detail in the patent disclosed in the said table|surface.

When printing and exposing the photosensitive material of the present invention, it is preferable to use the band stop filter described in US Pat. No. 4,880,726, which can remove mixed color light and significantly improve color reproducibility.

In the present invention, as described in European Patent Nos. EPO789270A1 and EPO789480A1, before image information is provided, the yellow micro-dot pattern may be pre-exposed to perform copy restriction.

For the processing of the photosensitive material of the present invention, it is best to use the 1st line in the lower right column on page 26 to the 9th line in the upper right column on page 34 in JP2-207250, and the 17th to the upper left column on page 5 in JP4-97355. The processing materials and processing methods described in the 20th line of the lower right column on page 18. As the retention agent used in the developer, it is preferable to use the compounds described in the disclosed patents in the above table.

The present invention is preferably suitable for photosensitive materials with suitable rapid processing properties. When performing rapid processing, the color development time is preferably less than 60 seconds, more preferably less than 50 seconds and more than 6 seconds, and most preferably less than 30 seconds and more than 6 seconds. . Similarly, the bleaching and fixing time is preferably less than 60 seconds, more preferably less than 50 seconds and more than 6 seconds, most preferably less than 30 seconds and more than 6 seconds. Washing or stabilization time is preferably less than 150 seconds, more preferably less than 130 seconds and more than 6 seconds.

The so-called chromogenic and developing time refers to the time from when the photosensitive material is loaded into the chromogenic and developing solution to in the bleaching and fixing solution of the next processing procedure. For example, when processing with an automatic developing machine, etc., the time for immersing the photosensitive material in the color-developing solution (so-called time in the liquid), and the bleaching of the photosensitive material from the color-developing solution for the next processing step The fixing bath is transported in the air (so-called air time), and the total time of the two is called the color development time. Similarly, the so-called bleaching and fixing time refers to the time from when the photosensitive material is loaded into the bleaching and fixing solution to the next water washing or into the stabilization bath. The so-called washing or stabilizing time refers to the time that the photosensitive material exists in the liquid (so-called in-liquid time) from the time the photosensitive material is washed or loaded into the stabilizing liquid to the drying process.

As a method of developing the photosensitive material of the present invention after exposure, the conventional method of developing using a developing solution containing an alkaline agent and a main developer is to incorporate the main developer in the photosensitive material without using In addition to the method of developing with an activated solution such as an alkaline solution containing a main developer, in addition to these wet methods, a thermal development method that does not use a treatment liquid, etc. can also be used. The activation method, because the treatment liquid does not contain the main imaging agent, so the treatment liquid is easy to manage and handle, and the load of waste liquid treatment is very small, which is the most ideal method in terms of environmental protection.

In the activation method, as the imaging main agent embedded in the photosensitive material or its precursor, JP-A No. 8-234388, No. 9-152686, No. 9-152693, and No. 9-211814 are preferable. No., the same as the hydrazine compound described in No. 9-160193.

It is also possible to use a developing method in which the amount of silver coated on the photosensitive material is reduced, and image amplification processing (assistant processing) using hydrogen peroxide is performed. This method is best used in activation methods. Specifically, it is preferable to use the method of forming an image using an activation solution containing hydrogen peroxide described in JP-A-8-297354 and JP-A-9-152695. In the above-mentioned activation method, after the activation solution is used, the desilvering treatment is usually carried out, while the image amplification treatment method using a photosensitive material with a low silver content eliminates the desilvering treatment, and the so-called water washing or stabilization treatment is carried out. Easy way. In the case of using a scanner or the like to read image information from a photosensitive material, even if a photosensitive material with a high silver content such as a photosensitive material for imaging is used, a processing form that does not require desilvering treatment can be adopted.

As the activation solution used in the present invention, known treatment materials and treatment methods for desilvering solution (bleaching/fixing solution), water washing and stabilizing solution can be used. It is preferable to use those described in Japanese Patent Application Laid-Open No. 8-234388, pp. 536 to 541, of Lisaichi.

Description of drawings

Figure 1 is a graph showing the concentration distribution of bromide and iodide ions in the depth direction of the emulsion G-4 particles in Example 2.

The present invention will be specifically described below based on examples, but the present invention is not limited by these examples.

Example 1

(Preparation of Emulsion B-1)

1000ml of lime-treated gelatin 3% aqueous solution was adjusted to pH3.3, pCl1.7, while vigorously stirring at 66°C, simultaneously added and mixed aqueous solution containing 2.12 moles of silver nitrate and aqueous solution containing 2.2 moles of sodium chloride. When silver nitrate was added to 80% to 90%, an aqueous solution of K ₄ [Ru(CN) ₆ ] was added so that the amount of Ru produced would be 3×10 ^-5 mol per 1 mol of silver halide. When silver nitrate was added to 83% to 88%, an aqueous solution of K ₂ [IrCl ₆ ] was added so that the amount of Ir produced would be 3×10 ^-8 mol per 1 mol of silver halide. When silver nitrate is added to 92% to 98%, an aqueous solution of K ₂ [Ir(H ₂ O)Cl ₅ ] is added so that the amount of Ir produced is 1×10 ^-6 mol per 1 mol of silver halide . After the dechlorination treatment was carried out at 40°C, 168g of lime was added to treat the gelatin, and the pH was adjusted to 5.7 and pCl 1.8. The obtained particles were a three-dimensional silver chloride emulsion with a side length of 0.6 µm and a coefficient of variation of 11%.

This emulsion was dissolved at 40° C., and 2×10 ⁻⁵ moles of sodium thiosulfonate were added per mole of silver halide. As sulfur sensitizers, sodium thiosulfate 5 hydrate and gold sensitizer (S- 2) Mature at 60°C to achieve the optimum. After cooling down to 40°C, add 2× ^10-4 moles of sensitizing pigment A for every mole of silver halide, add 1× ^10-4 moles of sensitizing pigment B for every mole of silver halide, and add Add 2× ^10-4 moles of 1-phenyl-5-mercaptotetrazole, for every 1 mole of silver halide, add 2× ^10-4 moles of 1-(5-methylureaphenyl)-5-mercaptotetrazole, 2 x 10 ^-3 moles of potassium bromide were added per 1 mole of silver halide. These obtained emulsions were referred to as emulsion B-1.

(Sensitizing Pigment A)

(Sensitizing Pigment B)

(Preparation of Emulsion B-2)

At the end of adding silver nitrate to 90%, an aqueous solution of potassium iodide was added while vigorously mixing to prepare an amount of 0.2 mol% per 1 mol of silver halide to prepare an emulsion different from Emulsion B-1. Cubic silver iodochloride emulsion with particle side length of 0.6 μm and coefficient of variation of 11%. The emulsion thus obtained was designated as emulsion B-2.

The iodide ion concentration distribution of the obtained emulsion B-2 was analyzed by the etching/TOF-SIMS method, and it was found that the iodide ion concentration was the highest on the particle surface, and gradually decreased toward the inside. Even when the addition of the iodide salt solution was terminated inside the particle (where 90% of the silver nitrate was added), iodide ions bleed out toward the particle surface. The morphology of the produced particles was not different from that of Emulsions B-1 and B-2, and Emulsion B-2 is considered to contain silver iodochloride particles having a silver iodide-containing phase on the outermost surface of the particles forming a layer.

(Preparation of Emulsion B-3)

When the addition of silver nitrate reaches 80% to 90%, potassium bromide is added while vigorously mixing, and the amount of Br produced is 2 mol% per 1 mol of silver halide, which is adjusted to be different from that of emulsion B-1. The emulsion obtained is a cubic silver bromide chloride emulsion with a particle side length of 0.6 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as emulsion B-3.

When the bromide ion concentration distribution of the obtained emulsion B-3 was analyzed by the etching/TOF-SIMS method, it was found that the bromide ion concentration was maximum inside the particles. A silver bromide-containing phase appeared on the inner side of the particle (where 80% to 90% of silver nitrate was added) to which the bromide salt solution was added. The morphology of the produced particles was almost indistinguishable from that of emulsions B-1 and B-3, and it is considered that emulsion B-3 contains silver bromide chloride particles in which a silver bromide-containing phase is layered inside the particles.

(Preparation of Emulsion B-4)

When the addition of silver nitrate reaches 90% to 100%, potassium bromide is added while vigorously mixing, and the amount of Br produced is 2 mol% per 1 mol of silver halide, and it is prepared to be different from emulsion B-1. The emulsion was a cubic silver bromide chloride emulsion obtained with a particle side length of 0.6 µm and a coefficient of variation of 11%. The emulsion thus obtained was designated as emulsion B-4.

When the bromide ion concentration distribution of the obtained emulsion B-4 was analyzed by the etching/TOF-SIMS method, it was found that bromide ions were mainly distributed near the surface. The formed silver bromide-containing phase appeared near the surface of the particle where the addition of the bromide salt solution was performed (position where silver nitrate was added 90% to 100%). The morphology of the produced particles was almost the same as that of Emulsions B-1 and B-4, and it is considered that Emulsion B-4 contains silver bromide chloride particles in which the silver bromide-containing phase forms a layer near the surface.

(Preparation of Emulsion B-5)

When the addition of silver nitrate reaches 80% to 100%, potassium bromide is added while vigorously mixing, and the amount of Br produced is 4 mol% per 1 mol of silver halide, and an emulsion different from emulsion B-1 is prepared. . The resulting cubic silver bromide chloride emulsion had a particle side length of 0.6 µm and a coefficient of variation of 11%. The emulsion thus obtained was designated as emulsion B-5.

When the bromide ion concentration distribution of the obtained emulsion B-5 was analyzed by the etching/TOF-SIMS method, it was found that bromide ions were distributed from the inside of the particle to the surface. The formed silver bromide-containing phase appears toward the surface (position where silver nitrate is added 80% to 100%) from the inside of the particle where the bromide salt solution is added. The morphology of the produced particles was not different from that of Emulsions B-1 and B-5, and Emulsion B-5 is considered to contain silver bromide chloride particles that contain silver bromide phases from the inside of the particles to the surface to form layers.

(Preparation of Emulsion B-6)

Add silver nitrate from 80% to 90%, vigorously mix and add potassium bromide, make the amount of Br to be 2 mol% per 1 mole of silver halide, and then finish when the addition of silver nitrate reaches 90% At the moment, the aqueous solution of potassium iodide was mixed vigorously and added so that the amount of I was 0.2 mol% per 1 mol of silver halide, and an emulsion different from Emulsion B-1 was prepared. The resulting cubic silver iodobromochloride emulsion had a particle side length of 0.6 µm and a coefficient of variation of 11%, and the thus obtained emulsion was designated as emulsion B-6.

When the iodide ion and bromide ion concentration distributions of the obtained emulsion B-6 were analyzed by the etching/TOF-SIMS method, it was found that the concentration of iodide ions was extremely high on the surface of the particles, and the concentration attenuated toward the inner side. The concentration of compound ions is extremely high. Even if the addition of the iodide salt solution ends on the inner side of the particle (the position where silver nitrate is added at 90%), the iodide ion oozes out to the surface of the particle. position) showing the formation of silver bromide-containing phases. There is no difference between the prepared particle morphology and emulsions B-1 and B-6. It is considered that emulsion B-6 contains iodobromochloride in which the silver bromide phase is formed inside the particles and the silver iodide phase is formed on the outermost surface of the particles. silver particles.

(Preparation of Emulsion B-7)

At the moment when the addition of silver nitrate reaches 90%, the aqueous solution of potassium iodide is added while vigorously mixing, so that the amount of I produced reaches 0.2 mol% for every mol of silver halide, and then the addition of silver nitrate reaches 90%～100% % Potassium bromide was added while vigorously mixing to prepare an amount of Br of 2 mol% per 1 mol of silver halide to prepare an emulsion different from Emulsion B-1. The resulting cubic silver iodobromochloride emulsion had a particle side length of 0.6 µm and a coefficient of variation of 11%. The emulsion thus obtained was designated as Emulsion B-7.

When the concentration of iodide ion and bromide ion of the obtained emulsion B-7 is analyzed by etching/TOF-SIMS method, it can be seen that the concentration of iodide ion on the surface of the particle is extremely high, and the concentration decays toward the inner side, and the bromide ion is mainly distributed near the surface. . Even if the addition of the iodide salt solution is terminated inside the particle (the position where silver nitrate is added at 90%), the iodized ions ooze out to the particle surface, and near the particle surface where the bromide salt solution is added (the silver nitrate is added at 90% to 100%) % position) exhibits the formation of silver bromide-containing phases. The morphology of the produced particles was not different from that of Emulsions B-1 and B-7, and Emulsion B-7 is considered to contain silver iodobromochloride particles on the surface of which the silver bromide-containing phase and the silver iodide-containing phase are layered.

(Preparation of Emulsion B-8)

When the addition of silver nitrate reaches 80% to 100%, potassium bromide is added while vigorously mixing, so that the amount of Br produced per 1 mole of silver halide reaches 4 mol%, and then the addition of silver nitrate reaches 90%. At the time of termination, an aqueous solution of potassium iodide was added while vigorously mixing to prepare an amount of 1 to 0.2 mol% per 1 mol of silver halide to prepare an emulsion different from Emulsion B-1. The resulting cubic silver iodobromochloride emulsion had a particle side length of 0.6 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as emulsion B-8.

When the iodide ion and bromide ion concentration distribution of the obtained emulsion B-8 was analyzed by etching/TOF-SIMS method, it was found that the concentration of iodide ion was extremely high on the surface of the particle, and the concentration decayed toward the inner side. Particles are distributed from the inside to the surface. Even if the iodide salt solution ends on the inside of the particle (where silver nitrate is added 90%), iodide ions ooze out to the surface of the particle, from the inside of the particle where the bromide salt solution is added to the surface (where silver nitrate is added 80% to 100%) position), showing the formation of silver bromide-containing phases. There is no difference between the prepared particle morphology and emulsions B-1 and B-8. It is considered that emulsion B-8 contains a silver bromide-containing phase forming a layer from the inside of the particle to the surface, and a silver iodide-containing phase forming a layer on the outermost surface of the particle. Silver iodobromochloride particles.

Polyethylene resin is coated on both sides of the paper, and on the surface of the support formed in this way, after corona discharge treatment, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate is set, and then the first layer~ For the photographic constituent layer of the seventh layer, a silver halide color photographic photosensitive material sample having the layer constitution shown below was prepared. The coating liquid for each photographic constituent layer was prepared as follows.

Preparation of the first layer of coating liquid

57g of yellow coupler (Exy), 7g of color stabilizer (Cpd-1), 4g of color stabilizer (Cpd-2), 7g of color stabilizer (Cpd-3), 2g of color stabilizer (Cpd- 8) be dissolved in 21g solvent (Solv-1) and 80ml ethyl acetate, this solution is in the 220g 23.5 mass % gelatin aqueous solution that contains 4g sodium dodecylbenzene sulfonate, with high-speed stirring emulsifier (dissolver ) is emulsified and dispersed, and water is added to modulate into 900g emulsified dispersion A.

On the other hand, the above-mentioned emulsified dispersion A and emulsion B-1 were mixed and dissolved to prepare a first-layer coating liquid having the following composition. The coating amount of the emulsion is shown as the coating amount converted to the amount of silver.

The coating liquids for the second to seventh layers were also prepared in the same manner as the coating liquid for the first layer. 1-Oxo-3,5-dichloro-S-triazine sodium salts (H-1), (H-2), and (H-3) were used as gelatin hardeners for the respective layers. Add Ab-1, Ab-2, Ab-3, and Ab-4 to each layer respectively, and the total amount reaches 15.0mg/m ² , 60.0mg/m ² , 5.0m/m ² and 10.0mg/m ² .

(H-1) Hard film agent

(H-2) Hard film agent

(H-3) Hard film agent

【chemical 8】

(Ab-1) Preservatives (Ab-2) Preservatives

(Ab-3) Preservatives

(Ab-4) Preservatives

R ₁ R ₂ abcd -CH ₃ -CH ₃ -HH -NHCH ₃ -NH ₂ -NH ₂ -NHCH ₃

1:1:1:1 mixture of A, b, c, d (molar ratio)

In the silver bromide chloride emulsions of the green and red sensitive emulsion layers, the following spectrally sensitizing dyes were used, respectively.

Green Sensitive Emulsion Layer

【Chemical 9】

(Sensitizing Pigment D)

(Sensitizing Pigment E)

(Sensitizing Pigment F)

(Sensitizing pigment D: For every 1 mole of silver halide, add 3.0×10 ^-4 moles to large size emulsion, add 3.6×10 ^-4 moles to small size emulsion. Sensitizing pigment E: For every 1 mole of silver halide, add Add 4.0×10 ^-5 moles to large size emulsions, add 7.0×10 ^-5 moles to small size emulsions. Sensitizing pigment F: for every 1 mole of silver halide, add 2.0×10 -4 moles to large size emulsions, and add 2.0×10 ^-4 moles to small size emulsions Emulsion added 2.8×10 ^-4 mol.)

red sensual emulsion layer

(Sensitizing pigments G and H: Add 8.0× ^10-5 moles to large-scale emulsions and 10.7× ^10-5 moles to small-size emulsions for every 1 mole of silver halide, respectively. Furthermore, in the red sensitive emulsion layer, for each 1 mole of silver halide, add 3.0×10 ^-3 moles of the following compounds.)

(Compound I)

In the green sensitive emulsion layer and the red sensitive emulsion layer, for every 1 mole of silver halide, 1.0×10 ^-3 moles and 5.9×10 ^-4 moles of 1-(3-methylureaphenyl)-5-mercapto tetra azole.

Furthermore, in the second layer, the fourth layer, the sixth layer, and the seventh layer, 0.2 mg/m ² , 0.2 mg/m ² , 0.6 mg/m ² , and 0.1 mg/m ² were added, respectively.

In the blue sensitive emulsion layer and the green sensitive emulsion layer, for every 1 mole of silver halide, add 1×10 ^-4 moles, 2×10 ^-4 moles of 4-hydroxy-6-methyl-1,3,3a , 7-tetrazine decane.

Add 0.05 g/m ² copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1:1, average molecular weight 200,000-400,000) to the red sensitive emulsion layer.

In the second layer, the fourth layer and the sixth layer, disodium catechol-3,5-disulfonate was added at 6 mg/m ² , 6 mg/m ² , and 18 mg/m ² , respectively.

In order to prevent light bleeding, the following dyes were added (coating amounts are indicated in parentheses).

(layer composition)

The configuration of each layer is shown below. The numbers indicate the coating amount (q/m ² ), and the silver halide emulsion indicates the coating amount in terms of silver.

Support body

Polyethylene resin laminated paper

[The polyethylene resin on the first layer side contains a white pigment (TiO ₂ : content rate 16% by mass, ZnO: content rate 4% by mass), fluorescent whitening agent (4,4'-bis(5-tolyloxazole) base) stilbene. Content rate 0.03% by mass) and blue dye (ultramarine blue)]

The first layer (blue sensitive emulsion layer)

Emulsion B-1 0.24

Gelatin 1.25

Yellow coupler (ExY) 0.57

Image Stabilizer (Cpd-1) 0.07

Image stabilizer (Cpd-2) 0.04

Image stabilizer (Cpd-3) 0.07

Image stabilizer (Cpd-8) 0.02

Solvent (Solv-1) 0.21

The second layer (anti-mixing color layer)

Gelatin 0.99

Anti-mixing agent (Cpd-4) 0.09

Image Stabilizer (Cpd-5) 0.018

Image Stabilizer (Cpd-6) 0.13

Image Stabilizer (Cpd-7) 0.01

Solvent (Solv-1) 0.06

Solvent (Solv-2) 0.22

The third layer (green sensual emulsion layer)

Silver bromide chloride emulsion BB (gold-sulfur sensitized cube, 1:3 mixture (silver molar ratio) of average particle size 0.45 μm large-size emulsion and 0.35 μm small-size emulsion. Coefficients of variation of particle size distribution are 0.10 and 0.08, respectively Each size emulsion contains 0.15 mol% silver iodide near the particle surface, and contains 0.4 mol% silver bromide locally on the particle surface) 0.14

Gelatin 1.36

Crimson coupler (ExM) 0.15

Ultraviolet absorber (UV-A) 0.14

Image stabilizer (Cpd-2) 0.02

Image stabilizer (Cpd-4) 0.002

Image stabilizer (Cpd-6) 0.09

Image stabilizer (Cpd-8) 0.02

Image Stabilizer (Cpd-9) 0.03

Image Stabilizer (Cpd-10) 0.01

Image stabilizer (Cpd-11) 0.0001

Solvent (Solv-3) 0.11

Solvent (Solv-4) 0.22

Solvent (Solv-5) 0.20

The fourth layer (anti-mixing color layer)

Gelatin 0.71

Anti-aliasing layer (Cpd-4) 0.06

Image stabilizer (Cpd-5) 0.013

Image stabilizer (Cpd-6) 0.10

Image Stabilizer (Cpd-7) 0.007

Solvent (Solv-1) 0.04

Solvent (Solv-2) 0.16

The fifth layer (red sensual emulsion layer)

Silver bromide chloride emulsion CC (gold sulfur sensitized cube, 5:5 mixture (silver molar ratio) of average particle size 0.40 μm large size emulsion and 0.30 μm small size emulsion. Coefficients of variation of particle size distribution are 0.09 and 0.11, respectively Each size emulsion contains 0.1 mol% silver iodide near the particle surface, and 0.8 mol% silver bromide locally on the particle surface) 0.12

Gelatin 1.11

Cyanogen coupler (ExC-2) 0.13

Cyanogen coupler (ExC-3) 0.03

Image Stabilizer (Cpd-1) 0.05

Image stabilizer (Cpd-6) 0.06

Image stabilizer (Cpd-7) 0.02

Image stabilizer (Cpd-9) 0.04

Image Stabilizer (Cpd-10) 0.01

Image stabilizer (Cpd-14) 0.01

Image Stabilizer (Cpd-15) 0.12

Image Stabilizer (Cpd-16) 0.03

Image stabilizer (Cpd-17) 0.09

Image Stabilizer (Cpd-18) 0.07

Solvent (Solv-5) 0.15

Solvent (Solv-5) 0.05

The sixth layer (ultraviolet absorbing layer)

Gelatin 0.46

Ultraviolet absorber (UV-B) 0.45

Compound (S1-4) 0.0015

Solvent (Solv-7) 0.25

The seventh layer (protective layer)

Gelatin 1.00

Acrylic denatured copolymer of polyvinyl alcohol (17% degree of denaturation) 0.04

Mobile paraffin 0.02

Surfactant (Cpd-13) 0.01

【chemical 13】

(ExY) yellow coupler

【Chemical 14】

(ExM) deep red coupler

【chemical 15】

(ExC-2) Cyanogen coupler

(ExC-3) Cyanogen coupler

【Chemical 16】

(Cpd-1) Color Image Stabilizer

(Cpd-2) Color Image Stabilizer

(Cpd-3) Color Image Stabilizer

(Cpd-4) anti-mixing agent

【Chemical 17】

(Cpd-5) Color Image Stabilizer

(Cpd-6) Color Image Stabilizer

(Cpd-7) Color Stabilizer (Cpd-8) Color Stabilizer

(Cpd-9) Color Stabilizer (Cpd-10) Color Stabilizer

【chemical 18】

(Cpd-11)

(Cpd-13)surfactant

【chemical 19】

(Cpd-14) (Cpd-15)

(Cpd-16) (Cpd-17)

(Cpd-18)

(Cpd-19) Anti-color mixing agent

【chemical 20】

(UV-1) Ultraviolet Absorber (UV-2) Ultraviolet Absorber

(UV-3) Ultraviolet Absorber (UV-4) Ultraviolet Absorber

(UV-5) Ultraviolet Absorber (UV-6) Ultraviolet Absorber

(UV-7) Ultraviolet absorber

UV-A: UV-1/UV-2/UV-3/UV-4=4/2/2/3 mixture (mass ratio)

UV-B: UV-1/UV-2/UV-3/UV-4/UV-5/UV-6=9/3/3/4/5/3 mixture (mass ratio)

UV-C: UV-2/UV-3/UV-6/UV-7=1/1/1/2 mixture (mass ratio)

【Chemical 21】

(Solv-1) (Solv-2)

(Solv-3) (Solv-4)

                        O＝P(OC₆H₁₃(n))₃

O=P(OC ₆ H ₁₃ (n)) ₃

(Solv-5) (Solv-7)

(Solv-8)

【Chemical 22】

(S1-4)

The sample obtained above was designated as sample B-1. Emulsions B-2 to B-8 were used to replace Emulsion B-1 in the blue-sensitive emulsion layer, and prepared in the same way as Sample B-1 to obtain Samples B-2 to B-8, respectively.

In order to study the photographic characteristics of these samples, the following experiments were carried out.

For each coating sample, a sensitometer for high-illuminance exposure (Model HIE manufactured by Yamashita Denso Co., Ltd.) was used. Gives grayscale exposure for sensitometric measurements. Mount the Fuji Photo Film Co., Ltd. SP-1 color filter for 10 ^-8 second high-illumination exposure.

After the exposure, color development treatment A shown below was performed.

The processing steps are shown below.

[Process A]

The sample of the above-mentioned photosensitive material was processed into a 127 mm wide roll, and after image exposure was performed using a small darkroom printing processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., it was continuously processed (flow test) in the following processing steps until replenishment 2 times the capacity of the color imaging tank. The treatment with this flow solution was referred to as treatment A.

Processing Procedure Temperature Time Time Supplementary Amount*

Color imaging 38.5℃ 45 seconds 45ml

Bleaching and fixing 38.0℃ 45 seconds 35ml

Rinse (1) 38.0°C 20 seconds -

Rinse (2) 38.0°C 20 seconds -

Rinse(3) **38.0℃ for 20 seconds -

Rinse (4) **38.0℃ 30 seconds 121ml

* Supplementary amount of photosensitive material per ^1m2

**The washing and purification system RC50D manufactured by Fuji Photo Film Co., Ltd. is installed in the washing (3), and the washing liquid taken out from the washing (3) is pumped into the reverse osmosis membrane storage (RC50D). The permeated water obtained from the same tank is sent to flushing (4), and the concentrated water is returned to flushing (3). The amount of permeated water to the reverse osmosis storage is maintained at 50-300ml/min by adjusting the pump pressure, and the temperature adjustment cycle is carried out for 10 hours a day.

(Flush from (1) to (4) groove flow mode)

The composition of each treatment liquid is as follows.

[Color developing solution] [Bath solution] [Replenishment solution]

Water 800ml 800ml

Dimethicone-based surfactant 0.1g 0.1g

(Silicon KF351A/Manufactured by Shin-Etsu Chemical Co., Ltd.)

Tri(isopropanol)amine 8.8g 8.8g

Ethylenediaminetetraacetic acid 4.0g 4.0g

Polyethylene glycol (molecular weight 300) 10.0g 10.0g

Sodium 4.5-dihydroxybenzene-1,3-disulfonate 0.5g 0.5g

Potassium chloride 10.0g -

Potassium bromide 0.040g 0.010g

Triazine aminostilbene fluorescent 2.5g 5.0g

Whitening agent (Hatsukoll FWA-SF/manufactured by Showa Chemical Co., Ltd.)

Sodium sulfite 0.1g 0.1g

Disodium-N,N-bis(sulfonate ethyl)hydroxylamine 8.5g 11.1g

N-ethyl-N-(β-methanesulfonamide ethyl)-3-methyl-4-

Amino-4-aminoaniline 3/2 sulfuric acid 1 hydrate

                                                                  ,

Potassium Carbonate 26.3g 26.3g

Add water 1000ml 1000ml

pH (25℃/adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach Fixer] [Bath Solution] [Replenisher]

Water 700ml 600ml

Iron(III) ammonium ethylenediaminetetraacetate 47.0g 94.0g

Ethylenediaminetetraacetic acid 1.4g 2.8g

m-carboxybenzenesulfinic acid 8.3g 16.5g

Nitric acid (67%) 16.5g 33.0g

Imidazole 14.6g 29.2g

Ammonium thiosulfate (750g/L) 107.0ml 214.0ml

Ammonium sulfite 16.0g 32.0g

Ammonium bisulfite 23.1g 46.2g

Add water 1000ml 1000ml

pH (25°C/adjusted with acetic acid and ammonia) 6.0 6.0

[Rinse solution] [Bath solution] [Replenishment solution]

Sodium isocyanurate chloride 0.02g 0.02g

Deionized water (conductivity below 5μs/cm) 1000ml 1000ml

pH 6.5 6.5

The yellow color density of each sample after treatment was measured to obtain a characteristic curve of 10 ⁻⁶ second high-illuminance exposure. The sensitivity specification has the inverse number of the exposure amount that gives a color density higher than the minimum color density of 0.7, and when the sensitivity of the sample B-1 is taken as 100, it is expressed as a relative value. The points of density 0.5 and density 2.0 are connected with a straight line, and the gradation is obtained from the inclination thereof. The results are shown in Table 2.

[Table 2] sample Br layer I layer Sensitivity grayscale Remark Location content Location content B-1 none - none - 100 1.8 comparative example B-2 none - 90% 0.2 mol% 230 1.6 comparative example B-3 80%～90% 2 mol% none - 130 2.0 comparative example B-4 90%～100% 2 mol% none - 140 1.9 comparative example B-5 80%～100% 4 mol% none - 140 2.0 comparative example B-6 80%～90% 2 mol% 90% 0.2 mol% 280 2.8 this invention B-7 90%～100% 2 mol% 90% 0.2 mol% 260 2.4 this invention B-8 80%～100% 4 mol% 90% 0.2 mol% 260 2.6 this invention

As can be seen from the results in Table 2, the samples B-6, B-7 and B-7 containing the silver iodobromochloride emulsions of the layered silver bromide-containing phase and the silver iodide-containing phase of the present invention respectively formed in the blue photosensitive emulsion layer B-8, confirm that the sensitivity to blue is remarkably high, and it is a hard tone.

Example 2

(Preparation of Emulsion G-1)

1000ml of lime-treated gelatin 3% aqueous solution was adjusted to pH 3.3, pCl 1.7, while vigorously stirring at 56° C., simultaneously adding and mixing aqueous solution containing 2.12 moles of silver nitrate and aqueous solution containing 2.2 moles of sodium chloride. When the addition of silver nitrate reached 80% to 90%, an aqueous solution of K ₄ [Ru(CN) ₆ ] was added to produce an amount of Ru of 5×10 ^-5 moles per mole of silver halide. When the addition of silver nitrate reached 83% to 88%, an aqueous solution of K ₂ [IrCl ₆ ] was added to produce an amount of Ir of 5×10 ^-8 moles per mole of silver halide. When the addition of silver nitrate reached 92% to 98%, an aqueous solution of K ₂ [Ir(5-methylthiazole)Cl ₅ ] was added to produce an amount of Ir of 1×10 ^-6 mol for 1 mol of silver halide. After the desalination treatment was carried out at 40°C, 168g of lime-treated gelatin was added to adjust pH to 5.7 and pCl to 1.8. The obtained particles were cubic silver chloride emulsions with a side length of 0.4 µm and a coefficient of variation of 11%.

This emulsion was dissolved at 40° C., 2×10 ⁻⁵ moles of sodium thiosulfinate were added per mole of silver halide, sodium thiosulfate 5 hydrate was used as a sulfur sensitizer, and sodium thiosulfate 5 hydrate was used as a gold sensitizer ( S-2), aged at 60°C to the optimum. After cooling down to 40°C, add 5× ^10-4 moles of sensitizing dye D per 1 mole of silver halide, add 2× ^10-4 moles of 1-phenyl-5-mercaptotetrazole per 1 mole of silver halide, 4×10 ⁻⁴ moles of 1-(5-methylureaphenyl)-5-mercaptotetrazole were added per 1 mole of silver halide, and 7×10 ⁻³ moles of potassium bromide were added per 1 mole of silver halide. The emulsion thus obtained was designated as emulsion G-1.

(Preparation of Emulsion G-2)

When the addition of silver nitrate reached 90%, an aqueous solution of potassium iodide was added while vigorously mixing to produce an amount of I of 0.3 mol% per 1 mol of silver halide to prepare an emulsion different from Emulsion G-1. The obtained particles were a cubic silver iodochloride emulsion with a side length of 0.4 μm and a coefficient of variation of 11%, and the emulsion thus obtained was designated as emulsion G-2.

(Preparation of Emulsion G-3)

When the addition of silver nitrate reached 80% to 100%, potassium bromide was added while vigorously mixing, and the amount of Br produced per 1 mol of silver halide was 4 mol%, and an emulsion different from emulsion G-1 was prepared. The obtained particles were a cubic silver bromide chloride emulsion with a side length of 0.4 μm and a coefficient of variation of 11%, and the thus obtained emulsion was designated as emulsion G-3.

(Preparation of Emulsion G-4)

When the addition of silver nitrate reaches 80% to 100%, potassium bromide is added while vigorously mixing, so that the amount of Br produced per 1 mole of silver halide reaches an amount of 4 mol%, and then when the addition of silver nitrate reaches 90% , A potassium iodide aqueous solution was added while vigorously mixing, and the amount of I was made to be 0.3 mol% per 1 mol of silver halide, and an emulsion different from Emulsion G-1 was prepared. The obtained particles were a cubic silver iodobromochloride emulsion with a side length of 0.4 μm and a coefficient of variation of 11%. The emulsion thus obtained was designated as emulsion G-4.

The concentration distribution of bromide and iodide ions in the depth direction of emulsion G-4 particles was measured by etching/TOF-SIMS method, and the results are shown in Fig. 1 . Even if the addition of iodide salt solution inside the particle is completed, iodide ions seep out to the surface of the particle, the concentration is extremely high on the outermost surface, and the concentration decreases toward the inside. On the other hand, the bromide ion concentration is extremely large inside the particles. From this, it is considered that the silver bromide-containing phases are layered inside the particles, respectively, compared with the silver iodide-containing phases.

A sample with a thinner layer than that of the sample of Example 1 was produced in the following variable layer configuration.

Production of samples

The first layer (blue sensitive emulsion layer)

Emulsion B-1 0.24

Gelatin 1.25

Yellow coupler (ExY) 0.57

Image stabilizer (Cpd-1) 0.07

Image Stabilizer (Cpd-2) 0.04

Image Stabilizer (Cpd-3) 0.07

Image stabilizer (Cpd-8) 0.02

Solvent (Solv-1) 0.21

The second layer (anti-mixing color layer)

Gelatin 0.60

Anti-mixing agent (Cpd-19) 0.09

Image stabilizer (Cpd-5) 0.007

Image stabilizer (Cpd-7) 0.007

Ultraviolet absorber (UV-C) 0.05

Solvent (Solv-5) 0.11

The third layer (green sensual emulsion layer)

Emulsion G-1 0.14

Gelatin 0.73

Crimson coupler (ExM) 0.15

Ultraviolet absorber (UV-A) 0.05

Image stabilizer (Cpd-2) 0.02

Image stabilizer (Cpd-7) 0.008

Image Stabilizer (Cpd-8) 0.07

Image stabilizer (Cpd-9) 0.03

Image Stabilizer (Cpd-10) 0.009

Image stabilizer (Cpd-11) 0.0001

Solvent (Solv-3) 0.06

Solvent (Solv-4) 0.11

Solvent (Solv-5) 0.06

The fourth layer (anti-mixing color layer)

Gelatin 0.48

Anti-aliasing layer (Cpd-4) 0.07

Image stabilizer (Cpd-5) 0.006

Image Stabilizer (Cpd-7) 0.006

Ultraviolet absorber (UV-C) 0.04

Solvent (Solv-5) 0.09

The fifth layer (red sensual emulsion layer)

Silver bromide chloride emulsion CC (same emulsion as sample B-1) 0.12

Gelatin 0.59

Cyanogen coupler (ExC-2) 0.13

Cyanogen coupler (ExC-3) 0.03

Image stabilizer (Cpd-7) 0.01

Image Stabilizer (Cpd-9) 0.04

Image stabilizer (Cpd-15) 0.19

Image Stabilizer (Cpd-18) 0.04

Ultraviolet absorber (UV-7) 0.02

Solvent (Solv-5) 0.09

The sixth layer (ultraviolet absorbing layer)

Gelatin 0.32

Ultraviolet absorber (UV-C) 0.42

Solvent (Solv-7) 0.08

The seventh layer (protective layer)

Gelatin 0.70

Acrylic denatured copolymer of polyvinyl alcohol (17% degree of denaturation) 0.04

Mobile paraffin 0.01

Surfactant (Cpd-13) 0.01

Polydimethylsiloxane 0.01

Silica 0.003

As the emulsion of the green sensitive emulsion layer, the sample of the above-mentioned emulsion G-1 was used as the sample G-1. Sample G-1 was also prepared in the same manner as the sample of Emulsion G-1 in which the green sensitive emulsion layer was replaced by Emulsions G-2 to G-4, and they were samples G-2 to G-4, respectively.

In order to investigate the photographic properties of these samples, the following experiments were carried out.

Using a sensitometer for high-illuminance exposure (HIE type manufactured by Yamashita Denso Co., Ltd.), each coating sample was given a gradation exposure for sensitometric measurement, and an SP-2 color filter manufactured by Fuji Photo Film Co., Ltd. was attached to carry out 10 ^-6 seconds high light exposure.

For the luminescence development treatment of each exposed sample, an ultra-rapid treatment was performed according to the development treatment B shown below.

[Process B]

The above-mentioned photosensitive material samples were processed into rolls with a width of 127 mm, and an experimental processing device modified from a small darkroom printing processor PP350 manufactured by Fuji Photo Film Co., Ltd. was used to change the processing time and processing temperature. Image exposure is carried out from the negative film of average density, and the continuous processing (flow test) is carried out according to the following processing procedures until the volume of the chromogenic and developing supplementary liquid used reaches 0.5 times the capacity of the chromogenic and developing tank.

Processing Procedure Temperature Time Time Supplementary Amount*

Hair color development 45.0℃ 15 seconds 45ml

Bleaching and fixing 40.0°C 15 seconds 35ml

Rinse 1 40.0°C 8 seconds -

Rinse 2 40.0°C 8 seconds -

Rinse 3 **40.0℃ for 8 seconds -

Rinse 4 38.0°C 8 seconds 121ml

Drying at 80.0°C for 15 seconds

(Note) *Replenishment amount of photosensitive material per ^1m2

** Install Fuji Photo Film Co., Ltd. washing and purification system RC50D in the washing (3), the washing liquid taken out from the washing (3) is pumped into the reverse osmosis storage (RC50D), and the washing liquid sent out from the tank Permeate water is supplied to the rinse and the concentrate is returned to the rinse (3). By adjusting the pump pressure, the permeate water volume of the reverse osmosis storage is kept at 50-300ml/min, and the temperature adjustment cycle is carried out for 10 hours a day. Flushing adopts 4-slot flow from (1) to (4).

The composition of each treatment liquid is as follows.

[Chroma developing solution] [Bath solution] [Replenishment solution]

Water 800ml 600ml

Fluorescent whitening agent (FL-1) 5.0g 8.5g

Triisopropanolamine 8.8g 8.8g

Sodium P-toluenesulfonate 20.0g 20.0g

Ethylenediamine 4-acetic acid 4.0g 4.0g

Sodium sulfite 0.10g 0.50g

Potassium chloride 10.0g -

Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.50g 0.50g

Disodium-N,N-bis(sulfonate ethyl)hydroxylamine 8.5g 14.5g

4-Amino-3-methyl-N-ethyl-N-(β-methanesulfonamide ethyl)

Aniline · 3/2 Sulfate · Monohydrate

|

Potassium Carbonate 26.3g 26.3g

Total amount of water added 1000ml 1000ml

pH (25°C, adjusted with sulfuric acid and KOH) 10.35 12.6

[Bleach and Fixer] [Bath Solution] [Replenishment Solution]

Water 800ml 800ml

Ammonium Thiosulfate (750g/ml) 107ml 214ml

Succinic acid 29.5g 59.0g

Ethylenediamine 4-acetate iron (III) ammonium 47.0g 94.0g

Ethylenediamine 4-acetic acid 1.4g 2.8g

Nitric acid (67%) 17.5g 35.0g

Imidazole 14.6g 29.2g

Ammonium sulfite 16.0g 32.0g

Ammonium metabisulfite 23.1g 46.2g

Total amount of water added 1000ml 1000ml

pH (25°C, adjusted with nitric acid and ammonia water) 6.00 6.00

[Rinse Solution] [Bath Solution] [Replenishment Solution]

Sodium isocyanuric chloride 0.02g 0.02g

Deionized water (conductivity below 5μs/cm) 1000ml 1000ml

pH(25℃) 6.5 6.5

The dark red color density of each sample after external treatment was measured to obtain a 10 ^-6 second high-illuminance exposure characteristic curve. The sensitivity specification has the inverse number of the exposure amount that gives a color density higher than the minimum color density by 0.7, and when the sensitivity of sample G-1 is taken as 100, it is expressed as a relative value. A straight line is connected between the points of density 0.5 and density 2.0, and the gradation is obtained from the inclination thereof.

In order to study latent image retention, characteristic curves were obtained when processing was started 10 seconds after exposure and when processing was started 10 minutes after exposure, and changes in density at an exposure level of 1.0 were studied when processing was started after 10 seconds. Furthermore, in order to study the dependence of exposure on temperature and humidity, the characteristics were obtained when the treatment was started after 10 seconds of exposure under the environment of 10°C and 55%, and when the treatment was started after 10 seconds of exposure under the environment of 30°C and 30%. In the graph, the concentration change at the exposure amount of 1.0 was studied when the treatment was started after 10 seconds of exposure at 10° C. and 55% environment. These results are shown in Table 3. sample Br layer I layer Sensitivity grayscale latent image preservation Exposure to temperature and humidity dependence Remark Location content Location content G-1 none - none - 100 1.9 0.20 0.15 comparative example G-2 none - 90% 0.3 mol% 180 1.6 0.21 0.12 comparative example G-3 80%～100% 4 mol% none - 140 2.0 0.09 0.13 comparative example G-4 80%～100% 4 mol% 90% 0.3 mol% 210 2.6 0.03 0.05 this invention

As is clear from the results in Table 3, sample G-4 containing a layered silver iodobromochloride emulsion formed of the silver bromide-containing phase and the silver iodide-containing phase of the present invention in the green photosensitive emulsion layer, the green photosensitivity It is remarkably high-sensitivity, hard-tuned, and it is confirmed that the latent image preservation and the dependence of exposure on temperature and humidity are excellent.

Furthermore, in sample G-4, only the emulsion B-1 of the first layer was changed to emulsion B-8, and a different sample G-4' was produced, and the above-mentioned evaluation was carried out, and the result was substantially the same as that of sample G-4. the result of.

Example 3

Using the sample of Example 2, imaging was performed by laser scanning exposure.

As a laser light source, YAG solid-state laser (oscillation wavelength 946 μm) using semiconductor laser GaAlAs (oscillation wavelength 808.5nm) as the excitation light source through the SHG crystal of LiNbO ₃ with an inverted domain light structure, the wavelength conversion of 473nm and through The SHG crystal of LiNbO ₃ with an inverted domain optical structure converts the wavelength of YVO ₄ solid-state laser (oscillation wavelength 1064nm) using semiconductor laser GaAlAs (oscillation wavelength 808.7nm) as excitation light source to take out 532nm, and uses AlGaInP (oscillation wavelength about 680nm) : Panasonic Manufacturing Model No.LN9R20). The laser light of each of the three colors is moved vertically with respect to the scanning direction by a polygonal prism, and the scanning exposure is sequentially performed on the sample. Fluctuations in the light intensity of semiconductor lasers due to temperature can be suppressed by a Peltier element to keep the temperature constant. The actual effective beam diameter is 80 μm, the scanning pitch is 42.3 μm (600 dpi), and the average exposure time per pixel is 1.7×10 ^-7 seconds.

After exposure, the result of the high-illuminance exposure in Example 2 was the same as that of the high-illuminance exposure in Example 2. The green-sensing layer of the sample G-4 of the present invention showed very high sensitivity and gray scale. The sample G-4' of the present invention shows the high sensitivity and gray scale of the blue-sensing layer and the green-sensing layer, and it can be known that it is applicable to any kind of laser scanning exposure imaging.

Example 4

(Preparation of Emulsion A)

To a 3% aqueous solution of limed gelatin was added 3.3 g of sodium chloride, 42.8 ml of 1N sulfuric acid and 25 ml of 1,8-dihydroxy-3,6-dithiooctane (1% aqueous solution). To this aqueous solution, an aqueous solution containing 2.12 moles of silver nitrate and an aqueous solution containing 2.18 moles of sodium chloride were added and mixed at 68° C. with vigorous stirring. Subsequently, sedimentation at 40° C., washing with water, and desalination were carried out. 168.0 g of lime-treated gelatin was added to adjust the pH and pAg of the emulsion to 7.3 and 5.6, respectively. Using electron microscope photography, it can be seen that the shape of the particles is cubic, the average particle size is 0.76 μm, and the coefficient of variation is 10%.

Add gold sensitizer (colloidal gold sulfide) 6×10 ^-5 mole/mole Ag to this emulsion, the blue sensitive spectroscopic sensitization pigment described in Example 1 3.1×10 ^-4 mole/mole Ag, carry out at 60 ℃ Appropriate chemical sensitization and spectroscopic sensitization, and then adding 1-(5-methylureaphenyl)-5-mercaptotetrazole 4.4×10 ^-4 mol/mol Ag to prepare emulsion A.

(modulation of emulsion B)

In the formation of emulsion particles, the preparation method of emulsion A was followed except that a silver iodide microparticle emulsion containing 0.4 mol % of iodide ions was added to the total amount of silver in the step of adding 80 to 81% of the total silver amount. The preparation of the silver iodide fine particle emulsion to be used can be carried out with a stirring mixer described in JP-A-10-43570.

(Preparation of Emulsion C)

In the formation of emulsion particles, the preparation method of emulsion A was followed except that 0.4 mol % of potassium iodide aqueous solution was added to the total silver amount in the step of adding 99 to 100% of the total silver amount.

(Preparation of Emulsion D)

In the formation of emulsion particles, the preparation method of emulsion A was followed except that 0.4 mol % of potassium iodide aqueous solution was added to the total silver amount in the step of adding 94 to 95% of the total silver amount.

(Preparation of Emulsion E)

In the formation of emulsion particles, the preparation method of emulsion A was followed except that 0.4 mol % of potassium iodide aqueous solution was added to the total silver amount in the step of adding 85 to 86% of the total silver amount.

A sample (101) of a silver halide color photographic photosensitive material differing from the sample B-1 in Example 1 in the following points was prepared. The spectrally sensitizing dyes of the silver halide emulsions in the green and red sensitive emulsion layers are the same as those of the sample B-1 of Example 1 for the large-size emulsion and the small-size emulsion, and the amount per 1 mole of silver halide is also the same. For the same amount. The same amount of Compound I as in Sample B-1 of Example 1 was added to the red sensitive emulsion layer.

Differences from Example 1

Only the emulsion type of the first layer, the third layer and the fifth layer is changed.

The first layer was changed to emulsion A, and the third layer was changed to silver chlorobromide emulsion Em-1 (a 1:3 mixture of gold-sulfur sensitized cube, a large-sized emulsion with an average particle size of 0.45 μm and a small-sized emulsion with an average particle size of 0.35 μm) (Silver molar ratio). The coefficient of variation of the particle size distribution is 0.10 and 0.08, and each size emulsion contains 0.15 mol % silver iodide near the particle surface, and the particle surface partially contains 0.4 mol % silver bromide), the fifth layer changed chlorine Silver bromide emulsion Em-2 (a gold-sulfur sensitized cube, a 5:5 mixture (silver molar ratio) of a large-size emulsion with an average particle size of 0.40 μm and a small-size emulsion of 0.30 μm. The coefficients of variation of the particle size distribution are respectively 0.09 and 0.11. Each size emulsion contained 0.1 mol% silver iodide near the particle surface and 0.8 mol% silver bromide locally on the particle surface).

Similarly, samples (102) to (105) were produced by changing emulsion A of sample (101) into emulsions B to E.

In order to investigate the photographic properties of these samples, the following experiments were carried out.

Experiment A: Sensitometric Assay

To each coating sample, a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.) was used to give grayscale exposure for sensitometric measurement. A 10-second low-light exposure was performed with an SP-1 filter attached.

Using a sensitometer for high-illuminance exposure (Model HIE manufactured by Yamashita Denso Co., Ltd.), grayscale exposure for sensitometric measurement was applied, an SP-1 color filter was attached, and high-illuminance exposure was performed for 10 ⁻⁴ seconds. After the exposure, the color development treatment A [treatment A] in Example 1 was carried out (the difference is that only the above-mentioned photosensitive material 101 was used to make the flow liquid).

The yellow color density of each sample after the treatment was measured, and the film concentrations, 10-second exposure low-illumination sensitivity, and 10 ^-4 -second exposure high-illuminance sensitivity were obtained for emulsions A to E, respectively. The sensitivity is defined as the inverse number of the exposure amount that gives a color density higher than the minimum color density by 1.0, and is expressed as a logarithmic value when the developing sensitivity of the sample (101) is taken as 100. The silver iodide ratios (= silver iodide content at the corners obtained by the electroanalytical method / silver iodide content at the main surface obtained by the ESCA method) of the corners and the main surface of each emulsion were used as a control, and these results are shown together in Table 4.

[Table 4] sample emulsion silver iodide ratio Film concentration low light sensitivity high light sensitivity 101 A (comparison) - 0.07 100 100 102 B (comparison) 0.95 0.07 120 135 103 C (this invention) 2.1 0.11 210 220 104 D (this invention) 1.6 0.08 193 210 105 E (this invention) 1.2 0.07 150 170

It can be seen from Table 4 that the silver chloroiodide emulsion of the present invention has higher sensitivity and excellent reciprocity law characteristics of high illumination. Before forming 98% of the particles, the emulsion of the present invention to which iodide ions were added had a clear image and was a high-sensitivity emulsion.

Example 5

(Preparation of Emulsion F)

To a 5% aqueous solution of limed gelatin was added 5.6 g of sodium chloride, followed by 42.8 ml of 1N sulfuric acid, and 1.1 ml of N,N'-dimethylimidazoline-2-thiocarbonate (1% aqueous solution). To this aqueous solution, an aqueous solution containing 0.21 mol of silver nitrate and an aqueous solution containing 0.21 mol of sodium chloride were added and mixed with stirring at 61°C. Continue to maintain 61°C, add and mix 1.27 moles of silver nitrate aqueous solution, 1.27 moles of sodium chloride aqueous solution and transition metals containing 1×10 ^-8 moles of K ₂ [Ru(NO)Cl ₅ ] per mole of total silver while stirring Complex aqueous solution, then add and mix the aqueous solution containing 0.21 mole of silver nitrate and the aqueous solution containing 0.21 mole of sodium chloride while stirring, continue to add and mix the aqueous solution containing 0.21 mole of silver nitrate, the aqueous solution containing 0.21 mole of sodium chloride and the total An aqueous transition metal complex solution containing 2×10 ^-5 moles of K ₄ [Ru(CN) ₅ ] in silver content. Then, at 61° C., an aqueous solution containing 0.02 mol of silver nitrate and an aqueous solution containing 0.02 mol of sodium chloride were added and mixed while stirring. Continue to add and mix the aqueous solution containing 0.11 moles of silver nitrate, the aqueous solution containing 0.11 moles of sodium chloride and the K ₂ [Ir(H ₂ O)Cl ₅ ] transition metal complex containing 2×10 ^-8 moles per mole of total silver. Add and mix the aqueous solution containing 0.04 mole of silver nitrate, 0.04 mole of sodium chloride and 4×10 ^-8 moles of K ₂ [IrCl ₆ ] per mole of total silver while stirring, Continue to add and mix the aqueous solution containing 0.04 molar silver nitrate and the aqueous solution containing 0.04 molar sodium chloride at 61° C. while stirring. Subsequent sedimentation and water washing were carried out at 40°C, and desalination was carried out. Add 168.0 g of lime-treated gelatin to adjust the pH and pAg of the emulsion to 7.3 and 5.6, respectively. Observed by electron microscope, the particle shape is cubic, the average particle size is 0.62 μm, and the coefficient of variation is 10%.

Add 1.5× ^10-5 mol/mol Ag gold sensitizer (gold(I) tetrafluoroborate=(1,4,5-trimethyl-1,2,4-triazolium-3 -sulfate), 6× ^10-7 mol/mol Ag sulfur sensitizer (sodium thiosulfate), and 2.3× ^10-4 mol/mol Ag and 1.5× ^10-4 mol/mol Ag in Example 1 The blue sensitivity and spectral sensitization pigments (A and B) recorded in , were properly chemically sensitized and spectrally sensitized at 60°C, and then 4.4×10 ^-4 mol/mol Ag of 1-(5-methylureabenzene was added base)-5-mercaptotetrazole.

(Preparation of Emulsion G)

In the emulsion particle form, the preparation method of the emulsion F was followed except that 0.6 mol% of potassium iodide aqueous solution was added to the total silver amount in the step of adding 90 to 91% of the total silver amount.

(Preparation of Emulsion H)

The preparation method of Emulsion G was followed except that no K ₂ [IrCl ₆ ] transition metal complex was added.

The layer constitution was completely the same as in Example 4, and the emulsion of the first layer was replaced with emulsions F to H to prepare samples (201) to (203). Experiment A of Example 4 and Experiment B described below were carried out on these samples.

Experiment B: Latent Image Stability After Exposure

For each sample, the sensitometric measurement was performed by changing the time from the above-mentioned 10 ^-4 second high-illuminance exposure to the treatment A, and the sensitivity difference between the 60-minute post-treatment and the 7-second post-treatment was obtained. These results are shown in Table 5.

[table 5] sample emulsion Film concentration low light sensitivity high light sensitivity Sensitivity difference between 7-second post-processing and 60-minute post-processing 201 F (comparison) 0.07 100 100 25 202 G (this invention) 0.07 240 260 5 203 H (this invention) 0.07 235 235 10

It can be seen from Table 5 that the silver chloroiodide emulsion of the present invention has high sensitivity, is a low fog emulsion, and has excellent latent image stability after exposure.

Example 6

(modulation of emulsion I)

Based on the emulsion F preparation method described in Example 5, the same particle formation was performed except that N,N'-dimethylimidazoline-2-thiono (1% aqueous solution) was added. Observed by electron microscope, the particle shape is cubic, the average particle size is 0.38 μm, and the coefficient of variation is 8%.

Add 2.4× ^10-5 mol/mol Ag gold sensitizer (gold(I) tetrafluoroborate=(1,4,5-trimethyl-1,2,4-triazolium-3 -sulfate)), 1×10 ^-7 mol/mol Ag sulfur sensitizer (sodium thiosulfate), and 3.6×10 ^-4 mol/mol Ag, 7.0×10 ^-5 mol/mol Ag and 2.8× 10 ^-4 mol/mol Ag of the green sensitivity and spectral sensitization pigments (D, E and F) described in Example 1, carry out appropriate chemical sensitization and spectral sensitization at 60°C, and then add 4.4×10 ^-4 mol 1-(5-methylureaphenyl)-5-mercaptotetrazole per mole of Ag.

(Preparation of Emulsion J)

In the formation of emulsion particles, the preparation method of emulsion I was followed except that 0.002 mol of potassium iodide aqueous solution was added in the step of adding 90 to 91% of the total silver amount.

(modulation of emulsion K)

The preparation method of Emulsion J was followed except that no K ₂ [IrCl ₆ ] transition metal complex was added.

In the layer constitution of Example 5, the green sensitive emulsion Em-1 of the third layer was replaced with the above-mentioned emulsions I to K to prepare samples (301) to (303). These samples were subjected to the same treatment as in Example 5, and the magenta color density of each sample after the treatment was measured, and the evaluations of Experiments A and B of Examples 4 and 5 were performed. The results are shown in Table 6 together.

[Table 6] sample emulsion Film concentration low light sensitivity high light sensitivity Sensitivity difference between 7-second post-processing and 60-minute post-processing 301 I (comparison) 0.07 100 100 twenty two 302 J (this invention) 0.07 180 202 4 303 K (this invention) 0.07 179 185 8

It can be seen from Table 6 that the silver chloroiodide emulsion of the present invention has high sensitivity, is a low fog emulsion, and has excellent latent image stability after exposure.

Example 7

The layer configuration was changed as follows to prepare thinner samples, and Experiment A of Example 4 and Experiment B of Example 5 were carried out on these samples.

The layer configuration is shown as a sample (401). Samples (402) and (403) are samples obtained by changing the emulsion F of the sample (401) into emulsions G and H, respectively.

The results were the same as those of Example 4, and it was confirmed from the results that the effect of the present invention can be achieved even with ultra-fast processing of the thinned sample.

Production of sample 401

Sample 401 of the silver halide photosensitive material is the sample G-1 of Example 2, only the types of silver halide emulsions in the first layer, third layer and fifth layer were changed as follows.

The first layer was changed to Emulsion F, the third layer was changed to Em-1, and the fifth layer was changed to Em-2. Em-1 and Em-2 are the same emulsions as the silver halide emulsion described in Example 4.

Each sample made was subjected to the same exposure as experiment A of embodiment 4 and experiment B of embodiment 5, and the color development process was according to the development process B [processing B] of embodiment 2 (the making of flowing liquid is different Only using the photosensitive material of Example 7) for ultra-fast processing.

Example 8

Using samples (401) to (403), imaging was performed by laser scanning exposure.

As the laser light source, YAG solid-state laser (oscillation wavelength 946nm) with semiconductor laser GaAlAs (oscillation wavelength 808.5nm) as the excitation light source is converted to 473nm by SHG crystal of LiNbO ₃ with inversion domain optical structure, and The SHG crystal of LiNbO ₃ with an inverted domain optical structure converts the wavelength of the YVO ₄ solid-state laser (oscillation wavelength 1064nm) that uses the semiconductor laser GaAlAs (oscillation wavelength 808.7nm) as the excitation light source to 532nm and AlGaInP (oscillation wavelength approx. 680nm: Panasonic Corporation Model No. LN9R20). The light beams of various lasers of three colors are moved vertically by the polygonal prism relative to the scanning direction, and can be scanned and exposed sequentially on the sample. Fluctuations in the light intensity of the semiconductor laser due to the influence of temperature are suppressed by the Peltier element, and a constant temperature can be maintained. The actual effective beam diameter is 80 μm, the scanning pitch is 42.3 μm (600 dpi), and the average exposure time per pixel is 1.7×10 ^-7 seconds.

After the exposure, the chromogenic development treatment B was used to obtain the same result as the high-illuminance exposure in Example 5. The samples (402) and (403) of the present invention showed very high sensitivity, which shows that they are suitable for use in laser scanning. Exposure imaging.

Effect of the invention

According to the present invention, even with digital exposure such as laser scanning exposure, a high-sensitivity, hard-graded silver halide emulsion and a silver halide photographic photosensitive material using the same can be obtained. Furthermore, according to the present invention, it is possible to obtain a silver halide emulsion excellent in latent image preservation and exposure temperature-humidity dependence and a silver halide photographic photosensitive material using the same. Furthermore, the silver halide photographic emulsion of the present invention can obtain high sensitivity, low fog, excellent reciprocity law characteristics at high illuminance, and the effect that sensitivity and gradation changes little with time until post-exposure processing.

Claims (11)

1, a kind of silver emulsion, be to form at 90 moles of silver halide particles more than the % by the silver chloride containing ratio, it is characterized in that the maximum containing ratio of silver iodide of the corner portions located of this silver halide particle is higher than the silver iodide containing ratio of this particle first type surface part, and above-mentioned silver halide particle contains 1 at least with H ₂O, OH, O, OCN, thiazole or displacement thiazole are made dentate, all the other dentates are formed, are 6 ligand complex bodies of central metal with Ir by Cl, Br or I.

2, according to the silver emulsion of claim 1 record, it is characterized in that above-mentioned silver halide particle is cube or 14 body particles.

3, according to the silver emulsion of claim 1 record, the electronics release time that it is characterized in that above-mentioned silver halide particle is from 10 ^-5Second was by 10 seconds.

4, according to the silver emulsion of claim 1 record, the sub-image oxidizing potential that it is characterized in that above-mentioned silver emulsion is than 70mV height.

5, according to the silver emulsion of claim 1 record, it is characterized in that above-mentioned silver emulsion carries out golden sensitizing.

6,, it is characterized in that above-mentioned silver emulsion is the complexing stability constant log β with colloidal aurosulfo or gold according to the silver emulsion of claim 5 record ₂Be that 21～35 golden sensitizer carries out golden sensitizing.

7, according to the silver emulsion of claim 1 record, it is characterized in that the first type surface of above-mentioned silver halide particle is made of (100) face.

8, according to the silver emulsion of claim 1 record, it is characterized in that carrying out beam split sensitizing with three methine anthocyanidins.

9, according to the silver emulsion of claim 1 record, the containing ratio that it is characterized in that iodide ion is 0.06 mole more than the % with respect to total silver amount of total emulsion particles.

10,, it is characterized in that the iodide ion containing ratio is 0.1 mole more than the % with respect to total silver amount of total emulsion particles according to the silver emulsion of claim 1 record.

11, a kind of silver halide photographic sensitive material is characterized in that containing the silver emulsion that claim 1 is put down in writing.