JPH08278607A - Developing method of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material which shows little fluctuation in sensitivity, contrast, etc., in rapid processing by an automatic developing machine and produces no irregular density by drying (irregular drying). CONSTITUTION: Silver halide particles included in at least one layer of photosensitive silver halide emulsion layers satisfy the conditions (1) to (3) described below. The amt. of org. material present in hydrophilic colloid layers including emulsion layers in this silver halide photographic sensitive material after development is <90wt.% of the amt. before development. (1) The silver halide particles contains planar silver halide particles having >2 aspect ratio which form >50% of the whole projected area of particles. (2) The principal plane of the planar silver halide particle has a (100) plane with <10 ratio of adjacent edges. (3) The planar silver halide particles are photosensitive silver halide particles having >30mol% silver chloride content.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for developing and processing a silver halide photographic light-sensitive material, and more particularly to a method for developing and processing a silver halide photographic light-sensitive material having little processing variability and no drying unevenness.

[0002]

2. Description of the Related Art In recent years, it has been more and more desired to shorten the processing time for the development processing of silver halide photographic light-sensitive materials. For example, in the medical field, the number of X-ray photographs taken is increasing due to a rapid increase in the number of examinations including regular medical examinations, widespread use of medical checkups, and general medical examinations, and there is an ever-increasing demand for faster development processing. is the current situation.

However, in order to speed up the processing, it is necessary to shorten the time of each processing step such as development, fixing, washing, drying, etc., which results in insufficient processing and various problems occur.

For example, when the developing time is shortened, the image density is lowered, that is, the sensitivity is lowered and the gradation is deteriorated. Further, if the fixing time is shortened, the fixing of silver halide becomes incomplete, which causes deterioration of image quality. Further, if the drying time is insufficient, density unevenness due to drying unevenness is caused, which causes fatal deterioration of image quality.

Generally, the developing property, fixing property, drying property and the like can be improved by reducing the water content by reducing the amount of the binder in the silver halide photographic light-sensitive material.

However, if the amount of the binder is reduced, the physical properties are deteriorated, for example, scratches are likely to occur during handling of the film, and there are problems such as fogging and desensitization due to bending of the film. Furthermore, since the suppression of development is suppressed, there is a drawback that the graininess of the image is deteriorated. Therefore, there is a limit in reducing the amount of binder.

On the other hand, as an approach from the side of the light-sensitive material, as a conventional means for increasing the developing speed and the fixing speed, it is well known to reduce the silver iodide content of silver halide grains. However, when the average silver iodide content is lowered, the inherent sensitivity of the silver halide grains is reduced, and the adsorptivity of the spectral sensitizing dye is deteriorated, which makes it difficult to obtain high spectral sensitivity. As another means, it is known to incorporate silver chloride into silver halide grains. However, when silver chloride is mixed with silver halide grains, the sensitivity is generally decreased, and it is difficult to obtain stable photographic performance during development processing.

By the way, in recent years, many uses of tabular silver halide grains have been disclosed as a technique for improving the sensitivity and the image quality of silver halide photographic light-sensitive materials.
-111935, 58-111936, 58-
111937, 58-113927, 59-9.
No. 9433 is disclosed.

Further, JP-A-5-281640 and 5-3.
Nos. 1327 and 6-19028 disclose the technology of tabular silver halide grains having a (100) plane as the main plane, all of which are aimed at high sensitivity and high image quality. It is a technique relating to grains, and does not suggest anything about grains having a high silver chloride content.

Regarding tabular grains containing silver chloride, for example, EP-584,817 or US Pat. No. 5,272,052 discloses tabular grains having a (111) plane as a main plane. However, in each case, since the (111) plane is formed by adding the specific compound, the compound has a great adverse effect on the photographic performance, and further breakthrough is required for practical use.

As a result of examining the silver chloride-containing emulsion having the (100) plane from various angles, the present inventor has a drawback that when the rapid processing is carried out by an automatic processor, uneven density due to uneven drying tends to occur. I found out that

The rapid processing improves the developability and fixability,
There has been a demand for a technique capable of obtaining high sensitivity and high trust without deteriorating the image quality and causing no unevenness in drying.

[0013]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a silver halide which has no processing variability such as sensitivity and contrast in rapid processing by an automatic processor and does not cause density unevenness (drying unevenness) due to drying. To provide a photographic light-sensitive material.

[0014]

The above problems have been solved by the present invention described below. That is, in the method for developing a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide contained in at least one light-sensitive silver halide emulsion layer. The grains satisfy the following conditions (1) to (3), and in the silver halide photographic light-sensitive material, the amount of the organic substance present in the hydrophilic colloid layer including the emulsion layer after the development treatment is the same as that before the development treatment. 90% by weight or less of the amount of the silver halide photographic light-sensitive material.

(1) The total projected area of silver halide grains is 5
0% or more are tabular silver halide grains having an aspect ratio of 2 or more.

(2) The main plane of the tabular silver halide grain has a (100) plane with an adjacent edge ratio of less than 10.

(3) The tabular silver halide grains are photosensitive silver halide grains having a silver chloride content of at least 30 mol% or more.

The present invention will be described in detail below.

According to the present invention, the organic substance (eg, gelatin, matting agent, plasticizer, synthetic polymer or other organic substance) coated in the hydrophilic colloid layer including the photosensitive emulsion layer is processed and dried. , 10% of total weight before development
The above is to be leaked. The flow-out method of the organic substance may be a simple physical elution or a chemical reaction. The amount of effluent in the treatment is 10% or more and 90% or less, preferably 15% or more, 3% of the total weight of organic substances.
It is preferably 0% or less.

Specifically, it is preferable that the silver halide photographic light-sensitive material contains an organic substance which easily flows out in the processing step.

In the present invention, preferred organic substances that easily flow out are polymeric substances, and examples thereof include hydrophilic polymers such as polyvinyl alcohol, polyacrylamide and polyvinylpyrrolidone, and sugars such as dextran, saccharose and pullulan. A preferable polymer substance is a water-soluble polymer described below.

The water-soluble polymer preferably used in the present invention does not necessarily need to have high solubility in water, but refers to a polymer that is soluble in water. For example, 20 ℃
In 100 g of water described above, about 0.05 g or more should be dissolved, preferably 0.1 g or more.

It is preferable that the water-soluble polymer used has a higher solubility in a developing solution or a fixing solution, and the solubility is 100%.
It is preferable that it dissolves by 0.05 g or more with respect to g. It is more preferably 0.5 g or more, and particularly preferably 1 g or more.

The water-soluble polymer may be natural or synthetic, and among the polymers usable in the present invention, the synthetic water-soluble polymer has, for example, a nonionic group or an anionic group in its molecular structure. ,
The thing which has both a nonionic group and an anionic group can be mentioned. Here, the nonionic group is, for example, an ether group, an ethylene oxide group, a hydroxy group or the like. Examples of the anionic group include a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, and a phosphoric acid group or a salt thereof.

The synthetic water-soluble polymer may be a homopolymer or a copolymer. The copolymer may be a copolymer partially with a hydrophobic monomer as long as the polymer itself is water-soluble.

The composition of the copolymer may be restricted depending on the place of addition and the amount added. For example, in the case of adding to the emulsion layer in a large amount, the composition range is set so that the addition does not hinder the effect.

Examples of natural water-soluble polymers include those having a nonionic group, those having an anionic group, and those having both a nonionic group and an anionic group in the molecular structure.

Preferred water-soluble polymers include those containing the repeating unit of the following general formula [1], particularly those containing 10 to 100 mol% of the repeating unit in the polymer.

[0029]

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In the formula, R ¹ and R ² may be the same or different and each is a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (including those having a substituent, such as a methyl group and an ethyl group). Group, propyl group, butyl group, etc., and those having a substituent attached thereto), a halogen atom or —CH ₂ COOM ¹ , and M ¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

L is -CONH-, -NHCO-, -COO-, -OCO-, -CO
_{-, - SO 2 -, -} NHSO 2 -, - representing the SO ₂ NH- or -O-.

J is an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms (including those having a substituent, such as methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, and the like; To those having a substituent), arylene groups (including those having a substituent, such as a phenylene group, and those having a substituent thereto), or

[0033]

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Represents a hydrogen atom or R ³ . Here, M ² represents a hydrogen atom or a cation group, and R ⁹ has 1 to 4 carbon atoms.
Alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, etc., or those with a substituent attached)
And R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are hydrogen atoms,
An alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group,
Hexadecyl group, etc., or those having a substituent attached thereto, alkenyl group (eg, vinyl group, allyl group, etc., or those having a substituent added thereto), phenyl group (eg, phenyl group, methoxyphenyl group, chlorophenyl group) Etc., or those having a substituent attached thereto), an aralkyl group (eg, a benzyl group, etc., or those having a substituent attached thereto), X represents an anion, and p and q are 0 or 1 respectively. Represents Polymers containing acrylamide or methacrylamide are particularly preferred.

Y represents a hydrogen atom or-(L-) _P- (J-) _q- Q.

The synthetic water-soluble polymer constituting the unit represented by the general formula [1] can be copolymerized with an ethylenically unsaturated polymer. Examples of the copolymerizable ethylenic monomer are styrene, alkyl styrene, hydroxyalkyl styrene (alkyl group having 1 to 4 carbon atoms,
For example, methyl, ethyl, butyl, etc.), vinylbenzenesulfonic acid and its salts, α-methylstyrene, 4
-Vinylpyridine, N-vinylpyrrolidone, monoethylenically unsaturated esters of aliphatic acids (eg vinyl acetate, vinyl propionate etc.), ethylenically unsaturated monocarboxylic acids or dicarboxylic acids and salts thereof (eg acrylic acid,
Methacrylic acid), maleic anhydride, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (eg n-butyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate), ethylenically unsaturated And amides of carboxylic acids (eg, acrylamide, sodium 2-acrylamido-2-methylpropanesulfonic acid, N, N-dimethyl-N′-methacryloylpropanediamineacetate betaine) and the like.

Next, specific examples of the synthetic water-soluble polymer having the repeating unit represented by the general formula [1] will be exemplified, but of course the present invention is not limited thereto. The numerical value in parentheses is the number average molecular weight Mn.

[0038]

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[0039]

[Chemical 4]

[0040]

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[0041]

[Chemical 6]

When the above synthetic water-soluble polymer is used, its molecular weight is preferably 1,000 to 100,000, more preferably 2,
Use one from 000 to 15,000.

Examples of the natural water-soluble polymer that can be used in the present invention include those described in detail in the water-soluble polymer water-dispersible resin general technical data collection (Business Development Center Publishing Department). Especially lignin, starch, vullan, cellulose, alginic acid, dextran, dextrin,
Guar gum, gum arabic, pectin, casein, agar, xanthanzam, cyclodextrin, locust bean gum, tragacanth gum, carrageenan, glycogen, laminaran, lichenin, nigeran and the like, and derivatives thereof are preferable.

Derivatives of natural water-soluble polymers include sulfonated, carboxylated, phosphorylated, sulfoalkylated, or carboxyalkylenated, alkylphosphorylated, and salts thereof, polyoxyalkylenated (eg, ethylene, glycerin, Propylene, etc.) and alkylation (methyl, ethyl, benzylation, etc.) are preferred.

The natural water-soluble polymers may be used in combination of two or more.

Among the natural water-soluble polymers, glucose polymers and their derivatives are preferable, and among the glucose polymers and their derivatives, starch, glycogen, cellulose, lichenin, dextran, nigeran and the like are preferable, and dextran and its derivatives are particularly preferable. Derivatives are preferred.

Dextran is a polymer of D-glucose linked with α-1,6, and is generally obtained by culturing a dextran-producing bacterium in the presence of a saccharide, and dextran-producing bacterium such as leuconostoc, mesenteroides and the like. It can be obtained by reacting dextran sucrase separated from the culture broth with saccharides. In addition, the native dextran is reduced to a desired molecular weight by a partial decomposition polymerization method using an acid or alkaline enzyme, and the intrinsic viscosity is 0.03.
Those in the range of up to 2.5 can also be obtained.

The dextran-modified product means dextran sulfate, carboxyalkyl dextran,
Examples thereof include hydroxyalkyl dextran.
The molecular weight of these natural water-soluble polymers is preferably 100 to 100,000, particularly preferably 2,000 to 20,000.

The method for producing these dextran and its derivatives is described in JP-B-35-11989, US Pat. No. 3,762,92.
No. 4, Japanese Patent Publication No. 45-12820, No. 45-18418, No. 45-40149
No. 46-31192.

In the present invention, the synthetic or natural water-soluble polymer is contained in the photographic light-sensitive material in an amount of 10% or more, preferably 10% or more and 30% or less, based on the total weight of the photographic material.

The tabular silver halide grain in the present invention means a grain having two parallel main planes facing each other,
Ratio of grain size to grain thickness (hereinafter referred to as aspect ratio)
The average value of is greater than 1.3. Here, the grain size means an average projected area diameter (hereinafter referred to as a grain size), and a diameter corresponding to a circle of a projected area of the tabular silver halide grains (a diameter of a circle having the same projected area as the silver halide grains). ),
Thickness refers to the distance between two parallel major planes forming a tabular silver halide grain.

The aspect ratio of the tabular silver halide grain of the present invention is 2 or more, preferably 2.0 or more and less than 15.0. It is particularly preferably 4 or more and less than 8.

In the present invention, 50% or more of the total projected area of the silver halide grains contained in the emulsion layer is characterized in that it is composed of tabular silver halide grains having a (100) plane as a main plane. Is 70% or more, more preferably 90% or more.

In the present invention, the main plane of the tabular silver halide grain is a right-angled parallelogram or a right-angled parallelogram with rounded corners. The ratio of adjacent sides of the right-angled parallelogram is less than 10, preferably less than 5, more preferably less than 2. In addition, the length of a side when the corner is rounded is represented by the distance between the intersection of the straight line portion of the side and the line obtained by extending the straight line portion of the adjacent side.

The average grain size of the tabular silver halide grains of the present invention is preferably 0.15 to 5.0 μm, and 0.4 to 3.0 μm.
Is more preferable, and most preferably 0.4 to 2.0 μ.
m.

The average thickness of the tabular silver halide grains of the present invention is preferably 0.01 to 1.0 μm, more preferably 0.02 to 0.40 μm, still more preferably 0.02 to 0.30 μm.

Particle size and thickness can be optimized to optimize sensitivity and other photographic properties. The optimum particle size and the optimum thickness are other factors that affect the sensitivity and other photographic characteristics, such as the thickness of the hydrophilic colloid layer, the degree of hardening,
Differs depending on the chemical ripening conditions, the set sensitivity of the light-sensitive material, the amount of silver deposited, and the like.

The tabular silver halide grains of the present invention are preferably monodisperse emulsions having a narrow grain size distribution. Specifically, (standard deviation of grain size / average grain size) × 100 = broadness of grain size distribution (% When the breadth of distribution is defined by), it is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

The tabular silver halide grains of the present invention preferably have a small thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) x 100 = width of thickness distribution (%), it is preferably 25% or less, more preferably 20%. It is as follows, and particularly preferably 15% or less.

In the tabular silver halide grains of the present invention, silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver iodochloride, silver chloroiodobromide and the like can be used as silver halide. The content of silver iodide is preferably 1.0 mol% or less as the average silver iodide content in the entire silver halide grain, and more preferably 0.5 mol%.
The following are preferred.

In the present invention, the halogen content and average halogen content of individual silver halide grains are determined by the EPMA method (El
ectron Probe Micro Analyzer method). In this method, a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared, an electron beam is irradiated, and an X-ray analysis by electron beam excitation is performed. Elemental analysis of extremely minute portions can be performed. By this method, the silver halide composition of each grain can be determined by determining the characteristic X-ray intensity of silver and halogen emitted from each grain. If the halogen content rate is determined by the EPMA method for at least 50 particles, the halogen content rate can be determined from the average thereof.

The tabular silver halide grains contained in the silver halide emulsion of the present invention (hereinafter sometimes abbreviated as tabular silver halide grains of the present invention) have a more uniform halogen content between grains. Preferably. When the halogen content distribution between particles is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

When the tabular silver halide grain in the present invention contains silver iodide, it is preferable that the silver halide grain is contained at least inside. In the case of the inside, it is more preferable that it exists at least in the central portion. Further, it is also preferable that it exists on the outermost surface in addition to the inside.

In the present invention, the halogen composition distribution inside the silver halide grain is obtained by pretreating the grain into an ultrathin section and then observing and analyzing with a transmission electron microscope while cooling. Specifically, after taking out silver halide grains from the emulsion, they are embedded in a resin and cut with a diamond knife to prepare a slice having a thickness of 60 nm.

While cooling this section with liquid nitrogen, observation and point analysis were performed with a transmission electron microscope equipped with an energy dispersive X-ray analyzer, and quantitative calculation was performed (Inoue, Nagasawa: Photographic Society, Showa 62). Annual Annual Conference Proceedings p62).

In the present invention, the silver iodide content on the outermost surface of tabular silver halide grains means the XPS method (X-ray Photoelec
(Tron Spectroscopy: X-ray photoelectron spectroscopy) is the silver iodide content in a portion up to a depth of 50Å, which can be determined as follows.

The sample was placed in an ultrahigh vacuum of 1 × 10 ^-8 torr or less--
Cool down to 110 ° C or below and use MgKα as X-ray for the probe.
Irradiate with a source voltage of 15kv and an X-ray source current of 40mA, Ag3d5 / 2, Br
Measure 3d and I3d3 / 2 electrons. The integrated intensity of the measured peak is corrected by the sensitivity factor (Sensitivity Factor), and the halide composition of the outermost surface is determined from the intensity ratio of these.

The purpose of cooling the sample is to eliminate the measurement error caused by the destruction of the sample (decomposition of silver halide and diffusion of halide {especially iodine}) by X-ray irradiation at room temperature and to improve the measurement accuracy. If cooled to -110 ° C, sample destruction can be suppressed to a level that does not hinder measurement.

In the present invention, the tabular silver halide grains may have various halogen compositions, but the silver halide content is 50 mol%.
It is preferable to contain the above, further preferably 70 mol% or more.

The tabular silver halide grains of the present invention may have dislocations. The dislocation is, for example, JF Hamilton, Phot.S.
ci.Eng, 57 (1967), T.Shiozawa, J.Soc.Phot.Sci.Jap
It can be observed by a direct method using a transmission electron microscope at low temperature described in an, 35, 213 (1972). That is, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample to prevent damage (printout etc.) due to electron beam In the cooled state, observation is performed by the transmission method.

At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to observe more clearly using a high-voltage electron microscope (200 kv or more for particles having a thickness of 0.25 μm). be able to.

The tabular silver halide grains of the present invention can be prepared by the method described in US Pat. No. 5,320,938. That is, it is preferable to nucleate with low pCl in the presence of iodide ions under the condition that the (100) plane is easily formed. After nucleation, Ostwald ripening and / or growth can be performed to obtain tabular silver halide grains having a desired grain size and distribution.

For example, first, a silver salt solution, a halide solution containing iodine ions, and a protective colloid solution are added to the first container to form nuclei, and after the nucleation, the mixed solution is transferred to the second container, Therefore, the method of growing is preferably used.

At this time, the growth may be temporarily stopped on the way and seed grains may be used to deposit silver halide on the seed grains. Specifically, an aqueous solution containing a protective colloid and seed particles may be present in advance in a reaction vessel, and silver ions, halogen ions, or silver halide fine particles may be supplied as necessary to grow the seed particles.

To prepare the tabular silver halide grains of the present invention, the pCl of the protective colloid solution is preferably in the range of 0.5 to 3.5, more preferably 1.0 to 3.0, most preferably 1.5 to 2.5.

In the preparation of the tabular silver halide grains of the present invention, nucleation is started at the time when the silver salt solution is added to the protective colloid solution, and iodide ions are added simultaneously with the silver salt solution or in the silver salt solution. It is preferable to add it prior to the salt solution, and most preferably when it is added prior to the silver salt solution.

In the preparation of the tabular silver halide grains of the present invention, iodine can be introduced up to the solid solution limit of silver iodide and silver chloride, but iodine ions in the protective colloid solution at the start of nucleation are contained. The concentration is preferably 10 mol% or less, more preferably 0.01 mol% or more, 10 mol% or less,
Most preferably, it is 0.05 mol% or more and 10 mol% or less.

In the preparation of the tabular silver halide grains of the present invention, the addition time of the silver salt solution during nucleation is preferably 5 seconds or more and less than 1 minute. Further, it is preferable to add both the silver salt solution and the halide solution at the time of nucleation. It is particularly preferable to add iodine ions.

The bromine ion in the protective colloid solution during nucleation may be present as long as the chlorine ion is present in an amount of 50 mol% or more.

In the present invention, the silver chloride content of the nucleus is 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more. The pH during nucleation is preferably 2-8. The temperature is preferably 30 to 90 ° C, more preferably 35 to 70 ° C.

The amount of silver added during nucleation is 0.1% of the total amount of silver.
It is preferably from mol% to 10 mol%.

In the preparation of the tabular silver halide grains of the present invention, a known silver halide solvent such as ammonia, thioether or thiourea can be present. In the preparation of the tabular silver halide grains of the present invention, a silver salt solution and a halide solution are added by a double jet method during the growth, and the rate of addition depends on the growth of the grains, new nucleation does not occur, and Ostwald ripening is carried out. Particles having a desired particle size and distribution can be obtained by a method in which the size distribution is not broadened by, that is, a method of gradually changing it within a range of 30 to 100% of the speed at which new nuclei are generated. As another condition for further growth, a method in which silver halide fine particles are added, dissolved, and recrystallized to grow, as described in Section 88 of 1983 Annual Meeting of the Photographic Society of Japan, is also preferably used. Particularly, silver iodide fine particles, silver bromide fine particles, silver iodobromide fine particles, and silver chloride fine particles are preferably used.

The tabular silver halide grains of the present invention may be so-called halogen conversion type grains. The amount of halogen conversion is preferably 0.2 mol% to 0.5 mol% with respect to the amount of silver, and the conversion time may be physical ripening or after physical ripening.

As a method for halogen conversion, an aqueous halogen solution or silver halide fine particles having a smaller solubility product with silver than the halogen composition on the surface of the grain before halogen conversion is usually added. At this time, the particle size is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

When silver iodide on the outermost surface of the tabular silver halide grains of the present invention is contained, as a method therefor, a silver nitrate solution and a solution containing iodine ions are added to an emulsion containing tabular grains as a base. Simultaneous addition method, method of adding fine silver halide grains such as silver iodide, silver iodobromide or silver chloroiodobromide, potassium iodide or a mixture of potassium iodide and potassium bromide, organic compound which releases iodo ion A method of adding a compound or the like can be applied.

Of these, the method of adding fine silver halide grains is preferable. Particularly preferred is the addition of fine silver iodide grains and the addition of an organic compound that releases iodine ions. The timing for adjusting the silver iodide content on the outermost surface is selected from the final step of the silver halide crystal production step to the chemical ripening step and further to the end of the solution preparation step immediately before the coating of the silver halide emulsion. However, it is preferable to make adjustments by the end of the chemical ripening step. The term "chemical ripening step" as used herein refers to a point from the time when physical ripening and desalting operations of the silver halide emulsion of the present invention are completed, to the time when a chemical sensitizer is added and then the operation for stopping the chemical ripening is performed. Up to. Further, the addition of silver halide fine particles may be carried out in several times with a time interval, and after the addition of the fine particles,
Further chemically ripened emulsions may be added.

The temperature of the emulsion according to the present invention at the time of adding fine silver halide grains is preferably in the range of 30 to 80 ° C.
A range of 40 to 65 ° C is particularly preferable. Further, the present invention is preferably carried out under the condition that the silver halide fine particles to be added are partially or wholly lost after the addition and immediately before coating. More preferable condition is that of the added silver halide fine particles.
20% or more has disappeared just before coating.

In producing the tabular silver halide grains of the present invention, stirring conditions during production are extremely important. As the stirring device, the device shown in JP-A-62-160128, in which the additive liquid nozzle is installed in the liquid near the mother liquor suction port of the stirrer, is particularly preferably used. The stirring speed at this time is 100 to 1
It is preferably 200 rpm.

The tabular silver halide grains of the present invention are used in the process of forming grains and / or the process of growing grains such as cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt) and rhodium salt (complex salt). It is preferable to add a metal ion by using at least one selected from the group consisting of the above) and an iron salt (including a complex salt) so that these metal elements are contained inside and / or on the surface of the particle.

In the present invention, it is also preferable to add a silver halide solvent before the desalting step in order to accelerate the developing rate. For example, it is preferable to add a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) in an amount of 1 × 10 ^{−3 to} 3 × 10 ⁻² mol per mol of silver.

In the present invention, it is preferable to use gelatin as the dispersion medium for the protective colloid of silver halide grains, and as the gelatin, alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 100,000),
Modified gelatin such as phthalated gelatin is used. Other hydrophilic colloids can also be used. Specifically, Research Disclos
ure. abbreviated as RD hereinafter) 176, No. 17643 (December 1978).

In the production of the tabular silver halide grains of the present invention, unnecessary soluble salts may be removed during the growth of the silver halide grains, or they may be contained therein.
The removal of the salts can be carried out according to the method described in Item II of RD Vol. 176, No. 17643.

The tabular silver halide grains of the present invention can be chemically sensitized. The conditions of the process of chemical ripening, that is, chemical sensitization, such as pH, pAg, temperature and time, are not particularly limited, and the conditions generally used in the art can be used. For chemical sensitization, a sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitizing method using a selenium compound, a tellurium sensitizing method using a tellurium compound, and a reducing substance are used. The reduction sensitization method, gold or other, a noble metal sensitization method using a noble metal or the like can be used alone or in combination, and among them, a selenium sensitization method, a tellurium sensitization method, a reduction sensitization method and the like are preferably used.
Particularly, the selenium sensitization method is preferably used.

In the present invention, selenium sensitization can be used in combination,
A wide variety of selenium compounds can be used as the selenium sensitizer. For example, U.S. Patents 1,574,944 and 1,6
02,592, 1,623,499, JP-A-60-150046, JP-A
The compounds described in 4-25832, 4-109240, 4-147250 and the like can be used. Examples of useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylselenourea). , N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4 -Nitrophenylcarbonyl selenoureas, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), Renaido acids (triphenylphosphine selenide, diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, selenoketones, and selenides.

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. The addition method may be a method in which water or an organic solvent such as methanol or ethanol is dissolved alone or in a mixed solvent and added depending on the properties of the selenium compound used.
Alternatively, a method of adding it in advance by mixing with a gelatin solution or a method of adding it in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent by the method disclosed in JP-A-4-140739 may be used.

The temperature of the chemical ripening using the selenium sensitizer is 40.
~ 90 ℃ range is preferred, more preferably 45 ℃ or more, 80
It is below ℃. The pH is preferably in the range of 4 to 9 and the pAg is preferably in the range of 6 to 9.5.

Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-dimethyl tellurourea, N, N'- Dimethyl-N′-phenyltellureas), phosphine tellurides (eg tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides ( Examples thereof include telluroacetamide, N, N-dimethyl tellurobenzamide), telluroketones, telluroesters, and isotelloocyanates.

The technique for using the tellurium sensitizer is in accordance with the technique for using the selenium sensitizer.

It is also preferable to carry out so-called reduction sensitization inside the grains by placing them in an appropriate reducing atmosphere. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and their derivatives. Other preferred reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

The addition amount of the reducing agent depends on the type of reduction sensitizer, the grain size of silver halide grains, the composition and crystal habit, the temperature of the reaction system, p
Although it is preferable to change it depending on environmental conditions such as H and pAg, for example, in the case of thiourea dioxide, a preferable result is obtained by using about 0.01 to 2 mg per mol of silver halide as a rough guide. In the case of ascorbic acid, it is preferably in the range of about 50 mg to 2 g per mol of silver halide.

The condition for reduction sensitization is that the temperature is about 40 to 70.
C, time about 10-200 minutes, pH about 5-11, pAg about 1-1
A range of 0 is preferred (where the pAg value is the reciprocal of the Ag + ion concentration).

Silver nitrate is preferable as the water-soluble silver salt. So-called silver ripening, which is one of reduction sensitization techniques, is performed by adding a water-soluble silver salt. The pAg during silver ripening is suitably 1-6, preferably 2-4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range. As a stabilizer for a silver halide photographic emulsion containing reduction-sensitized silver halide grains, a general stabilizer described below can be used, but the antioxidant disclosed in JP-A-57-82831 And / or paper by VS Gahler [Zeitshrift fur w
Issenschaftliche Photographie Bd. 63, 133 (1969)] and thiosulfonic acids described in JP-A-54-1019 are often used in combination with good results. still,
These compounds may be added at any stage of the emulsion production process from crystal growth to the preparation process immediately before coating.

[0103]

EXAMPLES The present invention will be described below with reference to examples.

Example 1 Preparation of Em-1 (Preparation of seed emulsion) Seed emulsion-1 was prepared as follows.

A1 ossein gelatin 24.2g water 9657ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78ml potassium bromide 10.8g 10% nitric acid 114ml B1 2.5N silver nitrate aqueous solution 2825ml C1 potassium bromide 841g 2825 ml of D1 1.75N potassium bromide aqueous solution with water At the following silver potential control amount of 42 ° C., each of solution B1 and solution C1 is added to solution A1 using the mixing stirrer shown in JP-B-58-58288 and 58-58289.
Nucleation was performed by adding 464.3 ml by the double-sided mixing method over 1.5 minutes.

After stopping the addition of solution B1 and solution C1, it took 60 minutes to raise the temperature of solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then add solution B1 again. Solution C1 was added by the double jet method at a flow rate of 55.4 ml / min each for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during this temperature increase from 42 ° C. to 60 ° C. and re-simultaneous mixing with the solutions B1 and C1 was +8 mv using the solution D1. And +16 mv.

After the completion of the addition, the pH was adjusted to 6 with 3% KOH, and the mixture was immediately desalted and washed with water. This seed emulsion has a maximum adjacent side ratio of 1.0 to 90% of the total projected area of silver halide grains.
It was confirmed by an electron microscope that the hexagonal tabular grains of 2.0 had an average thickness of 0.064 μm and an average grain size (circle diameter conversion) of 0.595 μm. The coefficient of variation of thickness is 40
%, And the coefficient of variation in the distance between twin planes was 42%.

Subsequently, tabular pure silver bromide emulsion Em-1 was prepared using seed emulsion-1 and the following three kinds of solutions.

A2 ossein gelatin 34.03g polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 2.25ml seed emulsion-1 1.218mol equivalent water to make 3150ml B2 potassium bromide 1747g water to make 3669ml C2 Silver nitrate 2493 g Finished with water to 4193 ml Solution A2 was vigorously stirred while maintaining the temperature at 60 ° C., and the total amount of solution B2 and solution C2 was added thereto by the simultaneous mixing method over 100 minutes. During this time, pH was 5.8 and pAg was 8.8.
Kept from beginning to end. Here, the addition rates of solution B2 and solution C2 were changed in a function-like manner with respect to time so as to match the critical growth rate. That is, the addition was performed at an appropriate addition rate so that small particles were not generated other than the growing seed particles and polydispersion did not occur due to Ostwald ripening.

After the completion of the addition, this emulsion was cooled to 40 ° C., and a 13.8% (weight) aqueous solution of modified gelatin modified with phenylcarbamoyl groups (a substitution rate of 90%) as an aggregating polymer agent 1800
ml was added and stirred for 3 minutes. Then acetic acid 56% (weight)
The pH of the emulsion was adjusted to 4.6 by adding an aqueous solution, stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation. Then, add 9.0 liters of distilled water at 40 ℃,
After stirring and standing, the supernatant was drained, 11.25 l of distilled water was further added, and after stirring and standing, the supernatant was drained. Then add gelatin aqueous solution and sodium carbonate 10% (by weight) aqueous solution to adjust the pH.
Was adjusted to 5.80, and the mixture was stirred at 50 ° C for 30 minutes and redispersed. After redispersion, pH was adjusted to 5.80 and pAg was adjusted to 8.06 at 40 ° C.

Subsequently, after the emulsion was heated to 60 ° C., the following amounts of the spectral sensitizing dyes D-1 and D-2 were added as a solid fine particle dispersion, and then ammonium thiocyanate, chloroauric acid and thiosulfate were added. A mixed aqueous solution of sodium and a methanol solution of triphenylphosphine selenide were added and aged for a total of 2 hours. At the end of ripening, an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

The additives other than the spectral sensitizing dye and the amount added (per 1 mol of AgX) are shown below.

Ammonium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate (pentahydrate) 2.0 mg Triphenylphosphine selenide 0.4 mg Stabilizer (TAI) 1000 mg Solid fine particle dispersion of spectral sensitizing dye is disclosed in Japanese Patent Application No. It was prepared by a method similar to that described in -99437.

That is, a predetermined amount of the spectral sensitizing dye was added to water whose temperature had been adjusted to 27 ° C. in advance, and the mixture was stirred by a high speed stirrer (dissolver) at 3,500 rpm for 30 to 120 minutes.

When the obtained silver halide emulsion was observed with an electron microscope, tabular silver halide grains having an average grain size of 1.11 μm, an average thickness of 0.25 μm, an average aspect ratio of about 4.5 and a grain size distribution of 18.1% were obtained. Met. Also, the average distance between twin planes is
It was 0.020 μm.

Sensitizing dye (D-1) 5,5′-dichloro-9-ethyl-3,3′-di- (3-sulfopropyl) -oxacarbocyanine sodium salt anhydride 2.0 × 10 ⁻³ Mol / mol Ag Sensitizing dye (D-2) 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) -benzimidazolocarbocyanine- Preparation of anhydrous sodium salt 1.5 × 10 ^-5 mol / mol Ag Em-2 A tabular silver iodochloride emulsion Em was prepared using the following three solutions.
-2 was prepared.

A3 low methionine gelatin 214.37 g sodium chloride 1.995 g potassium iodide 149.6 mg finished with water 6090 ml B3 sodium chloride 10.48 g potassium iodide 149.4 mg finished with water 90 ml C3 silver nitrate 30.58 g finished with water 90 ml D3 sodium chloride 165.0g Water finishes to 5640ml E3 Silver nitrate 479.0g Water finishes to 5640ml Solution A3 is stirred vigorously while keeping it at 40 ° C, and the total amount of solution B3 and solution C3 is added at a flow rate of 180ml / min for 30 seconds. And added by the simultaneous mixing method.

Next, this mixed solution was kept at 40 ° C. for 10 minutes, and then the solution D3 and the solution E3 were added by the simultaneous mixing method at a flow rate of 24 ml per minute over 40 minutes, and subsequently, the solution D3 and the solution E3 were further added. The total amount of the remaining mixture was added by the simultaneous addition method over 130 minutes while linearly increasing the flow rate so that the initial flow rate was 24 ml and the final flow rate was 48 ml. During this time, pCl was kept at 2.35 throughout. Then, it was adjusted to 1.30 with sodium chloride, pCl was adjusted to 2.0 using an ultrafiltration membrane, and pCl was adjusted to 1.65 by adding sodium chloride.

Subsequently, this emulsion was spectrally and chemically sensitized in the same manner as Em-1. The obtained silver halide emulsion contained 0.06 mol% iodide, and when observed by an electron microscope, the average grain size (circle diameter conversion) was 1.45 μm, and the average thickness was
It was a right parallelogram tabular silver halide grain with a mean aspect ratio of 11 and a grain size of 0.13 μm. The details of the emulsion thus obtained are shown below.

[0120]

[Table 1]

The following additives were added to the obtained emulsion to prepare an emulsion layer coating solution. At the same time, the following coating solution for protective layer was also prepared.

Using both coating solutions, the amount of silver per side was 1.9 g / m ² , and the amount of gelatin was as shown in Table 2 using two slide hopper molds at a speed of 80 m / min. Simultaneous coating on both sides, drying in 2 minutes 20 seconds, sample N
I got o.1 and No.2.

Glycidyl methacrylate as a support
The concentration of the copolymer consisting of 50 wt%, 10 wt% methyl acrylate and 40 wt% butyl methacrylate
A 175 μm thick polyethylene terephthalate base for X-ray film (blue colored to a concentration of 0.15) coated with an aqueous dispersion obtained by diluting with pure water to 10 wt% as an undercoating liquid was used. .

The additives used in the emulsion layer coating solution are as follows. The addition amount is shown as an amount per 1 m ² of the light-sensitive material.

1,1-dimethylol-1-bromo-nitromethane 1.4 mg t-butyl-catechol 8 mg polyvinylpyrrolidone (molecular weight 10,000) 0.02 g styrene-maleic anhydride copolymer 0.05 g trimethylolpropane 0.1 g nitrophenyl-triphenyl Phosphonium chloride 1 mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 0.04 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 0.02 g 1-phenyl-5-mercaptotetrazole 0.3 mg Table 2 Listed water-soluble polymer substances Table 2 Listed amount

[0126]

[Chemical 7]

Protective Layer Solution The following was prepared as a protective layer coating solution. The addition amount is shown as an amount per 1 m ^{2 on} one side of the light-sensitive material.

Lime-treated Inert Gelatin Table 2 Content Sodium-i-amyl-n-decylsulfosuccinate 0.02g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 0.02g Silicon dioxide particles (area average particle size 1.2 μm matting agent) 0.01g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O 0.01g C ₄ F ₉ SO ₃ K 0.04g C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 0.04g

[0129]

Embedded image

The obtained samples, for example, were evaluated as follows.

<Evaluation of contrast> N of the obtained sample
O.1 and No.2 are sandwiched between two X-ray intensifying screens KO-250,
Tube voltage 80kvp, tube current 100m through aluminum wedge
Exposure was performed by irradiation with X-rays for 0.05 seconds at A. Next, a roller transport type automatic developing machine SRX-502 (manufactured by Konica Corporation) was modified, and a developing solution and a fixing solution having the following compositions were used and processed under the following conditions.

Table 2 shows the slope of the characteristic curve connecting the points of density 1.0 and 2.0 with tan α.

<Evaluation of Drying Unevenness> For each large-angle sample, uniform exposure was applied to the entire surface so that the density was about 1.0, and the sample was processed by the above-mentioned automatic developing machine. The obtained samples were evaluated according to the following four grades based on the occurrence state of unevenness when viewed from above.

1: No occurrence was observed 2: Some occurrence was observed 3: Many occurrences (not practically possible) 4: All occurred.

<Measurement of Organic Substances after Processing> Development-Fixing-
After the washing-drying treatment, the following method can be used to measure what percentage (weight ratio) of the organic substance applied before the treatment remains.

First, the sample was allowed to stand at 25 ° C. and 10% RH until the water content of the sample was in equilibrium with the atmosphere, and then the weight of the sample was measured. Next, the sample was processed from development to drying by an automatic processor, and then left again under the conditions of 25 ° C. and RH 10%, and when the water content reached equilibrium, the weight measurement was carried out.

The weight of the support was measured in advance, and it was confirmed that the weight of the support alone was not changed. The amount of developed silver was determined by performing the exposure uniformly or not at all, and the weight loss due to the development and fixing of the silver halide grains themselves was calculated from this value and the specific gravity of the silver halide. The weight of the organic substance remaining after the treatment was determined from these values.

The processing solutions used are shown below.

(Developer composition) Part A (for 12 l finishing) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetriamine pentaacetic acid 120 g Sodium hydrogencarbonate 132 g Boric acid 40 g 5-Methylbenzotriazole 140 mg 1-phenyl-5 -Mercaptotetrazole 250mg 4-Hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 102g Hydroquinone 390g Diethylene glycol 550g Add water to make 6000ml.

Part B (for 12 l finishing) Glacial acetic acid 70 g 5-Nitroindazole 0.6 g Glutaraldehyde (50% solution) 8.0 g n-Acetyl-D, L-penicillamine 1.2 g (starter) Glacial acetic acid 120 g HO (CH ₂ ). ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH 1 g KBr 225 g CH ₃ N (C ₃ H ₆ NHCONHCH ₂ SC ₂ H ₅ ) ₂
Add 1g water
Finish to 1 liter.

(Fixing liquid composition) Part A (for finishing 18.3 l) Ammoniu thiosulfate (70 wt / vol%) 4500 g anhydrous sodium sulfite 450 g sodium acetate trihydrate 450 g boric acid 110 g tartaric acid 60 g sodium citrate 10 g gluconic acid 70 g 1 -(N, N-Dimethylamino) -ethyl-5-mercaptotetrazole 18g Glacial acetic acid 330g Aluminum sulfate 62g Make up to 7200ml with pure water.

To prepare a developing solution, add parts A and B to about 5 l of water at the same time, add water while stirring and dissolve to make 12 l, and p
The H was adjusted to 10.53. This is used as a development replenisher.

20 ml of the above-mentioned starter was added to 1 liter of this replenisher, and the pH was adjusted to 10.30 to prepare a working solution. For the fixer, add Part A to approximately 5 liters of water, add water while stirring and dissolve to make 18.3 liters, and use sulfuric acid and ammonia to adjust the pH to 4.
Adjust to 6 and use this as the fixer replenisher.

The above results obtained are shown in Table 2 below.

[0145]

[Table 2]

As is apparent from the table, the sample of the present invention has a small amount of the organic substance remaining after the film processing and does not cause uneven drying. Further, a silver halide photographic light-sensitive material was obtained in which the fluctuation of the contrast was small even in the rapid processing and the photographic performance was small in processing variability.

[0147]

As demonstrated in the examples, according to the present invention, it is possible to obtain a silver halide photographic light-sensitive material which has stable photographic performance even with rapid processing and does not cause uneven drying.

Claims (1)

[Claims] 1. A process for developing a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, which is included in at least one of the photosensitive silver halide emulsion layers. The silver halide grains satisfy the following conditions (1) to (3), and in the silver halide photographic light-sensitive material, the amount of the organic substance present in the hydrophilic colloid layer including the emulsion layer after development is A development processing method of a silver halide photographic light-sensitive material, which is 90% by weight or less of the amount before development processing. (1) 50% or more of the total projected area of silver halide grains is tabular silver halide grains having an aspect ratio of 2 or more. (2) The main plane of the tabular silver halide grains has an adjacent edge ratio of 10
Have less than (100) faces. (3) The tabular silver halide grains are photosensitive silver halide grains having a silver chloride content of at least 30 mol% or more.