JPH09269562A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material excellent in antistatic performance, adhesion property and color remaining property after development and to provide its processing method. SOLUTION: This photosensitive material has a base coating layer and hydrophilic colloid layers including silver halide emulsion layers formed on a base body. The hydrophilic colloid layers contain branched cyclodextrine and/or cyclodextrine polymer. The base coating layer contains a metal oxide sol. The photosensitive material is processed in an automatic developing machine having such a mechanism that a solid processing agent is supplied in a processing tank of the machine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a processing method thereof, and more particularly, to a silver halide photographic light-sensitive material excellent in antistatic performance, film formation after development processing and residual color, and processing thereof. Regarding the method.

[0002]

2. Description of the Related Art In recent years, not only high sensitivity and high image quality of silver halide photographic light-sensitive materials (hereinafter referred to as light-sensitive materials) but also stability of photographic performance have become increasingly strict, and silver halide emulsions are mainly used. Various improved techniques have been investigated.

Further, the speeding up of the development processing of the light-sensitive material is also progressing. Since the photosensitive material to be processed rapidly is transported at an extremely high speed in the automatic developing machine, friction with a transport roller or the like, peeling from other photosensitive materials laminated when being inserted into the automatic developing machine, etc. Is very easily charged,
It is easy to cause static mark fog due to charging.
In order to prevent such electrification, polyelectrolytes and surfactants have been used, but since these polyelectrolytes and surfactants have water solubility, they are eluted in the processing solution during development processing, May cause turbidity and sludge.

In order to improve them, there is known a technique of imparting conductivity by using metal oxide particles to prevent electrification, but there is a problem that film adhesion of the film after development processing and drying is deteriorated.

[0005]

In contrast to the problems described above, the object of the present invention is to provide a silver halide photographic light-sensitive material excellent in antistatic performance, film formation after development processing, and residual color, and a processing method thereof. Is to provide.

[0006]

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

(1) In a 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 contains a branched cyclodextrin and / or a cyclodextrin polymer. ,
A light-sensitive material, wherein the undercoat layer contains a metal oxide sol.

(2) A method of processing a light-sensitive material, characterized in that the light-sensitive material described in the above item (1) is processed in a processing step including a developing step and a fixing step.

(3) The method for processing a light-sensitive material according to the above item (2), wherein the developing step or the fixing step is carried out while being prepared by supplying a solid processing agent.

The present invention will be described in more detail below.

The present invention employs a metal oxide sol, preferably a colloidal tin oxide sol, as an antistatic agent. Here, since particles having a diameter of 10 ⁻⁵ to 10 ⁻⁷ cm are in a stable dispersed state, this size is referred to as a colloidal dimension. The dispersed state is called colloidal state in the present invention.

The method for producing the colloidal tin oxide sol of the present invention includes a method for producing ultrafine particles of tin oxide dispersed in a suitable solvent, a method for producing a solvent-soluble tin compound by decomposition reaction in a solvent, and the like. Either method can be adopted.

In the manufacturing method using ultrafine tin oxide 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. If you do, 300 ℃
Below, preferably 200 ° C. or lower, more preferably 150 ° C. or lower. However, heating in the range of 150-250 ° C is preferred for dispersion in the binder.

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

When the 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 that stably disperses the tin oxide sol is appropriately added and heated to 300 ° C. or lower, preferably 200 ° C. or lower, further 150 ° C. or lower, and the tin oxide ultrafine particles are dried and separated in water or other Redispersion in water with mixed solvent.

Examples of the tin compound used in the method of producing from a decomposition reaction of a tin compound soluble in a solvent in a solvent include compounds containing an oxo anion such as K ₂ SnO ₃ .3H ₂ O, and SnCl ₄ . water-soluble halide, R _'2 S
nR ₂ , R ₃ SnX, R ₂ SnX ₂ (C
H ₃ ) ₃ SnCl. (Pyridine), (C ₄ H ₉ ) ₂ Sn (O
CC ₂ H ₅₎ organometallic compounds such as _{2, Sn (SO 4) 2} · 2
Oxo salts such as H ₂ O can be mentioned. Where R,
R'represents a substituted or unsubstituted alkyl group, and X represents a halogen atom.

After dissolving the tin compound soluble in these solvents in the solvent, a tin oxide sol is produced by a physical method such as heating or pressurizing, a chemical method such as oxidation, reduction, hydrolysis or the like, or Alternatively, a tin oxide sol is produced via an intermediate.
For example, in Japanese Examined Patent Publication No. 35-6616, SnCl ₄ is
It is dissolved in 00 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 there is no smell of ammonia to produce a colloidal tin oxide sol. The method is described.

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

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

As the fluorine-containing compound soluble in the solvent,
Either an ionic fluoride or a covalent fluoride may be used, and metal fluorides such as K ₂ TiF ₆ , HF, KHF ₂ Sb, and F ₃ MoF ₆ , and fluoro complex anions such as NH ₄ MnF ₃ and NH ₄ BiF _4. Compounds that produce the compounds BrF ₃ , SF ₄ , and SF
Inorganic molecular fluorides such as ₆ , CF ₃ I, CF ₃ OOH, P
Examples thereof include organic fluorine compounds such as (CF ₃ ) ₃ .
Further, 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.

Examples of the metal compound soluble in a solvent and capable of having a trivalent or pentavalent coordination number include Al, Ga, In and Tl.
Or a group V element such as P, As, Sb, Bi, etc. Nb, V, which can take a trivalent or pentavalent coordination number
It is a group of compounds including transition metals such as Ti, Cr, Mo, Fe, Co, and Ni.

(Synthesis Example 1 of Colloidal Tin Oxide Dispersion)
65 g of stannic chloride hydrate in a water / ethanol mixed solution 2
Dissolved in 000 ml 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 distilled water from which the precipitate has been washed, distilled water is added to the washed precipitate to make the total volume 2000 ml. Further, add 30% ammonia water to 4
0 ml was added and heated in an aqueous solution to obtain a colloidal gel dispersion.

(Synthesis Example 2 of Colloidal Tin Oxide Dispersion)
Stannous chloride hydrate 65g and antimony trichloride 1.0g
Was dissolved in 2000 ml of a 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 distilled water from which the precipitate has been washed, distilled water is added to the washed precipitate to make the total volume 2000 ml.
Furthermore, 40 ml of 30% aqueous ammonia was added and heated in an aqueous solution to obtain a colloidal gel dispersion. The volume resistivity of the tin oxide sol obtained above is 2.1 × 10 ⁵ Ωcm
Met.

Next, the branched cyclodextrin and / or cyclodextrin polymer used in the present invention will be described.

The branched cyclodextrin used in the present invention is a known cyclodextrin in which a water-soluble substance such as glucose, maltose, cellobiose, lactose, sucrose, galactose and glucosamine, or a water-soluble substance such as disaccharide is branched or added. It is preferable that maltosyl cyclodextrin in which maltose is bound to cyclodextrin (the number of binding molecules of maltose is 1 molecule,
2 molecules, 3 molecules, etc.) and glucosyl cyclodextrin in which glucose is bound to cyclodextrin (the number of glucose-bonded molecules may be 1, 2, 3 molecules, etc.).

Specific synthesis methods of these branched cyclodextrins are described in, for example, Starch Science, Vol. 33, No. 2, P. et al.
119-126 (1989); 127-132
(1985), Starch Science, Vol. 30, No. 2, p. 23
For example, maltosyl cyclodextrin can be synthesized from cyclodextrin and maltose using an enzyme such as isoamylase or pullulanase to produce cyclodextrin. It can be produced by a method of binding maltose. Glucosylcyclodextrin can be produced in a similar manner.

The branched cyclodextrins preferably used in the present invention include the following specific exemplified compounds.

[Exemplified compounds] D-1 α-cyclodextrin having one molecule of maltose bound thereto, D-2 β-cyclodextrin having one molecule of maltose bound thereto, D-3
Γ-cyclodextrin with one molecule of maltose bound,
D-4 α-cyclodextrin having 2 molecules of maltose bound, D-5 β-cyclodextrin having 2 molecules of maltose bound, D-6 γ-cyclodextrin having 2 molecules of maltose bound, 3 molecules of D-7 maltose bound Α-cyclodextrin, D-8 β-cyclodextrin having 3 molecules of maltose bonded thereto, D-9 γ-Cyclodextrin having 3 molecules of maltose bonded thereto, D
-10 α-cyclodextrin having one molecule of glucose bound thereto, D-11 β-cyclodextrin having one molecule of glucose bound thereto, D-12 γ-cyclodextrin having one molecule bound to glucose, and two molecules of D-13 glucose bound to each other. α-Cyclodextrin, D-14 β-Cyclodextrin in which two molecules of glucose are bound, D
-15 γ-cyclodextrin having 2 molecules of glucose bonded thereto, D-16 α-cyclodextrin having 3 molecules bonded to glucose, D-17 β-cyclodextrin having 3 molecules bonded to glucose, D-18 3 molecules bonded with glucose The structures of γ-cyclodextrin and these branched cyclodextrins are described in HPLC. NM
R. TLC (thin layer chromatography), IMEPT method (Insensitive Nuclei enhan)
ced by polarization trans
Although various methods have been investigated by the definite method such as fer.), it has not been decided even with the current science and technology, and it is in the stage of the estimated structure.

Therefore, in the present invention, when monomolecules of disaccharides or disaccharides are bound to cyclodextrins, for example, when they are individually bound to each glucose of cyclodextrin, as shown below, It includes both those linearly linked to one glucose.

[0030]

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Since the ring structure of the existing cyclodextrin is retained as it is, it exhibits a clathrate action similar to that of the existing cyclodextrin, and maltose or glucose having high water solubility is added to the cyclodextrin, and the solubility in water is greatly increased. The characteristic is that it has improved.

The cyclodextrin in the above exemplified compounds is represented by the following general formula [A].

[0033]

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Of these, particularly useful for the present invention is n '=
4 is α-cyclodextrin, n ′ = 5 β-cyclodextrin, and n ′ = 6 γ-cyclodextrin. Among these branched cyclodextrins, particularly effective ones in the present invention are branched β-cyclodextrins.

Further, the cyclodextrin moiety according to the present invention acts as an inclusion compound to form an inclusion compound, but it is also possible to use the inclusion compound in the present invention.

The inclusion compound of cyclodextrin is
For example, F. Cramer, "Einschlußv"
erbindgen) Soringer (195)
4) Or M. Hagan, "Clathrate Inclusion Compound" (Clath
rate Inclusion Component)
As described in Reinh ld (1952), "a three-dimensional structure formed by combining atoms or molecules has pores of an appropriate size in which other atoms or molecules have a constant composition ratio. It is a substance that enters into a specific crystal structure.

Examples of the production of the inclusion compound of cyclodextrin are described in, for example, Journal of the American Chemical Society (Journal of the Ame).
rican Chemical Society) No. 7
Volume 1, page 354 (1949), Chemische Berichte, Volume 90, Volume 2
572 (1957), Vol. 90, 2561 (1)
957).

Also in the present invention, the inclusion compound of cyclodextrin can be prepared in advance by the methods described above and added to the fixing solution.

The branched cyclodextrin used in the present invention can be obtained as a commercial product. For example, maltosyl cyclodextrin is commercially available as Isoeryte (registered trademark) manufactured by Shimizu Minato Gyoza Co., Ltd. The branched cyclodextrin used in the present invention may be powder or liquid (for example, 70% liquid).

As the cyclodextrin polymer used in the present invention, those represented by the following general formula [B] are preferable.

[0041]

Embedded image

The cyclodextrin polymer used in the present invention can be produced by crosslinking cyclodextrin with, for example, shrimp chlorohydrin to form a crosslinked polymer.

The cyclodextrin polymer is water-soluble, that is, its solubility in water is 100 ° C at 25 ° C.
It is preferably 20 g or more per ml, and for that purpose the degree of polymerization n ⁻ in the above general formula [B] may be 3 to 4, and the smaller this value is, the water solubility of the cyclodextrin polymer itself and High solubilization effect.

These cyclodextrin polymers can be synthesized by a general method described in, for example, JP-A-61-97025 and German Patent 3,544,842. The cyclodextrin polymer may also be used as an inclusion compound of the cyclodextrin polymer as described above.

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 grain used in the present invention may be a normal crystal grain such as a cube, a tetradecahedron or an octahedron, and may be a spherical grain, a plate grain or a twin grain having an aspect ratio of less than 2. It may well have an irregular crystal form such as a potato. In the present invention, the term “spherical” means that the polygon having the largest area among the polygons forming the outer shape of the silver halide grain has a radius of curvature corresponding to 1/10 L to 1/2 L with respect to the length L. Is defined as having a ridge portion of the polygon before spheroidization.
Grain roundness can be determined by observing silver halide grains with an electron microscope.

In the present invention, the monodisperse silver halide grains mean that the weight of silver halide contained within a 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. (3 significant digits, rounding down to the least significant digit 4) The grain size referred to here is the diameter of a spherical silver halide grain, or the projection of a grain of a shape other than spherical. It is the diameter when the image is converted into a circular image of the same area.

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. (The number of measured grains 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.

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

The iodine content of the core is preferably 5 mol% or more and the solid solution limit or less, more preferably 7 mol% or more and the solid solution limit or less. Further, 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, if necessary, supplying silver ions, halogen ions or silver halide fine grains. What is obtained by crystal growth of seed particles is preferable. In this case, the grain center can have a halogen composition region different from that of the core. The halogen composition of the seed grains is arbitrary and may be any of silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride, silver chloroiodide and silver iodide.

The silver halide photographic emulsion is described in JP-A-3-16.
Known silver halide solvents such as ammonia, thioethers, thioureas, thiocyanates, etc. described in No. 8734 can be present and can be substantially rounded as defined above.

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

In the emulsion thus prepared, an appropriate amount of a halogenated solvent is added to the emulsion at an arbitrary time from the time when the silver halide grains are formed to the start of the chemical ripening. It may be mixed uniformly so that it is substantially rounded. After the silver halide emulsion is formed, the silver halide emulsion before the solvent treatment may be desalted (including washing with water).

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

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

The halogen composition distribution inside the silver halide grains can be determined by pretreating the grains into ultrathin sections and then observing and analyzing with a transmission electron microscope while cooling. Specifically, silver halide grains are taken out of the emulsion, embedded in a resin, and cut with a diamond knife to produce a 60-nm-thick section. While cooling this section with liquid nitrogen, observation and point analysis were performed with a transmission electron microscope equipped with an energy dispersive X-ray analyzer,
It can be obtained by quantitative calculation (Inoue, Nagasawa: Abstracts of the 62nd Annual Meeting of the Photographic Society of Japan, 1987 p62).

The silver iodide content on the outermost surface of the silver halide grains means the XPS method (X-ray Photoselectr).
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 less 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, and Ag3d.
5/2, Br3d, and I3d3 / 2 electrons are measured. The integrated intensity of the measured peak is used as the sensitivity factor (Sens
It is corrected by the intensity factor) and the halide composition of the outermost surface is obtained from the intensity ratio of these. The purpose of cooling the sample is to eliminate measurement errors caused by destruction of the sample by X-ray irradiation at room temperature (decomposition of silver halide and diffusion of halide (particularly iodine)), and to enhance measurement accuracy. -110
If cooled to ℃, sample destruction can be suppressed to a level that does not hinder measurement.

The tabular grain may be a tabular silver halide grain having two twin planes parallel to each other in two parallel (111) main planes, and two parallel (100) planes may be defined as main planes. Tabular silver halide grains may be used. What is twin?
Although it is a silver halide crystal having one or more twin planes in one grain, the morphology of twin crystals is classified by Klein and Moiser in the article Photographie Correspondents [P
hotgraphfish Korresponde
nz], Vol. 99, pp. 99, 100, 57. The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a silver halide photographic emulsion is applied so that the silver halide grains contained therein are oriented on a support to prepare a sample.
This is cut with a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. The presence of twin planes can be confirmed by observing this section with a transmission electron microscope.

As a method of obtaining a tabular silver halide emulsion, a method of precipitating silver halide on a seed crystal may be used. To obtain a tabular silver halide emulsion, a water-soluble silver salt solution and a water-soluble silver salt solution are used. (A) a step of introducing a silver salt and a halide salt into a dispersion medium to form a tabular nuclei in a method for producing a silver halide photographic emulsion which is carried out by supplying a protective halide solution to the presence of a protective colloid. (B) Subsequent to the nucleation, a step of performing Ostwald ripening under the condition that the (100) or (111) main surface of the tabular grain 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 as to have a desired particle size and halogen composition.

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

The average value of the aspect ratio of the tabular silver halide grains is preferably 2 or more. In the present invention, the emulsion layer containing tabular silver halide grains contains 50% of the total projected area.
The above consists of tabular silver halide grains, preferably 7
It is 0% or more, more preferably 90% or more. The average grain size of the tabular silver halide grains is preferably from 0.15 to 5.0 µm, more preferably from 0.4 to 3.0 µm, and most preferably from 0.4 to 2.0 µm. . The average thickness of the tabular silver halide grains is 0.15
It is preferably 0.3 μm, and the particle size and thickness can be optimized to optimize sensitivity and other photographic properties. Sensitivity and other factors that influence the photographic characteristics of the photosensitive material (thickness of hydrophilic colloid layer, hardness,
The optimum particle size and thickness differ depending on the chemical ripening conditions, the sensitivity of the photosensitive material, the amount of silver, etc.).

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

The tabular silver halide grains may have dislocations. Dislocations 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 the pressure from the emulsion to the point where dislocations occur in the grains are placed on a mesh for electron microscope observation, and damaged by electron beams (printout, etc.)
In order to prevent the above, the sample is observed by a transmission method while being cooled. At this time, the thicker the particles, the more difficult it is for an electron beam to pass therethrough. Therefore, it is possible to observe more clearly by using a high-voltage electron microscope (200 kv or more for particles having a thickness of 0.25 μm). it can.

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

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

The seed grains produced can also be enlarged in order to obtain silver halide grains. For example, a water-soluble silver salt solution and a water-soluble halide solution may be added by the double jet method, and the addition rate may be gradually changed in accordance with the enlargement of particles within the range where new nucleation does not occur and Ostwald ripening does not occur. As another condition for enlarging the seed grains, a method of adding silver halide fine grains, dissolving and recrystallizing the grains, as shown in the 88th Annual Meeting of the Photographic Society of Japan, 1988, may be used.

For the growth, an aqueous silver nitrate solution and an aqueous halide solution can be added by double jet, but the iodine can also be supplied into 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, a device in which the additive liquid nozzle is installed in the liquid near the mother liquid suction port of the stirrer is particularly preferably used. At this time, the stirring rotation speed is 100 to 1200 rpm.
Is preferable.

Further, in the preparation of the emulsion, during the seed grain forming step and the seed grain growth, ammonia, thioether,
Known silver halide solvents such as thiourea can be present.

In the production of silver halide grains, a silver salt solution and a halide solution are added by the double jet method during the growth, and the addition rate is adjusted according to the growth of the grains so that new nucleation does not occur and the size by Ostwald ripening is increased. Velocity without distribution spread, that is, 30 to 1 of the velocity at which new nuclei are generated
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 used in the present invention are:
So-called halogen conversion type (conversion type) particles may be used. The amount of halogen conversion is 0.
The conversion is preferably 2 mol% to 0.5 mol%, and the conversion may be performed either during physical ripening or after completion of physical ripening.

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

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

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

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

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

In the present invention, 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, and low molecular weight gelatin (having a molecular weight of 1,000 to 5).
And modified gelatin such as phthalated gelatin. Other hydrophilic colloids can also be used.

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. When removing the salts, see RD Vol. It can be carried out based on the method described in 17643, Section II.

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

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

The oxidizing agent may be added at any time from the time of silver halide grain formation to the time of adding the gold sensitizer in the chemical sensitization step (chemical sensitizer when the gold sensitizer is not used). is there.

In the silver halide photographic emulsion, unnecessary soluble salts may be removed at the end of the growth of silver halide grains, or may be contained. When removing the salts, Research Disclosure (Resea)
rch Disclosure, hereinafter abbreviated as RD) N
o. It can be performed based on the method described in 17643 No. II.

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

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. The addition method may be a method in which water or an organic solvent such as methanol and ethanol is dissolved alone or in a mixed solvent and added depending on the properties of the selenium compound used. Further, a method in which the mixture is added in advance with a gelatin solution, or a method in which the mixture is added in the form of an emulsified dispersion of a mixed solution with a polymer soluble in an organic solvent by the method disclosed in JP-A-4-140739 may be used. The temperature of chemical ripening using a selenium sensitizer is preferably in the range of 40 to 90C, more preferably 45C or more and 80C or less. The pH is 4 ~
9, pAg is preferably in the range of 6 to 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 derivatives thereof.
Other preferable reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like. The amount of the reducing agent added is preferably changed according to the environmental conditions such as the type of reduction sensitizer, the grain size of the silver halide grains, the composition and crystal habit, the temperature of the reaction system, pH and pAg. In the case of urea, a preferable result is obtained by using about 0.01 to 2 mg per mol of silver halide as a rough guide. In the case of ascorbic acid, the range is preferably about 50 mg to 2 g per mol of silver halide.

As the conditions for reduction sensitization, the temperature is about 40 to 7
0 ° C., time is about 10 to 200 minutes, pH is about 5 to 11, p
Ag is preferably in the range of about 1 to 10 (here, pAg
The value is the reciprocal of Ag + ion concentration).

Silver nitrate is preferred as the water-soluble silver salt. So-called silver ripening, which is one of reduction sensitization techniques, is performed by adding a water-soluble silver salt. The pAg during silver ripening is suitably 1 to 6, and preferably 2 to 4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range.

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

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

The merocyanine dye or the complex merocyanine dye has 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.
Member heterocyclic nuclei can be applied.

These sensitizing dyes may be used alone or in combination, and the combination is often used particularly for the purpose of supersensitization. In addition, the emulsion layer may contain, in addition to the sensitizing dye, a dye having no spectral sensitization or a substance which does not substantially absorb visible light and exhibits a supersensitizing effect. For example, it may contain a substituted aminostilbene compound having a nitrogen-containing heterocyclic nucleus group, an aromatic organic acid formaldehyde condensate, a cadmium salt, an azaindene compound and the like. The sensitizing dye may be added during or during each of the nucleation, growth, desalting, and chemical sensitization steps, or after the 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. Therefore, it is preferable to reduce the water content in the light-sensitive material before the start of drying.

The photosensitive material of the present invention preferably has a swelling ratio of 150 to 250% during the development processing and a film thickness after expansion of 70.
μm or less is preferred. When the water swelling ratio exceeds 250%, poor drying occurs, and for example, conveyance failure also occurs in automatic developing machine processing, particularly in rapid processing.

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

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

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

As a cause of fluctuation in photographic performance, it is effective to reduce the opening coefficient of the developer in the automatic processor. Particularly, the aperture coefficient is preferably 80 cm ² / l or less. That is,
If the aperture coefficient exceeds 80 cm ² / l, the undissolved solid processing agent or the concentrated solution immediately after dissolution is easily subject to air oxidation, resulting in the formation of insoluble matter and scum, and an automatic processor or a photosensitive material to be processed. However, when the aperture coefficient is 80 cm ² / l or less, these problems can be solved. The opening coefficient referred to here is represented by the contact area with the air per unit volume of the processing liquid, and the unit is (cm ² / l). Opening coefficient of preferably 80 cm ² / l or less in the present invention, more preferably 50~3cm ² / l, more preferably from 35~10cm ² / l.

The aperture coefficient can be generally reduced by using a resin or the like for air blocking as a floating pig, or can be reduced by a slit type developing device.

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

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

In the present invention, as the means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, JP-B-63-137783 and 63-975 are used.
No. 22, Japanese Utility Model Laid-Open No. 1-85732, etc., but any method may be used as long as the function of supplying the tablets to the processing tank is provided at a minimum. When the solid processing agent is a granule or a powder, Japanese Utility Model Application Laid-Open No. 62-81964, 6
3-84151, JP-A-1-292375, and the gravity drop method described in JP-A-63-105159 and JP-A-63-105159.
There is a known method using a screw or a screw described in 195345 or the like, but the method is not limited thereto.

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

In addition to the dihydroxybenzenes, aminophenols and pyrazolidones, reductones are preferably used as the developing agent in the developer. Among the pyrazolidones to be used, those substituted at the 4-position (dimesone, dimeson S, etc.) are particularly preferable because their water solubility and the solid treating agent themselves do not change over time.

In addition to sulfite as a preservative, an organic reducing agent can be used as a preservative. In addition, a chelating agent or a bisulfite adduct of a hardening agent can be added.
Also, a silver sludge inhibitor is disclosed in JP-A-5-289255.
JP-A-6-308680 (general formula [4-a] [4
It is also preferable to add the compound described in -b]). It is also preferable to add a cyclodextrin compound.
The compounds described in No. 124853 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 in the developer, and 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, o-hydroxybenzoic acid Sodium (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like. Can be mentioned.

Examples of development accelerators include thioether compounds, p-phenylenediamine compounds, quaternary ammonium salts, p-aminophenols, amine compounds, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, and hydrozine. If desired, compounds, mesoionic compounds, ionic compounds, imidazoles, etc. can be added.

As the antifoggant, an alkali metal halide such as potassium iodide and an organic antifoggant can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Examples thereof include nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine, and 1-phenyl-5-mercaptotetrazole.

Further, the developer composition may, if necessary,
It can be used as an organic solvent for increasing the solubility of methyl cellosolve, methanol, acetone, dimethylformamide, a cyclodextrin compound, and other developing agents.

Furthermore, various other additives such as stain inhibitors, sludge inhibitors, and stacking effect accelerators 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 can be added. In addition, a bisulfite adduct of a hardener and a known fixing accelerator can also be added.

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

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

Generally, in the developer used for the development processing of the black-and-white light-sensitive material, hydroquinones are used as a developing agent in many cases, but the present invention improves work safety and protects the environment. From the viewpoint, a developer containing substantially no hydroquinone, for example, ascorbic acid may be used.

The development time of the light-sensitive material of the present invention is 3 to 90 seconds, more preferably 5 to 60 seconds, and the processing time is Dr.
y to Dry is 15 to 210 seconds, and more preferably 15 to 90 seconds.

In the light-sensitive material of the present invention, various additives can be further added to the silver halide emulsion according to the purpose.

Examples of the support that can be used in the light-sensitive material of the present invention include those described on page 28 of RD-17643 and page 1009 of RD-308119.

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

[0121]

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 A 1 Ossein gelatin 37.5 g KI 0.625 g NaCl 16.5 g Distilled water 7500 ml B1 solution Silver nitrate 1500 g Distilled water 2500 ml C1 solution KI 4 g NaCl 140 g Distilled water 684 ml D1 liquid NaCl 375 g distilled water 1816 ml At 40 ° C., A1 liquid in the mixing stirrer shown in Japanese Patent Publication No. 58-58288 is mixed with 684 ml of B1 liquid and C
The whole amount of one solution was added over 1 minute. EAg is 149m
The mixture was adjusted to V, and after Ostwald ripening for 20 minutes, the entire remaining amount of solution B1 and the entire 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 with water were performed to obtain seed emulsion A. In the seed emulsion A thus prepared, 60% or more of the total projected area of silver halide grains consisted of tabular grains having an aspect ratio of 2 or more with the (100) plane as the main plane.
Average thickness 0.07μ, average diameter 0.5μ, coefficient of variation 2
It was found to be 5% by electron microscope observation.

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

[0125] A2 solution ossein gelatin _{29.4g HO (CH 2 CH 2)} m- (CH (CH 3) CH 2 O) 17 - (CH 2 CH 2 O) n-H (m + n ≒ 5.7 molecular weight 1700 ) 10% methanol solution 1.25 ml seed emulsion A 0.98 mole equivalent distilled water 3000 ml B2 solution 3.5N silver nitrate aqueous solution 2240 ml C2 solution NaCl 455 g distilled water 2240 ml D2 solution 1.75N NaCl aqueous solution The following silver potential control amount 40 ° C. At the start of the addition, the mixing stirrer shown in JP-B-58-58288 is used to mix all the amounts of solution B2 and solution C2 with solution A2 by the simultaneous mixing method (double jet method). The flow rate of
Addition growth was performed over a period of 110 minutes. During this time, the EAg was controlled at 120 mV using the D2 solution. After completion of the addition, the precipitate is immediately desalted to remove excess salts,
Washing was performed.

Approximately 3,000 emulsions B thus obtained were observed and measured by electron microscope observation, and the shape was analyzed. As a result, 80% or more of the total projected area had an aspect ratio of 2 or more with 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 25%.

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

(Preparation of solid fine particle dispersion of spectral sensitizing dye) 5,5'-dichloro-9-ethyl-3,3'-di-
(3-Sulfopropyl) oxacarbocyanine salt anhydride (sensitizing dye A) and 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) Benzimidazolocarbocyanine-sodium salt anhydride (sensitizing dye B) was previously added at a ratio of 100: 1 to 2%.
High-speed stirrer (dissolver) in addition to water adjusted to 7 ° C
At 3500 r. p. m. By stirring for 30 to 120 minutes at, a solid fine particle dispersion of the spectral sensitizing dye was obtained. At this time, the concentration of the sensitizing dye A was adjusted to 2%.

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

After the emulsion was heated to 60 ° C., the sensitizing dye A was added to 46
After adding the solid fine particle dispersion so as to be 0 mg / AgX1 mol, ammonium thiocyanate was added to 7 ×
10 ^-4 mol / AgX 1 mol, potassium chloroaurate, sodium thiosulfate and triphenylphosphine selenide were added at 3 × 10 ^-6 mol / AgX 1 mol, and optimal chemical sensitization was carried out. After adding the fine grain emulsion at 3 × 10 ⁻³ mol / AgX 1 mol, the mixture was stabilized at 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1 × 10 ⁻² mol / AgX 1 mol.

Next, 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.

(Preparation of comparative undercoated support 1) 170 x blue polyethylene terephthalate film base for X-rays (thickness: 175 μm) was subjected to a corona discharge treatment of 0.5 kV · A · min / m 2 on both sides, and then the undercoating latex liquid shown in (L-2) below. So that the film thickness after drying is 0.2 μm.
-1) was sequentially applied so that the film thickness after drying became 0.053 μm, and dried at 123 ° C. for 2 minutes. This support is referred to as support 1.

[0133]

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

(Preparation of tin oxide sol undercoated support 2) An undercoat layer similar to that of the support 1 was provided on one side of the same base, and (Synthesis example 1) was synthesized on the underside of the other side. SnO ₂ sol, the (L-2) solution, and the following (L-4)
The coating solution prepared by mixing the solutions at a volume ratio of 35:15:50 was used to obtain a dried film thickness of 0.12 μm and a sol component coverage of 250 mg.
/ M at ^2, so that the (L-1) and the following (L-3) solution thickness 0.053μm after drying a coating solution obtained by mixing in 70:30 ratio by volume in the upper layer It was applied simultaneously and dried at 120 ° C. for 1 minute. 0.5k before application
Corona discharge treatment of V · A · min / m ² was performed. This support is referred to as support 2.

(L-3) Dimethyl terephthalate 34.0
2 parts by weight, 25.52 parts by weight of dimethyl isophthalate, 5
-Sulfoisophthalic acid dimethyl sodium salt 12.97
Parts by weight, 47.85 parts by weight of ethylene glycol, 1,4
Cyclohexanedimethanol 18.95 parts by weight, calcium acetate monohydrate 0.065 parts by weight, manganese acetate tetrahydrate 0.022 parts by weight under a nitrogen stream 170 to 22 parts
After carrying out an ester exchange reaction while distilling off methanol at 0 ° C., 0.04 part by weight of trimethyl phosphate, 0.04 part by weight of antimony trioxide as a polycondensation catalyst and 15.08 parts by weight of 1,4-cyclohexanedicarboxylic acid. Add 2 parts
At a reaction temperature of 20 to 235 ° C., almost the theoretical amount of water was distilled off to carry out esterification. Thereafter, the pressure inside the reaction system was further reduced and the temperature was raised over about 1 hour, and finally polycondensation was performed at 280 ° C. and 1 mmHg or less for about 1 hour to obtain a polyester polymer.
(Intrinsic viscosity 0.35) 30 g of styrene, 30 g of butyl methacrylate, 20 g of glycidyl methacrylate, 20 g of acrylamide and 1.0 g of ammonium persulfate were added to 7300 g of the obtained aqueous solution of the polyester polymer, and the mixture was reacted at 80 ° C. for 5 hours, and then allowed to reach room temperature. After cooling, the solid content was adjusted to 10% by weight to obtain a coating solution.

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

(Preparation of Photosensitive Material) Next, branched cyclodextrins as shown in Table 1 were formed on both surfaces of the support 1 and the support 2 in the following first layer (transverse light blocking layer) in an amount of 0. 0
8 g / m ² , 0.2 g / m ^{2 was} added to the second layer (emulsion layer), and the following transverse light blocking layer coating solution, emulsion layer coating solution and protective layer coating solution were added in the following prescribed coating amounts. Simultaneous multi-layer coating so as to be dried and dried to prepare Samples 1 to 7.

First layer (transverse light shielding layer) Gelatin 0.2 g / m ² Solid fine particle dispersion dye (AH) 20 mg / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2, 4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² second layer (emulsion layer) 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 5 mg / m ² polyvinylpyrrolidone ( Molecular weight 10,000) 20 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 1 mg / M ² 1,3-dihydroxybenzene-4-sulfonic acid ammonium 50 mg / m ² 2-mercaptobenzimidazole-5-sulfonic acid sodium 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 C OOH) ₂ 20 mg / m ² compound (M) 5 mg / m ² compound (N) 5 mg / m ² colloidal silica 0.5 g / m ² latex (L) 0.5 g / m ² sodium styrenesulfonate (molecular weight about 500,000) ) 7 mg / m ² However, the amount of gelatin was adjusted to 1.0 g / m ² per side.

[0141] The third layer (protective layer lower) Gelatin 0.4 g / m ² of dioctyl phthalate 195 mg / m ² Sodium styrene sulfonate (molecular weight: about 500,000) 7 mg / m ² 4th layer (upper protective layer) Gelatin 0.28g / M ² Polymethylmethacrylate matting agent (area average particle size 7.0 μm) 27 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10000) 0.1 g / m ² sodium polyacrylate 30 mg / m ² polysiloxane (SI) 50 mg / m ² compound (I) 30 mg / m ² compound (S-1) 7 mg / m ² C ₉ F ₁₉ —O— (CH ₂ CH ₂ O) ₁₁ —H 3 mg / m ²

[0142]

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C ₇ F ₁₅ CH ₂ (OCH ₂ CH ₂ ) ₁₃ OH 10 mg / m ²

[0144]

[Chemical 6]

[0145]

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The coating amount of the material was for one side, and the coated silver amount was adjusted to be 1.5 g / m ² for one side.

(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 to an average particle size of 10 μ. In this grinding, 3000 g of sodium sulfite and 20 g of potassium sulfite were used.
00g and 1000 g of Dimaison S were added, mixed in a mill for 30 minutes, and at room temperature for about 10 minutes in a commercially available stirring granulator.
After granulating by adding 30 ml of water, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the moisture of the granulated material. 25 g of polyethylene glycol 6000 (100 g) was added to the granules thus prepared.
After mixing uniformly for 10 minutes using a mixer in a room humidified at 40 ° C. and below 40% RH, one tablet of the obtained mixture was obtained using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. Compression tableting was performed with the filling amount per unit being 3.84 g to prepare 2500 tablets A for development replenishment.

Procedure (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of KOH, N-acetyl-D, 10 g of L-penicillamine. Pulverize and granulate 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 and tableted with the tableting machine at a filling amount of 1.73 g per tablet to prepare 2500 tablets B for replenishment of development.

DTPA: diethylenetriamine 5 acetic acid 5
Na (Preparation of Fixing Replenishing Tablet) A fixing replenishing tablet was prepared by the following procedure.

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

Operation (D) 1000 g boric acid, 150 aluminum sulphate-18-hydrate
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), tartaric acid 200
g is ground and granulated in the same manner as in the operation (A). The amount of water added is 100 ml, and after granulation, the granulated product is dried at 50 ° C. for 30 minutes to almost completely remove the water content of the granulated product. 4 g of sodium N-lauroylalanine was added to the granules thus prepared and mixed for 3 minutes, and the obtained mixture was filled with the above tableting machine at a filling amount of 4.562 g per tablet.
Then, compression tableting was performed to prepare 1250 fixing replenishing tablets D.

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

At the start of processing of the developing solution (starting of running), 434 parts of each of agent A and agent B of the developer replenishing tablet were diluted with diluting water to prepare 16.5 l of developing solution, and the starter 33 was added.
The processing was started by filling the developing tank with the liquid to which 0 ml was added as a starting liquid. The pH of the developer to which the starter was added was 10.45. As the fixing start solution, 11.0 l of the fixing solution prepared by diluting the fixing replenishing tablet with the equivalent of 298 g of the agent C and the equivalent of 149 g of the agent D was used as the starting solution to fill the fixing tank. The sample was exposed so that the optical density after the development processing was 1.0, and the sample was run.
For running, Konica Corporation's automatic processor SRX-50
2 was equipped with a solid processing agent charging member, and was modified so that the processing speed could be reduced to 25 seconds.

During running, the developing solution contained 0.6% light-sensitive material.
The above-mentioned ^two agents A and B and 2 ml of water were added per 2 m ² . When each of the agents A and B was dissolved in 38 ml of water, the pH 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.

[0156] The following evaluation was performed about the obtained sample.

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

A: No static mark was generated. B: Static mark was slightly generated. C: Static mark was generated. D: Static mark was generated on the entire surface.

<Evaluation with Film> The blackened film treated by the above-mentioned treatment method was conditioned at 23 ° C. and 70% RH for 2 hours, and then sapphire needle having a diameter of 0.3 mm was applied with a load of 500 g for 3 times.
A length of 20 cm was rubbed 10 times at a speed of 0 cm / sec. The film peeling of the emulsion film was evaluated according to the following criteria from the way of scratching.

A: No scratches at all B: Invisible to the naked eye, slightly detected with a 10 times magnifying glass, 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.

<Evaluation of Remaining Coloring Property> An unexposed sample was processed by the above processing method and evaluated according to the following criteria.

A: No occurrence B: Slightly reddish edge of the film when observed, but no problem in practical use C: Slightly reddish edge of film when observed,
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 obtained results are shown in Table 1.

[0164]

[Table 1]

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

[0166]

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

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a silver halide emulsion layer and an undercoat layer on a support, wherein the hydrophilic colloid layer is a branched cyclodextrin and / or cyclodextrin polymer. And a silver halide photographic light-sensitive material, wherein the undercoat layer contains a metal oxide sol. 2. A method for processing a silver halide photographic light-sensitive material, which comprises processing the silver halide photographic light-sensitive material according to claim 1 in a processing step including a developing step and a fixing step. 3. The method of processing a silver halide photographic light-sensitive material according to claim 2, wherein the developing step or the fixing step is carried out while being prepared by supplying with a solid processing agent.