JPH09325448A - Silver halide photographic material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photographic material excellent in electrification preventing performance and filming after the development process and having little color retention by containing a specific compound in a hydrophilic colloidal layer, and containing a metal oxide in an undercoat layer. SOLUTION: The compound expressed by the formula is contained in a hydrophilic colloidal layer, and a metal oxide is contained in an undercoat layer, where R1 and R2 represent hydrogen atom, alkyl group, aryl group, alkyl carbonyl group, aryl carbonyl group, alkyl sulfonyl group, aryl sulfonyl group, carboxy alkyl group, or carbamoyl group respectively, R1 and R2 may be combined together to form a heterocycic ring R3 , R4 , R5 , R6 represent hydrogen atom or substituent respectively, and adjacent two of R3 -R6 may be combined together to form a ring. Metal oxide fine grains easily forming a non- stoichiometric compound, e.g. an oxygen-deficient oxide or a metal-excess oxide, are used for a conductor made of oxide sol containing a metal atom and used for the undercoat layer.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a silver halide photographic light-sensitive material and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, silver halide photographic light-sensitive materials (hereinafter also simply referred to as "light-sensitive materials") are required not only to have high sensitivity and high image quality but also to have stable photographic performance. Various improved techniques have been investigated, focusing on emulsions. At the same time, development of photosensitive materials has been accelerated.

Since the light-sensitive material to be rapidly processed is conveyed at a very high speed in the automatic developing machine, it is rubbed with a conveying roller or the like, and when it is inserted into the automatic developing machine, it is laminated with other materials. It is very easy to be charged due to peeling from the photosensitive material, and static mark fog is likely to occur due to charging.

Polyelectrolytes and surfactants have been used for the purpose of preventing such electrification. However, since these polyelectrolytes and surfactants are water-soluble, they are added to the processing solution during development processing. May elute, producing turbidity or sludge.

In order to improve them, metal oxide particles such as those disclosed in JP-A-56-143431 and JP-A-58-62.
There is known a technique of imparting conductivity by using the crystalline metal oxide particles described in No. 647 to prevent electrification, but there is a problem that film adhesion of the film after development and drying is deteriorated. .

[0006]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in antistatic performance, has a film formed after development and has less residual color, and a processing method thereof. .

[0007]

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

(1) 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 (I). A silver halide photographic light-sensitive material containing a compound according to claim 1, wherein the undercoat layer contains a metal oxide.

[0009]

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In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a carboxyalkyl group or a carbamoyl group. Further, R ₁ and R ₂ may combine with each other to form a heterocycle. R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom or a substituent. Two adjacent R ₃ , R ₄ , R ₅ , and R ₆ may be bonded to each other to form a ring.

(2) The silver halide photographic light-sensitive material described in (1) is processed by an automatic processor having a processing tank for development, fixing and washing and having a mechanism for supplying a solid processing agent to the processing tank. A method for processing a silver halide photographic light-sensitive material.

The present invention will be described in more detail below.

First, the metal oxide used in the undercoat layer of the present invention will be described. Examples of the conductor composed of an oxide sol containing a metal atom include metal oxide fine particles that easily form a non-stoichiometric compound such as an oxygen-deficient oxide, a metal-excess oxide, and a metal-deficient oxide. Among them, the most preferable one is metal oxide fine particles which can adopt various production methods.

Specifically, ZnO, TiO ₂ , SnO ₂ , A
I ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, B ₂ O, MoO ₃
And complex oxides thereof. In the present invention, colloidal tin oxide sol is used as the metal oxide.

Here, colloidal means 10 ^-5 to 10 ^-7 c
Since the dispersed state of particles having a diameter of m is stable, this size is referred to as a colloidal dimension. Particles having a size of the colloidal dimension are used as colloidal particles, and the state in which the colloidal particles are dispersed is the colloid in the present invention. Say a state.

The colloidal tin oxide sol can be produced by any method such as a method in which ultrafine tin oxide particles are dispersed in a suitable solvent, a method in which a solvent-soluble tin compound is decomposed in a solvent, or the like. The method can also be adopted.

In the manufacturing method using the tin oxide ultrafine particles, the temperature condition is particularly important, and the method involving heat treatment at a high temperature is not preferable because of the growth of primary particles and the appearance of crystallinity. When heat treatment is performed without heat treatment, 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 the manufacturing process of 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 used in a solvent. The redispersion method is not very suitable for use as a photographic antistatic agent because redispersion is very difficult and agglomerated particles are generated.

When the compatibility of the solvent of the tin oxide sol dispersion liquid with the protective colloid binder at the time of production is poor, the solvent having a good compatibility with the production solvent is used in order to substitute the solvent suitable for dispersing in the binder. Alternatively, a compound capable of stably dispersing the tin oxide sol is appropriately added, and the temperature is 300 ° C. or lower, preferably 20
The tin oxide ultrafine particles are dried and separated together with the compound added by heating to 0 ° C or lower, further 150 ° C or lower, and redispersed in water or water mixed with another solvent.

The tin compound used in the method of producing from the decomposition reaction of the tin compound soluble in the solvent in the solvent is K
Compounds containing oxo anions such as ₂ SnO ₃ .3H ₂ O, water-soluble halides such as SnCl ₄ , R ′ ₂ Sn
(CH ₃ ) ₃ having the structure of R ₂ , R ₃ SnX, R ₂ SnX ₂
SnCl · _{(pyridine), (C 4 H 9)} 2 Sn (COC 2 H
₅ ) _{2 and} other organometallic compounds, and Sn (SO ₄ ) ₂ .2H ₂ O and other oxo salts.

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

For example, Japanese Patent Publication No. 35-6616 discloses Sn.
Cl ₄ is dissolved in 100 times the volume of distilled water to precipitate stannic hydroxide, and then aqueous ammonia 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 making a sol is described.

As the solvent, in addition to water, alcohol solvents such as methanol, ethanol and i-propanol; ether solvents such as tetrahydrofuran, dioxane and diethyl ether; aliphatic organic solvents such as hexane and heptane; benzene and pyridine. Various solvents such as an aromatic organic solvent can be used depending on the tin compound, 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. For example, a fluorine-containing compound or a metal capable of adopting a trivalent or pentavalent coordination number. A compound can be introduced.

The fluorine-containing compound soluble in the solvent may be either an ionic fluoride or a covalent fluoride, K
₂ TiF ₆ , HF, KHF ₂ Sb, F ₃ MoF _{6 and} other metal fluorides, NH ₄ MnF ₃ , NH ₄ BiF _{4 and} other compounds that generate fluoro complex anions, BrF ₃ , SF ₄ , SF _{6 and} other compounds Inorganic molecular fluoride, CF ₃ I, CF ₃ COOH, P (C
Organic fluorine compounds such as F ₃ ) ₃ can be mentioned, and when the solvent is water, a combination of a fluorine-containing compound and a non-volatile acid can be used, such as a combination of CaF ₂ and sulfuric acid.

As the metal compound soluble in a solvent and capable of adopting a coordination number of trivalent M or pentavalent, Al, Ga, In and Tl are available.
Group III elements such as V or P, As, S, b, Bi, etc.
Group element, Nb which can have trivalent or pentavalent coordination number,
It is a group of compounds containing transition metals such as V, Ti, Cr, Mo, Fe, Co and Ni.

(Synthesis Example 1 of Colloidal Tin Oxide Dispersion) 65 g of stannic chloride hydrate was mixed with 200 parts of water / ethanol.
It was dissolved in 0 cc to obtain a uniform 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 the 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. 40c of 30% ammonia water
c, and heated in an aqueous solution to obtain a colloidal gel dispersion.

(Synthesis example 2 of colloidal tin oxide dispersion liquid) 65 g of stannic chloride hydrate and 1.0 g of antimony trichloride were dissolved in 2000 cc of water / ethanol mixed solution to obtain a uniform 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 the 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. Further, 40 cc of 30% aqueous ammonia was added, and the mixture was heated in an aqueous solution to obtain a colloidal gel dispersion. The volume resistivity of the tin oxide sol thus obtained is 2.1 × 10 ⁵ Ωcm.
Met.

Next, the compound of the general formula (I) used in the present invention will be described.

In formula (I), the alkyl group, aryl group, alkylcarbonyl group, arylcarbonyl group, alkylsulfonyl group, arylsulfonyl group, carboxyalkyl group or carbamoyl group represented by R ₁ and R ₂ are all substituted. Alternatively, it may be unsubstituted.

Examples of the heterocyclic group which may be formed by combining R ₁ and R ₂ include piperidino, pyrrolidino, piperazino, imidazolyl and morpholino groups.

The substituent represented by R ₃ , R ₄ , R ₅ and R ₆ is a halogen atom, an alkyl group having up to 20 carbon atoms, a monocyclic or bicyclic aryl group, an alkoxy group, an alkylthio group,
Acylamino group, alkanoylamino group, alkoxycarbonyl group, alkylsulfonamide group, alkylsulfamoyl group, alkylcarbamoyl group, arylcarbamoyl group, acyloxy group, nitro group, cyano group, carboxyl group, sulfo group, ureido group, alkylureido Group, a secondary or tertiary amino group substituted with an alkyl group or an aryl group, an alkyl carbonate group, an alkylsulfonyl group, an alkylsulfinyl group, an aryloxy group having 6 to 20 carbon atoms, an arylthio group, a benzoylamino group,
Aryloxycarbonyl group, arylsulfonamide group, sulfamoyl group, arylsulfamoyl group, carbamoyl group, arylureido group, amino group, aryl carbonate ester group, arylsulfonyl group, arylsulfinyl group, acyl group having 2 to 20 carbon atoms And so on.

R _{3 to} R ₆ may be the same or different,
Two adjacent groups may be connected to each other to form a carbon ring.

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

[0035]

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[0036]

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When the compound represented by the general formula (I) is an acid, it may be a free acid or a salt form. Further, the oxidation product may be contained. Usually, the compound of the general formula (I) contains an appropriate amount of oxidation product for natural oxidation such as by air.

The above compound is dissolved in water or a hydrophilic solvent such as methanol, acetone, ethyl acetate or the like and added to the hydrophilic colloid layer.

The compound may be added at 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 the compound to the hydrophilic colloid layer near the undercoat layer.

When the compound of the general formula (I) is added to the silver halide emulsion layer, 2 × 1 is added per mol of silver halide.
0 ^{−6 to} 5 × 10 ⁻¹ mol is preferable, and ¹ is more preferable.
× 10 ^-5 ~5 × 10 ^-2 mol are preferred.

When the compound is added to the non-photosensitive gelatin layer, it is preferably 2 × 10 ^{−7 to} 5 × 10 ⁻² mol / m ^{2, and} more preferably 1 × 10 ^{−6 to} 5 × 10 ^{−. 3} mol / m
²

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

The silver halide grains are cubic, 14-sided, 8-sided.
It may be a normal crystal grain such as a tetrahedron, a spherical grain, a tabular grain or a twin crystal grain having an aspect ratio of less than 2, and may have an irregular crystal form such as a potato.

In the present invention, the term "spherical" means that the surface having the largest area among the polygons forming the outer shape of the silver halide grain is focused on and the length L is 1/10 L to 1/2 L.
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 grain means 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 diameter d is defined as the particle diameter di when the product ni × di ³ of the frequency ni and di ³ of the particles having the particle diameter di becomes maximum (three significant digits and the minimum digit). Numbers are rounded to 4). The term "particle size" as used herein means the diameter of spherical silver halide grains, or the diameter of the projected image converted to a circular image of the same area in the case of grains having a shape other than spherical. Is.

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 measuring the particle diameter on the print or the area at the time of photographing (measurement). The number of particles is indiscriminately 1000 or more).

The monodisperse silver halide grains have a distribution width of 20% or less, and 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. It is preferable that the core and the shell have different iodide contents, and it is particularly preferable that the core portion is formed with the highest iodide content.

The iodide 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 particles is arbitrary,
It may be any of silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride, silver chloroiodide and silver iodide.

A silver halide photographic emulsion is described in JP-A-3-16.
Known silver halide solvents such as ammonia, thioethers, thioureas, thiocyanates, etc., as described in 8734 can be present to make them substantially round as defined above.

In the silver halide grain forming step,
By making the pAg after adding 70% of the water-soluble silver salt used for grain formation of the silver halide emulsion at least one or more larger than the pAg before adding 70% of the water-soluble silver salt, the above-mentioned definition is achieved. It may be substantially round as described above.

In the emulsion thus prepared, an appropriate amount of a halogenating 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. May be mixed uniformly to have a substantially rounded 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 can be produced by any of the acidic method, the neutral method and the ammonia method. or,
It may be produced at a pH of 7.5 or less using an ammoniacal silver nitrate aqueous solution.

The silver iodide content and the average silver iodide content of each silver halide grain are EPMA (Electron).
It can be determined using the Probe Micro Analyzer) method. According to this method, a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared, and an X-ray analysis by electron beam excitation and 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. When the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content is determined from the average thereof.

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 carried out with a transmission electron microscope equipped with an energy dispersive X-ray analyzer, and it was obtained by quantitative calculation (Inoue, Nagasawa: Photographic Society, 1987). Conference Proceedings, page 62).

The silver iodide content on the outermost surface of the silver halide grain 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 to -110 ° C. or lower in an ultrahigh vacuum of 1 × 10 ^-8 torr 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 the destruction of the sample (the decomposition of silver halide and the diffusion of halide (particularly iodine)) by the X-ray irradiation at room temperature and to improve the measurement accuracy. By cooling to -110 ° C, sample destruction can be suppressed to a level that does not hinder measurement.

The plate-like grain may be a tabular silver halide grain having two twin planes parallel to each other on two parallel (111) main planes, and two parallel (100) planes are the 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 by Klein and Moiser in the article Photographiesche Correspondents. (Photographish
Korrespondenz) 99, 99, 10
0, page 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 coated so that the silver halide grains contained are oriented on a support to prepare a sample. This was cut using a diamond cutter to a thickness of 0.1
Obtain a thin section of about 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 that the (100) or (111) main plane of the tabular grains is maintained. (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 that the desired particle diameter and halogen composition are obtained.

The tabular silver halide grain means a grain having two parallel main planes opposed to each other, and an 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 grain size), which is a circle equivalent diameter of a projected area of a tabular silver halide grain (diameter of a circle having the same projected area as the silver halide grain). ),
Thickness refers to the distance between two parallel major planes forming a tabular silver halide grain.

The average value of the aspect ratio of the tabular silver halide grains is preferably 2 or more.

In the present invention, 50% or more of the total projected area of the emulsion layer containing tabular silver halide grains consists of tabular silver halide grains, preferably 70% or more, more preferably 90% or more. is there.

The tabular silver halide grains have an average grain size of 0.
It is preferably from 15 to 5.0 μm, and from 0.4 to 3.0 μm.
More preferably, it is 0 μm, most preferably 0.1 μm.
4 to 2.0 μm. The average thickness is 0.15
0.3 .mu.m is preferred and the grain size and thickness can be optimized to optimize sensitivity and other photographic properties. Optimum particle size and optimum depending on other factors constituting the photosensitive material (sensitivity of hydrophilic colloid layer, hardness, chemical ripening conditions, sensitivity of photosensitive material, amount of silver coating, etc.) that affect sensitivity and other photographic characteristics The thickness is different.

The silver halide grains preferably have a more uniform halogen composition ratio between grains. For example, when the distribution of the iodide content between 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: Pho
t. Sci. Eng., 57 (1967); Shi
Ozawa: J.M. Soc. Photo. Sci. Japan
n, 35, 213 (1972), and can be observed by a direct method using a transmission electron microscope at low temperature. That is, the silver halide grains taken out carefully so as not to apply a pressure such that dislocations are generated in the grains from the emulsion are placed on a mesh for electron microscope observation so as to prevent damage (printout etc.) by an electron beam. The sample is cooled and observed by the transmission method. At this time, the thicker the particles, the more difficult it is for an electron beam to pass therethrough.
The use of an electron microscope (200 kV or more for a particle having a thickness of 5 μm) allows a clearer observation.

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 width (%) of grain size distribution. When the width of the 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, and further, It is preferably 20% or less.

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 also 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 the production of the silver halide emulsion used in the present invention, the 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 liquid 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, a known silver halide solvent such as ammonia, thioether or thiourea can be present during the seed grain forming step and the seed grain growth.

In the preparation of silver halide grains, a silver salt solution and a halide solution are added by a double jet method during the growth, and the addition rate is adjusted according to the growth of grains such that new nucleation does not occur and the size is determined by Ostwald ripening. Velocity without spread of distribution, that is, 30 to 1 of new nucleus generation rate
Particles having a desired particle diameter and distribution can be obtained by a method of gradually changing the particle diameter in the range of 00%.

The silver halide grains may be so-called halogen conversion type grains. The halogen conversion amount is preferably from 0.2 to 0.5 mol% based on the silver amount, and the conversion may be performed during physical ripening or after physical ripening.

As a method for halogen conversion, an aqueous halogen solution having a smaller solubility product with silver than the halogen composition on the grain surface before halogen conversion or silver halide fine particles 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 is contained on the outermost surface of silver halide grains, the method is to simultaneously add a silver nitrate solution and a solution containing iodide ions to the emulsion containing the base silver halide grains. Method, a method of adding fine silver halide grains such as silver iodide, silver iodobromide or silver chloroiodobromide, and a method of adding potassium iodide or a mixture of potassium iodide and potassium bromide. Of these, the method of adding fine silver halide grains is preferable. It is particularly preferable to add 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 until the end of the solution preparation step immediately before the coating of the silver halide emulsion. Although it can be selected in a timely manner, it is preferable to adjust it by the end of the chemical ripening step. The term "chemical ripening step" as used herein means from the time when the physical ripening and desalting operations of the silver halide emulsion are completed to the time when the chemical sensitizer is added and then the operation for stopping the chemical ripening is performed. Refers to. Further, the addition of silver halide fine grains may be carried out 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 when adding silver halide fine grains is preferably in the range of 30 to 80 ° C, and more preferably 40 to 40 ° C.
The range of 65 ° C. is particularly preferred. Further, it is preferable that the silver halide fine particles to be added are partially or wholly disappeared until just before coating, and more preferable condition is that 20% or more of the added silver halide fine particles are coated. It has disappeared just before.

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 1 × 10 ^{−3 to} 3 × 10 ⁻² mol of a thiocyanic acid compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) per mol of silver.

It is preferable to use gelatin as the dispersion medium for the protective colloid of silver halide grains. Examples of the gelatin include alkali-processed gelatin, acid-processed gelatin, low molecular weight gelatin (molecular weight of 1,000 to 50,000), phthalated gelatin and the like. Modified gelatin is used. Other hydrophilic colloids can also be used. Specifically, Research Disclosure magazine
ure, hereinafter abbreviated as RD) 176, 17643 (19
, 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 be contained therein. The removal of the salts can be carried out according to the method described in Item II of RD 176, 17643.

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

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

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

The silver halide emulsion may remove unnecessary soluble salts at the end of the growth of silver halide grains,
Alternatively, it may be kept contained. The removal of the salts can be carried out according to the method described in the above-mentioned RD17643 item II.

The silver halide grains can be chemically sensitized. The conditions of the step 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, 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 Reduction sensitization method, gold and others,
A noble metal sensitization method using a noble metal can be used alone or in combination.

The amount of the selenium sensitizer used depends 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 of adding it by dissolving it in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent depending on the properties of the selenium compound to be used, or a method of premixing with a gelatin solution and adding ,
Alternatively, the method disclosed in JP-A-4-140739 may be used in which it is added in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent.

The temperature of chemical ripening using a selenium sensitizer is 4
The range of 0 to 90 ° C. is preferable, and more preferably 45 to 8
0 ° C. The pH is preferably in the range of 4-9 and the pAg is preferably in the range of 6-9.5.

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 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 their derivatives. Other preferable reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, and sulfites.

The amount of the reducing agent added depends on the type of reduction sensitizer, the particle size of silver halide grains, the composition and crystal habit, the temperature of the reaction system,
It is preferable to change the pH according to environmental conditions such as pH and pAg, but in the case of thiourea dioxide, for example, as a rough guide, about 0.01 to 2 mg per mol of silver halide is used.
Is used with good results. 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 about 40 to 70 ° C.
About 10 to 200 minutes, pH about 5 to 11 and pAg about 1
The range of 10 to 10 is preferable (here, the pAg value is Ag +
It is the reciprocal of the ion concentration).

As the water-soluble silver salt, silver nitrate is preferable. By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. 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 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.

Any of commonly used nuclei can be applied to these dyes. 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.

The merocyanine dye or the complex merocyanine dye contains pyrazoline-containing nuclei 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.
A membered heterocyclic nucleus can be applied.

The sensitizing dyes may be used alone or in combination, and the combination is often used particularly for the purpose of supersensitization. Further, together with a sensitizing dye, a dye having no spectral sensitizing property or a substance that does not substantially absorb visible light,
A substance exhibiting a supersensitizing effect may be contained in the emulsion layer.
For example, a substituted aminostilbene compound having a nitrogen-containing heterocyclic nucleus group (for example, US Pat. No. 2,933,390)
No. 3,635,721), an aromatic organic acid formaldehyde condensate (for example, US Pat. No. 3,74).
No. 3,510), a cadmium salt, an azaindene compound and the like may be contained. US Pat. No. 3,615,6
No.13, No.3,615,641, No.3,617,29
The combinations described in No. 5, No. 3,635,721 and the like are particularly useful.

The sensitizing dye may be added during or during each step of nucleation, growth, desalting, chemical sensitization, or after chemical sensitization.

In order to make the 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 keep the water content in the light-sensitive material before the start of drying low.

The swelling ratio of the light-sensitive material of the present invention during development is preferably 150 to 250%, and the film thickness after expansion is 7%.
It is preferably 0 μm or less. When the water swelling rate exceeds 250%, poor drying occurs, and, for example, poor handling occurs in automatic processor processing, especially rapid processing. On the other hand, the water swelling ratio is 150
If it is less than%, uneven development or residual color tends to increase when developed. 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, solid processing agents such as tablets, pills, and granules may be used, and if necessary, those which have been subjected to moisture-proof processing may be used. .

The powder used in the present invention refers to an aggregate of fine crystal grains. Granules are obtained by adding a granulation step to powders and refer to granules having a particle size of 50 to 5000 μm. The tablet referred to in the present invention is obtained by compressing and molding 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. In particular, the opening coefficient is preferably 80 cm ² / liter or less. That is, when the opening coefficient exceeds 80 cm ² / liter, the undissolved solid processing agent or the concentrated liquid immediately after dissolution is susceptible to air oxidation, and as a result, insoluble matter or scum is generated, and the processing machine or the processing machine is processed. However, when the aperture coefficient is 80 m ² / liter or less, these problems can be solved. The opening coefficient here is represented by the contact area with air per unit volume of the processing liquid, and the unit is (cm ² /
Liter). In the present invention, the aperture coefficient is 80c
m ² / liter or less is preferable, more preferably 50 to
3 cm ² / liter, more preferably 35 to 10
cm ² .

The opening coefficient can be generally reduced by using a resin or the like for air blocking as a floating lid, or the opening coefficient can be reduced.
131138, 63-216050, 63-2
The size can be reduced by the slit type developing device described in Japanese Patent No. 35940.

The solid processing agent used in the present invention is used as a photographic processing agent such as a developing agent, a fixing agent, a rinsing agent, etc., but the effect of the present invention, especially the effect of stabilizing photographic performance is great. It is an agent.

The solid processing agent may be solidified by only a part of the components of a certain processing agent, but it is preferable that all the components of the processing 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 be packaged in the order in which they are periodically added repeatedly 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, JP-B-63-137783 and 63-975 are used.
There are known methods such as No. 22, No. 22 and Jitsukaihei 1-85732, 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 practice.
No. 63-84151, Japanese Patent Laid-Open No. 1-292375, etc.
Nos. 63-195345 and the like are known, but are not limited to these.

The solid processing agent may be charged in a processing tank, but it is preferable that the processing solution is in communication with the processing section for processing the light-sensitive material. In addition, a structure in which there is a certain amount of processing liquid circulation between the processing section and the dissolved components move to the processing section is preferable.
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, pp. 19 to 20, as a developing agent in the developer, there are described in JP-A-5-165161. Reductones are also preferably used.

Among the pyrazolidones to be used, those substituted at the 4-position (dimesone, dimeson S, etc.) are particularly preferable because the water solubility and the solid processing agent itself do not change with time.

As the preservative, an organic reducing agent other than the sulfite described in JP-A-6-138591 can be used as the preservative. In addition, a chelating agent or a bisulfite adduct of a hardening agent can be added. Further, as a silver sludge inhibitor, JP-A-5-289255 and JP-A-6-308 are known.
No. 680 described compound (general formula [4-a], [4-
It is also preferred to add 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 buffering agent for the developer. As the buffering agent, 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), o- Potassium hydroxybenzoate,
Sodium 5-sulfo-2-hydroxybenzoate (5-
Sodium sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned.

As the development accelerator, Japanese Patent Publication No. 37-160
88, 37-5987, 38-7826, 44-12380, 45-9019 and U.S. Pat. No. 3,813,247; thioether compounds; JP-A-52-49829. No. and ibid. 50-1555
P-phenylenediamine compounds represented by No. 4; JP-A-50-137726, JP-B-44-30074,
Quaternary ammonium salts disclosed in JP-A-56-156826 and JP-A-52-43429; US Pat.
P-aminophenols described in US Pat. No. 10,122, 4,119,462 and the like; US Pat. No. 2,494,903.
No. 3,128,182, 4,230,796
No. 3,253,919, Japanese Patent Publication No. 41-11431
No. 2,482,546 and 2,596,9
26 and 3,582,346 and the like; amine compounds described in JP-B-37-16088 and 42-2520.
No. 1, US Pat. No. 3,128,183, Japanese Patent Publication No. 41-1
1431, 42-23883 and U.S. Pat.
No. 32,501 or the like; polyalkylene oxides; 1-phenyl-3-pyrazolidones, hydrazines, mesoionic compounds, ionic compounds, imidazoles, and the like can be added if 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, 2
As a representative example, a nitrogen-containing heterocyclic compound such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine can be mentioned as 1-phenyl-5-mercaptotetrazole.

Further, in the developer composition, if necessary, methyl cellosolve, methanol, acetone, dimethylformamide, a cyclodextrin compound, and other compounds described in JP-B Nos. 47-33378 and 44-9509 are developed. It can be used as an organic solvent for increasing the solubility of the main drug. In addition, various additives such as an anti-stain agent, an anti-sludge agent, and a multi-layer effect accelerator 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 those described in JP-A-5-113632, pages 2-4 can be used.

In addition, a bisulfite addition product of a hardener and a known fixing accelerator can be added.

It is also preferable to add a starter prior to the treatment, and it is also preferable to solidify the starter and add the starter. As the starter, in addition to organic acids such as polycarboxylic acid compounds, halides of alkaline earth metals such as potassium bromide, organic inhibitors, and development accelerators are used.

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

Generally, in a developing solution used for developing a black-and-white light-sensitive material, hydroquinones are used as a developing agent in many cases. In the present invention, however, the working safety is improved and the environment is protected. In view of the above, it is substantially free of hydroquinones, for example, US Pat. No. 5,236,81.
The developing solution using ascorbic acid described in No. 6 may be used.

The development time of the black-and-white light-sensitive material of the present invention is 3-9.
It is 0 second, 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.

Various additives may be added to the light-sensitive material of the present invention depending on the purpose. Examples of additives and the like used include RD17643 (1978, 1
(Feb.) Page 23, Item III to Page 28, Item XVI, Ibid. 18716 (19)
(November 1979) pp. 648-651 and 308119.
(December, 1989) pp. 996 item III to 1009 item XVI.

Examples of the support that can be used in the light-sensitive material of the present invention include those described on page 28 of RD17643 and page 1009 of RD308119. A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer to improve the adhesion of the coating layer, corona discharge, ultraviolet irradiation or the like.

[0134]

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) Solution A1 Oscein gelatin 37.5 g Potassium bromide 0.625 g Sodium chloride 16.5 g Distilled water 7500 ml B1 solution Silver nitrate 1500 g Distilled water 2500 ml C1 solution Potassium bromide 4 g Sodium chloride 140 g 684 ml of distilled water D1 liquid Sodium chloride 375 g of distilled water 1816 ml At 40 ° C., 684 ml of liquid B1 and the total amount of liquid C1 for 1 minute are added to liquid A1 in the mixing stirrer shown in JP-B-58-58288. It was added over. 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. During that time, the EAg was controlled at 149 mV.

Immediately after the completion of the addition, desalting and washing 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).
It was found by electron microscope observation that it consisted of tabular grains having a plane as a main plane and an aspect ratio of 2 or more, an average thickness of 0.07 μm, an average diameter of 0.5 μm, and a variation coefficient of 25%.

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

A2 solution Ocein gelatin 29.4 g 10% methanol solution of surfactant (SU-1) 1.25 ml seed emulsion A 0.98 mol equivalent Distilled water 3000 ml B2 solution 3.5N silver nitrate aqueous solution 2240 ml C2 solution chloride Sodium 455 g Distilled water 2240 ml D2 liquid 1.75N sodium chloride aqueous solution Silver potential control amount SU-1: 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) At 40 ° C., using a mixing stirrer disclosed in JP-B-58-58288, liquid A2, liquid B2 and liquid C2 are mixed. The total amount of the liquid was adjusted by the simultaneous mixing method (double jet method) so that the flow rate after the addition was 3 times the flow rate at the start of the addition.
Additive growth was performed for 0 minutes. EA during this time
g was controlled to 120 mV by using the D2 liquid.

After the addition is completed, 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
The tabular grains had a thickness 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 liquid Oscein gelatin 100 g Potassium bromide 8.5 g Distilled water 2000 ml B3 liquid Silver nitrate 360 g Distilled water 605 ml C3 liquid Potassium bromide 352 g Distilled water 605 ml A3 liquid in a reactor B3 while stirring and maintaining at 40 ℃
The liquid and the C3 liquid were added at a low speed by a simultaneous mixing method over 30 minutes. PAg during the addition is 1% by a conventional PAg control means.
It was kept at 3.5.

The produced silver iodide had an average grain size of 0.06 μm. This emulsion is called silver iodide fine grains.

(Preparation of Solid Fine Particle Dispersion of Spectral Sensitizing Dye) Sensitizing dyes (SD-1) and (SD-2) were mixed with 100:
A solid fine particle dispersion of the spectral sensitizing dye was obtained by adding water in a ratio of 1 to 27 ° C. in advance and stirring with a high-speed stirrer (dissolver) at 3500 rpm for 30 to 120 minutes. It was At this time, sensitizing dye (SD-1)
Was adjusted to be 2%.

SD-1: 5,5'-dichloro-9-ethyl-3,3 '
-Anhydrous sodium salt of di (3-sulfopropyl) oxacarbocyanine SD-2: 5,5'-di (butoxycarbonyl) -1,
Anhydrous of 1'-diethyl-3,3'-di (4-sulfobutyl) benzimidalocarbocyanine sodium salt (chemical sensitization) Emulsion B was spectrally and chemically sensitized by the following method. A chemically sensitized emulsion was obtained.

After the emulsion B was heated to 60 ° C., the sensitizing dye (SD
-1) was added to the above solid fine particle dispersion so that -1) was 460 mg / AgX1 mol, and then ammonium thiocyanate salt was added at 7 × 10 ^-4 mol / AgX1 mol, and potassium chloroaurate, sodium thiosulfate and triphenyl were added. Optimum chemical sensitization was carried out by adding 3 × 10 ^-6 mol / AgX1 mol of phosphine selenide, and 3 × of the above silver iodide fine grain emulsion was obtained.
Stabilizer (ST-1) after addition of 10 ^-3 mol / AgX 1 mol
Stabilized at 1 × 10 ⁻² mol / AgX 1 mol.

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

ST-1: 4-hydroxy-6-methyl-
1,3,3a, 7-Tetrazaindene (Preparation of Comparative Crystalline Tin Oxide Substrate Substrate 1) On both sides of a polyethylene terephthalate film base for X-rays (blue) with a concentration of 0.170 (thickness 175 μm) , 0.5 kV · A · min / m ² of corona discharge treatment, and then one side of the base is coated with an undercoating latex liquid represented by the following (L-2) so that the film thickness after drying becomes 0.2 μm. In addition, the film thickness after drying (L-1) is 0.053 μm.
And the lower layer on the other side is Japanese Patent Laid-Open No. 58-
The tin oxide powder dispersion [III] of Example 1 of No. 62647 was applied so that the amount of tin oxide powder applied would be 250 mg / m ² , and dried at 123 ° C. for 2 minutes. This support is referred to as support 1.

[0147]

Embedded image

(L-2) Butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl acrylate (10/35/27/28% by weight) copolymer latex liquid (solid content 30%).

(Preparation of support 2 with tin oxide sol subbing)
One side of the same base is similar to support 1 (L-2)
An undercoat layer is provided, and the tin oxide sol synthesized in (Synthesis example 1), the (L-2) solution and the following (L-
4) A coating solution prepared by mixing the solutions at a volume ratio of 35:15:50 was used to obtain a dry film thickness of 0.12 μm and a sol component loading of 250 mg.
/ M at ^2, in the upper layer the (L-1) and the following (L-3) solution volume ratio mixed coating solution applied dry film thickness to be 0.053μm simultaneously 70:30 Then 1
It was dried at 20 ° C. for 1 minute.

Before coating, 0.5 kV · A · min / m
² was subjected to corona discharge treatment. This support is referred to as support 2.

(L-3) Dimethyl terephthalate 34.0
2 parts, dimethyl isophthalate 25.52 parts, 5-sulfoisophthalic acid dimethyl sodium salt 12.97 parts, ethylene glycol 47.85 parts, 1,4-cyclohexanedimethanol 18.95 parts, calcium acetate monohydrate 0.
After transesterification of 065 parts and manganese acetate tetrahydrate 0.022 parts under a nitrogen stream at 170 to 220 ° C. while distilling off methanol, trimethyl phosphate 0.0
4 parts, 0.04 part of antimony trioxide and 15.08 parts of 1,4-cyclohexanedicarboxylic acid as a polycondensation catalyst were added, and at a reaction temperature of 220 to 235 ° C., a theoretical amount of water was distilled off to effect esterification. It was After that, the pressure inside the reaction system is further reduced over about 1 hour and the temperature is raised to 280 ° C. and 1 mmH.
Polycondensation was carried out for about 1 hour at a pressure of not more than g to obtain a polyester polymer having an intrinsic viscosity of 0.35 (“parts” of the raw material indicate “parts by weight”).

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) Butyl acrylate / styrene / glycidyl methacrylate (40/20/40% by weight) copolymer latex liquid.

(Preparation of Photosensitive Material) Next, as shown in Table 1, the compound of the general formula (I) was added to the coating solution for the first layer (crossover cut layer) or the second layer (emulsion layer) described below. .
Further, as shown below, after adding an additive to each coating solution, a crossover cut layer, an emulsion layer, and a protective layer are formed on the both surfaces of the support 1 and the support 2 in the order given below. Simultaneous multi-layer coating and drying were carried out so that the coating amounts would be obtained, to prepare photosensitive material samples 1 to 9.

The amount of silver attached on one side of the sample was 1.5 g.
/ M ^2, the amount with gelatin per one side, cross over cut layer 0.2 g / m ^2, the emulsion layer is 1.0 g / m ^2, the protective layer is adjusted to be 0.68 g / m ² Applied. In addition, the coating amount of the material is indicated by the coating amount per 1 m ^{2 on} one side.

First layer (crossover cut layer) Gelatin 0.2 g Solid fine particle dispersion dye (AH) 20 mg Sodium dodecylbenzenesulfonate 5 mg Compound (E) 5 mg Hardener (H-1) 5 mg Colloidal silica (average particle size) Diameter 0.014 μm) 10 mg Second layer (emulsion layer) The following various additives were added to the emulsion obtained above.

Compound (F) 0.5 mg Compound (G) 5 mg t-butyl-catechol 5 mg Polyvinylpyrrolidone (molecular weight 10,000) 20 mg Styrene-maleic anhydride copolymer 80 mg Sodium polystyrene sulfonate 80 mg Trimethylolpropane 350 mg Diethylene glycol 50 mg nitrophenyl - triphenyl - phosphonium chloride 1mg resorcin-4-sulfonic acid ammonium 50 mg 2-mercaptobenzimidazole-5-sulfonate sodium 5mg compound _{(H) 0.5mg C 4 H 9} OCH 2 CH (OH) CH 2 N ( CH ₂ COOH) ₂ 20mg stabilizer (ST-2) 5mg stabilizer (ST-3) 5mg colloidal silica 0.5g latex (L) 0.5g styrene sulfonic acid sodium Beam (molecular weight: about 500,000) 7 mg but was adjusted to one side per 1.0 g / m ² as gelatin.

Third layer (lower layer of protective layer) Gelatin 0.4 g Dioctyl phthalate 195 mg Sodium styrenesulfonate (molecular weight about 500,000) 7 mg Fourth layer (upper layer of protective layer) 0.28 g Matting agent consisting of polymethylmethacrylate 27 mg ( Area average particle size 7.0 μm) Hardener (H-1) 10 mg Latex (L) 0.2 g Polyacrylamide (average molecular weight 10000) 0.1 g Sodium polyacrylate 30 mg Polysiloxane (SI) 50 mg Compound (E) 30 mg sulfosuccinate -i- amyl - decyl sodium salt _{7mg C 9 F 19 O (CH} 2 CH 2 O) 11 H 3mg C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2 O) 15 H 2 mg C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₄ (CH ₂ ) ₄ SO ₃ Na 1m g C ₇ F ₁₅ CH ₂ (OCH ₂ CH ₂ ) ₁₃ OH 10 mg H-1: 2,4-dichloro-6-hydroxy-s-triazine / sodium Compound G: 2,6-bis (hydroxyamino) -4- Diethylamino-s-triazine ST-2: 1- (3-sodiumsulfonato) phenyl-
5-Mercaptotetrazole ST-3: 1- (3-carboxy) phenyl-5-mercaptotetrazole

[0159]

[Chemical 6]

[0160]

[Chemical 7]

(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 commercially available bandam mill until the average particle size becomes 10 μm. 3000 g of sodium sulfite, 2000 g of potassium sulfite, and 1000 g of dimezone S were added to this pulverized product,
After mixing for 0 minutes and granulating by adding 30 ml of water in a commercial stirred granulator at room temperature for about 10 minutes, the granulate is dried in a fluid bed dryer at 40 ° C. for 2 hours. To almost completely remove the water content of the granulated product.

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%. After uniformly mixing for 10 minutes using a mixer in a room whose humidity was adjusted to RH or less, the filling amount per tablet was 3.84 g by a tableting machine modified from Tough Pressed Collect 1527HU manufactured by Kikusui Seisakusho.
After that, the tablets were compressed and compressed into 2,500 developing replenishment tablets A.
I got an agent.

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 potassium hydroxide, N-acetyl-D. ，
10 g of L-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 by the above-mentioned tableting machine with the filling amount per tablet being 1.73 g to obtain 2,500 development-supplementing tablet B agents.

DTPA: diethylenetriaminepentaacetic acid
5 Sodium (Preparation of Replenishing Tablet for Fixing) A replenishing tablet for fixing was prepared by the following operations (C, D).

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.

To the granulated product thus prepared, 4 g of sodium N-lauroylalanine was added, and the mixture was mixed at 25 ° C. × 4.
Mix for 3 minutes using a mixer in a room conditioned at 0% RH or less. Next, the obtained mixture was compressed into tablets by the above-mentioned tableting machine at a filling amount of 6.202 g per tablet,
2500 fixer replenishment tablets C were obtained.

Operation (D) 1000 g of boric acid, 1500 parts of aluminum sulfate and 18 hydrates
g, sodium hydrogen acetate (equimolar mixture of glacial acetic acid and sodium acetate and dried) 3000 g, tartaric acid 200 g
Is pulverized and granulated in the same manner as in the operation (A). Add 1 amount of water
After the granulation, the granulated product is dried at 50 ° C. for 30 minutes to almost completely remove the water content of the granulated product.

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

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

At the start of processing of the developing solution (starting of running), a solution in which 330 ml of a starter was added to 16.5 liters of a developing solution prepared by diluting 434 pieces of each of agent A and agent B of developing replenishing tablet with diluting water was started. The developing tank was filled with the liquid 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 sample was exposed to light so that the optical density after development was 1.0, and the sample was run. For running, an automatic developing machine SRX-502 manufactured by Konica was used with a solid processing agent charging member attached and modified so that processing could be performed at a processing speed of 25 seconds.

During running, the developing solution contained 0.6% light-sensitive material.
2 pieces of each of the above-mentioned agents A and B and 76 water per 2 m ²
It was performed by adding ml. 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 photographic characteristics) <Static mark generation rate> The temperature of unexposed sample was 25 ° C.
The humidity was adjusted at 20% RH for 2 hours, and the pieces were independently rubbed with a neoprene rubber roller and a nylon roller, and then the above-described development processing was performed and evaluated according to the following criteria.

A: No static mark was generated at all B: Static mark was slightly generated C: Static mark was generated considerably D: Static mark was generated on the whole.

<With film> After the blackened film treated under the above conditions was conditioned at 23 ° C. and 70% RH for 2 hours, 0.3 m
30cm / se with 500g load on mφ sapphire needle
A length of 20 cm was rubbed 10 times at a speed of c. The film peeling of the emulsion film was evaluated according to the following criteria from the scratching method.

A: No scratches at all B: Not visible to the naked eye, slightly detected with a 10x loupe, but practically no problem C: Slightly detected with the naked eye D: Clearly peeled film and scratched Occurrence and problematic level E: A level where scratches are large and unusable.

<Residual Color Property> An unexposed sample was processed by the above-mentioned processing method and evaluated according to the following criteria.

A: No occurrence at all 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 unevenly when gazing,
No problem in practical use D: Reddish unevenness occurs in the center of the film, and there is a problem in practical use E: Dark reddish unevenness occurs in the center of the film, making it unusable.

The results obtained are summarized in Table 1.

[0183]

[Table 1]

As is clear from Table 1, the samples of the present invention are excellent in antistatic performance, film adhesion after development and improved residual color.

[0185]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is excellent in antistatic performance, has a film formed after development and has less residual color, and a processing method thereof.

Claims (2)

[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 is represented by the following general formula (I). A silver halide photographic light-sensitive material containing a compound and the undercoat layer containing a metal oxide. Embedded image [In the formula, R ₁ and R ₂ each represent a hydrogen atom, an alkyl group, an aryl group, an alkylcarbonyl group, an arylcarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a carboxyalkyl group or a carbamoyl group. Also, R
₁ and R ₂ may combine with each other to form a heterocycle.
R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom or a substituent. Two adjacent R ₃ , R ₄ , R ₅ , and R ₆ may be bonded to each other to form a ring. ] 2. Processing the silver halide photographic light-sensitive material according to claim 1 with an automatic processor having a processing tank for development, fixing and washing, and having a mechanism for supplying a solid processing agent to the processing tank. A method for processing a silver halide photographic light-sensitive material, comprising: