JP2001013612A - Silver halide photographic sensitive material and processing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high covering power and an improved silver tone while retaining high sensitivity and to provide a processing method for the sensitive material. SOLUTION: This silver halide photographic sensitive material has photographic constituent layers including at least one silver halide emulsion layer on the substrate. In the sensitive material, grains which occupy >=50% of the projected area of all the silver halide grains are flat platy grains having an aspect ratio of >=3, grains which occupy >=80% of the projected area of all the silver halide grains are flat platy grains having >=30 dislocation lines per one grain in the fringe part and the coefficient of variation in the inter-grain distribution of the number of dislocation lines in one grain and the coefficient of variation in the inter-grain distribution of the silver iodide content in one grain are <=30% each. The silver halide grains have been prepared in the presence of water-dispersible cationic starch.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having a high covering power and an improved silver tone while maintaining high sensitivity. About the method.

[0002]

2. Description of the Related Art As a method for increasing the sensitivity of a silver halide emulsion, US Pat. No. 4,956,269 discloses a technique for introducing dislocation lines into tabular silver halide grains.
Japanese Patent Application Laid-Open No. Hei 3-189624 discloses that tabular silver halide grains having an aspect ratio of 2 or more and having 10 or more dislocation lines in a fringe portion are contained, and the size of the tabular silver halide grains is reduced. Silver halide emulsions having a monodisperse distribution are disclosed.

Conventionally, it has been known that when pressure is applied to silver halide grains, fogging or desensitization occurs. However, with respect to silver halide grains having dislocation lines introduced,
Although the sensitivity is improved, there is a problem that desensitization becomes more remarkable when pressure is applied.

[0004] Further, higher sensitivity than before,
Techniques for improving the sensitivity / size ratio per silver halide grain have been studied in order to achieve high image quality. As one of the techniques, a technique using tabular silver halide grains is disclosed in JP-A-58-111935. No. 58-111936,
Nos. 58-111937, 58-113927, and 59-99433. When these tabular silver halide grains are compared with so-called normal-crystal silver halide grains such as hexahedral, octahedral, or dodecahedral grains, the surface area per unit volume of the silver halide grains is increased, so that the silver halide grains have a larger surface area. Sensitizing dye can be adsorbed, and high sensitivity including improvement of color sensitization efficiency can be expected.

On the other hand, among the techniques for improving silver halide emulsions for the purpose of improving the sensitivity and image quality of silver halide photographic materials, silver halide emulsions are one of the most basic and important techniques. There is monodispersion technology. Since the optimal conditions for chemical sensitization and color sensitization are different between large and small silver halide grains, the chemical sensitization and color sensitization are optimal for a mixed silver halide emulsion with a wide grain size distribution. It is difficult to perform sensitization, and as a result, fog is increased or sufficient chemical sensitization cannot be performed in many cases. However, in the case of a monodisperse (narrow size distribution) silver halide emulsion, it is easy to perform optimal chemical sensitization and color sensitization, and it is highly sensitive, has low fog, and has excellent graininess. It becomes possible to prepare a silver emulsion.

As a technique for monodispersing tabular silver halide grains, Japanese Patent Application Laid-Open No. 1-213637 discloses a monodisperse silver halide grain having two parallel twin planes to improve sensitivity and graininess. The technology is described. JP-A-5-173268 and JP-A-6-202258 disclose methods for producing tabular silver halide emulsions having a small particle size distribution.

In recent years, speeding up and low replenishment in development processing have been rapidly spread. Although research on photosensitive materials suitable for such development processing has been promoted, there are problems such as deterioration of residual color, reduction of sensitivity, and reduction of covering power (hereinafter abbreviated as CP). It was an issue. Further, in order to increase the sensitivity and CP, attempts have been made to lower the hardening of the photosensitive material and to reduce the amount of binder such as gelatin, but the effect obtained was insufficient.

Further, for the purpose of environmental protection, it is required to reduce development processing waste liquid.

[0009] Hydroquinones, which are conventionally used as developing agents, have not been sufficiently safe, and ascorbic acids and derivatives thereof (eg, reductones) have recently been studied as alternatives.

On the other hand, for rapid processing of a silver halide photographic light-sensitive material, it is essential to shorten processing time such as development, fixing, washing and drying. However, if the conventional photosensitive material is simply shortened by the developing time, for example, the image density and the sensitivity are greatly reduced and the gradation is deteriorated. Further, if the fixing time is shortened, the fixing becomes defective, which causes deterioration of the image quality.

Therefore, basically, it is necessary to increase the developing speed, fixing speed, drying speed, etc. of the silver halide photographic light-sensitive material. 2. Description of the Related Art In order to increase the drying speed of a photosensitive material, a method of containing a hardener in a developing solution and a fixing solution to reduce moisture in the photosensitive material brought into a drying step has been conventionally performed.

A dialdehyde compound such as glutaraldehyde is generally used as a developing hardener, and an aluminum ion or the like is generally used as a fixing hardener. With respect to these hardeners, problems such as precipitation of aluminum have occurred during storage of the treating agent, and it is desired to reduce or eliminate them.

Further, there is a demand for reducing boric acid, which is used as a buffer agent in a developing solution and as a preservative in a fixing solution, from the same problem.

[0014]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having a high CP and an improved silver tone while maintaining high sensitivity, and a processing method thereof.

[0015]

The object of the present invention has been attained by the following items 1 to 6.

1. In a silver halide photographic light-sensitive material having a photographic component layer including at least one silver halide emulsion layer on a support, tabular grains having an aspect ratio of 3 or more in an area of 50% or more of the projected area of all silver halide grains. And
In addition, grains having 80% or more of the projected area of all silver halide grains are tabular grains having at least 30 dislocation lines per grain in a fringe portion, and furthermore, intergranular distribution of the number of dislocation lines in one grain. And the coefficient of variation of the intergranular distribution of the silver iodide content in one grain contains silver halide grains of 30% or less, and the silver halide grains contain water-dispersible cationic starch. A silver halide photographic material prepared in the presence of a silver halide photographic material.

2. In a silver halide photographic light-sensitive material having a photographic component layer including at least one silver halide emulsion layer on a support, tabular grains having an aspect ratio of 3 or more in an area of 50% or more of the projected area of all silver halide grains. And
In addition, grains having 80% or more of the projected area of all silver halide grains are tabular grains having at least 30 dislocation lines per grain in a fringe portion, and furthermore, intergranular distribution of the number of dislocation lines in one grain. And the coefficient of variation of the intergranular distribution of the silver iodide content in one grain contains silver halide grains of 30% or less, and the silver halide emulsion layer contains a gelatin crosslinkable group. A silver halide photographic material comprising a polysaccharide compound having the same.

3. 3. The silver halide photographic light-sensitive material as described in 1 or 2 above, wherein the growth of the silver halide grains is performed while separating an aqueous solution containing a salt from a reaction solution using an ultrafiltration method.

4. 4. A processing method, wherein the silver halide photographic light-sensitive material according to any one of the above items 1 to 3 is processed with a developing solution and a fixing solution containing substantially no boric acid or a salt thereof.

[5] 4. A processing method, wherein the silver halide photographic light-sensitive material according to any one of the above items 1 to 3 is processed with a developer and a fixer which do not substantially contain a hardener.

6. 6. The processing method according to 4 or 5, wherein the developer or the fixing solution is prepared using a solid processing agent.

Hereinafter, the present invention will be described in more detail.

The silver halide grains used in the present invention will be described.

The aspect ratio of the silver halide grains used in the present invention means the ratio of the area-converted grain size to the grain thickness (aspect ratio = diameter / thickness). Here, the area-converted particle size means the diameter of a circle having an area equal to the area when the particle is projected perpendicular to the main plane. The volume-converted particle size means the diameter of a sphere having the same volume as each silver halide particle. Grain thickness is the thickness of a grain in a direction perpendicular to the major plane and generally corresponds to the distance between the two major planes.

The projected area and thickness of the particles for calculating the area-converted particle diameter and the volume-converted particle diameter can be obtained by the following methods.
A sample was prepared by coating a latex ball having a known particle size as an internal standard on a support and silver halide particles such that the main plane was oriented parallel to the substrate, and shadowing was performed by carbon deposition from a certain angle. Thereafter, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area and thickness of each particle are determined using an image processing device or the like. In this case, the projected area of the particle can be calculated from the projected area of the internal standard, and the thickness of the particle can be calculated from the length of the internal standard and the shadow of the particle. In the present invention, the average value of the aspect ratio, the area-converted particle size, the grain thickness, and the volume-converted particle size is arbitrarily set to 500 by using the above-mentioned replica method for the silver halide grains contained in the silver halide emulsion.
A value obtained by measuring more than one piece and calculating as an arithmetic average thereof.

In the present invention, the coefficient of variation of the silver halide grain in terms of volume is a value defined by the following equation using the value obtained from the above measurement. The coefficient of variation of the silver halide grains related to the present invention in terms of volume is preferably 0.2 or less, more preferably 0.15 or less, and particularly preferably 0.1 or less.

Coefficient of variation of volume-converted grain size = (standard deviation of volume-converted grain size) / (average value of volume-converted grain size) Similarly, the variation coefficient of the area-converted grain size of silver halide grains is determined from the above measurement. be able to. Here, the variation coefficient of the area-converted particle diameter is a value defined by the following equation. The variation coefficient of the area-converted grain size of the silver halide grains related to the present invention is preferably 0.2 or less, more preferably 0.15 or less, and particularly preferably 0.1 or less.

Coefficient of variation of area-converted grain size = (standard deviation of area-converted grain size) / (average value of area-converted grain size) In the present invention, the total projected area of the silver halide grains contained in the silver halide emulsion. 50% or more of the aspect ratio is 3
Although the tabular grains are as described above, it is preferable that 50% or more of the total projected area be tabular silver halide grains having an aspect ratio of 5 or more. It is preferable that 80% or more of the total projected area of the silver halide grains is tabular silver halide grains. The aspect ratio of the tabular grains used in the present invention is from 3 to 20, and preferably from 4 to 15.

Next, the fringe portions and dislocation lines of the silver halide grains will be described.

In the present invention, tabular grains are used in which at least 80% of the projected area of all silver halide grains has at least 30 dislocation lines per grain in the fringe portion.

The dislocation lines of tabular silver halide grains are described in J. Am. F. Hamilton, Photo. Sci. E
ng. , 11, 57, (1967); Shioz
awa, J. et al. Soc. Photo. Sci. Japan,
35, 213, (1972).

In the present invention, the dislocation lines are introduced at the fringe portions of the silver halide grains. Can also. The number of dislocation lines introduced into the fringe portion is 30 or more per particle, but preferably 30 or more and 50 or less.

In the present invention, the fringe portion refers to an outer peripheral portion of the tabular silver halide grains. More specifically, in the distribution of silver iodide from the sides to the center of the tabular silver halide grains, the distribution state is determined from the side. , When the silver iodide content increased or decreased for the first time, or from the side,
The portion outside the point corresponding to either the point exceeding or falling below the average silver iodide content of the whole grain for the first time.

The introduction position and the number of dislocation lines can be observed by a direct method using a transmission electron microscope at a low temperature.
That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for an electron microscope so as to prevent damage by electron beams (such as printout). Observation is performed by a transmission method while the sample is cooled. At this time, the thicker the particles, the more difficult it is for an electron beam to pass through, so that a clearer observation can be obtained by using a high-pressure electron microscope. From the grain photograph obtained by such a method, the position and number of dislocation lines in each grain can be determined.

When the number of dislocation lines exceeds 50, it is difficult to confirm the dislocation lines. The upper limit of the number of dislocation lines cannot be specified.
The effects of the present invention are exhibited.

As a method of introducing dislocation lines into silver halide grains, for example, a method of adding an aqueous solution containing iodide ions such as potassium iodide and a water-soluble silver salt solution by double jetting, or a method of introducing silver iodide fine grains. Adding method, adding only solution containing iodide ion,
A known method such as a method using an iodide ion releasing agent as described in No. 1 can be used to form a dislocation originating a dislocation line at a desired position. Among these methods, a method of adding an aqueous solution containing iodide ions and a water-soluble silver salt solution by double jet, a method of adding silver iodide fine particles, and a method of using an iodide ion releasing agent are preferable.

Further, by using a manufacturing facility capable of controlling the average distance between silver halide grains, the efficiency of dislocation line introduction into a silver halide emulsion can be drastically increased. For example, it is preferable to control the average intergranular distance when dislocation lines are introduced during the growth process of silver halide grains to be 0.60 times or more and 1.00 times or less the average intergranular distance at the start of growth. More preferably, it is controlled to be at least twice and at most 0.80 times. Specifically, it is preferable to control the value of the average intergranular distance at the time of dislocation line introduction to 0.40 μm or less, more preferably to 0.30 μm or less, and particularly to 0.20 μm or less. preferable.

In the present invention, the coefficient of variation of the intergranular distribution of the number of dislocation lines in one grain is 30% or less. That is, it means a direction in which the number of dislocation lines present in each particle is constant, in other words, a direction in which the number of dislocation lines for each particle is uniform.

In the present invention, the coefficient of variation of the intergranular distribution of the number of dislocation lines in one grain is preferably 25% or less, and 20% or less.
It is particularly preferred that:

In the present invention, the coefficient of variation of the intergranular distribution of the silver iodide content in one grain is 30% or less. That is, it means the direction in which the silver iodide content present in each grain is constant, in other words, the direction in which the silver iodide content of each grain is uniform.

In the present invention, the coefficient of variation of the intergranular distribution of the silver iodide content in one grain is preferably 25% or less.
% Is particularly preferable.

A technique for introducing dislocation lines into the fringe portions of silver halide grains is disclosed in JP-A-3-189624.
No. 8-334850. The point of the present invention is that, for grains corresponding to 80% or more of the projected area of silver halide grains, dislocation lines are densely formed in the fringe portion, that is, 30 or more dislocation lines per grain, and Are tabular silver halide grains introduced so that the number of dislocation lines is uniform.

In the present invention, the term "inside of the grain" refers to the inside of one atomic layer formed by silver ions or halide ions present on the surface of the silver halide grain, but preferably refers to the inside of the grain. Say the inside of 50 ° or more.

The technique for introducing dislocation lines inside silver halide grains is described in JP-A-4-140737 and JP-A-4-140737.
No. 178,643. The point of the present invention is that, for grains corresponding to 80% or more of the projected area of silver halide grains, dislocation lines are densely formed inside the grains, that is, 30 or more dislocation lines per grain, and Are tabular silver halide grains introduced so that the number of dislocation lines is uniform.

In the present invention, the main plane portion of the particle refers to the outer surface pair having the largest area among the outer surface pairs formed of opposing parallel surfaces. The main plane is crystallographically $ 11
Preferably, it is a 1 ° plane. Introducing dislocation lines into the main plane portion of a tabular grain, which is characterized in that the area of the main plane is large with respect to the grain volume, is an effective technique that makes maximum use of the advantages of the tabular grain.

Techniques for introducing dislocation lines into the main plane of silver halide grains are disclosed in JP-A-4-251241 and JP-A-8-334852. The point of the present invention is that, for a grain corresponding to 80% or more of the projected area of a silver halide grain, dislocation lines are densely provided on a main plane portion of the grain, that is, 30 or more dislocation lines are formed per grain. Moreover, it is a tabular silver halide grain introduced so that the number of dislocation lines per grain becomes uniform.

Techniques for introducing dislocation lines near the apexes of silver halide grains are described in JP-A-3-175440, JP-A-4-166926, JP-A-4-149541 and JP-A-4-1954.
No. 56448, No. 4-195035 and the like. The point of the present invention is that, for grains corresponding to 80% or more of the projected area of silver halide grains, dislocation lines are densely provided near the vertices of the grains, that is, 30 or more dislocation lines per grain. Tabular silver halide grains introduced so that the number of dislocation lines per grain is uniform.

The vicinity of the apex of the tabular silver halide grain is as follows.
In the case of having a triangular, quadrangular, or hexagonal outer surface, a straight line connecting the center of a tabular grain and each vertex has two points sandwiching the vertex of the tabular grain from a point at x% from the center. A perpendicular line is placed on each side, and a region surrounded by the two perpendicular lines and the two sides is a three-dimensional region including the thickness direction of tabular grains. Here, the value of x is 50
It is not less than 100 and preferably not less than 75 and less than 100.

When the tabular grains have a triangular outer surface, there are three vertices. When the tabular grains have a quadrangular outer surface, there are four vertices. If the particle has a hexagonal outer surface, there are six vertices, but it is preferable that dislocation lines are concentrated near all vertices, but at least one near each vertex The effect of the present invention can be obtained even when dislocation lines are concentrated in

As a general method of introducing dislocation lines in a concentrated manner near the apex, a silver halide having a halogen composition different from that of the tabular grains of the substrate is once bonded to the apex of the tabular grains of the substrate, and then the tabular grains are again formed. Is obtained by growing. For example, when the tabular grains of the substrate are silver iodobromide, silver iodobromide or silver iodide having a higher iodine degree, or silver chloride or silver chlorobromide may be bonded. Alternatively, JP-A-6-1178
There is a method using an iodide ion releasing agent as described in No. 1. Particularly, sodium p-iodoacetamidobenzenesulfonate, 2-iodoethanol, 2-iodoacetamide and the like are preferable.

Tabular silver halide grains are crystallographically classified as twins. Twins are crystals having one or more twin planes in one grain. Classification of twin morphology in silver halide grains is based on a report by Klein and Moiser in "Photographhishhe Korrespon."
denz, Vol. 99, p. 99, and Vol. 100, p. 57. The tabular silver halide grains related to the present invention have one or two or more twin planes parallel to each other in the grains, and these twin planes are planes forming the surface of the tabular grains. Exists almost parallel to a plane having the largest area (also referred to as a main plane). The most preferable form in the present invention is a case having two parallel twin planes.

The tabular silver halide grains used in the present invention have one or two or more twin planes parallel to each other in the grains, but 50% of the tabular silver halide grains related to the present invention. The above are preferably tabular grains having two twin planes parallel to each other in the grains, and more preferably 80% or more. These twin planes can be observed with a transmission electron microscope. The specific method is as follows. First, the main plane of the tabular grains contained is
A silver halide emulsion is coated on the substrate so as to be oriented substantially parallel to the substrate to prepare a sample. This is continuously cut perpendicular to the substrate using a diamond cutter to obtain a continuous thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the existence and position of the twin plane can be confirmed.

The composition of the silver halide grains in the present invention is preferably silver iodobromide, silver bromide, silver chlorobromide, or silver chloroiodobromide. In particular, the silver halide emulsion is preferably silver iodobromide containing silver iodide having an average silver iodide content of 10 mol% or less, and more preferably an average silver iodide content of 0.1 mol% or less.
It is preferably at least 10 mol% and not more than 10 mol%.
It is particularly preferably from 2 mol% to 6 mol%. The composition of the silver halide grains can be determined by a composition analysis method such as an EPMA method and an X-ray diffraction method.

The average silver iodide content of the surface phase of the silver halide grains related to the present invention is preferably at least 0.2 mol%, more preferably at least 0.5 mol% and at most 20 mol%. More preferably, it is 1 mol% or more and 15 mol% or less. Here, the average silver iodide content of the surface phase of the silver halide grains is a value obtained by using the XPS method or the ISS method. For example, the surface silver iodide content by the XPS method can be obtained as follows. Sample is 1 × 10 ^-4 to
After cooling to -155 ° C. or lower in an ultrahigh vacuum of rr or lower, MgKa is irradiated as a probe X-ray at an X-ray source current of 40 mA, and Ag3d5 / 2, Br3d, and I3d3 / 2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the composition such as the silver iodide content of the silver halide surface phase is determined from these intensity ratios.

Further, in the silver halide emulsion used in the present invention, the silver iodide content between silver halide grains is preferably more uniform. That is, the coefficient of variation of the silver iodide content in the silver halide emulsion is preferably 30% or less, and more preferably 20% or less. Here, the coefficient of variation is defined as a value obtained by dividing the standard deviation of the silver iodide content by the average value of the silver iodide content.
And a value obtained by arbitrarily measuring 500 or more silver halide grains contained in the silver halide emulsion.

The photographic silver halide grains are microcrystals composed of silver chloride, silver bromide, silver iodide, or a solid solution thereof. Two or more phases having different silver halide compositions are contained in the crystal. It is possible to form. As a grain having such a structure, a grain composed of an inner core phase and an outer surface phase having mutually different silver halide compositions is known, and is generally called a core / shell type grain. The silver halide grains related to the present invention preferably have a core / shell type grain structure in which the outer surface phase has a higher silver iodide content than the inner core phase.

As a preparation form of the silver halide emulsion used in the present invention, a method known in the art can be appropriately applied. For example, a so-called controlled double jet method or controlled triple jet method for controlling pAg of a reaction solution at the time of forming silver halide grains can be used. In addition, a silver halide solvent can be used if necessary. Examples of useful silver halide solvents include ammonia, thioethers, and thioureas. Regarding thioethers, U.S. Pat.
271, 151, 3,790,387 and 3,574,626. The method for preparing the grains is not particularly limited, and an ammonia method, a neutral method using no ammonia, an acidic method, and the like can be used.From the viewpoint of suppressing fog during silver halide grain formation, it is preferable. pH (the logarithm of the reciprocal of the hydrogen ion concentration) is 5.5 or less, more preferably 4.5.
It is preferable to form particles in the following environment.

The silver halide emulsion used in the present invention is:
A dispersion medium is contained together with the silver halide grains. The dispersion medium is a compound having a protective colloid property for silver halide grains, and is preferably present from the nucleation step to the end of grain growth. Dispersion media that can be preferably used in the present invention include gelatin and protective colloid polymers. As gelatin, alkali-treated gelatin or oxidized gelatin having a molecular weight of about 100,000 or low-molecular-weight gelatin having a molecular weight of about 5,000 to 30,000 can be preferably used. In particular, at the time of nucleation, oxidized gelatin, low molecular weight gelatin, and oxidized low molecular weight gelatin can be suitably used.

In order to more precisely control the silver halide composition between silver halide grains and inside the grains, at least a part of the formation of the silver iodide-containing phase of the silver halide grains is controlled by 1
It can be formed by supplying only silver halide fine particles of more than one kind.

For the same reason, at least part of the formation of the silver iodide-containing phase of the silver halide grains can be carried out in the presence of silver halide grains having a lower solubility than the silver halide grains. It is desirable to use silver iodide fine grain emulsions as silver halide grains having low solubility.

The silver halide grains used in the present invention preferably have a particle size in terms of volume of 1.2 μm or less, preferably 0.1 to 0.1 μm.
8 μm is more preferred. If the thickness is 0.1 μm or less, it is difficult to obtain practical sensitivity, while if it is 1.2 μm or more, the grain size of the photographic image is significantly deteriorated due to the large particle size.

In the silver halide emulsion used in the present invention, Research Disclosure No. 30
8119 (hereinafter abbreviated as RD308119) can be used.

The following shows the places to be described.

[0064]

[Table 1]

The silver halide emulsion used in the present invention can be subjected to physical ripening, other chemical ripening and spectral sensitization according to a known method.

The additives used in such a step include Research Disclosure No. 17643,
No. 18716 and no. 308119 (respectively,
RD17643, RD18716, RD30811
9) can be used. The places to be described are shown below.

[0067]

[Table 2]

The silver halide emulsion used in the present invention is
In the growth process of the silver halide grains contained in the silver halide emulsion, the average intergranular distance represented by the following formula, from the start of the growth of the silver halide grains to the end of the growth,
It is preferable to add iodide ions at a time near the minimum value.

In general, the step of preparing a silver halide emulsion is roughly divided into a nucleation step (consisting of a nucleation step and a ripening step) and a subsequent step of growing the nucleus. It is also possible to separately grow a previously prepared nuclear emulsion (or seed emulsion). The growth process may include several stages, such as a first growth process and a second growth process.

The growth process of silver halide grains means all the growth steps from the nucleus (or seed) formation to the end of grain growth, and the start of growth means the start of the growth step.

The average distance between grains in the present invention is the average value of the spatial distance between the centers of gravity of silver halide grains due to growth in a reaction product (silver halide emulsion) solution at the time of preparing a silver halide emulsion. In other words, in other words, in a reactant (silver halide emulsion) solution, one side of a cube having a volume equal to the space of one grain, assuming that all the grown grains have the same space. I say the head.
Specifically, it is a value defined by the following equation.

Average intergranular distance = (volume of reaction solution / number of grown particles in reaction solution) In the growth process of ^1/3 silver halide grains, addition of an aqueous silver salt solution or an aqueous halide salt solution mainly used for grain growth is carried out. By
The amount of the reactant solution in the reaction vessel increases as the particles grow,
At the same time, the average interparticle distance increases. The average intergranular distance during the growth process of silver halide grains is directly reflected in the volume of a reactant (silver halide emulsion) solution during the growth of silver halide grains.

In the present invention, the minimum value of the average distance between silver halide grains means the average distance between the silver halide grains (μm) on the vertical axis and the time when the growth of the silver halide grains starts on the horizontal axis. It takes the time from to the end of growth, and means at least one of the minimum value or the minimum value in the obtained graph. That is, the point at which the average intergranular distance of the silver halide grains decreases and starts increasing, or the point at which the average distance between the grains decreases and ends, is the final point.

The minimum value may be plural, and it is preferable to add iodide ions at a time near at least one of them including the minimum value.

In the present invention, the time in the vicinity is preferably within a range of ± 30 minutes, more preferably within a range of ± 15 minutes with respect to the time when the minimum value or the time when the minimum value is shown. And particularly preferably within a range of ± 5 minutes. It is important to add iodide ions at a time within this range.

When dislocation lines are formed inside silver halide grains, the minimum value is preferably set at a relatively early time from the start of the growth of the silver halide grains to the end of the growth. When dislocation lines are formed around the silver halide grains, the minimum value is preferably set at a relatively late time from the start of the growth of the silver halide grains to the end of the growth.

As one embodiment of a silver halide emulsion producing apparatus applicable to the production of silver halide grains according to the present invention,
An example of an apparatus for producing a silver halide emulsion in which the average intergranular distance in the grain growth process can be arbitrarily controlled and maintained by an ultrafiltration apparatus will be described with reference to FIG.

The reaction vessel 1 initially contains the dispersion medium 3. The apparatus comprises a reaction vessel 1 and a silver addition line 4 for adding at least one aqueous solution of a silver salt, preferably an aqueous solution of silver nitrate, and at least one aqueous solution of a halide salt, preferably an alkali metal such as bromine, iodine or chlorine. It has a halide addition line 5 for adding an aqueous salt solution, an aqueous ammonium salt solution, or a mixture thereof. Further, it has a stirring mechanism 2 for stirring the dispersion medium and the reactant solution (a mixture of the dispersion medium and the silver halide grains) in the process of preparing the silver halide emulsion. The stirring mechanism can be in any conventional manner. Silver salt aqueous solution is silver addition line 4
From the reaction vessel at a flow rate controlled by the silver addition valve 20. The halide aqueous solution is added to the reaction vessel from the halide addition line 5 at a flow rate controlled by the halide addition valve 21. The addition of the solution through the silver addition line 4 and the halide addition line 5 may be liquid level addition, but is more preferably performed in the liquid near the stirring mechanism 2. The stirring mechanism 2 mixes the aqueous silver salt solution and the aqueous halide salt solution with a dispersion medium, and enables the soluble silver salt to react with the soluble halide salt to produce silver halide.

During the first stage of silver halide formation, ie, in the nucleation step, a dispersion (reactant solution) containing the base silver halide nucleus particles is formed. Subsequently, the nucleation step is completed through an aging step as required. Subsequently, when the addition of the aqueous silver salt solution and the aqueous halide solution is continued, the second stage of silver halide formation, that is, the growth process stage, is performed, and additional silver halide produced as a reaction product in the process is first formed. Deposited on the coated silver halide nucleus grains to increase the size of these grains. In the present invention, during the particle formation process by adding the aqueous silver salt solution and the aqueous halogen salt solution to the reaction vessel, a part of the reactant solution in the reaction vessel is sent to the ultrafiltration unit 12 through the liquid take-out line 8 by the circulation pump 13. It is sent and returned to the reaction vessel through the liquid return line 9. At that time, the pressure applied to the ultrafiltration unit 12 is adjusted by a pressure adjusting valve 18 provided in the middle of the liquid return line 9 to partially remove the water-soluble salt solution contained in the reaction solution. It is separated by a filtration unit and discharged out of the system through a permeated liquid discharge line 10. With such a method, it is possible to form grains while arbitrarily controlling the distance between grains even during the grain growth process by adding the aqueous silver salt solution and the aqueous halide salt solution to the reaction vessel.

When this method is applied in the present invention, it is preferable to arbitrarily control the permeate amount (ultrafiltration flux) of the water-soluble salt solution separated by the ultrafiltration membrane. For example, in that case, the permeated liquid discharge line 10
The ultrafiltration flux can be arbitrarily controlled using the flow control valve 19 provided in the middle of the process. At that time, in order to minimize the pressure fluctuation of the ultrafiltration unit 12, the valve 25 provided in the middle of the permeate return line 11 may be opened to use the permeate return line 11.

Alternatively, it is not necessary to use the permeated liquid return line 11 by closing the valve 25, and it can be arbitrarily selected according to the operating conditions. For detecting the ultrafiltration flux, the flow meter 14 provided in the middle of the permeated liquid discharge line 10 may be used.
Alternatively, the change may be detected by weight change using the balance 28.

In the present invention, the concentration by the ultrafiltration method in the particle growth process may be performed continuously throughout the particle formation process or may be performed intermittently. However, when applying the ultrafiltration method in the particle growth process, after starting the circulation of the reactant solution to the ultrafiltration step, the circulation of the reactant solution may be continued at least until the end of the particle formation. preferable. Therefore, it is preferable that the circulation of the reactant solution to the ultrafiltration unit be continued even when the concentration is interrupted. This is to avoid uneven distribution between particles in the reaction vessel and particles in the ultrafiltration step. Further, it is preferable that the circulation flow rate through the ultrafiltration step is sufficiently high. Specifically, the residence time of the silver halide reactant solution in the ultrafiltration unit including the liquid take-out line and the liquid return line is preferably within 30 seconds, and is preferably within 15 seconds.
Within 2 seconds is more preferable, and further within 10 seconds is particularly preferable.

The volume of the ultrafiltration step including the liquid take-out line 8, the liquid return line 9, the ultrafiltration unit 12, the circulation pump 13, etc. is preferably 30% or less of the volume of the reaction vessel, and 20% or less. It is more preferably at most 10%, particularly preferably at most 10%.

Thus, by applying the ultrafiltration step, the volume of the total silver halide reactant solution can be arbitrarily reduced during grain formation. Further, by adding water from the addition line 7, the volume of the silver halide reactant solution can be arbitrarily maintained.

In the present invention, there are no particular restrictions on the ultrafiltration module and the circulating pump which can be used in carrying out the ultrafiltration, but the ultrafiltration module and the circulating pump may act on the silver halide emulsion to adversely affect photographic performance and the like. It is preferable to avoid any material and structure. In addition, the molecular weight of the ultrafiltration membrane used in the ultrafiltration module can be arbitrarily selected. For example, when it is desired to remove a dispersion medium such as gelatin contained in a silver halide emulsion or a compound used during the preparation of the emulsion during the grain growth process, an ultrafiltration membrane having a separated molecular weight not less than the molecular weight of the object to be removed is selected. Can also
If removal is not desired, an ultrafiltration membrane having a separation molecular weight less than or equal to the molecular weight of the removal target can be selected.

The silver halide photographic material of the present invention described in the above item 1 is characterized in that silver halide grains in a silver halide emulsion layer are produced in the presence of a water-dispersible cationic starch.

The term "starch" as used herein includes both natural starch and modified derivatives such as dextrinized, hydrolyzed, oxidized, alkylated, hydroxyalkylated, acetylated or fractionated starch.

Examples of the starch include those derived from corn starch, wheat starch, potato starch, tapioca starch, sago starch, rice starch, waxy corn starch or high amylose corn starch.

Starch is two structurally distinct polysaccharides comprising α-amylose and amylopectin, both of which contain α-D-glucopyranose units. α
-In amylose, the α-D-glucopyranose units form a 1,4-long chain polymer. The repeating unit takes the following form.

[0090]

Embedded image

In amylopectin, the repeating unit 1, 1
In addition to 4-linked, branched chain at position 6 (the -CH ₂ OH
Group) is also apparent, resulting in a branched polymer.

[0092] The repeating units of starch and cellulose are diastereoisomers that confer different overall geometries to the molecule. The α-anomer found in starch and represented by the above formula can crystallize and have some degree of hydrogen bonding between repeating units in adjacent molecules (not to the same degree as the β anomeric repeating units of cellulose and cellulose derivatives). A polymer is obtained. The polymer molecules formed by the β-anomer show strong hydrogen bonding between neighboring molecules, resulting in much higher crystallinity than a cluster of polymer molecules.

Starches and starch derivatives that lack the alignment of substituents favoring the strong intermolecular bonds found in cellulose repeating units disperse in water much more readily.

The water-dispersible starch used in the present invention is cationic, that is, contains an overall net positive charge when dispersed in water. Starch is typically made cationic by attaching a cationic substituent to the α-D-glucopyranose unit, usually by esterification or etherification at one or more free hydroxyl sites.

The reactive cation-donating reagent is typically a primary, secondary or tertiary amino group (which can subsequently be protonated to the cationic form under the intended use conditions) or a quaternary ammonium, sulfonium or Contains phosphonium groups.

The cationic starch must be water-dispersible. Many starches have a short duration (eg, 5-30
Disperse in water when heated to below boiling temperature. High shear mixing also facilitates starch dispersion.

The presence of a cationic substituent increases the polarity of the starch molecule and facilitates dispersion. The starch molecules preferably disperse at least at the colloid level and ideally disperse, ie, dissolve, at the molecular level.

The water-dispersible cationic starch used in the present invention is described, for example, in JP-A-9-166838.

It is preferable to use an oxidized product before or after the addition of the cation substituent, and this oxidation is achieved by treating starch with a strong oxidizing agent.

Both hyposulphite (ClO ⁻ ) or periodate salt (IO ₄ ⁻ ) are both widely used in the preparation of applied starch derivatives and have been investigated and are preferred. While any convenient counterion can be used, preferred counterions are those that are well compatible with the preparation of silver halide emulsions, such as alkali and alkaline earth cations, most commonly sodium, potassium Or calcium.

In the present invention, the above-mentioned water-dispersible cationic starch is present during the formation of silver halide grains. Some or all of the gelatino-peptizer usually used in forming silver halide grains can be replaced with the water-dispersible cationic starch to form silver halide grains. The timing of addition of the water-dispersible cationic starch is not particularly limited, and it is used in any one of the steps of nucleation, ripening, and grain growth generally known as the step of forming silver halide grains. However, it is preferably present in the grain growth process. In the present invention, the effects described in the present invention can be obtained by introducing a dislocation line in the presence of the water-dispersible cationic starch.

The silver halide photographic material of the present invention described in the above item 2 is characterized in that the silver halide emulsion layer contains a polysaccharide compound having a gelatin crosslinkable group. The polysaccharide compound having a gelatin crosslinkable group is a polysaccharide compound in which a part of a hydroxy group is modified with a compound having a crosslinkability with gelatin. For the classification and naming of polysaccharides, see "Biochemical Encyclopedia (2nd edition), Tokyo Kagaku Dojin Publishing"
based on.

As the polysaccharide compound used in the present invention, dextran, dextrin, and cyclodextrin having a cyclic structure are preferable, and cyclodextrin is particularly preferably used.

Specific examples of the cyclodextrin having a gelatin crosslinkable group are shown below.

The cyclodextrin having a gelatin crosslinkable group used in the present invention can be obtained by modifying a part of the hydroxy group of cyclodextrin with a compound having a crosslinkability with gelatin.

The cyclodextrin includes known cyclodextrins such as α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, as well as branched cyclodextrins to which glucose, maltose, sucrose, etc. have been branched or bonded, and the above-mentioned cyclodextrins. Compounds in which the ring structure of cyclodextrin is retained, such as cyclodextrin or a compound in which a part of branched cyclodextrin is substituted with a substituent such as an alkyl group, are preferably used.

The cyclodextrin having a gelatin crosslinkable group of the present invention is preferably a compound represented by the following general formula [A].

[0108]

Embedded image

In the general formula [A], R ₁ , R ₂ , R
₃ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group or a gelatin crosslinkable group,
n represents an integer of 4 to 10. However, at _{least two of} R ₁ , R ₂ and R ₃ in one molecule represent a gelatin crosslinkable group.

The gelatin crosslinkable group may be any group having at least one alcoholic hydroxy group and at least one group which reacts with an amino group or a carboxyl group in gelatin.
Examples include, for example, aldehyde groups, carboxyl groups, amino groups, active vinyl groups, oxazoline groups, N-methylol groups, acrylamide groups, methacrylamide groups, ethyleneimine groups, carbodiimide groups, epoxy groups, 2,4-
Dichloro-6-oxy-s-triazine group, epichlorohydrin group, epibromohydrin group, epifluorohydrin group, epiiodohydrin group, ethyl chloroformate group, phenylchloroformate group, 3-hydroxy Examples thereof include a phenyl chloroformate group, a 3-methoxyphenyl chloroformate group, a 2-chloroethyl chloroformate group, and a 4-chlorophenyl chloroformate group, and preferably 2,4 dichloro-6-oxy-s-.
A triazine group, an epichlorohydrin group and an ethyl chloroformate group, particularly preferably 2,4-dichloro-
6-oxy-s-triazine group.

Modification to cyclodextrin may have at least two gelatin crosslinkable groups per molecule in order to function as a crosslinker.

The amount of cyclodextrin having a gelatin-crosslinkable group used in the present invention may be added to the silver halide emulsion layer in an amount of 0.01 to 1 per m ^{2 of the} light-sensitive material to be coated.
4.0 g is preferred, and more preferably 0.1 to 2.0 g.
g, particularly preferably 0.1 to 1.0 g.
The timing of addition is preferably before the step of coating the emulsion coating solution. It is preferable to add the compound by dissolving it in water or a water-miscible solvent.

Specific examples are shown below, but the present invention is not limited to these.

K1: β-cyclodextrin / 2-hydroxy-4,6-dichloro-s-triazine sodium salt (average modification rate: 2.3 per molecule) K2: β-cyclodextrin to which one molecule of maltose is bound 2-Hydroxy-4,6-dichloro-s-triazine sodium salt (average modification rate per molecule: 2.3) K3: β-cyclodextrin / epichlorohydrin (average modification rate per molecule: 2.4) K4: β-cyclodextrin / epichlorohydrin bound to one molecule of maltose (average modification rate per molecule: 2.4) K5: β-cyclodextrin / ethyl chloroformate (average modification rate per molecule: 2. 4) These compounds are described in German Patent Publication 2,357,252.
And JP-A-63-83720 and JP-A-63-168463.
The compound can be synthesized with reference to the following synthesis method described in (1).

(Synthesis of K1) β-cyclodextrin 3
6.0 g was dissolved in 500.0 g of pure water, and NaOH was added.
H was adjusted to 8.5. Add 2-hydroxy-4,
41.0 g of sodium 6-dichloro-s-triazine was added, and the mixture was stirred for 5 hours while maintaining the pH at 8 to 9 and the temperature at 15 ° C with NaOH. After purifying the obtained reaction mixture, it was obtained as a powder by a spray drying method.

The cyclodextrin moiety can form an inclusion compound.

The inclusion compound of cyclodextrin is described, for example, by F. Cramer, "Einschlubveen".
rbindgen) Soringer (1954)
Or M. Hagen, Clathrate Inclusion Compound (Clathr)
a Inclusion Compound) Re
As described in inh 1d (1952), there is a hole of an appropriate size inside a three-dimensional structure formed by bonding atoms or molecules, into which other atoms or molecules enter at a fixed composition ratio. Substance that forms a specific crystal structure. "

The cyclodextrin having a gelatin-crosslinkable group (gelatin-crosslinkable cyclodextrin) used in the present invention is one of the compounds forming the above-mentioned inclusion compound, and can include the compound in the photosensitive material. Therefore, the formation of an inclusion compound of the gelatin-crosslinked cyclodextrin and the compound that inhibits development in the light-sensitive material makes it possible to reduce the elution of the development-inhibiting compound into the developer.

The layer containing the gelatin-crosslinkable cyclodextrin described above is provided above the emulsion layer from the viewpoint of the support, from the viewpoint of suppressing the elution of the compound in the light-sensitive material into the developer during development. Is preferred.

When the polysaccharide compound having a gelatin crosslinkable group used in the present invention is added to the hydrophilic colloid layer, it is preferable to add 5 to 50% by weight of the total binder amount of the hydrophilic colloid layer. Preferably 10-45
% By weight.

The silver halide emulsion used in the present invention is:
Various photographic additives can be used before and after physical ripening or chemical ripening of the emulsion.

Compounds that can be used in such a step include, for example, Research Disclosure (RD) 17
No. 643, (RD) 18716 (November 1979)
And (RD) 308119 (December 1989). The types and locations of the compounds described in these three (RD) are described below.

[0123]

[Table 3]

As the support used in the present invention, those described in the above-mentioned RD can be mentioned. A suitable support is a polyethylene terephthalate film or the like, and the surface of the support has good adhesion of the coating layer. For this purpose, an undercoat layer may be provided, or corona discharge or ultraviolet irradiation may be applied. Then, the constituent layer according to the present invention can be applied to both surfaces of the support thus treated. The light-sensitive material of the present invention may be provided with an antihalation layer, an intermediate layer, a filter layer, a backing layer, and the like, if necessary.

In the silver halide photographic light-sensitive material of the present invention, the silver halide emulsion layer and other hydrophilic colloid layers can be coated on a support or other layers by various coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, a slide hopper method, or the like can be used. For details, see Research Disclosure, Vol. 27-28 "Coa
The method described in the section "Ting procedures" can be applied.

In the present invention, the processing of the photographic light-sensitive material comprises
For example, treatment with a treatment liquid as described in RD-17643 and RD-308119 described above may be performed.

As the developer, those having a commonly used composition can be used. As the developer in the developer,
Dihydroxybenzenes, reductones, and 3-pyrazolidones can be used alone or in combination. The developer used in the present invention may not substantially contain dihydroxybenzenes. Further, the following known additives can be used in the developer, if necessary. That is, preservatives, alkaline agents, pH buffers, antifoggants, hardeners, sensitizers, chelating agents, development accelerators, surfactants, defoamers, colorants, dissolution aids, viscosity-imparting agents And so on. The pH of the developer is 8.5 to 12.0
Is preferably adjusted, and particularly preferably adjusted to 9.0 to 10.9.

As the fixing solution, those having a commonly used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components, and has a pH of usually 3.8 to 3.8.
5.8 is preferred. As the fixing agent, those generally known as fixing agents can be used. The fixer contains a hardener, a preservative, a pH buffer, a pH adjuster,
Compounds such as chelating agents can be added.

In the present invention, the silver halide photographic light-sensitive material is processed with a developing solution and a fixing solution containing substantially no boric acid or a salt thereof. , The content of boric acid or a salt thereof in the developing solution and the fixing solution is 0.03 mol / L or less, respectively, and it is preferable that boric acid or a salt thereof is not contained at all.

In the present invention, the silver halide photographic light-sensitive material is treated with a developer and a fixer containing substantially no hardener. It indicates that the content of the hardener in the fixing solution is 0.05 mol / liter or less.

As a mother liquor and a replenisher such as a developing solution, a fixing solution, and other processing solutions (such as a stabilizing solution), it is usual to supply a use solution or a concentrated solution diluted immediately before. The stock of the mother liquor and the replenisher may be in the form of a working solution, a concentrated solution, a viscous liquid in a semi-kneaded state having a high viscosity, or a method of dissolving a simple substance or a mixture of solid components at the time of use. When a mixture is used, a method in which components that are difficult to react with each other are adjacently packed in layers and then vacuum-packaged, and then opened and dissolved at the time of use, or a method of tableting can be used.

Regarding the development processing, the development temperature is set to 20 to 5
It can be set to the normal temperature range of 0 ° C. The photographic material of the present invention is preferably processed using an automatic processor. At this time, processing is performed while replenishing a fixed amount of a developing solution and a fixing solution in proportion to the area of the photographic light-sensitive material. The development replenishment amount and the fixing replenishment amount are preferably 330 ml or less per 1 m ² in order to reduce the waste liquid amount, and more preferably the development replenishment amount is 20 to 200 ml per 1 m ² .
The fixing replenishment amount is 20 to 200 ml.

According to the present invention, the total processing time (Dry to Dry) from the insertion of the leading end of the film into the automatic developing machine to the emergence of the film from the drying zone when processing using the automatic developing machine is desired due to the demand for shortening the developing time. It is preferably 60 seconds or less, and more preferably 10 to 40 seconds. The term "total processing time" as used herein includes the total process time required for processing a photographic light-sensitive material, and specifically, for example, steps such as development, fixing, bleaching, washing, stabilizing processing, and drying required for processing. Is a time including all of the time, that is, a time of Dry to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 20 to 40 seconds.

[0134]

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

Example 1 All the emulsions shown below were prepared in a reaction vessel having a volume of 32 liters. Asahi Kasei SIP-1013 ultrafiltration unit and DAID circulating pump
O Rotary Pump was used. The volume of the emulsion circulating portion in the ultrafiltration step was 1.2 liters, and the distance between the grains in the grain growth process was controlled by appropriately controlling the permeation flux in the ultrafiltration step.

<< Preparation of Emulsion EM-1 >> A1 Ossein Gelatin 75.5 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol) 6.78 ml Potassium bromide 64.7 g Finish with water to 10800 ml B10. 7N silver nitrate aqueous solution 470ml C1 3.5N silver nitrate aqueous solution 1500ml D1 1.3N potassium bromide aqueous solution 410ml E1 3.5N potassium bromide aqueous solution The following silver potential control amount F1 ossein gelatin 125g water 4000ml G1 3% by weight gelatin and iodide Fine particle emulsion (*) composed of silver particles (average particle diameter 0.05μ) Equivalent to 0.007 mol (Preparation method of fine particle emulsion (*)) A 5.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide 6.64 liters of 7.06 mole of nitric acid And silver, respectively 2 liter aqueous solution containing potassium iodide 7.06 mole, was added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

<< Nucleation >> JP-A-62-1601 at 55 ° C.
Using a mixing and stirring device described in No. 28, stirring speed 400
The solution B1 was added to the solution A1 for 400 while stirring at a rotation / minute.
ml and the entire amount of the solution D1 were added by the simultaneous mixing method over 40 seconds to perform nucleation.

<< Aging >> After the addition of the solution B1 and the solution D1, the solution F1 was added, and then the remaining amount of the solution B1 was added over 25 minutes. Further, 30 ml of a 10% aqueous ammonium nitrate solution is added, and then the pH is adjusted using a 10% aqueous KOH solution.
= 9.4, aging was performed for 10 minutes, and the pH was adjusted to 6.0 with acetic acid.

<< Growth >> The solution C1 and the solution E1 were pAg =
Simultaneous addition and mixing were carried out at a rate commensurate with the critical growth rate while maintaining the value at 7.8. After addition of 1250 ml of the solution C1, the solution G1 was further added simultaneously with the solutions C1 and E1 at such a rate that the addition was completed simultaneously with the completion of the addition of the solution C1. After stirring for 5 minutes, soluble salts were desalted and removed by the sedimentation method.

In the preparation of this emulsion, no circulation to the ultrafiltration unit was performed.

<< Preparation of Emulsion EM-2 >> The processes from nucleation to ripening were carried out in the same manner as for emulsion EM-1. During the growth process, the solution C1 and the solution E1 were simultaneously added and mixed at a speed commensurate with the critical growth rate while maintaining pAg = 7.8.
1 and 1250 ml of solution C1 and solution E1
Was once stopped. After the solution G1 was added for 1 minute, the remaining portions of the solution C1 and the solution E1 were simultaneously added and mixed at a speed commensurate with the critical growth rate while maintaining pAg = 7.8. Thereafter, desalting treatment was performed in the same manner as in the emulsion EM-1.

<< Preparation of Emulsion EM-3 >> The processes from nucleation to ripening were carried out in the same manner as for emulsion EM-2. After the ripening, the reaction solution was circulated from the reaction vessel to the circulation line using a circulating pump using the apparatus shown in FIG. 1 and circulated through the ultrafiltration unit to carry out concentration. Grain growth was carried out in the same manner as for emulsion EM-2 while keeping constant throughout the process. The circulation rate was set at a flow rate within a range not affecting the grain growth, and then desalting was performed in the same manner as in the emulsion EM-2.

<< Preparation of Emulsion EM-4 >> A1 Ossein gelatin 75.5 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous solution of ethanol) 6.78 ml Potassium bromide 64.7 g Finish with water to 10800 ml B10. 7N silver nitrate aqueous solution 470ml C1 3.5N silver nitrate aqueous solution 1500ml D1 1.3N potassium bromide aqueous solution 410ml E1 3.5N potassium bromide aqueous solution The following silver potential control amount F1 cationic potato starch 100g water 4000ml G1 3% by weight gelatin and iodine Fine particle emulsion (*) composed of silver particles (average particle diameter 0.05μ) Equivalent to 0.007 mol (Preparation method of fine particle emulsion (*)) A 5.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide 7.06 to 6.64 liters Mole of silver nitrate, respectively 2 liter aqueous solution containing potassium iodide 7.06 mole, was added over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

<< Nucleation >> JP-A-62-1601 at 55 ° C.
Stirring speed of 40 using a mixing and stirring device described in JP-A-28
The solution B1 was added to the solution A1 for 40 while stirring at 0 revolutions / minute.
0 ml and the whole amount of the solution D1 were added by the simultaneous mixing method over 40 seconds to perform nucleation.

<< Aging >> After the addition of the solution B1 and the solution D1, the solution F1 was added, and then the remaining amount of the solution B1 was added over 25 minutes. Further, 30 ml of a 10% aqueous ammonium nitrate solution is added, and then the pH is adjusted using a 10% aqueous KOH solution.
= 9.4, aging was performed for 10 minutes, and the pH was adjusted to 6.0 with acetic acid.

<< Growth >> The solution C1 and the solution E1 were pAg =
Simultaneous addition and mixing were performed at a rate commensurate with the critical growth rate while maintaining the value at 7.8. When 1250 ml of the solution C1 was added, the addition of the solution C1 and the solution E1 was temporarily stopped. Solution 1
Minutes, then add the remainder of solution C1 and solution E1 to pAg =
Simultaneous addition and mixing were carried out at a rate commensurate with the critical growth rate while maintaining 7.8. After stirring for 5 minutes, soluble salts were desalted and removed by the sedimentation method.

In the preparation of this emulsion, circulation to the ultrafiltration unit was not performed.

<< Preparation of Emulsion EM-5 >> The processes from nucleation to ripening were carried out in the same manner as for emulsion EM-4. After ripening, the reaction solution was circulated from the reaction vessel to the circulation line using a circulating pump and circulated to the ultrafiltration unit using the apparatus shown in FIG. 1 to carry out concentration, and the average interparticle distance was measured in the particle growth step. Grain growth was carried out in the same manner as for emulsion EM-4, while keeping it constant over the entire area. The circulation speed was set at a flow rate within a range not affecting the particle growth.

Thereafter, desalting was carried out in the same manner as for the emulsion EM-2.

The characteristics of each emulsion prepared as described above were examined by using a replica method. Table 4 shows the results.

[0151]

[Table 4]

Next, the above emulsions EM-1 to EM-5 were added to 60
° C, a predetermined amount of the spectral sensitizing dye was added as a solid particulate dispersion, and 10 minutes later, a mixed aqueous solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate and triphenylphosphine selenide were added. Was added, and after 30 minutes, a silver iodide fine grain emulsion was added, followed by ripening for a total of 2 hours. At the end of ripening, 4-hydroxy-6-methyl-1,3,3a, 7 is used as a stabilizer.
-A predetermined amount of tetrazaindene (TAI) was added.

The above additives and their amounts (AgX1
(Per mole) is shown below.

5,5′-dichloro-9-ethyl-3,3′-di- (sulfopropyl) -oxacarbocyanine sodium salt 400 mg 5,5′-di- (butoxycarbonyl) -1,1 ′ -Diethyl-3,3'-di (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride 4.0 mg adenine 15 mg potassium thiocyanate 95 mg chloroauric acid 2.5 mg sodium thiosulfate 2.0 mg triphenylphosphine selena 0.2 mg of silver iodide fine particles 280 mg 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 500 mg
It was obtained by adding to water adjusted to 7 ° C. and stirring with high speed stirring (dissolver) at 3,500 rpm for 30 to 120 minutes.

A dispersion of the above selenium sensitizer was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., and the mixture was stirred and completely dissolved. 3.8 kg of photographic gelatin on the other hand
Was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto. Next, these two liquids were mixed and dispersed by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm at a dispersion blade peripheral speed of 40 m / sec at 50 ° C. for 30 minutes. Then, immediately under reduced pressure, the residual concentration of ethyl acetate was reduced to 0.3.
Ethyl acetate was removed while stirring until the amount became less than wt%. Then, this dispersion is diluted with pure water to 80 kg.
Finished. A part of the dispersion thus obtained was fractionated and used in the above Examples.

The following additives were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, a coating solution for a protective layer described below was prepared. Using the two coating solutions, two slide hopper type coaters were used so that the coating amount was 1.6 g / m ² per side and the amount of gelatin was 2.5 g / m ² per side.
Both sides were simultaneously coated on the support at a speed of 0 m, and dried for 2 minutes and 20 seconds to obtain a sample. As a support, glycidyl methacrylate 50 wt%, methyl acrylate 10 w
The copolymer aqueous dispersion obtained by diluting the concentration of the copolymer composed of three monomers of 10% by weight and 40% by weight of butyl methacrylate to 10% by weight was used as a subbing liquid, and 175 μm was obtained.
A polyethylene terephthalate film base colored blue to a concentration of 0.17 for an X-ray film of m was used.

The additives used in the emulsion are as follows.
The amount of addition is shown in an amount per mole of silver halide.

First Layer (Dye Layer) Solid Fine Particle Dispersion Dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2,4- Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² Second layer (emulsion layer) Various additives were added.

Polysaccharide Compound Having Gelatin Crosslinking Group Gelatin shown in Table 5 Gelatin shown in Table 5 Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5 -Triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² styrene-maleic anhydride copolymer 80 mg / m ² sodium polystyrene sulfonate 80 mg / m ² trimethylol Propane 350 mg / m ² diethylene glycol 50 mg / m ² nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² sodium ² -mercaptobenzimidazole-5-sulfonate 5 mg / M ² compound Compound (H) 0.5 mg / m ² nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 350 mg / m ² Compound (M) 5 mg / m ² Compound (N) 5 mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.2 g / m ² Third layer (protective layer) Gelatin 0.8 g / m ² Matting agent composed of polymethyl methacrylate 50 mg / m ² (Area average particle size 7 0.0 μm) formaldehyde 20 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonylmethyl ether 36 mg / m ² latex (L) 0.2 g / m ² Polyacrylamide (average molecular weight 10,000) 0.1 g / m ² Sodium polyacrylate 30 mg / m ² Polysiloxane (SI) 20 mg / m ² Compound (I) 12 mg / m ² compound (J) 2 mg / m ² compound (S-1) 7 mg / m ² compound (K) 15 mg / m ² compound (O) 50 mg / m ² compound (S-2) 5 mg / m ² C _{9 F 19 O (CH 2 CH 2} O) 11 H 3mg / m 2 C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2 O) 15 H 2mg / m 2 C 8 F 17 SO 2 N ( C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₃ Na 1 mg / m ²

[0160]

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[0161]

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[0162]

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The following characteristics were evaluated for the obtained light-sensitive materials and samples.

<< Evaluation of Sensitivity >> The obtained sample was sandwiched between fluorescent intensifying screens SRO-250 (manufactured by Konica Corporation), and a tube voltage of 90 was used.
X-rays were irradiated at kVp and 20 mA for 0.05 seconds, a sensitometric curve was prepared by a distance method, and the sensitivity was determined.
The sensitivity was determined as the reciprocal of the X-ray dose required to obtain a density of fog + 1.0. The results are shown as relative sensitivities when the sensitivity in the processing 1 described below is 100. The developing process was performed using an automatic developing machine SRX-701 (manufactured by Konica Corporation), and the developing temperature and the fixing temperature were both 35 ° C. in a 30-second mode.
Set to.

<< Evaluation of Covering Power >> After the sample was exposed so as to have the highest density, development processing was performed in the same manner as in the evaluation of the sensitivity. The amount of silver (mg / dm ² ) of the obtained sample was measured by X-ray fluorescence analysis, and the covering power was determined by the following equation. The larger the value, the better the covering power.

Covering power (CP) = ｛(Dmax
-Base density) / silver amount｝ × 1000, but silver amount: mg / dm ² << Evaluation of silver tone >> After the prepared sample was exposed so that the transmission density after development was 1.2, the automatic developing machine was used. Was used for development processing. The obtained developed sample was observed on a Schaukasten, and the silver tone due to transmitted light was visually evaluated.

5: Pure black tone 4: Slightly reddish black tone 3: Reddish black tone 2: Slightly yellowish black tone 1: Yellowish black tone Level 4 The above is the practically acceptable level.

Table 5 shows the obtained results.

[0169]

[Table 5]

As is clear from Table 5, the sample of the present invention has high sensitivity, high covering power, and improved silver tone.

Example 2 Using the coating sample prepared in Example 1, a developing solution and a fixing solution having the following compositions were prepared, and the photographic performance was evaluated.

(Treatment 1) << Preparation of Developing Concentrate >> Diethylenetriaminepentaacetic acid 5 g Sodium sulfite 24 g Sodium carbonate monohydrate 87.5 g Potassium carbonate 97.5 g Sodium erythorbate 120 g N-acetyl-D, L-penicylamine 0.1 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 16.0 g 5-methylbenzotriazole 0.15 g Glutaraldehyde (50 wt% aqueous solution) 8.0 g Water was added to make up to 1 liter, and the pH was adjusted with KOH. 10.
Adjust to 20.

The preparation method of the working solution was prepared by adding 600 ml of water to 400 ml of the developing concentrated solution to obtain 1 liter of the working solution.

20 ml of a starter solution was added per liter of the used developer, and the pH was adjusted to 10.40 to obtain a used solution.

The same amount of the starter solution was added to the developing solutions used in the following processes 2 and 3 for the processing.

<< Preparation of Fixing Concentrate >> Ammonium thiosulfate (70 wt / vol%) 400 ml Sodium sulfite 40 g Boric acid 16 g β-alanine 36 g Glacial acetic acid 60 g Tartaric acid 5 g Aluminum sulfate 20 g 4.
Adjust to 60.

The preparation method of the working solution is such that 500 ml of water is added to 500 ml of the fixing concentrate to make 1 liter of the working solution.

The above processing agent was added to SRX-70 of an automatic developing machine.
1 (manufactured by Konica Corporation), and the developing process was performed in a 30-second mode with both the developing temperature and the fixing temperature being 35 ° C.

(Treatment 2) << Preparation of Developing Concentrate >> Diethylenetriaminepentaacetic acid 5g Sodium sulfite 24g Sodium carbonate monohydrate 87.5g Potassium carbonate 97.5g Sodium erythorbate 120g N-acetyl-D, L-penicylamine 0.1g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 16.0 g 5-methylbenzotriazole 0.15 g Water was added to make up to 1 liter, and the pH was adjusted to 10.1 with KOH.
Adjust to 20.

The method of preparing the working solution is to add 600 ml of water to 400 ml of the developing concentrated solution to make a developing solution of 1 liter of working solution.

<< Preparation of Fixing Concentrate >> Ammonium thiosulfate (70 wt / vol%) 400 ml Sodium sulfite 40 g β-alanine 36 g glacial acetic acid 60 g tartaric acid 5 g Add water to make up to 1 liter, and adjust the pH to 4 with NaOH.
Adjust to 60.

The method of preparing the working solution is to add 500 ml of water to 500 ml of the fixing concentrate to obtain a fixing solution of 1 liter of working solution.

The above-mentioned processing agent was added to SRX-70 of an automatic developing machine.
1 (manufactured by Konica Corporation), and the developing process was performed in a 30-second mode with both the developing temperature and the fixing temperature being 35 ° C.

(Process 3) << Preparation of Solid Developer >> (Preparation of Developing Tablet (1)) 360 g of 1-phenyl-3-pyrazolidone, N-acetyl D, L-penicillamine 10
g, glutaraldehyde bisulfite sodium 500
g, sodium metabisulfite 1200 g, sodium sorbate 4000 g, and D-sorbit 5
After adding water at room temperature in a commercially available stirred granulator and granulating, the granulated product was dried at 40 ° C. for 2 hours with a fluidized bed drier to reduce the water content of the granulated product to 1. It was removed to 0% or less, and further sized with a sizing machine equipped with a 1.0 mm mesh to obtain a granulated product.

The granulated product thus obtained was heated at 25 ° C.
After mixing uniformly for 7 minutes using a rotary mixer in a room humidified to 40% RH or less, Tough Press Collect 152H manufactured by Kikusui Seisakusho Co., Ltd. equipped with a 30 mm diameter punch.
U was filled with 10.3 g per tablet using a modified tableting machine, and compression tableting was performed to produce a cylindrical developing tablet (1).

(Preparation of Developed Tablet (2)) Potassium carbonate (5170 g) was used as a carbonate in a commercially available bantam mill at an average of 50 kg.
Grind to about μm. To this powder, 100 g of diethylenetriaminepentaacetic acid, 5 g of 1-phenyl-5-mercaptotetrazole, 5 g of sodium 5-mercapto- (1H) -tetrazole, 1000 g of D-mannite,
After adding 300 g of D-sorbit and granulating by adding 220 ml of water at room temperature in a commercially available stirring granulator, the obtained granulated product is dried at 40 ° C. for 2 hours with a fluidized dryer, The granulated product was obtained by sizing with a sizing machine equipped with a 1.0 mm mesh.

The granules thus obtained were treated with methyl-
β-cyclodextrin was added at 1.5% of the total weight, and sodium 1-hexanesulfonate was added at 1.0% of the total weight.
% In a room humidified at 25 ° C. and 40% RH or less using a rotary mixer for 7 minutes, and then the resulting mixture is fitted with a 30 mm-diameter punch. 1527HU Tough Press Collect Co., Ltd.
Was filled with 12.6 g per tablet using a modified tableting machine, and compression tableting was performed to prepare a cylindrical developing tablet (2).

The preparation of the working solution is performed by adding water to 18 developing tablets (1) and 30 developing tablets (2) to make 3.36 liters of the working solution.

<< Preparation of Solid Fixing Agent >> [Preparation of Fixing Tablet (1)] In a commercially available bantam mill, 14580 g of ammonium thiosulfate / sodium thiosulfate (weight ratio: 90/10) is pulverized to an average of 10 μm. To this fine powder, 550 g of sodium sulfite, 750 g of sodium metabisulfite, and 1220 g of pine flow were added, and the amount of water was added to 50 ml, and the mixture was stirred and granulated. The granulated product was dried at 50 ° C. with a fluidized bed dryer to remove water. 1.0%
(Weight ratio) or less, and the mixture was sized with a sizing machine equipped with a 1.0 mm mesh to obtain a granulated product.

The granules thus obtained were added to 3000 g of β-alanine, 4330 g of sodium acetate, and 1-
Sodium hexanesulfonate was added to 1.5% of the total weight and mixed with a rotary mixer for 5 minutes. The obtained mixture was tough press collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. equipped with a 30 mm diameter punch. Was filled with 10.9 g per tablet using a modified tableting machine, and compression tableting was performed to prepare a cylindrical fixing tablet (1).

(Preparation of Fixing Tablet (2)) Succinic acid 1100
g, 300 g of tartaric acid in a commercially available bantam mill on average 10
Grind to μm. 250 g of D-mannitol and 50 g of D-sorbite are added to these fine powders, and the amount of water added is 30 ml, and the mixture is stirred and granulated. It was removed to 0% (weight ratio) or less, and further sized with a sizing machine equipped with a 1.0 mm mesh to obtain a granulated product.

Further, sodium acetate 750 was added to the granules.
g of sodium 1-hexanesulfonate in a total weight of 1.
0%, uniformly mixed for 7 minutes using a rotary mixer in a room conditioned at 25 ° C. and 40% RH or less, and equipped with a 30 mm diameter punch, Kikusui Seisakusho Co., Ltd.
Using a modified tableting machine, Toughpress Collect 1527HU was filled with 10.4 g per tablet and compression tableting was performed to prepare a cylindrical fixing tablet (2).

The preparation method of the working solution is to add 3.36 liters of working solution by adding water to 56 tablets of the fixing tablet (1) and 12 tablets of the fixing tablet (2).

The above-mentioned processing agent was added to SRX-70 of an automatic developing machine.
1 (manufactured by Konica Corporation), and the developing process was performed in a 30-second mode with both the developing temperature and the fixing temperature being 35 ° C.

<< Evaluation of Photographic Performance >> Processes 1 to 3 above
The above steps were performed. The sensitivity in the table indicates that the sample No. The reciprocal of the exposure amount that gives an optical density of fog density +1.0 to 1 is shown as a relative value with 100 being the reciprocal. The capacity of the developing tank was adjusted to 13.5 liters.

<< Evaluation of Silver Tone >> After the prepared sample was exposed so that the transmission density after development became 1.2, each of the above-mentioned processes 1 to 3 was performed. The obtained developed sample was observed on a Schaukasten, and the silver tone due to transmitted light was visually evaluated.

5: Pure black tone 4: Slightly reddish black tone 3: Reddish black tone 2: Slightly yellowish black tone 1: Yellowish black tone Level 4 The above is the practically acceptable level.

<< Evaluation of Remaining Color >> The above-mentioned treatments 1 to 3 were carried out without exposing the prepared sample. The obtained processed sample was observed on a Schaukasten, and the residual color due to transmitted light was visually evaluated.

A: no residual color is observed B: very slight residual color is observed C: residual color is observed D: residual color is clearly observed over the entire surface. is there.

<< Evaluation of Processing Unevenness >> Samples giving a density of 1.0 in each processing were prepared and visually evaluated. The evaluation criteria were based on the following four steps.

4: No occurrence.

3: Observable unevenness is observed when carefully observed. 2: Slightly strong unevenness is observed. 1: Clearly visible unevenness is observed. Level 3 or higher is a practically acceptable level.

Table 6 shows the results.

[0204]

[Table 6]

As is clear from Table 6, the sample of the present invention has less sensitivity deterioration, residual color and unevenness in development processing, and has improved silver tone.

[0206]

According to the present invention, while maintaining high sensitivity, C
It was possible to provide a silver halide photographic light-sensitive material having a high P and an improved silver tone, and a processing method thereof.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of a silver halide emulsion manufacturing apparatus applicable to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Reaction container 2 Stirring mechanism 3 Dispersion medium 4 Silver addition line 5 Halide addition line 6 Dispersion medium addition line 7 Addition line 8 Liquid take-out line 9 Liquid return line 10 Permeate discharge line 11 Permeate return line 12 Ultrafiltration unit 13 Circulation Pump 14 Flow meter 15, 16, 17 Pressure gauge 18 Pressure adjusting valve 19 Flow adjusting valve 20 Silver addition valve 21 Halide addition valve 22 Liquid extraction valve 23, 24, 25 Valve 26 Ultrafiltration permeate 27 Permeate receiver 28 scales

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/025 G03C 1/025 1/04 1/04 1/30 1/30 5/26 520 5/26 520 5/29 5/29 5/38 5/38

Claims (6)

[Claims] In a silver halide photographic material having a photographic component layer including at least one silver halide emulsion layer on a support, the projected area of all silver halide grains is 5%.
0% or more are tabular grains having an aspect ratio of 3 or more, and grains having 80% or more of the projected area of all silver halide grains are tabular grains having 30 or more dislocation lines per grain in a fringe portion. And silver halide grains having a coefficient of variation of the intergranular distribution of the number of dislocation lines in one grain and a coefficient of variation of the intergranular distribution of the silver iodide content in one grain of 30% or less. And a silver halide photographic material, wherein the silver halide grains are prepared in the presence of a water-dispersible cationic starch. 2. A silver halide photographic light-sensitive material having a photographic component layer including at least one silver halide emulsion layer on a support, wherein the projected area of all silver halide grains is 5%.
0% or more are tabular grains having an aspect ratio of 3 or more, and grains having 80% or more of the projected area of all silver halide grains are tabular grains having 30 or more dislocation lines per grain in a fringe portion. And silver halide grains having a coefficient of variation of the intergranular distribution of the number of dislocation lines in one grain and a coefficient of variation of the intergranular distribution of the silver iodide content in one grain of 30% or less. And a silver halide photographic material, wherein the silver halide emulsion layer contains a polysaccharide compound having a gelatin crosslinkable group. 3. The halogen according to claim 1, wherein the grain growth of the silver halide grains is performed while separating an aqueous solution containing a salt from the reaction solution using an ultrafiltration method. Silver halide photographic material. 4. A processing method comprising processing the silver halide photographic light-sensitive material according to claim 1 with a developing solution and a fixing solution containing substantially no boric acid or a salt thereof. Method. 5. A processing method, comprising processing the silver halide photographic light-sensitive material according to claim 1 with a developing solution and a fixing solution containing substantially no hardener. 6. The processing method according to claim 4, wherein the developing solution or the fixing solution is prepared using a solid processing agent.