JPH09211786A - Silver halide photographic sensitive material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve performances such as scratching resistance, irregular drying and silver tone while adding conductivity to the material by applying a silver halide emulsion layer and drying the layer under specified conditions in the period for the water content to decrease. SOLUTION: This photographic sensitive material has a conductive layer containing a metal oxide colloid and a nonphotosensitive layer containing 0.1-1.8g/m<2> gelatin formed between a silver halide emulsion layer and the conductive layer. During the silver halide emulsion layer is applied and dried, the layer is dried under such conditions that the period T for the water content in the silver halide emulsion layer side to decrease from 500 to 50% satisfy 2.0<=T/(DB-WB)<=10.0. T is the drying time (sec) that the water content (water amt./total weight of hydrophilic colloid) decreases from 500% to 50%, DB is the dry-bulb temp. ( deg.C) of the drying air and is 28 to 45 deg.C while the water content decreases from 500% to 50%, and WB is the wet-bulb temp. ( deg.C) of the drying air during the water and is 18 to 38 deg.C while the water content decreases from 500% to 50%.

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 (hereinafter, simply referred to as a light-sensitive material) and a method for producing the same, and more specifically, it is capable of ultra-high-speed processing excellent in antistatic performance, uneven drying, scratches, and silver tone Photosensitive material and its manufacturing method.

[0002]

2. Description of the Related Art In recent years, with the advance of electronics, the shortening of access time to video has been dramatically advanced, and photosensitive materials are required to be processed more and more rapidly. For this reason, photosensitive materials are increasingly required to have various physical properties, and one of such demanding performances is antistatic performance.

Conventionally, polymer electrolytes and surfactants have been used as antistatic agents for photosensitive materials. But,
Since these polymer electrolytes and surfactants are water-soluble, they are eluted into the processing solution during the development processing, and may cause turbidity or sludge. Therefore, as these polymer electrolytes and surfactants, those having high water solubility have been selected or means for crosslinking the polymer electrolyte have been taken. However,
In recent years, due to strict environmental regulations, it has been required to reduce the amount of waste liquid of the treatment liquid. In such a case, the above-described means cannot solve the problems of turbidity and sludge.

Japanese Patent Publication No. 60-49894 proposes to use water-insoluble crystalline metal oxide particles together with a hydrophobic binder such as vinylidene in order to avoid such problems. In this case, since the hydrophobic binder does not have conductivity, the crystalline metal oxide particles need to increase the packing ratio of the particles in the conductive layer in order to exhibit conductivity. % Or more, since the crystalline metal oxide particles scatter light, the addition of such an amount causes a problem of deterioration in devitrification after development. In order to deal with this, in JP-B-3-24656, it is possible to use a nonionic surfactant having a hydrophilic binder and a polyoxyethylene group together with crystalline metal oxide particles, in JP-B-3-24657. The use of hydrophilic binders and F-based surfactants with crystalline metal oxide particles has been shown. However, even with these techniques, it has been shown that the charging rate of the particles is required to be 50% or more in order to impart conductivity, and the problem of devitrification has not been sufficiently solved.

With respect to pressure resistance in ultra-rapid processing, a technique for improving pressure characteristics by adding colloidal silica to an emulsion layer is disclosed in JP-A-4-214551 and 4-340951.
No. 5-53230, No. 5-53237 and the like. According to this, although the deterioration of the physical properties of the film is surely small, when it is added to such an amount that the effect can be obtained, the film is cracked during storage of the processed film after image formation, which is a serious problem in practical use. As a means for improving this, Japanese Patent Application Laid-Open No. 6-95300 discloses a technique using a colloidal silica surface-treated to introduce a functional group capable of crosslinking with gelatin. According to this, although the cracking of the film during storage is improved, when a rapid drying method in a short time is adopted for rapid processing, especially the drying process is performed by an automatic processor equipped with a heat roller. If you do, uneven drying occurs,
It turned out to be a problem. The drying unevenness mainly appears as unevenness in the gloss of the film surface, and causes deterioration in image quality.

Further, the development processing has been accelerated, and tabular grains have been used for increasing the color sensitization efficiency. However, the use of tabular grains has drawbacks such that the developed silver color tone has a yellowish tint and is likely to deteriorate due to rapid processing or the like, and a solution has been desired.

As described above, it has been necessary to develop an ultra-rapid photosensitive material which has improved properties such as scratches, uneven drying and silver tone while imparting sufficient conductivity.

[0008]

In contrast to the above problems, an object of the present invention is to provide a light-sensitive material which is excellent in antistatic performance, uneven drying, scratches, and silver tone, and which can be processed extremely rapidly, and a method for producing the same. To provide.

[0009]

The above object of the present invention is achieved by the following means.

In a method for producing a photosensitive material having a photosensitive silver halide emulsion layer on both sides of a transparent support and at least one conductive layer on at least one side, the conductive layer contains a metal oxide colloid, In addition, when a non-photosensitive layer containing 0.1 to 0.8 g / m ² of gelatin is provided between the silver halide emulsion layer and the conductive layer, a silver halide emulsion layer is coated, and coating and drying are performed. The method for producing a light-sensitive material, characterized in that the period for which the water content on the silver halide emulsion layer side is reduced to 500 to 50% is dried under the condition represented by the above formula (1).

A light-sensitive material produced by the method for producing a silver halide photographic light-sensitive material described in the above item.

In a photosensitive material having a photosensitive silver halide emulsion layer and at least one conductive layer on both sides of a transparent support, the conductive layer contains a metal oxide colloid, and the surface matting degree is 100 mmHg or more, and The photosensitive material is
A light-sensitive material characterized in that at least one is packaged with a polyethylene sheet containing polyethylene having a density of 0.95 g / m ³ or more.

In a silver halide photographic light-sensitive material having a photosensitive silver halide emulsion layer on both sides of a transparent support and at least one conductive layer on at least one side, the conductive layer contains a metal oxide colloid, In addition, the photosensitive material contains the compound represented by the general formula [A], and the thickness of all hydrophilic colloid layers other than the conductive layer is 3.5 μm or less and the swelling degree is 250% or less. A photosensitive material characterized by being hardened so that

Hereinafter, the present invention will be described specifically.

Examples of the metal oxide colloid of the present invention include oxide colloids of zinc, magnesium, silicon, calcium, aluminum, strontium, barium, zirconium, titanium, manganese, iron, cobalt, nickel, tin, indium, molybdenum, vanadium and the like. Is preferably used. Especially ZnO, TiO ₂ and Sn
O ₂ is preferable, and SnO ₂ is particularly preferable. In addition, as an example of doping with different kinds of atoms, ZnO is Al, In
Etc., Nb, Ta, etc. for TiO ₂ , Sb, Nb, halogen elements, etc. for SnO ₂ .

The average particle size of the inorganic colloidal particles is preferably 0.001 to 1 μm in terms of dispersion stability.

Regarding the method for producing the metal oxide colloid used in the present invention, particularly the colloidal SnO ₂ sol comprising stannic oxide, the method for producing the SnO ₂ ultrafine particles by dispersing it in a suitable solvent or the solvent is applicable. Any method such as a method of producing from a decomposition reaction of a soluble Sn compound in a solvent may be used.

Regarding the method for producing SnO ₂ ultrafine particles,
Especially the temperature condition is important, and the method involving high temperature heat treatment is
Undesirably, heat treatment must be performed at 300 ° C. or lower, preferably 200 ° C. or lower, and more preferably 150 ° C. or lower, when it is necessary to perform heat treatment. But 25
Heating from 0 ° C. to 150 ° C. is a means preferably selected when dispersion in the binder is considered.

Further, due to recent advances in powder manufacturing technology, in manufacturing ultrafine particles, a method of spraying a compound manufactured by a wet method into an electric furnace, a high temperature thermal decomposition method of an organometallic compound, etc. have been developed. However, it is economically not preferable to redisperse ultrafine particles produced by such a method in a solvent, and it may cause serious defects as a photosensitive material such as generation of aggregated particles. There is. For this reason, the method of redispersing in a solvent after the production process in which only the metal oxide is isolated is not adopted in the present invention which is used as a photographic antistatic agent. However, when the compatibility between the binder and the solvent of the SnO ₂ sol is poor, solvent replacement is necessary. In such a case, another compound having good compatibility or dispersion stability with the solvent of the SnO ₂ sol is used. Add an appropriate amount of S from SnO ₂ sol
The nO ₂ ultrafine particles and the compound added in an appropriate amount are mixed at a temperature of 300 ° C. or less, preferably 200 ° C. or less, more preferably 150 ° C. or less.
After being dried and separated by heating at a temperature of not more than ℃, it is redispersed in another solvent.

A method for producing a Sn compound soluble in a solvent from a decomposition reaction in the solvent will be described below. The solvent-soluble Sn compound is a compound containing an oxo anion such as K ₂ SnO ₃ .3H ₂ O, a water-soluble halide such as SnCl ₄ , R ′ ₂ SnR ₂ , R ₃ SnX or R ₂ Sn
A compound having the structure of X ₂ (where R and R ′ represent an alkyl group), for example, (CH ₃ ) ₃ SnCl. (Pyridine), (C ₄ H ₉ ) ₂ Sn (O ₂ CC ₂ H _{5) 2} ) and oxo salts such as Sn (SO ₄ ) ₂ .2H ₂ O.

As a method for producing a SnO ₂ sol using Sn compounds soluble in these solvents, after dissolving in a solvent,
There are physical methods such as heating and pressurizing, chemical methods such as oxidation, reduction and hydrolysis, and methods of producing SnO ₂ sol after passing through an intermediate. For example, Japanese Patent Publication No. 35-66
According to the method for producing a SnO ₂ sol described in No. 16, SnCl ₄ is dissolved in 100 times volume of distilled water to form a precipitate of stannic hydroxide as an intermediate. Ammonia water is added to this stannic hydroxide to make it slightly alkaline and dissolve.
Then, the mixture is heated until the smell of ammonia disappears, whereby a colloidal SnO ₂ sol is obtained. In this example, water was used as the solvent, but an alcohol solvent such as methanol, ethanol and isopropanol, tetrahydrofuran,
Various solvents can be used depending on the Sn compound such as an ether solvent such as dioxane and diethyl ether, an aliphatic organic solvent such as hexane and heptane, and an aromatic organic solvent such as benzene and pyridine. There is no particular limitation on. Preferably, solvents such as water and alcohols are selected.

In the method of producing from a decomposition reaction of a solvent-soluble Sn compound in a solvent, a compound containing an element other than Sn, which is soluble in the solvent, can be added during the process. For example, adding a fluorine-containing compound soluble in a solvent,
This is the addition of a metal compound that can take a trivalent or pentavalent coordination number that is soluble in a solvent.

The solvent-soluble fluorine-containing compound may be either an ionic fluoride or a covalent fluoride. For example, HF or a metal fluoride such as KHF ₂ , SbF ₃ , or MoF ₆ , a compound that generates a fluoro complex anion such as NH ₄ MnF ₃ or NH ₄ BiF ₄ , BrF ₃ , SF ₄ , S
Inorganic molecular fluorides such as _{F 6, CF 3 I, CF} 3 COO
Organic fluorine compounds such as H and P (CF ₃ ) ₃ can be cited, but when the solvent is water, a combination of a fluorine-containing compound and a non-volatile acid, such as a combination of CaF ₂ and sulfuric acid, can also be used. Can be used.

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

As the binder for the conductive layer used in the present invention, proteins such as gelatin, derivative gelatin, colloidal albumin and casein; cellulose compounds such as carboxymethyl cellulose, hydroxyethyl cellulose, diacetyl cellulose and triacetyl cellulose;
Sugar derivatives such as agar, sodium alginate and starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol,
Poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamides or their derivatives, and vinyl polymers such as partial hydrolysates, polyvinyl acetate, polyacrylic acid esters and their copolymers, rosins, sierracs, etc. Natural products and derivatives thereof, and many other synthetic resins are used. In addition, water emulsions such as styrene-butadiene copolymer, polyacrylic acid, polyacrylate, and derivatives thereof, polyvinyl acetate, vinyl acetate-acrylate copolymer, polyolefin, and olefin-vinyl acetate copolymer are also used. can do. Other organic semiconductors such as carbonate-based, polyester-based, urethane-based, epoxy-based resins, polyvinyl chloride and polypyrrole can also be used. These binders can be used as a mixture of two or more kinds.

Of these binders, polyacrylic acid polymers, polyacrylamides, polyacrylonitriles,
Polyacrylic esters, polycarbonates, polyesters, polyvinyl chloride and polyvinylidene chloride are preferred.

The resistance of the conductive layer in the present invention is controlled by controlling the volume content of the conductive particles in the conductive layer and / or
Or 10 to 10 ¹⁰ Ω by adjusting the thickness of the conductive layer.
・ It can be easily adjusted to the range of cm. However, in order to have sufficient strength as a conductive layer, the amount of the binder is preferably not less than 5% by weight. The ratio of the conductive fine particles is 10 to 70% by volume, preferably 15 to 50% by volume, and the amount of use is 0.05 to 5%.
0 g / m ^2, preferably from 0.1 to 2.0 g / m ^2.

Upon coating the conductive layer, a solvent is appropriately selected to prepare a dispersion liquid of the above composition. Selection of a solvent can be easily performed by those skilled in the art. The coating method is not particularly limited and can be arbitrarily selected from known methods to be used. When applying, known coating aids and hardeners such as saponin and dodecylbenzene sulfonic acid,
A colorant, an ultraviolet absorber, a heat ray-cutting agent, etc. can be appropriately added to the coating solution as needed. In addition, an undercoat layer may be provided between the support and the conductive layer in order to improve the adhesion between the two.

In the present invention, a non-photosensitive layer is provided between the emulsion layer and the conductive layer. Amount of gelatin contained in the non-photosensitive layer is a single-sided per 0.1 to 0.8 g / m ^2, preferably 0.15~0.65g / m ^2. In addition to gelatin, a crossover cut dye or the like may be added to the non-photosensitive layer.

It has been found that the above-mentioned drying conditions of the present invention are very effective for producing a light-sensitive material in which fogging is less likely to occur due to drying in a short time.

In the present invention, the water content means the amount of water contained in the total hydrophilic colloid layer coated on the side containing the emulsion layer of the present invention, divided by the total amount of hydrophilic colloid in the hydrophilic colloid layer. The calculated value (ie, water content / total hydrophilic colloid) is 1
It is shown as a percentage (%) multiplied by 00.

In the step of drying the light-sensitive material of the present invention, the drying condition for the region where the water content of the coating material exceeds 500% is that the coating layer of the light-sensitive material does not melt due to the temperature rise due to drying. In addition, if the coating layer is not deformed by the wind pressure (that is, the pressure by the dry air), the photographic performance is not very seriously affected. Therefore,
From the viewpoint of productivity, a region where the water content exceeds 500% is preferably within a range where the coating layer is not melted and drying unevenness is not caused by the pressure of the drying air, and as short as possible.

As a preferred drying condition in the water content range of 1000% or more, a drying temperature of 28 ° C. or more and 40 ° C. or less and a wet bulb temperature of 12 ° C. or more and 25 ° C. or less are preferable. The difference between the temperature and the wet bulb temperature is preferably 12 ° C or higher and 21 ° C or lower.

In the region where the water content is less than 1000% to more than 500%, the dry bulb temperature is preferably 30 ° C. or higher and 42 ° C. or lower, and the wet bulb temperature is 18 ° C. or higher and 21 ° C. or lower. And the difference in wet bulb temperature is preferably 10 ° C. or higher and 20 ° C. or lower.

The dry-bulb temperature of the dry air in the region where the water content decreases from 500% to 50% is 28 ° C. or higher and 45 ° C. or lower, and
The wet bulb temperature is preferably from 18 ° C to 38 ° C.

The thermal conductivity coefficient [Kcal / m ² · hr · ° C.] for a dry wind sensitive material is preferably 30 to 120, more preferably 50 to 90, from the start to the end of drying. preferable.

Usually, in the drying step with a water content of 500% or more,
In many cases, the difference between the dry-bulb temperature and the wet-bulb temperature is dried at 12 ° C. or more in order to increase the drying speed.
When set below ℃, the difference between dry bulb temperature and wet bulb temperature is 12 ℃
In order to achieve the above, the wet bulb temperature becomes too low and it is difficult to produce a desired dry air.

It has been found that dry fog occurs when the dry-bulb and wet-bulb temperatures are lower in the drying step of 500% or less than in the drying step in which the water content exceeds 500%. Further, it has been discovered that fog due to drying is very likely to occur even at a high dry-bulb temperature of more than 45 ° C. in the drying process in which the water content is 500% or less to 50%.

Further, even if the dry-bulb temperature and the wet-bulb temperature in the drying step from the water content of 500% or less to 50% satisfy the above conditions, the dry-bulb temperature and the wet-bulb temperature are increased to shorten the drying time. If too much, fog becomes large, and even if the difference between the dry-bulb temperature and the wet-bulb temperature is 15 ° C. or less and within the conditions of the present invention, the drying air pressure is increased to shorten the drying time. Since the fog increases when dried rapidly, the formula (1)
If the value obtained by the method exceeds 10.0, fogging is less likely to occur, but the value of the drying time T is large and the value of the formula (1) is 1
If it exceeds 0.0, the productivity will drop significantly, and (DB-W
When the value of B) is small and exceeds 10.0, it is not preferable because it is necessary to supply dry air with high humidity at a strong wind pressure. Further, it was found that if it is less than 2.0, generation of fog due to drying cannot be avoided.

In order to produce a coated sample of a light-sensitive material containing silver halide grains according to the present invention, which is dried in a short period of time while suppressing the occurrence of fog, the drying conditions corresponding to the formula (1) of the present invention are used. It was discovered that drying under the satisfying conditions is the most preferable range from the two aspects of shortening the drying time and suppressing the occurrence of fog.

The conditions from the moisture content of less than 50% to the completion of drying and accumulation are preferably dry bulb temperature of 20 ° C. or more and 40 ° C. or less and relative humidity of 35% or more and 70% or less.

The average dry-bulb temperature of DB and the average wet-bulb temperature of WB of the present invention are obtained as follows.

When the DB is changed in the drying step within the range of water content of 500% or less and 50% or more, the water content of 500%
It was obtained as a so-called weighted average value from the sum of the products of the ratio of the time occupied by each DB temperature to the total time required for drying to 50%. Water content 500% or less, 50%
The average DB in the drying process in the above region may be within the range of the present invention, and a part of this region may be under conditions other than the present invention.

When the WB is changed in the drying step in the water content range of 500% or less and 50% or more, the ratio of the time occupied by each WB temperature to the total time required to dry the water content from 500% to 50% It is calculated as a so-called weighted average value from the sum of products of. The average WB of the drying step in a region having a water content of 500% or less and 50% or more may be within the range of the present invention, and a part of this region may be other than the conditions of the present invention.

The coated silver amount of the light-sensitive material of the present invention is 3.5 g / m ² or less, preferably 1.0 g / m ^{2 on} one side of the support.
It is in the range of not less than m ^{2 and not} more than 3.0 g / m ² .

The total amount of binder on the emulsion layer side having the emulsion layer of the present invention is preferably less than 4.8 g / m ² .

The surface matte degree on the silver halide emulsion layer side in the present invention is 100 mmHg or more. The matteness referred to here indicates the roughness of the film surface and can be measured as follows. That is, the matting degree in the present invention means an unexposed light-sensitive material (so-called raw film) which has been humidity-controlled for 4 hours under the conditions of a temperature of 23 ° C. and a humidity of 48% RH. Is measured
It refers to a numerical value expressed in mmHg. The larger this value is, the higher the matteness is. In the examples described below, a smoother (manufactured by Toei Denshi Kogyo Co., Ltd.) was used for measuring the suction pressure.

Usually, a matting agent is used to impart a matting degree to the light-sensitive material. The matting agent is generally fine particles of a water-insoluble organic or inorganic compound. In the present invention, any matting agent can be used, and those well known in the art can be used.

Specific examples of the organic compound that can be used as the matting agent include polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, and acrylonitrile-α as examples of water-dispersible vinyl polymers.
-Methylstyrene copolymer, polystyrene, styrene-
Examples of cellulose derivatives such as divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, and polytetrafluoroethylene include methyl cellulose, ethyl cellulose, cellulose acetate, and cellulose acetate propionate.Examples of starch derivatives include carboxy starch and carboxynitrilophenyl. Gelatin hardened with a known hardener, such as starch and urea-formaldehyde-starch reactant, and hardened gelatin formed into microcapsule hollow granules by coacervate hardening can be preferably used.

Preferred examples of the inorganic compound include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass and diatomaceous earth. be able to.

The above matting agents can be used by mixing different kinds of substances as needed.

The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. In carrying out the present invention, it is preferable to use particles having a particle size of 0.1 to 15 μm.

The particle size distribution of the matting agent used may be narrow or wide, and may be monodisperse or polydisperse. Here, the monodisperse matting agent is one in which the number of particles having a particle diameter within ± 20% of the average particle diameter is 90% or more of the total number of particles.

In the present invention, the matte degree on the emulsion layer side is
It is preferably 100 to 250 mmHg, and 0 to 7
It is more preferably 0 mmHg, and further 100 to 2
It is particularly preferable that the pressure is 00 mmHg.

In the present invention, the matting agent is preferably contained in the outermost surface layer of the light-sensitive material or a layer functioning as the outermost surface layer, or a layer close to the outer surface, and is a layer which functions as a so-called protective layer. It is preferably contained. That is, it is preferably contained in the protective layer which is a non-photosensitive layer on the emulsion layer side.

The polyethylene sheet used for packaging the light-sensitive material of the present invention is polyester such as polyethylene terephthalate and has a polyethylene density of 0.95 g / cm.
It is a high-density polyethylene film containing ³ or more polyethylene, and is processed into a sheet shape by dispersing carbon black powder to impart light-shielding properties.

The thickness of the polyethylene sheet is preferably 1
It is 50 μm or less, and more preferably 100 μm or less. When the thickness of the polyethylene sheet exceeds 150 μm, the rigidity is increased, and it becomes inconvenient to handle the package or the photosensitive material therein.

The polyethylene density of the polyethylene sheet of the present invention is 0.95 g / cm ³ or more, but two or more polyethylene sheets having different densities may be laminated to form one sheet. However, the structure of the sheet at that time may be such that the density of at least one polyethylene sheet of the structural unit is 0.95 g / cm ³ or more. The polyethylene sheet of the present invention can be manufactured by a usual method.

The preferred packaging form of the light-sensitive material of the present invention is
Bag-making using the polyethylene sheet of the present invention, in which 50 or more photosensitive materials cut into a certain size are used as one packaging unit,
Package and vacuum suction to keep the polyethylene bag anaerobic and light-tight. At this time, it is preferable that nothing other than the photosensitive material is enclosed in the polyethylene bag, but an oxygen absorber or the like may be enclosed.

A packaging unit in which a predetermined number of sheets are protected by U-shaped cardboard and one sheet of single leaf interleaf paper is applied only to the surface in contact with the cardboard, so-called non-interleaf packaging, may be used. Alternatively, interleaf packaging may be used in which one sheet is held by interleaf paper made of thin paper folded back and a predetermined number of the held sheets are sandwiched by U-shaped cardboard. Further, it is preferable to store these photosensitive material packages in an outer box made of cardboard from the viewpoint of preventing external pressure.

In another embodiment, the light-sensitive material of the present invention is packaged under the conditions of a temperature of 15 to 30 ° C. and a relative humidity of 40 to 60%, but a temperature of 18 to 25 ° C. and a relative humidity of 45 to 55%. It is more preferable to carry out below.

Next, the general formula [A] will be described.

In the general formula [A], R ₁ is a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a carbamoyl group, a thiocarbamoyl group, Represents a sulfamoyl group, and R ₂ and R ₃ each represent a hydrogen atom, a halogen atom, an alkyl group, a cyclic alkyl group, an aryl group, a cyano group, an alkylthio group, an arylthio group, an alkyl sulfoxide group, an alkylsulfonyl group, or a heterocyclic group. . Also, R ₂ and R ₃
May combine with each other to form a benzene ring. Of the above, the alkyl group, cyclic alkyl group, alkenyl group, heterocyclic group, alkoxy group, aralkyl group, aryl group, carbamoyl group, thiocarbamoyl group and sulfamoyl group may have a substituent.

As the compound represented by the general formula [A],
The compounds of the following general formulas [A-1] and [A-2] are more preferably used.

[0065]

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In R ₄ of the above general formula [A-1], the alkyl group and the alkenyl group have 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms. Carbon number of cyclic alkyl group is 3
-12, more preferably 3-6. The alkyl group represented by R ₄ may have a substituent, and examples of the substituent include a halogen atom (Br, Cl, etc.), a hydroxyl group, an amino group, an alkylamino group and the like.

The aryl group includes a phenyl group which may have a substituent, and examples of the substituent include a halogen atom,
Examples thereof include a nitro group and a cyano group.

The carbamoyl group, the thiocarbamoyl group and the sulfamoyl group may each have a substituent, and examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms and a phenyl group. The group may be substituted with a halogen atom, a nitri group, a cyano group or the like.

The heterocyclic ring which may be substituted for R ₄ is
5 containing at least one heterocycle of N, O, S
A 6-membered ring includes, for example, a furyl group, a thiazolyl group, a cenyl group, and the like, and these heterocycles have, for example, 1 to 5 carbon atoms.
The alkyl group, halogen atom and the like may be substituted.

Next, typical specific examples of the compound represented by the above general formula [A-1] are shown below, but the compound of the present invention is not limited thereto.

[0071]

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[0072]

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[0073]

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[0074]

[Chemical 6]

[0075]

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[0076]

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Next, in the above general formula [A-2], R
₇ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.
4 alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group. Examples of the heterocycle include those having the same meaning as R _{4 in the} above general formula [A-1]. R ₈ and R ₉ may be the same or different and each may be a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group or the like.

Next, typical examples of the compound represented by the above general formula [A-2] are shown below. However, it is not limited to these.

[0079]

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These compounds are water or organic solvents such as alcohols (methanol, ethanol, isopropanol, etc.), ketones (acetone, etc.), glycols (ethylene glycol, propylene glycol, etc.), esters (ethyl acetate, etc.), etc. Of these, it may be dissolved in a solvent that does not adversely affect the photographic performance and added to the hydrophilic colloid as a solution, or may be applied on the protective layer,
Alternatively, the photographic light-sensitive material may be contained by immersing it in the compound solution of the present invention. Alternatively, a method of dissolving in a high-boiling organic solvent, a low-boiling organic solvent or a mixed solvent thereof, emulsifying and dispersing in the presence of a surfactant, and adding the resulting solution to a solution containing a hydrophilic colloid, or further applying the solution on a protective layer. Is also good. Alternatively, after being contained in a polymer compound such as polybutyl acrylate and dispersed in the presence of a surfactant, it may be added to a liquid containing a hydrophilic colloid or applied on a protective layer.

The isothiazolin-3-one compound represented by the general formula [A-1] used in the present invention is preferably in the range of 1 × 10 ^-4 to 10% by weight with respect to the hydrophilic colloid, and particularly 3 The range of ^x10-4 to 1% by weight is preferable.

Further, 1,2-represented by the general formula [A-2]
The benzisothiazolin-3-one compound is preferably contained in the hydrophilic colloid in the range of 1 × 10 ⁻³ to 10% by weight, particularly preferably in the range of 1 × 10 ⁻⁴ to 1% by weight. The amount of addition may, of course, be outside the above range depending on the type of photographic light-sensitive material, the layer to be added, the coating method and the like.

The compound represented by the general formula [A] can be obtained by the method described in French Patent No. 1555416, or
According to it, it can be easily synthesized.

The film thickness of the one-sided all-hydrophilic colloid layer of the present invention is preferably 3.5 μm or less, and particularly preferably 3.0 μm or less. Further, it is important that the swelling rate is 250% or less. It is preferably 200% or less, more preferably 180% or less. The swelling ratio is a ratio of the swelling ratio to the film thickness (the thickness of the entire hydrophilic colloid layer) expressed as a percentage. The swelling thickness is an increment of the film thickness obtained by measuring the swelling swelling thickness by dropping distilled water of 25 ° C. on the light-sensitive material and then leaving still at 25 ° C. for 5 minutes.

As the silver halide binder, it is advantageous to use gelatin or a gelatin derivative. Examples of gelatin include lime-processed gelatin, Bulletin of Society of Scientific Photography of Japan (Bull. Soc. Sc.)
i. Photo. Japan) No. Pages 16 and 30 (19
Acid-treated gelatin as described in (1966), and a hydrolyzate or oxygen hydrolyzate of gelatin can also be used. As the gelatin derivative, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid alkane salts, vinylsulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds are reacted with gelatin. What is obtained by using is used.

The photosensitive silver halide emulsion of the light-sensitive material of the present invention may be silver bromide, silver iodobromide or a silver iodochlorobromide emulsion containing a small amount of silver chloride. The silver halide grains may be of any crystal type as long as they have the constitution of the present invention. For example, they may be single crystals such as cubic, octahedral, and tetrahedral, and have various shapes. Polytwin particles may be used.

That is, the solution method conditions such as the acidic method, the ammonia method, the neutral method and the like are used as the forward mixing method, the reverse mixing method, the double jet method, the controlled double jet method and the like, the conversion method and the core / shell method. It can be produced using the particle preparation conditions such as and the like and a combination method thereof.

A preferred embodiment of the emulsion used in the light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grain. The term “monodisperse” as used herein means that when the average particle diameter is measured by a conventional method, at least 95% of the particles by number or weight are within ± 40% of the average particle diameter,
The silver halide grains are preferably within ± 30%.

The grain size distribution of the silver halide grains may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The crystal structure of silver halide may have a different silver halide composition between the inside and the outside. For example, a high silver iodide core portion is coated with a low silver iodide shell layer to form a clear two-layer structure. The core / shell type monodisperse emulsion may be used.

The method for producing the above-mentioned monodisperse emulsion is known, and is described in, for example, J. Photo. Sci. The emulsion used in the light-sensitive material of the present invention is, for example, a seed crystal as a method for obtaining the above monodisperse emulsion, and the seed crystal is used as a growth nucleus to supply silver ions and halide ions for growth. Other emulsions may be used.

The core / shell type emulsions described above are known in the art and can be produced according to known methods.

The emulsion used in the light-sensitive material of the present invention is a tabular grain having an aspect ratio (ratio of grain size / grain thickness) of 3 or more, preferably an aspect ratio of 4 or more. The advantages of such tabular grains are that they can improve the spectral sensitization efficiency and improve the graininess and sharpness of an image. For example, British Patent No. 2,112,157 and US Patent No. 4,414,310. No. 4,434,226, etc., and emulsions can be prepared by referring to the methods described in these publications.

The above-mentioned emulsion is either a surface latent image type that forms a latent image on the surface of a grain, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on both the surface and inside. May be

These emulsions are subjected to physical ripening or grain preparation at the stage of, for example, cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof, iron salt or complex salt thereof. You may use.

The emulsion may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method in order to remove soluble salts. As a preferred water washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or JP-A-2-70.
A method using G-3, G-8, or the like, which is an example of an aggregated polymer agent described in No. 37, is a particularly preferred desalting method.

In the silver halide emulsion according to the present invention, various photographic additives can be used in addition to the metal salt or its complex salt in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure No. No. 1764323-29 (December 1978); 18716, pages 648 to 651 (1
No. 997) and the same No. 308119 996-
Compounds described on page 1009 (December 1989).

Examples of the support that can be used in the light-sensitive material of the present invention include the above-mentioned RD-17643-2.
8 and RD-308119, page 1009.

A suitable support is a polyethylene terephthalate film or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer.

The processing method of the light-sensitive material of the present invention is processed by an automatic processor including the steps of development, fixing, washing and drying,
The processing steps from development to drying are within 45 seconds, preferably within 30 seconds.

[0100]

Embodiments of the present invention will be described below. Note that, needless to say, the present invention is not limited to the embodiments described below.

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

A1 ossein gelatin 100 g potassium bromide 2.05 g with water to 11.5 l B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml with water to 2.6 l C1 ossein gelatin 75 g Potassium bromide 950 g Potassium iodide 27 g Water to 3.0 l D1 Silver nitrate 95 g Water to 2.7 l E1 Silver nitrate 1410 g Water to 3.2 l A1 solution kept at 60 ° C in a reaction kettle Solution B1 and solution D1 were added by the control double jet method over 30 minutes, and then solutions C1 and E1 were added by the control double jet method over 105 minutes. Stirring is 5
It was carried out at 00 rpm. The flow rate was such that no new nuclei were generated with the growth of the particles and so-called Ostwald ripening was performed, and the flow rate was such that the particle size distribution did not spread. At the time of adding the silver ion solution and the halide ion solution, the pAg was adjusted to 8.3 ± 0.05 using a potassium bromide solution, and the pH was adjusted to 2.0 ± 0.1 using sulfuric acid. After the addition is complete
After adjusting the pH to 6.0, desalting treatment was performed by the method described in JP-B-35-16086 to remove excess salts.

When this seed emulsion was observed with an electron microscope, it was a cubic tetradecahedral monodisperse emulsion having an average grain size of 0.27 μm and a grain size distribution with a width of 17%.

(Preparation of Em-1) A monodisperse core / shell type emulsion was prepared by using the seed emulsion EM-A and the following seven kinds of solutions.

A2 ossein gelatin 10 g Ammonia water (28%) 28 ml Glacial acetic acid 3 ml Seed emulsion EM-A 0.119 mol Equivalent to 600 ml with water B2 ossein gelatin 0.8 g Potassium bromide 5 g Potassium iodide 3 g With water Make 110 ml C2 ossein gelatin 2 g Potassium bromide 90 g Make up to 240 ml with water D2 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Make up to 110 ml water E2 Silver nitrate 130 g Ammonia water (28%) 100 ml To 240 ml water F2 Potassium bromide 94 g Water to 165 ml G2 Silver nitrate 9.9 g Ammonia water (28%) 7.0 ml Water to 110 ml A2 solution was kept at 40 ° C and stirred at 800 rpm with a stirrer. The pH of the A2 solution was adjusted to 9.90 with acetic acid,
The seed emulsion EM-A was collected and dispersed and suspended, and then the G2 solution was added at a constant speed over 7 minutes to adjust the pAg to 7.3. Further, solution B2 and solution D2 were added simultaneously over 20 minutes. At this time, the pAg was kept constant at 7.3. PH = 8.83 with potassium bromide solution and acetic acid over a further 10 minutes,
After adjusting the pAg to 9.0, the C2 solution and the E2 solution were simultaneously added over 30 minutes.

At this time, the flow rate ratio at the time of addition and at the end of addition was 1:10, and the flow rate was increased with time.
Also, the pH was lowered from 8.83 to 8.00 in proportion to the flow rate ratio. When the C2 solution and the E2 solution were added in only 2/3 of the total amount, the F2 solution was additionally injected and added at a constant speed over 8 minutes. At this time, the pAg was from 9.0 to 11.0.
Up. Further, acetic acid was added to adjust the pH to 6.0.

After completion of the addition, precipitation and desalting were carried out using an aqueous solution of Demol (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate to remove excess salts.
5, an emulsion having an average silver iodide content of about 2 mol% at pH 5.85 was obtained at 40 ° C.

Observation of the obtained emulsion with an electron microscope revealed that the average grain size was 0.55 μm and the grain size distribution was 14%.
A rounded tetradecahedral monodisperse core / shell emulsion was obtained.

(Preparation of Hexagonal Tabular Seed Emulsion) A pure silver bromide hexagonal tabular seed emulsion EM-B was prepared by the following method.

[0110] A3 ossein gelatin 60.2g Distilled water _{20.0l HO- (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5-7) 10% methanol aqueous solution _{5.6ml KBr 26.8g 10% H 2 SO} 4 144ml B3 nitrate 1487.5g D3 1.75N KBr solution following silver to 3500ml with C3 KBr 1050 g of distilled water to 3500ml with distilled water Potential control amount at 35 ° C, Japanese Patent Publication Nos. 58-58288 and 58-58
Solution A3 using a mixing stirrer described in No. 58289.
64.1 ml of the solution B3 and 64.1 ml of the solution C3 were added to the mixture by the simultaneous mixing method over a period of 2 minutes to form nuclei.

After the addition of the solutions B3 and C3 was stopped, it took 60 minutes to raise the temperature of the solution A3 to 60 ° C., and the solution B3 and the solution C3 were mixed again by the simultaneous mixing method.
Each was added at a flow rate of 68.5 ml / min for 50 minutes.
During this period, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to be +6 mV using the solution D. After completion of the addition, p is added with 3% KOH.
H was adjusted to 6 and immediately desalted and washed with water to give seed emulsion EM-
B. The seed emulsion EM-B thus prepared is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0 at least 90% of the total projected area of the silver halide grains, and the average thickness of the hexagonal tabular grains. 0.07 μm, average diameter (converted to circular diameter) is 0.
It was found by electron microscope observation that the variation coefficient was 5 μm and the variation coefficient was 25%.

(Preparation of silver iodobromide emulsion EM-2) The following 4
Tabular pure silver bromide emulsions were prepared using the various solutions.

[0113] A4 ossein gelatin _{29.4g HO- (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5~7) 10 % Methanol aqueous solution 1.25 ml seed emulsion EM-B 2.65 mol equivalent distilled water to 3000 ml B4 3.50N AgNO ₃ aqueous solution 1760 ml C4 KBr 737 g distilled water to 1760 ml D4 1.75N KBr aqueous solution At 60 ° C, Japanese Patent Publication Nos. 58-58288 and 58-58
Using a mixing stirrer described in No. 58289, solution A4
Then, the entire amount of the solution B4 and the solution C4 was added and grown by a simultaneous mixing method (double jet method) for 110 minutes so that the flow rate at the end of the addition was three times the flow rate at the start of the addition. During this time, the silver potential was controlled to be +40 mV using solution D4.

After the addition, in order to remove excess salts,
Precipitation and desalting were performed by the following method.

1. The temperature of the reaction mixture after completion of mixing is raised to 40 ° C.
20 g / AgX1 mol of Exemplified Aggregated Gelatin Agent G-3 is added, the pH is lowered to 4.30 by adding 56 wt% acetic acid, the mixture is allowed to stand, and decantation is performed.

After adding 1.8 l / AgX1 mol of pure water at 2.40 ° C. and stirring for 10 minutes, the mixture was left standing and decanted.

3. The above step 2 is repeated once.

4. Thereafter, 15 g of gelatin / 1 mol of AgX, sodium carbonate and water were added, and the mixture was dispersed to pH 6.0.
Finish to 450 ml / AgX1 mol.

About 3000 grains of the obtained emulsion EM-2 were observed and measured by an electron microscope to analyze the shape. As a result, they were hexagonal tabular grains having an average equivalent circle diameter of 0.59 μm and an average thickness of 0.17 μm. The coefficient of variation was 24%.

(Preparation of silver chloride emulsion) [Preparation of EM-C (pure silver chloride tabular seed emulsion)] A5 ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g Distilled water 7500 ml B5 silver nitrate 1500 g Distilled water to 2500 ml C5 KI 4 g NaCl 140 g Distilled water to 684 ml D5 NaCl 375 g Distilled water to 1816 ml At 40 ° C, Japanese Patent Publication Nos. 58-58288 and 58-58
To solution A5 in a mixing stirrer described in No. 58289, 684 ml of solution B5 and the total amount of solution C5 were added over 1 minute. The EAg was adjusted to 149 mV, and after aging for 20 minutes at Ostwald, the total amount of the remaining solution A5 and the total amount of the solution D5 were added over 40 minutes. Meanwhile, EAg is 149m
Controlled to V.

Immediately after the completion of the addition, desalting and washing were carried out to obtain a seed emulsion EM-C. Seed emulsion EM-C thus prepared
Means that at least 60% of the total projected area of silver halide grains is (1
00) a tabular grain having a plane as a main plane, an average thickness of 0.07 μm, an average diameter of 0.5 μm, and a variation coefficient of 25.
% By electron microscope observation.

(Preparation of Pure Silver Chloride Emulsion EM-3) The following 4
Tabular pure silver chloride emulsions were prepared using the various solutions.

[0123] A6 ossein gelatin _{29.4g HO- (CH 2 CH 2 O} ) n - [CH (CH 3) CH 2 O] 17 - (CH 2 CH 2 O) m H (n + m = 5~7) 10 % Methanol aqueous solution 1.25 ml seed emulsion EM-C 0.98 mol equivalent distilled water to 3000 ml B6 3.50N AgNO3 aqueous solution 2240 ml C6 NaCl 455 g distilled water to 2240 ml D6 1.75N NaCl aqueous solution silver potential control amount 40 At ℃, Japanese Patent Publication No. 58-58288, 58-58
Solution A6 using a mixing stirrer described in No. 58289.
The total amount of the solution B6 and the solution C6 was added to the mixture by a simultaneous mixing method (double jet method), and a growth time of 110 minutes was required so that the flow rate at the end of the addition was three times the flow rate at the start of the addition. During this period, the silver potential was +120 mV using solution D6.
It controlled so that it might become. After completion of the addition, precipitation and desalting were carried out in the same manner as in EM-1 to remove excess salts.

Approximately 3,000 emulsions EM-3 thus obtained were observed and measured by an electron microscope to analyze their shapes. As a result, 80% or more of the total projected area had the (100) plane as the main plane.
The tabular grains had an average diameter of 1.17 μm and an average thickness of 0.12 μm, and the coefficient of variation was 24%.

(Preparation of EM-4 (AgBr _0.45 Cl _0.55 tabular grains)) In the method for preparing EM-3, solution C6 was used.
473 g of potassium bromide was added thereto, and the solution B6 and the solution C6 were added.
Except that the silver potential during addition was controlled to +100 mV, tabular grains EM-4 were prepared in exactly the same manner.

Approximately 3000 emulsions EM-4 thus obtained were observed and measured by an electron microscope to analyze the shape, and 80% or more of the total projected area had the (100) plane as the main plane.
The tabular grains had an average diameter of 1.17 μm and an average thickness of 0.12 μm, and the coefficient of variation was 24%.

(Preparation of silver iodide fine particles) A7 ossein gelatin 100 g KI 8.5 g made to 2000 ml with distilled water B7 AgNO3 360 g made to 605 ml with distilled water C7 KI 352 g made to 605 ml with distilled water Solution A7 was placed in a reaction vessel. In addition, the solution B7 and the solution C7 were added at a constant rate over 30 minutes by the simultaneous mixing method while maintaining the temperature at 40 ° C. and stirring. The pAg during the addition is the normal pAg
It was kept at 13.5 by control means. The formed silver iodide was a mixture of β-AgI and γ-AgI having an average grain size of 0.06 μm. This emulsion is called a silver iodide fine grain emulsion.

(Preparation of Solid Fine Particle Dispersion of Spectral Sensitizing Dye) The following spectral sensitizing dyes (A) and (B) were added at a ratio of 100: 1 to water preliminarily adjusted to 27 ° C., and a high speed stirrer ( A solid fine particle dispersion of the spectral sensitizing dye was obtained by stirring with a dissolver) at 3,500 rpm for 30 to 120 minutes. At this time, the sensitizing dye (A) was adjusted to have a concentration of 2%.

Sensitizing dye (A): 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine salt Anhydride Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3, 3'-Di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride (selenium sensitized) Each emulsion EM-1 to EM-4 was spectrally and chemically sensitized by the following method.

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, and then ammonium thiocyanate was added to 7.0 per mol of silver. × 10 ^-4 mol was added, and potassium chloroaurate, sodium thiosulfate and triphenylphosphine selenide were added in an amount of 3.0 × 10 ^-6 mol per mol of silver,
After the addition of the silver iodide fine grain emulsion, 3 × 10 ⁻³ mol / Ag mol was added, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added. ) Stabilized at 3 × 10 ^-2 mol.

Next, the emulsion EM thus sensitized
Additives described below were added to -1 to EM-4 to prepare an emulsion layer coating solution. At the same time, a coating solution for the protective layer was prepared.

<Preparation of undercoated support> (Dispersion of conductive particles P1) Stannous chloride hydrate 65 g
Was dissolved in 2000 cc of an aqueous solution to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The generated precipitate is taken out by decantation, and the precipitate is washed with distilled water many times. Silver nitrate is dropped into distilled water from which the precipitate has been washed to confirm that there is no reaction of chloride ions. This precipitate was added to 1000 cc of distilled water and dispersed, and the total amount was 2000 c.
Let be c. Further, add 40cc of 30% ammonia water,
When heated in a water bath, a SnO ₂ sol solution is produced.

When it is used as a coating liquid, it is concentrated to a concentration of about 8% while blowing ammonia into this sol solution. Regarding the volume resistivity of the particles contained in this sol solution, a thin film was formed on silica glass using the sol solution, and the value measured by the four probe method was defined as the volume resistivity of the particles. The measured volume resistivity is 3.4 × 10 ^4.
Ωcm.

(Dispersion of Conductive Particles P2) Aqueous solution 20 of stannic chloride hydrate 65 g and antimony trichloride 1.0 g
The solution was dissolved in 00 cc to obtain a homogeneous solution. Then, this was boiled to obtain a coprecipitate. The formed precipitate is taken out by decantation, and the precipitate is washed with distilled water many times. Silver nitrate is dropped into distilled water from which the precipitate has been washed to confirm that there is no reaction of chloride ions. The precipitate is distilled water 1000
After adding and dispersing in cc, the total amount is made 2000 cc.
When 40 cc of 30% aqueous ammonia is further added and heated in an aqueous solution, a SnO ₂ sol solution is generated.

This sol solution was sprayed in an electric furnace heated to 400 ° C. to synthesize a conductive powder. After molding the obtained powder with a tablet molding machine, the volume resistivity measured by the four-terminal method was 1.5 × 10 ¹ Ωcm.

This electroconductive powder was dispersed in ammonia water having a pH of 10 so as to have a concentration of 8 wt%.

(Preparation of support for silver halide photographic light-sensitive material) (Support 1) 8 W / min. On both sides of a polyethylene terephthalate film having a thickness of 175 μm after biaxial stretching and heat setting and a density of 0.15. subjected to corona discharge treatment in m ^2, an undercoat layer so that the following subbing coating liquid B-1 on a dry film thickness of 0.8μm as one surface in JP 59-19941 JP B-1 And then dried at 100 ° C. for 1 minute. On the surface of the polyethylene terephthalate film opposite to the subbing layer B-1, there is disclosed in JP-A-59-774.
As described in JP-A-39-39, the undercoating coating solution B-2 shown below was applied as an undercoating layer B-2 and dried at 110 ° C. for 1 minute.

Undercoating 1st layer <Undercoating coating liquid B-1> Copolymer latte of 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25% by weight of 2-hydroxyethyl acrylate. X liquid (solid content 30%) 270 g Compound A 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Water is made up to 1 liter.

<Undercoating Liquid B-2-1> Copolymer latex liquid (solid content 30%) of butyl acrylate 40% by weight, styrene 20% by weight, and glycidyl acrylate 40% by weight 23 g Conductive P1 dispersion Liquid 415 g Polyethylene glycol (molecular weight 600) 0.00012 g Water 568 g Subbing second layer Further, a corona discharge of 8 W min / m ² was applied on the above subbing layers B-1 and B-2-1, and the following coating liquid B was obtained. -3 was applied to give a dry film thickness of 0.1 μm and dried at 100 ° C. for 1 minute.

<Undercoating Coating Liquid B-3> Gelatin 10 g Compound A 0.4 g Compound B 0.1 g Silica particles having an average particle size of 3 μm 0.1 g Water is made up to 1 liter.

[0141]

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(Support 2) Sample preparation conditions are as follows: instead of the above-mentioned undercoating coating solution B-2-1, the following undercoating coating solution B-2-
Except for using No. 2, it was prepared in the same manner as the support 1.

<Undercoating liquid B-2-2> Copolymer latex liquid (solid content 30%) of butyl acrylate 40% by weight, styrene 20% by weight and glycidyl acrylate 40% by weight 23 g Conductive P2 dispersion liquid 760 g Polyethylene Glycol (Molecular weight 600) 1.65 g Water 700 g (Support 3) Sample preparation conditions are undercoating liquid B-2-1.
Substrate 1 was prepared in the same manner as in Support 1, except that Subbing Coating Solution B-2-3 was used instead of.

<Undercoating liquid B-2-3> Copolymer latex liquid of butyl acrylate 40% by weight, styrene 20% by weight and glycidyl acrylate 40% by weight (solid content 30%) 27 g Conductive P1 dispersion liquid 83 g Polyethylene Glycol (molecular weight 600) 0.48 g Water 700 g (preparation of sample) The above-mentioned cross-over cut layer, emulsion layer, intermediate layer, and protective layer were applied evenly on both sides of the support in the order listed below, and the sample was dried. Created. Simultaneous multi-layer coating was performed so that the following coating amount was obtained, and the coating was dried under the drying conditions shown in Tables 1 and 2.

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

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone ( Molecular weight 10,000) 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / M ² 1,3-dihydroxybenzene-4-ammonium sulfonate 500 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 COOH) 2 350mg / m} 2 Compound (M) 5 mg / m ² Compound (N) 5 mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.2 g / m ² Dextrin (average molecular weight 1000) 0 0.2 g / m ² dextran (average molecular weight 40,000) 0.1 g / m ² However, the gelatin was adjusted to 1.0 g / m ² .

Third layer (intermediate layer) Gelatin 0.4 g / m ² formaldehyde 10 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² bis-vinylsulfonylmethyl Ether 18 mg / m ² latex (L) 0.05 g / m ² sodium polyacrylate 10 mg / m ² compound (S-1) 3 mg / m ² compound (K) 5 mg / m ² hardener (B) 1 mg / m ² 4th layer (protective layer) Gelatin 0.4 g / m ² Matting agent consisting of polymethylmethacrylate 50 mg / m ² (area average particle size 7.0 μm) Formaldehyde 10 mg / m ² 2,4-dichloro-6-hydroxy- 1,3,5-Triazine sodium salt 5 mg / m ² bis-vinylsulfonylmethyl ether 18 mg / m ² latex (L) 0.1 g / m ² Polyacrylamide (average molecular weight 10000) 0.05g / m ² Sodium polyacrylate 20 mg / m ² polysiloxane (S1) 20mg / m ² Compound (I) 12mg / m ² Compound (J) 2mg / m ² Compound (S-1) 7 mg / m ² Compound (K) 15 mg / m ² Compound (O) 50 mg / m ² Compound (S-2) 5 mg / m ² C ₉ F ₁₉ —O— (CH ₂ CH ₂ O) _11- H 3 mg / m ² compound (S-3) 2 mg / m ² compound (S-4) 1 mg / m ² Hardener (B) 1.5 mg / m ^{2 The} amount of the material is one side , The coated silver amount was 1.6 g / m ² for one side, and the gelatin amount in the emulsion layer was 1.0 g / m ² .
It was adjusted to m ^2.

[0148]

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[0149]

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[0150]

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[0151]

[Table 1]

[0152]

[Table 2]

(Evaluation of Drying Unevenness) An SRX-503 automatic developing machine was modified so that the processing time was as follows, using an SR-DF processing solution at a developing temperature of 35 ° C. A large angle size (35.6 x 35.6 cm) was uniformly exposed to X-rays so that the density was 1.0, and this was exposed to 10
0 sheets were continuously processed. Thereafter, 10 large-sized samples uniformly exposed to white light so as to have a density of 2.5 were continuously processed.
The unevenness observed when the developed sample was reflected on light and observed was divided into the following four stages, and evaluated as drying unevenness. Replenishment amount of processing solution is 125m for both developer and fixer
1 / m ² .

Development time: 8 seconds Fixing time: 6.2 seconds Water washing time: 4 seconds Water washing-drying (squeeze): 3.2 seconds Drying time: 8.6 seconds Total processing time: 30 seconds At this time, the drying temperature is , The surface temperature of the heat roller is 60
Drying was performed at ° C. As the heat roller, one using a halogen heater as a heat source coated with aluminum Teflon was used.

4: No drying unevenness is observed 3: Drying unevenness is observed at the edge (periphery) of the film in a frame shape 2: About half of the film is irritated unevenly from the edge to the center 1: Film Large dry unevenness is observed on the entire surface (Evaluation of antistatic performance: ash adhesion test method) 23 ° C, 20
Under the condition of% RH, the emulsion side of the developed sample was rubbed several times with a rubber roller, and the ash of the tobacco was brought close to the sample to determine whether it adhered to the film according to the following evaluation.

[0156] No adhesion even at a distance of less than 4: 1 cm. 3: 1 Adhesion at a distance of 1 to 4 cm. 2: Adhesion at a distance of 4 to 10 cm. Even at 1:10 cm or more. Table 3 shows the evaluation results.

[0157]

[Table 3]

From the results shown in Table 3, it can be seen that the samples of the present invention have excellent antistatic performance and little unevenness in drying.

Example 2 Samples shown in Table 4 were prepared using the emulsion and the preparation liquid prepared in Example 1 except for the protective layer.

A matting agent (area average particle size of 7.0 μm) made of polymethylmethacrylate for the fourth layer (protective layer) was used.
The same formulation as in Example 1 was prepared except that the amount of matting degree shown in Table 4 was added.

The antistatic performance was measured by the method described in Example 1 and the scratches by the following method.

(Scratch flaw) The obtained sample was cut into four pieces, left for 12 hours in an atmosphere of 40% RH and 25 ° C., and then 50 sheets in an environment of 23 ° C. and 50% RH. A non-interleaf wrapping is made into a packaging unit, and the depressurization is 50 m in a polyethylene sheet moisture-proof seal bag with a thickness of 100 μm and carbon black dispersed as a light-shielding agent.
It was vacuum sealed with mHg and light-tightly packaged. The densities of the polyethylene sheets used are those shown in Table 4.

Each packaged sample was stored at 23 ° C. for 8 hours.
After leaving it for 3 months in an environment of 0% RH, an unexposed sample film was used with a commercially available nylon scrubbing brush to weigh 100 g.
After rubbing under a load of / cm ² , the film developed by the method of Example 1 was visually evaluated as follows.

4: Almost no scratches 3: No problem in practical use, but slight scratches 2: Occurrence of noticeable scratches, which is a problem in practical use 1: Very many scratches, Table 4 shows the above evaluation results.

[0165]

[Table 4]

From the results shown in Table 4, it can be seen that the samples of the present invention have excellent antistatic performance and few scratches.

Example 3 Using the emulsion and the preparation liquid prepared in Example 1, samples shown in Table 5 were prepared.

At this time, the hardener (B) for the fourth layer (protective layer)
Was added in an amount to achieve the swelling degree shown in Table 5. Further, the compound represented by the general formula (A) according to the present invention and the comparative compound were added as shown in Table 5 below.

A development replenishing tablet was prepared according to the following procedure (A, B).

Operation (A) 12500 g of a developing agent, sodium erythorbate, is pulverized in a commercially available bandam mill until the average particle size becomes 10 μm. To this fine powder, 2000 g of sodium sulfite, 2700 g of dimezone S, 1250 g of DTPA, 12.5 g of 5-methylbenzotriazole, 4 g of 1-phenyl-5-mercaptotetrazole, 4 g of N-acetyl-D, L-penicillamine were added and mixed in a mill for 30 minutes. After granulating by adding 30 ml of water in a commercially available stirred granulator at room temperature for about 10 minutes, the granulated product is dried at 40 ° C. in a fluidized bed dryer.
And dried for 2 hours to almost completely remove the water content of the granulated product.

1670 g of polyethylene glycol 6000 was added to the granules thus prepared,
After 670 g of the mixture was uniformly mixed for 10 minutes using a mixer in a room whose humidity was adjusted to 25 ° C. and 40% RH or less, the obtained mixture was toughly pressed to collect 152 by Kikusui Seisakusho KK
Using a tableting machine modified from 7HU, the filling amount per tablet was adjusted to 8.77 g, and compression tableting was performed to prepare 2,500 development-supplementing tablet A agents.

Operation (B) 4000 g of potassium carbonate, 2100 g of mannitol, and 2100 g of polyethylene glycol 6000 were operated (A).
Pulverize and granulate as in The amount of water to be added is 30.0 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated material. The mixture obtained in this manner was applied to Kikusui Seisakusho Co., Ltd. Tough Presto Collect 1527HU.
Tableting machine was modified to reduce the filling amount per tablet to 3.28.
g and compression tableting to prepare 2500 replenishing tablets B.

Next, a fixing supplementary 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 ground in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), the amount of water added was 500 m
Granulate with l. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. In this way, 4 g of sodium N-lauroylalanine is added to the adjusted granulated product, and mixed for 3 minutes using a mixer in a room whose humidity is controlled to 25 ° C. and 40% RH or less. Next, the resulting mixture was compressed into tablets with a filling amount of 6.202 g per tablet by a tableting machine modified from Tough Pressto Correct 1527HU manufactured by Kikusui Seisakusho Co., Ltd., and 2500 fixing supplement tablets A were fixed. The agent was created.

Operation (D) 1000 g of boric acid, 150 aluminum sulfate and 18 hydrates
0 g, sodium hydrogen acetate (dried by mixing equimolar amounts of glacial acetic acid and sodium acetate) 3000 g, 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 granules are dried for 30 minutes to almost completely remove the water content. 4 g of sodium N-lauroylalanine was added to the thus-prepared product, and after mixing for 3 minutes, the obtained mixture was used per tablet with a tableting machine modified from Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Was compression-compressed at 4.562 g to prepare 1250 fixing replenishing tablets D.

Developer Solution Starter Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make 1 liter.

At the start of processing of the developing solution (start of running), 16.5 l of developing solution prepared by diluting the developing tablet with diluting water
The processing was started by filling the developing tank with a liquid having 330 ml of a starter added thereto as a starting liquid. The pH of the developer to which the starter was added was 10.45.

The photosensitive material prepared above was exposed to light so that the optical density after development processing was 1.0, and the photosensitive material was run. For the running, an automatic developing machine SRX-502 equipped with a charging member of a solid processing agent and modified so as to be able to process at a processing speed of 25 seconds was used. During the running, the developer was added with ^two of the above-mentioned A and B agents and 76 ml of water per 0.62 m ² of the photosensitive material. 38 ml each for A and B agents
PH when dissolved in water was 10.70. The fixing solution contains ^two C agents per 0.62 m ² of the photosensitive material and D
One agent and 74 ml of water were added. The rate of water addition to each of the treatment agents was started almost at the same time as the addition of the treatment agent, and was added at a constant rate for 10 minutes in proportion to the dissolution rate of the treatment agent.

[0179] The scratches were measured by the following method using the developing solution and the fixing solution of Example 1. Also, the antistatic performance was measured by the method of Example 1.

(Silver tone) The large angle size (35.6 × 35.6 cm) of the sample obtained by the above-mentioned processing method has a density of 1.2.
X-rays were uniformly exposed and processed. This developed sample was allowed to stand for 7 days at a temperature and humidity of 50 ° C. and 80% RH and then observed with a Schaukasten to visually evaluate the silver tone due to transmitted light.

4: Pure black 3: Slightly reddish black 2: Reddish black 1: Yellowish black The above evaluation results are shown in Table 5.

[0182]

[Table 5]

From the results shown in Table 5, it can be seen that the samples of the present invention have excellent antistatic performance and good silver color tone.

[0184]

According to the present invention, it is possible to provide a light-sensitive material which is excellent in antistatic performance, uneven drying, scratches, and silver tone and which can be processed extremely rapidly, and a method for producing the same.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location G03C 1/46 G03C 1/46 1/74 1/74 3/00 510 3/00 510X 560 560Q 560F

Claims (4)

[Claims] 1. A method for producing a silver halide photographic light-sensitive material having a photosensitive silver halide emulsion layer on both sides of a transparent support and at least one conductive layer on at least one side, wherein the conductive layer is metal oxide. 0.1 to 0.8 g / m between the silver halide emulsion layer and the conductive layer.
² has a non-light-sensitive layer containing gelatin, is coated with a silver halide emulsion layer, and the period during which the water content on the silver halide emulsion layer side is reduced to 500 to 50% is shown in the following formula. A method for producing a silver halide photographic light-sensitive material, which comprises drying under the condition represented by (1). Formula (1) 2.0 ≦ T / (DB-WB) ≦ 10.0 where T: water content (water content / total hydrophilic colloid weight) is 50
It represents the drying time (seconds) until it is reduced to 0 to 50%. DB: Water content (water content / total hydrophilic colloid weight) is 50
Dry-bulb dry-bulb temperature (℃) until it decreases to 0-50%
And 28 to 45 ° C. However, when the drying conditions are changed continuously or stepwise until the temperature is reduced to 500 to 50%, the average dry-bulb temperature during the period is shown. WB: Water content (water content / total hydrophilic colloid weight) is 50
Wet-bulb temperature (° C) of dry air until it decreases to 0-50%
And 18 to 38 ° C. However, when the drying conditions are changed continuously or stepwise until the temperature is reduced to 500 to 50%, the average wet-bulb temperature during that period is shown. 2. A silver halide photographic light-sensitive material produced by the method for producing a silver halide photographic light-sensitive material according to claim 1. 3. A silver halide photographic light-sensitive material having a light-sensitive silver halide emulsion layer and at least one conductive layer on both sides of a transparent support, the conductive layer containing a metal oxide colloid, and having a surface matte degree. Is 100 mmHg or more, and
A silver halide photographic light-sensitive material, wherein at least one of the silver halide photographic light-sensitive materials is packaged with a polyethylene sheet containing polyethylene having a density of 0.95 g / m ³ or more. 4. A silver halide photographic light-sensitive material having a photosensitive silver halide emulsion layer on both sides of a transparent support and at least one conductive layer on at least one side, the conductive layer containing a metal oxide colloid. In addition, the silver halide photographic light-sensitive material contains a compound represented by the following general formula [A], and the thickness of all hydrophilic colloid layers other than the conductive layer is 3.5 μm or less and swelling A silver halide photographic light-sensitive material, characterized in that it is hardened to a degree of 250% or less. Embedded image [Wherein R ₁ is a hydrogen atom, a linear or branched alkyl group, a cyclic alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an aryl group, a heterocyclic group, a carbamoyl group,
Represents a thiocarbamoyl group or a sulfamoyl group,
R ₂ and R ₃ are each a hydrogen atom, a halogen atom, an alkyl group,
It represents a cyclic alkyl group, an aryl group, a cyano group, an alkylthio group, an arylthio group, an alkylsulfoxide group, an alkylsulfonyl group or a heterocyclic group. Further, R ₂ and R ₃ may combine with each other to form a benzene ring. Of the above, the alkyl group, cyclic alkyl group, alkenyl group, aralkyl group, alkoxy group, aryl group, heterocyclic group, carbamoyl group, thiocarbamoyl group and sulfamoyl group may have a substituent. ]