JPH09304881A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the photosensitive material enhanced in antistaticizing power due to conductivity and freed of residual dye stains without deteriorating film adhesion after development processing by incorporating dextran or a specified compound in a hydrophilic colloidal layer and a metal oxide in an undercoat layer. SOLUTION: This photosensitive material has the hydrophilic colloidal layers including an silver halide emulsion layer and the undercoat layer on a support. The hydrophilic colloidal layers contain the dextran or the compound represented by the formula in which each of R1 and R2 is, independently, a hydroxy or OM or amino group or the like; M is an alkali metal atom or an ammonium group; and X is an atomic group necessary to form a 5- or 6-membered ring together with the vinyl 2 carbons and the carbonyl carbon. The undercoat layer contains the metal oxide in the form of any of fine crystalline grains or colloid, preferably, a colloidal form.

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 excellent antistatic performance, good film formation after development processing and less residual color contamination, and a method thereof. Regarding processing method.

[0002]

2. Description of the Related Art In recent years, not only high sensitivity and high image quality but also stable performance have been strongly demanded for silver halide photographic light-sensitive materials. Further, in terms of processing, further rapid processability is required, and for this reason, various studies have been made from the light-sensitive material and the processing side.

In rapid processing of silver halide photographic light-sensitive materials, since the film is conveyed at a high speed in an automatic processor, it is very easy to be charged due to contact with a conveying roller, friction, contact between photosensitive materials, peeling or the like. Therefore, a fog called a static mark is generated by the discharge, resulting in a fatal failure in the image.

Conventionally, many reports have been made on antistatic agents for silver halide photographic light-sensitive materials, including antistatic agents. For example, polymer electrolytes and various surfactants are widely known. There is. However, since these materials are generally water-soluble, they have the drawback that they are dissolved in the processing solution during the development processing and turbidity or sludge is generated in the processing solution.

Recently, an antistatic method using a metal oxide as a conductive antistatic agent, particularly ultrafine particle metal oxide, has been disclosed in, for example, JP-A-57-104931.
According to this method, the problem of the processing solution due to elution described above is solved, but on the other hand, the film attachment (physical properties of the image-bearing gelatin film, etc.) of the treated film is deteriorated, and the film peeling and scratches are likely to occur. Showed an obstacle.

Further, according to this technique, the spectral sensitizing dyes and various dyes, which are essential materials for silver halide photographic light-sensitive materials, are less likely to be eluted during the processing, and as a result, residual color contamination is caused on the processed film. There is an unexpected problem of occurrence, and a further improvement technique using a conductive antistatic agent has been strongly desired.

[0007]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide a silver halide photographic light-sensitive material which has excellent antistatic performance due to conductivity, does not deteriorate the film-forming property after development processing, and has no residual color contamination. And to provide a processing method thereof.

[0008]

The above object of the present invention has been attained by the following constitutions.

(1) A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a silver halide emulsion layer and an undercoat layer on a support, wherein the hydrophilic colloid layer contains dextran and the undercoat layer A silver halide photographic light-sensitive material comprising a layer containing a metal oxide.

(2) In a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a silver halide emulsion layer and an undercoat layer on a support, the hydrophilic colloid layer is represented by the following general formula (1). And a metal oxide in the undercoat layer.

[0011]

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In the formula, R ₁ and R ₂ each independently represent a hydroxy group, -OM, amino group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonylamino group, mercapto group or alkylthio group, M represents an alkali metal atom or an ammonium group, and X represents an atomic group necessary for forming a 5- or 6-membered ring with the two vinyl carbons substituted by R ₁ and R ₂ and the carbonyl carbon.

(3) Processing the silver halide photographic light-sensitive material described in the above item (1) or (2) with an automatic processor having a mechanism for supplying a solid processing agent to a processing tank of the automatic processor. A method for processing a silver halide photographic light-sensitive material, which is characterized.

Hereinafter, the present invention will be described in detail.

First, the metal oxide used in the undercoat layer of the present invention will be described. Examples of the conductor made of an oxide containing a metal atom include crystalline metal oxide fine particles or colloidal metal oxide containing a non-stoichiometric compound such as an oxygen-deficient oxide, a metal-excess oxide, and a metal-deficient oxide. Either of them may be used, but a colloidal metal oxide is preferable.

In the present invention, colloidal means a state in which particles having an average particle size of 0.001 to 1 μm are dispersed.

The metal oxide of the present invention includes zinc, magnesium, silicon, calcium, aluminum, strontium, barium, zirconium, titanium, manganese,
Examples include oxides of iron, cobalt, nickel, tin, indium, molybdenum and vanadium, and complex oxides thereof. Preferably ZnO, SnO ₂ , V ₂ O ₅
As an example of the complex oxide, ZnO is Al, In
Etc., SnO ₂ includes Sb, Nb, etc., In ₂ O ₃ includes Sb, etc.

For example, Japanese Examined Patent Publication No. 1-20735 and 1-
No. 1,020,733 and JP-A-58-62647 describe a method for producing crystalline metal oxide fine particles and a method for providing a layer containing them.

For example, Japanese Patent Laid-Open No. 7-319122 discloses that
Methods of preparing colloidal oxides and providing layers containing them are described in US Pat.
No. 769 describes a method for preparing colloidal V ₂ O _{5 and} a method for providing a layer containing them.

For example, a method for producing a colloidal oxide will be described by taking tin oxide as an example.

The colloidal tin oxide can be produced by any method such as a method in which fine particles of tin oxide are dispersed in an appropriate solvent, or a method in which a tin compound soluble in a solvent is decomposed in a solvent. But it's okay.

In the production method using tin oxide fine particles, the temperature condition is particularly important, and the method involving high temperature heat treatment is not preferable because of the growth of primary particles and the appearance of crystallinity, and the heat treatment is unavoidable. In this case, the temperature is 300 ° C. or lower, preferably 200 ° C. or lower, and further 150 ° C. or lower. However, heating in the range of 150 to 250 ° C. is preferable for dispersion in the binder.

Further, following a manufacturing process for isolating only tin oxide, such as a method of spraying a tin compound manufactured by a wet method in an electric furnace or a high temperature thermal decomposition method of an organic tin compound, tin oxide is added to a solvent. The method of redispersion is not very suitable for use as an antistatic agent for photography because redispersion is very difficult and agglomerated particles are generated.

When the solvent of the colloidal tin oxide dispersion at the time of production and the compatibility of the protective colloid binder are poor, in order to replace with a solvent suitable for dispersing in the binder,
A compound that has good compatibility with the production solvent or that stably disperses colloidal tin oxide is added as appropriate, and the compound is heated to 300 ° C or lower, preferably 200 ° C or lower, and further 150 ° C or lower, and then oxidized together with the added compound Tin fine particles are separated by drying and redispersed in water or water mixed with another solvent.

Examples of the tin compound used in the method of producing from a decomposition reaction of a tin compound soluble in a solvent in a solvent include compounds containing an oxo anion such as K ₂ SnO ₃ .3H ₂ O and SnCl ₄ . Water-soluble halide,
(CH ₃ ) ₃ SnCl · (pyridine), (C ₄ H ₉ ) ₂ Sn having the structure of R ′ ₂ SnR ₂ , R ₃ SnX, R ₂ SnX _2.
Organometallic compounds such as (OCC ₂ H ₅ ) ₂ and Sn (SO ₄ ) ₂
An oxo salt such as 2H ₂ O can be mentioned.

After the tin compounds soluble in these solvents are dissolved in the solvent, colloidal tin oxide is produced by a physical method such as heating or pressurizing, or a chemical method such as oxidation, reduction or hydrolysis. Or, a colloidal tin oxide is produced via an intermediate.

For example, Japanese Patent Publication No. 35-6616 discloses Sn.
Cl ₄ is dissolved in 100 times volume of distilled water to precipitate stannic hydroxide, and then ammonia water is added to make it weakly alkaline to dissolve the precipitate, and the mixture is heated until ammonia odor disappears and colloidal tin oxide is added. A method of manufacturing is described.

As the solvent, in addition to water, alcohol solvents such as methanol, ethanol and isopropanol, ether solvents such as tetrahydrofuran, dioxane and diethyl ether, aliphatic organic solvents such as hexane and heptane, aromatic organics such as benzene and pyridine. Various solvents can be used depending on the tin compound such as the solvent, but water and alcohols are preferable.

According to this method, it is possible to add a compound containing an element other than a tin compound which is soluble in a solvent during the production, and for example, a fluorine-containing compound or a metal capable of taking a trivalent or pentavalent coordination number. A compound can be introduced.

As the fluorine-containing compound soluble in the solvent,
Either an ionic fluoride or a covalent fluoride may be used, and metal fluorides such as K ₂ TiF ₆ , HF, KHF ₂ Sb, and F ₃ MoF ₆ , and fluoro complex anions such as NH ₄ MnF ₃ and NH ₄ BiF _4. Compounds that produce the compounds BrF ₃ , SF ₄ , S
Inorganic molecular fluorides such as F ₆ , CF ₃ I, CF ₃ OOH,
Organic fluorine compounds such as P (CF ₃ ) ₃ can be mentioned, and when the solvent is water, a combination of a fluorine-containing compound and a non-volatile acid can also be used such as a combination of CaF ₂ and sulfuric acid. .

As the metal compound soluble in a solvent and capable of having a trivalent or pentavalent coordination number, a group III element such as Al, Ga, In and Tl or a group V element such as P, As, Sb and Bi, Nb, V, T which can have trivalent or pentavalent coordination number
It is a group of compounds containing a transition metal such as i, Cr, Mo, Fe, Co, and Ni.

(Synthesis Example 1 of colloidal tin oxide) 65 g of stannic chloride hydrate was mixed with 2000 of water / ethanol.
Dissolved in cc to obtain a homogeneous solution. Then, this was boiled to obtain a coprecipitate. The generated precipitate is taken out by decantation and washed with distilled water many times. After dropping the silver nitrate into the distilled water after washing the precipitate and confirming that there is no reaction of chloride ions, add distilled water to the washed precipitate to bring the total amount to 2
000 cc. 40cc of 30% ammonia water
In addition, the mixture was heated in an aqueous solution to obtain colloidal tin oxide.

(Synthesis example 2 of colloidal tin oxide) 65 g of stannic chloride hydrate and 1.0 g of antimony trichloride were added to water /
A homogeneous solution was obtained by dissolving in 2000 cc of an ethanol mixed solution. Then, this was boiled to obtain a coprecipitate. The generated precipitate is taken out by decantation and washed with distilled water many times. After confirming that there is no reaction of chloride ions by dropping silver nitrate into distilled water from which the precipitate has been washed, distilled water is added to the washed precipitate to bring the total amount to 2000 cc. 3 more
40 cc of 0% ammonia water was added and heated in an aqueous solution,
A colloidal tin oxide was obtained. The volume resistivity of the colloidal tin oxide thus obtained is 2.1 × 10 ⁵ Ωc
m.

In the present invention, the dextran contained in the hydrophilic colloid layer is a polymer of D-1, glucose linked with α-1,6, and is generally obtained by culturing a dextran-producing bacterium in the presence of saccharides. ,
Native dextran obtained by acting dextran-producing bacterium such as Mesentereutes or dextran sucrase isolated from the culture solution of these bacteria on sucrose solution is reduced to a desired molecular weight by partial decomposition weight method with acid, alkali or enzyme. It is a thing.

The dextran used in the present invention has a weight average molecular weight of 5,000 to 300,000, preferably 15,000 to 1.
It is 0,000, and more preferably 20,000 to 70,000.

Dextran may be any layer as long as it is a hydrophilic colloid layer, but when there are a plurality of hydrophilic colloid layers, it is preferable to add it to the hydrophilic colloid layer near the undercoat layer.

When dextran is added to the hydrophilic colloid layer, 5 to 5% of the total amount of the binder in the hydrophilic colloid layer is added.
It is preferable to add 0% by weight, more preferably 10% by weight.
~ 45% by weight.

In the present invention, the hydrophilic colloid layer preferably contains the compound of the general formula (1).

In the general formula (1), R ₁ and R ₂ are each independently a hydroxy group, —OM (M represents an alkali metal atom or an ammonium group), an amino group (a methyl group or an ethyl group as a substituent). , N-butyl group, hydroxyethyl group and the like having an alkyl group having 1 to 10 carbon atoms), acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.) ), An arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), an alkoxycarbonylamino group (methoxycarbonylamino group, etc.), a mercapto group, an alkylthio group (methylthio group, ethylthio group, etc.), and preferably Is a hydroxy group, amino group, alkylsulfonylamino group, aryl It is a sulfonylamino group. X is -O
_{-, - C (R 3)} (R 4) -, - C (R 5) =, - C (=
O)-, -N (R ₆ )-, -N = and the like, preferably a carbon atom, an oxygen atom or a nitrogen atom, which is in combination with two vinyl carbons and carbonyl carbons substituted by R ₁ and R _2. Form a 5- to 6-membered ring. Here, R _{3 to} R ₆ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent (such as a hydroxy group, a carboxy group, or a sulfo group); , A hydroxy group, a carboxy group, a sulfo group, etc.)
Represents an aryl group, a hydroxy group or a carboxy group. The constituent 5- or 6-membered ring may form a saturated or unsaturated condensed ring, such as a dihydrofuranone ring, a dihydropyrone ring,
Examples thereof include a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolidone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring, and preferably a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolidone ring. , An azacyclohexenone ring, and a uracil ring.

Specific examples of the compound represented by formula (1) are shown below, but the invention is not limited thereto.

[0041]

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[0042]

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[0043]

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[0044]

[Chemical 6]

When the compound represented by the general formula (1) of the present invention is an acid, it may be a free acid or a salt form.

The compound represented by the general formula (1) may be any layer as long as it is a hydrophilic colloid layer, but when there are a plurality of hydrophilic colloid layers, it is added to the hydrophilic colloid layer near the undercoat layer. Is preferred.

When the compound represented by the general formula (1) is added to the silver halide emulsion layer, it is preferably 5 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, and more preferably 1 mol per mol of silver halide. It may be in the range of x10 ^-5 to 1 x 10 ^-2 mol.

When the compound represented by the general formula (1) is added to the non-photosensitive gelatin layer, it is 5 × 10 ^-7 to 1 × 1.
0 ⁻² mol / m ² is preferable, and more preferably 1 × 10 ^−6
-1 x 10 ^-3 mol / m ² is sufficient.

The halogen composition of the silver halide grains used in the present invention is arbitrary, and may be silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride, silver chloroiodide, iodide. Any of silver may be used.

The silver halide grains used in the present invention are:
Normal crystal grains such as cubes, tetradecahedrons, and octahedrons may be used, and spherical grains, plate-like grains or an aspect ratio of 2
And may have an irregular crystal form such as a potato.

In the present invention, the term “spherical” means that 1/10 L to 1/2 L of the length L when focusing on the surface having the maximum area among the polygons forming the outer shape of the silver halide grains.
Is defined at the polygonal ridge portion before the spheroidization, with a radius of curvature corresponding to. Grain roundness can be determined by observing silver halide grains with an electron microscope.

In the present invention, the monodisperse silver halide grains mean that the weight of silver halide contained in the grain size range of ± 20% around the average grain size d is 60% or more of the total weight of silver halide. It is preferably 70% or more, more preferably 80% or more. Here, the average particle size d is the particle size d
product ni × di ³ of the frequency ni and di ³ of particles having i is defined as the particle size di of when maximized. (Significant number 3
Digits and minimum digits are rounded off to 4) The grain size referred to here is the diameter of spherical silver halide grains, and the projected image of grains of a shape other than spherical. It is the diameter when converted to a circle image.

The particle size can be obtained, for example, by magnifying the particles with an electron microscope from 10,000 times to 50,000 times, and actually measuring the particle diameter on the print or the area at the time of photographing (measurement). It is assumed that the number of particles is 1000 or more indiscriminately.)

The monodisperse silver halide grains have a distribution width of 20% or less, more preferably 15% or less. Here, the method of measuring the particle size is in accordance with the above-described measuring method, and the average particle size is a simple average.

Average grain size = Σdini / Σni The monodisperse core / shell type silver halide grains used in the present invention are halogenated grains having a grain structure composed of two or more layers having different silver iodide contents. It is composed of silver particles, and is a particle composed of a core (inner layer) and a shell covering the core, and the shell is formed by one or more layers. The iodine content of the core and the shell are preferably different from each other, and it is particularly preferable that the iodine content of the core is maximized.

The iodine content of the core is preferably 5 mol% or more and the solid solution limit or less, more preferably 7 mol% or more and the solid solution limit or less. The iodine content of the core is preferably at least 3 mol% or more than the iodine content of the shell. The iodine distribution of the core is usually uniform, but it may have a distribution. For example, as the concentration goes from the center to the outside, the concentration may become higher, or the intermediate region may have a maximum or minimum concentration.

The monodisperse core / shell type silver halide grains are prepared by preliminarily allowing an aqueous solution containing a protective colloid and seed grains to be present in a reaction vessel, and supplying silver ions, halogen ions or silver halide fine particles as needed. What is obtained by crystal growth of seed particles is preferable. In this case, the grain center can have a halogen composition region different from that of the core.

The halogen composition of the seed grains is arbitrary and is any of silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride, silver chloroiodide and silver iodide. Good.

A silver halide photographic emulsion is disclosed in JP-A-3-168.
734, ammonia, thioether,
Known silver halide solvents, such as thiourea and thiocyanate, can be present and can be substantially rounded as defined above.

In the step of forming silver halide grains, at least 70% of the water-soluble silver salt used for grain formation of the silver halide emulsion is added before pAg is added to 70% of the water-soluble silver salt. It may be substantially rounded as defined above by making it larger than pAg by 1 or more.

In the emulsion thus prepared, an appropriate amount of a halogenated solvent is added to the emulsion at an appropriate time at any time from the formation of silver halide grains to the start of chemical ripening. It may be mixed uniformly to have a substantially round shape.

After the silver halide emulsion is formed, the silver halide emulsion before the solvent treatment may be desalted (including washing with water).

The silver halide grains used in the present invention are
It can be produced by any of the acidic method, the neutral method and the ammonia method. Alternatively, it may be produced at a pH of 7.5 or less using an aqueous ammoniacal silver nitrate solution.

The silver iodide content and the average silver iodide content of each silver halide grain are determined by the EPMA method (Electron method).
It can be determined by using the Probe Micro Analyzer method). According to this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared, an electron beam is irradiated, and X-ray analysis by electron beam excitation is performed. By determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the silver halide composition of each grain can be determined. EPM for at least 50 particles
If the silver iodide content is determined by method A, the average silver iodide content is determined from the average of them.

The halogen composition distribution inside the silver halide grains can be determined by pretreating the grains into ultrathin slices and then observing and analyzing with a transmission electron microscope while cooling. Specifically, silver halide grains are taken out of the emulsion, embedded in a resin, and cut with a diamond knife to produce a 60-nm-thick section. 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,
It can be obtained by quantitative calculation (Inoue, Nagasawa: Abstracts of the 62nd Annual Meeting of the Photographic Society of Japan, 1987 p62).

The silver iodide content on the outermost surface of silver halide grains means the XPS method (X-ray Photoelectricr).
on Spectroscopy: X-ray photoelectron spectroscopy)
Means the silver iodide content of a portion up to a depth of 50 °, which can be determined as follows.

The sample was cooled in an ultrahigh vacuum of 1 × 10 ^-8 torr or less to -110 ° C. or less, and MgKα was irradiated as an X-ray for a probe with an X-ray source voltage of 15 kV and an X-ray source current of 40 mA to obtain Ag3d5 /. 2, Br3d, I3d 3/2 electrons are measured. The integrated intensity of the measured peak is corrected by a sensitivity factor, and the halide composition on the outermost surface is determined from these intensity ratios.

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

The tabular grain may be a tabular silver halide grain having two twin planes parallel to each other on the main planes of two parallel (111) planes, and the two parallel (100) planes may be main planes. Tabular silver halide grains may be used.

A twin is a silver halide crystal having one or more twin planes in one grain. The morphology of twins is classified into Klein and Moiser's article Photographiesch.
Correspondents [Photographies K
orrespondenz] 99, 99, 100
Vol., P. 57.

The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a silver halide photographic emulsion is applied so that the silver halide grains contained therein are oriented on a support to prepare a sample.
This is cut with a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. The presence of twin planes can be confirmed by observing this section with a transmission electron microscope.

As a method of obtaining a tabular silver halide emulsion, a method of precipitating silver halide on a seed crystal may be used. To obtain a tabular silver halide emulsion, a water-soluble silver salt solution and a water-soluble silver salt solution are used. (A) a step of introducing a silver salt and a halide salt into a dispersion medium to form a tabular nuclei in a method for producing a silver halide photographic emulsion which is carried out by supplying a protective halide solution to the presence of a protective colloid. (B) Subsequent to the nucleation, a step of performing Ostwald ripening under the condition of maintaining the (100) face or (111) face of the tabular grain. (C) Next, a water-soluble silver salt solution and a water-soluble halide solution and / or halogen. It is also possible to use a method in which a step (particle forming step) is performed in which the seed particles are enlarged by the addition of activated fine particles and the particles are grown so as to have a desired particle size and halogen composition.

The tabular silver halide grain means a grain having two parallel main planes opposed to each other, and the aspect ratio is represented by a ratio of grain diameter to grain thickness. Here, the grain size means an average projected area diameter (hereinafter referred to as a grain size), and is a circle equivalent diameter 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 main planes forming tabular silver halide grains.

The average value of the aspect ratio of the tabular silver halide grains is preferably 2 or more. In the present invention, the emulsion layer containing tabular silver halide grains contains 50% of the total projected area.
The above consists of tabular silver halide grains, preferably 7
It is 0% or more, more preferably 90% or more. The average grain size of the tabular silver halide grains is preferably from 0.15 to 5.0 µm, more preferably from 0.4 to 3.0 µm, and most preferably from 0.4 to 2.0 µm. .

The average thickness of tabular silver halide grains is 0.
It is preferably from 15 to 0.3 μm, and the particle size and thickness can be optimized to optimize sensitivity and other photographic properties. Sensitivity and other factors that make up the photosensitive material that affect the photographic characteristics (thickness of hydrophilic colloid layer, degree of hardening, chemical ripening conditions, sensitivity setting of the photosensitive material, silver coating amount, etc.)
The optimum particle size and optimum thickness differ depending on the type.

The silver halide grains preferably have a more uniform halogen composition ratio between grains. For example,
When the distribution of the iodide content among the grains is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

The tabular silver halide grains may have dislocations. Dislocations are described in F. Hamilton, P
hot. Sci. Eng, page 57 (1967) and T.S.
Shiozawa, J .; Soc. Photo. Sci. J
Apan, 35, 213 (1972), which can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time, the thicker the particle, the more difficult it is for an electron beam to pass.
Can be observed more clearly using an electron microscope.

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

The tabular silver halide grains preferably have a small thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) × 100 = width of thickness distribution (%), it is preferably 25% or less, more preferably 20% or less. belongs to.

The conditions under which the produced seed grains are enlarged in order to obtain silver halide grains are described in JP-A-51-39.
Nos. 027, 55-142329 and 58-1139
Nos. 28, 54-48521 and 58-49938
As can be seen in the above issue, a water-soluble silver salt solution and a water-soluble halide solution were added by the double jet method, and the addition rate was gradually increased within a range in which new nucleation did not occur and Ostwald ripening did not occur in accordance with the enlargement of the particles. To be changed. As another condition for enlarging seed particles, as seen in the 88th Annual Meeting of the Photographic Society of Japan 1988,
A method of adding silver halide fine particles, dissolving and recrystallizing to enlarge the particles may be used.

For growth, an aqueous solution of silver nitrate and an aqueous solution of halide can be added by double jet, but the iodide can be supplied to the system as silver iodide. The addition rate is preferably such that no new nuclei are generated and at a rate such that the size distribution does not spread due to Ostwald ripening, that is, 30 to 100% of the rate at which new nuclei are generated.

In producing the silver halide emulsion used in the present invention, stirring conditions during production are extremely important. As the stirrer, an apparatus described in JP-A-62-160128, in which an additive liquid nozzle is installed in the liquid near the mother liquor suction port of the stirrer, is particularly preferably used. In this case, the rotation speed of the stirring is preferably set to 100 to 1200 rpm.

In preparing the emulsion, ammonia, thioether,
Known silver halide solvents such as thiourea can be present. In the preparation of silver halide grains, a silver salt solution and a halide solution are added by the double jet method during the growth, the nucleation does not occur according to the growth rate of the grains, and the size distribution is broadened by Ostwald ripening. There is no velocity, that is, the rate at which a new nucleus is generated is 30 to 10
The desired particle size by the method of gradually changing in the range of 0%,
Particles with a distribution can be obtained.

The silver halide grains used in the present invention are
So-called halogen conversion type (conversion type) particles may be used. The amount of halogen conversion is 0.
The conversion is preferably 2 mol% to 0.5 mol%, and the conversion may be performed either during physical ripening or after completion of physical ripening.

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

When silver iodide on the outermost surface of the silver halide grains is contained, the method is to simultaneously add a silver nitrate solution and a solution containing iodide to an emulsion containing the base silver halide grains. A method of adding fine silver halide grains such as silver iodide, silver iodobromide or silver chloroiodobromide,
An addition method of potassium iodide or a mixture of potassium iodide and potassium bromide can be applied. Of these, the method of adding fine silver halide grains is preferable. Especially preferred is the addition of fine silver iodide grains.

The time for adjusting the silver iodide content on the outermost surface is from the final step of the silver halide crystal production step to the chemical ripening step, and further from the completion of the solution preparation step immediately before the coating of the silver halide emulsion. Although it can be selected in the meantime, it is preferable to adjust it by the end of the chemical ripening step. The chemical ripening step referred to here is a point in time when physical ripening and desalting of the silver halide emulsion of the present invention are completed, when a chemical sensitizer is added, and thereafter, an operation for stopping chemical ripening is performed. Up to. Further, the addition of silver halide fine grains may be carried out in several times with a time interval, or another chemically ripened emulsion may be added after the addition of the fine grains.

The temperature of the emulsion of the present invention when the silver halide fine grains are added is preferably in the range of 30 to 80 ° C, more preferably 40 to 65 ° C. Further, the present invention is preferably carried out under the condition that part or all of the silver halide fine grains to be added disappears immediately before coating immediately after the addition, more preferably 20% of the added silver halide fine grains. The above is the disappearance immediately before the application.

In the present invention, it is preferable to add a silver halide solvent before the desalting step in order to accelerate the developing speed. For example, a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) is added in an amount of 1 × 10 ⁻³ mol or more and 3 × 10 ³ mol / mol of silver.
It is preferable to add ^-2 mol or less.

Gelatin is preferably used as the dispersion medium for the protective colloid of silver halide grains, and examples of the gelatin include alkali-processed gelatin, acid-processed gelatin, low molecular weight gelatin (molecular weight of 1,000 to 50,000), and phthalated gelatin. Modified gelatin is used. Other hydrophilic colloids can also be used. Specifically, Research Disclosure Magazine (Research Disclosure)
sur. (Hereinafter abbreviated as RD) Vol. 1764
3 (December 1978).

In the production of silver halide grains, unnecessary soluble salts may be removed during the growth of silver halide grains, or they may remain contained. When removing the salts, see RD Vol. It can be carried out based on the method described in 17643, Section II.

Further, the silver halide grain used in the present invention is a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt), a rhodium salt in the process of forming the grain and / or the process of growing. At least one metal ion selected from (including complex salt) and iron salt (including complex salt) can be added to make these metal elements contained inside the particles and / or in the surface layer of the particles. By placing in a reducing atmosphere, reduction sensitizing nuclei can be provided inside and / or on the surface of the grain.

Further, the action of the reducing agent added at a desired time of particle formation is to add an oxidizing agent such as hydrogen peroxide (water) and its adduct, peroxo acid salt, ozone and I ₂ at a desired time. It is preferable to deactivate the reducing agent and suppress or stop the reducing agent.

The oxidizing agent may be added at any time from when the silver halide grains are formed until before the gold sensitizer in the chemical sensitization step (or when the gold sensitizer is not used, the chemical sensitizer) is added. is there.

The silver halide grains of the present invention can be chemically sensitized. Chemical ripening or chemical sensitization process conditions,
For example, the pH, pAg, temperature, time and the like are not particularly limited, and the reaction can be performed under conditions generally performed in the art. For chemical sensitization, sulfur sensitization using a compound containing sulfur that can react with silver ions or active gelatin, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, using a reducing substance A reduction sensitization method, a gold or other noble metal sensitization method using a noble metal, or the like can be used alone or in combination.

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. Depending on the properties of the selenium compound to be used, the addition may be carried out by dissolving in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent. Further, a method in which the mixture is added in advance with a gelatin solution, or a method in which the mixture is added in the form of an emulsified 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 chemical ripening using a selenium sensitizer is 4
The range is preferably from 0 to 90 ° C, more preferably from 45 ° C to 80 ° C. The pH is 4-9 and the pAg is 6
The range of -9.5 is preferable.

The technique for using the tellurium sensitizer is the same as the technique for using the selenium sensitizer.

It is also preferable to carry out so-called reduction sensitization on the grain surface by placing it in a suitable reducing atmosphere. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and derivatives thereof.
Other preferable reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

The amount of the reducing agent added is the type of reduction sensitizer, the grain size of the silver halide grains, the composition and crystal habit, the temperature of the reaction system, and 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, the range is preferably about 50 mg to 2 g per mol of silver halide.

The conditions for reduction sensitization are as follows:
0 ° C., time is about 10 to 200 minutes, pH is about 5 to 11, p
Ag is preferably in the range of about 1 to 10 (here, pAg
The value is the reciprocal of Ag + ion concentration).

As the water-soluble silver salt, silver nitrate is preferable. 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 to 6, and preferably 2 to 4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range.

The silver halide grains in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

As these dyes, any of the nuclei usually used can be applied. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc. A renin nucleus, a benzindolenin nucleus, an indole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may have a substituent on a carbon atom.

The merocyanine dye or the complex merocyanine dye includes pyrazoline- as a nucleus having a ketomethine structure.
5-6 nuclei, thiohydantoin nuclei, 2-thiooxazolidine-2,4-dione nuclei, thiazoline-2,4-dione nuclei, rhodanine nuclei, thiobarbituric acid nuclei, etc.
Member heterocyclic nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for supersensitization. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, a substituted aminostilbene compound which is a nitrogen-containing heterocyclic nucleus group (for example, US Pat.
33,390, 3,635,721), aromatic organic acid formaldehyde condensate (for example, also described in US Pat. No. 3,743,510), cadmium salt, azaindene compound, etc. Good.

US Pat. Nos. 3,615,613 and 3,6
No. 15,641, No. 3,617,295, No. 3,63
The combinations described in No. 5,721 and the like are particularly useful. The sensitizing dye may be added during or during each step of nucleation, growth, desalting, and chemical sensitization, or after chemical sensitization.

In order to make the photographic light-sensitive material of the present invention suitable for rapid processing, an appropriate amount of a hardener is added in advance in the step of applying the light-sensitive material to adjust the water swelling rate in the developing-fixing-washing step. By doing so, it is preferable to reduce the water content in the light-sensitive material before the start of drying.

The silver halide light-sensitive material of the present invention preferably has a swelling ratio during development of 150 to 250% and a film thickness after expansion of 70 μm or less. Water swelling rate is 250%
If it exceeds the above range, poor drying occurs, and, for example, defective transport occurs in automatic processor processing, especially in rapid processing.

If the water swelling ratio is less than 150%, uneven development and residual color tend to increase during development. The water swelling ratio as referred to herein means the difference between the film thickness after swelling in each processing solution and the film thickness before development processing, and this is divided by the film thickness before processing and multiplied by 100. .

In the present invention, powder processing agents, tablets, pills,
Solid processing agents such as granules may be used, and those subjected to moisture-proof treatment as needed may be used.

The powder in the present invention means an aggregate of fine crystal grains. The term “granules” as used in the present invention refers to granules having a particle diameter of 50 to 5000 μm, which are obtained by adding a granulation step to powder. The tablet referred to in the present invention refers to a tablet obtained by compressing powder or granules into a certain shape.

As a cause of fluctuations in photographic performance, it is effective to reduce the opening coefficient of the developer in the automatic processor. Particularly, the aperture coefficient is preferably 80 cm ² / l or less. That is, when the opening coefficient exceeds 80 cm ² / l, the undissolved solid processing agent or the concentrated liquid immediately after dissolution is easily subjected to air oxidation, and as a result, insoluble matter or scum is generated, which is processed by the automatic processing machine or processed. Problems such as contamination of the sensitive material occur, but the aperture coefficient is 8
These problems are solved at 0 m ² / l or less. The opening coefficient referred to here is represented by the contact area with the air per unit volume of the processing liquid, and the unit is (cm ² / l). In the present invention, the aperture coefficient is preferably 80 cm ² / l or less, more preferably 50 to ³ cm ² / l, and even more preferably 35 to 10 cm ² / l.

The opening coefficient can be generally reduced by using a resin or the like for blocking the air as a floating pig.
131138, 63-216050, 63-2
The size can be reduced by the slit type developing device described in JP-A-35940.

The solid processing agent used in the present invention is a developer,
Although used for photographic processing agents such as fixing agents and rinsing agents, it is the developer that has a great effect of the present invention, especially an effect of stabilizing photographic performance.

The solid treating agent used in the present invention may have only one part of a certain treating agent solidified, but preferably, all the components of the treating agent are solidified. It is desirable that each component be molded as a separate solid processing agent and packaged in the same manner. It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly placed in a package.

In the present invention, as the means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Utility Model Publication Nos. 63-137783 and 63-9752.
There are methods described in No. 2, No. 1-85732, etc., but any method may be used as long as it has at least the function of supplying tablets to the processing tank. Further, when the solid processing agent is granules or powders, it is used in the actual method of Sho 62-81964.
No. 63-84151, JP-A-1-292375.
No., the gravity drop method described and the actual opening 63-105159
And a method using a screw or a screw described in JP-A-63-195345 are known methods, but are not limited thereto.

The solid processing agent of the present invention may be put in a processing tank, but preferably, it is communicated with a processing section for processing a light-sensitive material, and a processing solution flows between the processing section and the processing section. It is preferable that the structure is such that the dissolved components move to the processing section because there is a certain amount of processing liquid circulation between the processing section and the processing section. The solid processing agent is preferably added to the temperature-controlled processing liquid.

In addition to the dihydroxybenzenes, aminophenols and pyrazolidones described in JP-A-6-138591 (pages 19 to 20) as the developing agent, reductones described in JP-A-5-165161 can be used in the developer. It is preferably used. Among the pyrazolidones to be used, those substituted at the 4-position (dimesone, dimeson S, etc.) are particularly preferable because their water solubility and the solid treating agent themselves do not change over time.

As the preservative, in addition to the sulfite described in JP-A-6-138591, an organic reducing agent can be used as the preservative. In addition, a chelating agent or a bisulfite adduct of a hardening agent can be added. Further, as an anti-sludge agent, JP-A-5-289255 and JP-A-6-3086 are used.
It is also preferable to add a compound described in No. 80 (general formulas [4-a] and [4-b]). Addition of a cyclodextrin compound is also preferable, and compounds described in JP-A-1-124852 are particularly preferable.

An amine compound may be added to the developer, and the compounds described in US Pat. No. 4,269,929 are particularly preferable.

It is necessary to use a buffer for the developer,
As the buffer, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate,
Tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borate),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
2-hydroxybenzoic acid potassium (potassium 5-sulfosalicylate) etc. can be mentioned.

As the development accelerator, thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, amine compounds, polyalkylene oxides,
In addition, 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added as necessary.

As the antifoggants, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine can be exemplified by 1-phenyl-5-mercaptotetrazole as a typical example.

Further, in the developer composition, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, a cyclodextrin compound, other Japanese Patent Publication No.
The compounds described in 7-33378 and 44-9509 can be used as an organic solvent for increasing the solubility of the developing agent. Further, various additives such as a stain inhibitor, an anti-sludge agent and a layering effect promoter can be used.

As the fixing agent, a compound known as a fixing agent can be added. Fixing agent, chelating agent, pH buffering agent, hardening agent,
Preservatives and the like can be added.
2246 (page 4) and JP-A-5-113632 (2-
Those described in page 4) can be used. In addition, a bisulfite adduct of a hardener and a known fixing accelerator can also be added.

Prior to the treatment, it is also preferable to add a starter, and it is also preferable to solidify the starter and add the starter. As the starter, in addition to an organic acid such as a polycarboxylic acid compound, a halide of an alkaline earth metal such as KBr, an organic inhibitor, and a development accelerator are used.

The present invention comprises a black-and-white silver halide photographic light-sensitive material (for example, a medical light-sensitive material, a printing light-sensitive material, a negative light-sensitive material for general photography), a color photographic light-sensitive material (for example, a color negative light-sensitive material,
Color reversal light-sensitive material, color print light-sensitive material), diffusion transfer photosensitive material, heat-developable photosensitive material, etc.
It can be more preferably applied to a black and white silver halide photographic material.

Generally, in a developing solution used for developing a black-and-white photographic light-sensitive material, hydroquinones are used as a developing agent in many cases. However, the present invention improves work safety and protects the environment. From the viewpoint of containing substantially no hydroquinone, for example, US Pat. No. 5,236,816.
Alternatively, a developing solution using ascorbic acid described in Japanese Patent Publication No. 1994-242242 may be used.

The development time of the black-and-white photographic light-sensitive material of the present invention is 3
~ 90 seconds, more preferably 5 to 60 seconds, and the processing time is 15 to 210 seconds in terms of Dry to Dry, and more preferably 15 to 90 seconds.

In the silver halide photographic light-sensitive material of the present invention, various additives can be added to the silver halide emulsion according to the purpose. Examples of additives and the like used include RD-17643 (December 1978) and RD 1871.
6 (November 1979) and 308119 (1989).
December, 2012). The places where they are written are listed below.

[0132]

[Table 1]

The support usable in the silver halide photographic light-sensitive material of the present invention is, for example, RD-1 described above.
7643 and RD-308119, page 1009.

A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer for improving the adhesion of the coating layer, corona discharge or ultraviolet irradiation.

[0135]

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

Example 1 (Preparation of Seed Emulsion A) Liquid A1 Ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g Distilled water 7500 ml B1 liquid Silver nitrate 1500 g Distilled water 2500 ml C1 liquid KI 4 g NaCl 140 g Distilled water 684 ml D1 liquid NaCl 375 g distilled water 1816 ml At 40 ° C., 684 ml of the B1 liquid and the total amount of the C1 liquid were added to the A1 liquid in the mixing stirrer described in JP-B-58-58288 over 1 minute. The EAg was adjusted to 149 mV, and after aging for 20 minutes in Ostwald, the total amount of the remaining solution B1 and the total amount of solution D5 were added over 40 minutes. Meanwhile, E
Ag was controlled at 149 mV.

Immediately after the completion of the addition, desalting and washing with water were carried out to obtain a seed emulsion EM-A. Seed emulsion A prepared in this manner has 60% or more of the total projected area of silver halide grains (100).
Electron microscopic observation revealed that the particles consisted of tabular grains having an aspect ratio of 2 or more, having a plane as a main plane, having an average thickness of 0.07 μm, an average diameter of 0.5 μm, and a coefficient of variation of 25%.

(Preparation of Emulsion B) A tabular silver iodochloride emulsion was prepared using the following four kinds of solutions.

[0139] A2 solution ossein gelatin _{29.4g HO (CH 2 CH 2)} m - (CH (CH 3) CH 2 O) 17 - (CH 2 CH 2 O) n -H (m + n ≒ 5.7 molecular weight 1700 ) (10% methanol solution) 1.25 ml seed emulsion A 0.98 mole equivalent distilled water 3000 ml B2 solution 3.5N silver nitrate aqueous solution 2240 ml C2 solution NaCl 455 g distilled water 2240 ml D2 solution 1.75N NaCl aqueous solution Using a mixing stirrer described in Japanese Patent Publication No. 58-58288 at 40 ° C., the flow rate after the addition is completed by the simultaneous mixing method (double jet method) with the total amount of the B2 solution and the C2 solution in the A2 solution is the flow rate at the start of the addition. The growth was made to be three times as much as that of the above and additional growth was performed for 110 minutes. EAg during this period is
The voltage was controlled to 120 mV using the D2 liquid.

After the addition, in order to remove excess salts,
Immediately, the precipitate was desalted and washed with water. About 3 of the obtained emulsion B
When 000 pieces were observed and measured by electron microscope observation and the shape was analyzed, 80% or more of the total projected area was (100)
Average diameter 1.1 with aspect ratio of 2 or more
It was a tabular grain having a particle size of 7 μm and an average thickness of 0.12 μm, and the coefficient of variation was 25%.

(Preparation of silver iodide fine particles) A3 solution Oscein gelatin 100 KI 8.5 g Distilled water 2000 ml B3 solution Silver nitrate 360 g Distilled water 605 ml C3 solution KI 352 g Distilled water 605 ml A3 solution was added to the reactor, 40 While maintaining at ℃ and stirring, B
Solution 3 and solution C3 were added at a low speed over 30 minutes by the simultaneous mixing method. PAg during the addition is 1% by a conventional PAg control means.
It was kept at 3.5. The formed silver iodide has an average grain size of 0.06 μm.
m. This emulsion is called silver iodide fine grains.

(Preparation of solid fine particle dispersion of spectral sensitizing dye) 5,5'-dichloro-9-ethyl-3,3'-di-
(3-Sulfopropyl) -oxacarbocyanine-sodium salt anhydride (sensitizing dye A) and 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-
Di- (4-sulfobutyl) -benzimidazolocarbocyanine-sodium salt anhydride (sensitizing dye B) was added to 100:
In a ratio of 1 to water preliminarily adjusted to 27 ° C., a high-speed stirrer (dissolver) was operated at 3500 r.p.m. p. m. At 30-1
By stirring for 20 minutes, a solid fine particle dispersion of the spectral sensitizing dye was obtained. At this time, the sensitizing dye was adjusted to have a concentration of 2%.

(Chemical Sensitization) Emulsion B was spectrally sensitized and chemically sensitized by the following method to obtain a chemically sensitized emulsion.

After the emulsion was heated to 60 ° C., the above solid fine particle dispersion was added so that the sensitizing dye A was 460 mg per mol of silver halide, and then ammonium thiocyanate salt was added in an amount of 7 × 10 ⁻⁴ mol. Add potassium chloroaurate, sodium thiosulfate and triphenylphosphine selenide
Optimum chemical sensitization was carried out by adding × 10 ^-6 mol, and after adding 3 × 10 ^-3 mol of the above silver iodide fine grain emulsion, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaine was added. Stabilization was carried out by adding 1 × 10 ^-2 mol of den (addition amount per mol of silver halide).

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

(Production of Support 1) Next, the concentration was 0.170.
0.5 kV on both sides of the polyethylene terephthalate film base for X-rays colored blue with a thickness of 175 μm
After applying a corona discharge treatment of A · min / m ^2, the undercoating latex liquid represented by L-2 below is applied so that the film thickness after drying becomes 0.2 μm, and then the following L-1 was sequentially applied so that the film thickness after drying would be 0.053 μm, and dried at 123 ° C. for 2 minutes. This support is referred to as support 1.

[0147]

[Chemical 7]

(L-2) 10% by weight of n-butyl acrylate, 35% by weight of t-butyl acrylate, styrene 2
7% by weight and 28% by weight of 2-hydroxyethyl acrylate copolymer latex liquid (solid content 30%).

(Preparation of Support 2) The same corona discharge-treated blue-colored polyethylene terephthalate film base as Support 1 was provided with an undercoat layer similar to Support 1 on the other side. A coating liquid obtained by mixing the colloidal tin oxide synthesized in (Synthesis example 1), the above-mentioned (L-2) liquid and the following (L-4) liquid at a volume ratio of 35:15:50 was used as the lower layer. The upper layer has the above (L) so that the film thickness is 0.12 μm and the amount of tin oxide component is 250 mg / m ^2.
-1) and the following (L-3) solution were mixed at a volume ratio of 70:30, and the coating solutions were simultaneously applied so that the film thickness after drying would be 0.053 μm, and dried at 120 ° C. for 1 minute.

This support is referred to as support 2.

(L-3) Dimethyl terephthalate 34.0
2 parts by weight, 25.52 parts by weight of dimethyl isophthalate, 5
-Sulfoisophthalic acid dimethyl sodium salt 12.97
Parts by weight, 47.85 parts by weight of ethylene glycol, 1,4
Cyclohexanedimethanol 18.95 parts by weight, calcium acetate monohydrate 0.065 parts by weight, manganese acetate tetrahydrate 0.022 parts by weight under a nitrogen stream 170 to 22 parts
After carrying out an ester exchange reaction while distilling off methanol at 0 ° C., 0.04 part by weight of trimethyl phosphate, 0.04 part by weight of antimony trioxide as a polycondensation catalyst and 15.08 parts by weight of 1,4-cyclohexanedicarboxylic acid. Add 2 parts
At a reaction temperature of 20 to 235 ° C., almost the theoretical amount of water was distilled off to carry out esterification. Thereafter, the pressure inside the reaction system was further reduced and the temperature was increased over about 1 hour, and finally polycondensation was performed at 280 ° C. and 1 mmHg or less for about 1 hour to obtain a polyester polymer (intrinsic viscosity 0.35).

Aqueous Solution 73 of Polyester Polymer Obtained
30 g of styrene and 30 g of butyl methacrylate
g, glycidyl methacrylate 20 g, acrylamide 20 g and ammonium persulfate 1.0 g.
The mixture was reacted at 5 ° C. for 5 hours, cooled to room temperature, and the solid content was adjusted to 10% by weight to obtain a coating solution.

(L-4) A copolymer latex liquid containing 40% by weight of n-butyl acrylate, 20% by weight of styrene and 40% by weight of glycidyl methacrylate.

(Preparation of Support 3) The same corona discharge-treated blue-colored polyethylene terephthalate film base as Support 1 was provided with an undercoat layer similar to Support 1 on the other side. The lower layer is JP-A-58-62.
No. 647 Example 1 tin oxide powder dispersion [III] was used to coat the tin oxide powder so that the amount of tin oxide powder was 250 mg / m ² , and the upper layer was treated in the same manner as in Support 2 (L-
1) and (L-2) is applied, and the temperature is 123 ° C.
For 2 minutes. Let this support be 3.

(Preparation of Support 4) The same corona discharge-treated blue-colored polyethylene terephthalate film base as Support 1 was provided with an undercoat layer similar to Support 1 on the other side. The lower layer is JP-A-58-62.
The ZnO dispersion of Example 1 of No. 646 was applied so that the amount of ZnO applied would be 250 mg / m ² , and the upper layer was the same as the support 2 except that the above (L-1) and (L-2) were used. ) Was applied and dried at 123 ° C. for 2 minutes. This support is designated as 4.

(Preparation of Support 5) The same undercoating layer as that of the support 1 is provided on one side of the blue-colored polyethylene terephthalate film base which has been subjected to the same corona discharge treatment as the support 1, and the other side of the base 1 is provided. US Pat. No. 4,20 for the lower layer
V ₂ O ₅ solution of Example 13 of JP 3,769, the (L-
The coating liquid obtained by mixing the liquid 2) and the liquid (L-4) at a volume ratio of 35:15:50 is dried to a film thickness of 0.12 μm and a V ₂ O ₅ component loading of 230 mg / m ^2. The coating liquid consisting of (L-1) and (L-2) was applied to the upper layer in the same manner as the support 2, and dried at 120 ° C. for 1 minute. This support is designated as 5.

(Preparation of Photosensitive Material) Obtained Support 1
As shown in Table 2, the average molecular weight of 40,0
A first layer of dextran of the following 00 (crossover cut layer) The 0.08 g / m ^2, the second layer (emulsion layer) was added 0.2 g / m ^2, further each as shown below Additives were added to the coating solution, and then the crossover cut layer, the emulsion layer and the protective layer were uniformly coated on both surfaces in that order and dried to prepare Samples 1 to 8 shown in Table 2.

The amount of silver attached on one surface of the sample was 1.5.
g / m ^2, gelatin amount emulsion layer 1.0 g / m ^2, the protective layer is 0.4 g / m ^2, the cross-over cut layer is 0.2g
/ M ² was adjusted and applied.

First layer (crossover cut layer) Gelatin 0.2 g / m ² Solid fine particle dispersion dye (AH) 20 mg / 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) The following various additives were added to the emulsion obtained above.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 5 mg / m ² polyvinylpyrrolidone ( Molecular weight 10,000) 20 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 1 mg / M ² 1,3-dihydroxybenzene-4-ammonium sulfonate 50 mg / m ² 2-mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² n-C ₄ H _{9 OCH 2 CH (OH) CH 2} N (CH 2 OOH) ^₂ 20mg / m ₂ Compound (M) 5mg / m ² Compound (N) 5mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.5g / ^{m 2} Sodium styrene sulfonate (molecular weight about 500,000 ) 7 mg /
m ² The third layer (protective layer lower) Gelatin 0.4 g / m ² of dioctyl phthalate 195 mg / m ² Sodium styrene sulfonate (molecular weight: about 500,000) 7 mg / m ² 4th layer (upper protective layer) Gelatin 0.28 g / Matting agent consisting of m ² polymethylmethacrylate 27 mg / m ² (area average particle size 7.0 μm) 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² latex (L) 0 .2g / m ² polyacrylamide (average molecular weight 10000) 0.1g / m ² sodium polyacrylate 30 mg / m ² compound (SI) 50mg / m ² compound (I) 30mg / m ² compound (S-1) 7mg / _{^{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 1mg / m 2 C 7 F 15 CH 2 (CH 2 CH 2 O) 13 H 10 mg / m ^{2 The} amount of material applied is for one side.

[0161]

Embedded image

[0162]

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(Preparation of Development Replenishing Tablet) A development supplementing tablet was prepared according to the following procedure (A, B).

Operation (A) 3000 g of hydroquinone as a developing agent is ground in a commercial Bantam mill until the average particle size becomes 10 μm. In this grinding, 3000 g of sodium sulfite and 20 g of potassium sulfite were used.
00g and 1000 g of Dimaison S were added, mixed in a mill for 30 minutes, and at room temperature for about 10 minutes in a commercially available stirring granulator.
After granulating by adding 30 ml of water, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the moisture of the granulated material.

Dimezone S: 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone (registered name by EK) 100 g of polyethylene glycol 6000 was added to the granules thus prepared at 25 ° C. and 40% RH. After uniformly mixing for 10 minutes in a humidity-controlled room using a mixer, the obtained mixture was loaded by a tableting machine which was modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Was compressed to 3.84 g and compressed into tablets.
00 developing replenishing tablet A agents were prepared.

Operation (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of KOH, N-acetyl-D, L-. 10 g of penicillamine is crushed and granulated in the same manner as in the operation (A).
The amount of water to be added is 30 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove the moisture of the granulated material. The mixture thus obtained was compressed into tablets using the same tableting machine as described above, with the filling amount per tablet being 1.73 g.
500 tablets of developer replenishment tablet B were prepared.

DTPA: diethylenetriamine pentaacetic acid
5 Sodium (Preparation of fixing replenishing tablet) A fixing replenishing tablet was prepared by the following procedure.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is pulverized in the same manner as in the operation (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in the operation (A), the amount of water added is adjusted to 500 ml and granulation is performed. After granulation, the granulated product is
For 30 minutes to remove the moisture of the granules almost completely. 4 g of sodium N-lauroylalanine was added to the granules thus prepared, and the mixture was added at 25 ° C. and 40% RH.
Mix for 3 minutes using a mixer in a conditioned room below. Next, the obtained mixture was subjected to compression tableting using the above-mentioned tableting machine at a filling amount per tablet of 6.202 g and a compression tableting of 250%.
Zero fixing replenishing tablets C were prepared.

Operation (D) Boric acid 1000 g, aluminum sulfate.18 hydrate 150
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), tartaric acid 200
g is ground and granulated in the same manner as in the operation (A). The amount of water added is 100 ml, and after granulation, the granulated product is dried at 50 ° C. for 30 minutes to almost completely remove the water content of the granulated product.

Thus, 4 g of sodium N-lauroylalanine was added to the thus-prepared granulated product, and the mixture was mixed for 3 minutes. Then, the resulting mixture was charged with the tableting machine at a loading amount of 4.562 g per tablet. And press tableting,
0 fixing replenishing tablet D agents were prepared.

(Development Processing of Photosensitive Material) Developer Solution Starter Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make 1 liter.

At the start of the processing of the developing solution (starting of running), 434 pieces of each of the agent A and the agent B of the developing replenishment tablet were diluted with 16.5 liter of the developing solution prepared by diluting water, and 330 ml of the starter was added. The developing tank was filled with the solution as a starting solution to start the processing. The pH of the developer to which the starter was added was 10.45.

As the fixing start solution, 11.0 liters of the fixing solution prepared by diluting 298 g of C agent and 149 g of D agent of fixing replenishing tablet with diluting water was used as a starting solution to fill the fixing tank.

The film sample was exposed to light so that the optical density after development was 1.0, and was run.
Konica Corporation's automatic processor SRX-50 for running
2 was equipped with a solid processing agent charging member, and was modified so that the processing speed could be reduced to 25 seconds.

During running, the developing solution contained 0.6% light-sensitive material.
^Two A and B agents and 76 ml of water were added per 2 m ² . The pH when each of the agents A and B was dissolved in 38 ml of water was 10.70. To the fixing solution, ^{two of the} above-mentioned C agent, one of the D agent and 74 ml of water were added per 0.62 m ² of the photosensitive material. The rate of addition of water to each treating agent started almost simultaneously with the addition of the treating agent, and was added at a constant speed for 10 minutes approximately in proportion to the dissolution rate of the treating agent.

[0176] <Evaluation of degree of occurrence of static marks> The unexposed sample of the obtained film sample was conditioned for 2 hours at a temperature of 25 ° C. and a humidity of 20% RH, and then rubbed independently with a neoprene rubber roller and a nylon roller, and then the above-mentioned. Was developed and evaluated according to the following criteria.

A: No static marks were generated at all B: Static marks were slightly generated C: Static marks were generated D: Static marks were generated on the whole <Evaluation with film> By the above treatment method 0.3m after conditioning the treated blackened film at 23 ° C and 70% RH for 2 hours
30cm / se with 500g load on mφ sapphire needle
The length of 20 cm was rubbed 10 times at the speed of c, and the peeling of the emulsion film was evaluated according to the following criteria from the scratching method.

A: No scratches at all B: Scratches are slightly detected with a magnifying glass 10 but practically no problem C: Slightly detected with the naked eye D: Clearly peeled film and scratches Level E: large number of scratches and unusable level <Evaluation of residual color> The unexposed sample was processed by the above-mentioned processing method and evaluated according to the following criteria.

A: There is no residual color B: The edge of the film is slightly reddish when gazing, but there is no problem in practical use C: The edge of the film is reddish in an uneven shape when gazing,
No problem in practical use D: Reddish unevenness occurred in the center of the film, and there was a problem in practical use E: Dark reddish unevenness occurred in the center of the film, impractical. The results obtained are shown in Table 2. .

[0180]

[Table 2]

As is clear from Table 2, the samples of the present invention were less likely to generate static marks and were excellent in film formation after development processing. Further, it can be seen that the sample of the present invention has less residual color contamination.

Example 2 Example 1 was repeated except that compounds (A-1), (A-9) and (A-18) of the general formula (1) were added as shown in Table 3 in place of the dextran of Example 1. Operate in the same manner as in Samples 9 to 18
Was prepared and evaluated in the same manner as in Example 1. Table 3 shows the obtained results.

[0183]

[Table 3]

As is clear from Table 3, the samples of the present invention are excellent in antistatic property (static mark preventing property) and film forming property after development processing, and have no residual color contamination. It can be seen that a photographic light-sensitive material can be obtained.

[0185]

As demonstrated in the examples, according to the present invention, the silver halide is excellent in antistatic property (static mark preventing property) and film-forming property after development processing, and has no residual color contamination. A photographic light-sensitive material and a processing method thereof were obtained.

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Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a silver halide emulsion layer and an undercoat layer on a support, wherein the hydrophilic colloid layer contains dextran, and the undercoat layer is contained. A silver halide photographic light-sensitive material characterized by containing a metal oxide therein. 2. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a silver halide emulsion layer and an undercoat layer on a support, wherein the hydrophilic colloid layer is represented by the following general formula (1). A silver halide photographic light-sensitive material containing a compound and a metal oxide in the undercoat layer. Embedded image In the formula, R ₁ and R ₂ are each independently a hydroxy group, —OM,
Represents an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group,
M represents an alkali metal atom or an ammonium group, and X represents an atomic group necessary for forming a 5- or 6-membered ring with the two vinyl carbons substituted by R ₁ and R ₂ and the carbonyl carbon. 3. A silver halide photographic material characterized in that the silver halide photographic light-sensitive material according to claim 1 or 2 is processed by an automatic developing machine having a mechanism for supplying a solid processing agent to a processing tank of the automatic developing machine. Method of processing photosensitive material.