JPH09114045A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sensitive material using a lightweight syndiotactic polystyrene film as the photographic substrate, not causing trouble due to oil sludge in development and having a permanent antistatic effect even after development. SOLUTION: This sensitive material has at least one layer of an antistatic agent contg. electrically conductive particles with a water-soluble polymer positioned around polymer particles and has a photographic substrate of biaxially stretched syndiotactic polystyrene. The weight of the water-soluble polymer is 35-500% of that of the polymer particles and the water-soluble polymer has sulfo groups and carboxyl groups.

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 using a biaxially stretched syndiotactic polystyrene film as a photographic support, and more particularly to a novel lightweight syndiotactic polystyrene photographic support. Then
The present invention relates to a silver halide photographic light-sensitive material having an excellent antistatic effect.

[0002]

2. Description of the Related Art An X-ray medical silver halide photographic light-sensitive material (hereinafter sometimes abbreviated as X-ray film) is inserted into a Schaukasten for diagnosing an affected area after photography and development. Strength is an important issue for an X-ray film. Previously, a cellulose triacetate (TAC) film had been used as a photographic support, but it could not be used unless it had a thickness of 230 μm due to its weak stiffness. Later, P as a photographic support with strong stiffness
Although an ET film was used, there was a demand for a photographic support that had a specific gravity of 1.4, had a large product weight, was strong, and was lighter than PET.

Recently, a biaxially stretched syndiotactic polystyrene described in JP-A-3-131843 (hereinafter referred to as SP
It has been proposed to use a film based on S) as a photographic support. This film has a specific gravity of about 1.0 and P
It is lighter than that of ET by 25% or more and has a very small coefficient of hygroscopic expansion, so that it has attracted attention as a next-generation photographic support in the art.

On the other hand, the silver halide photographic light-sensitive material is in contact with the surface of the same or different substance and the silver halide photographic light-sensitive material in contact with each other during the process of manufacturing the same and during use by the user. The silver halide photographic light-sensitive material is easily charged with static electricity due to peeling or peeling. When the electrostatic charge accumulated and charged is discharged, the silver halide photographic light-sensitive material is fatally damaged. The silver halide photographic light-sensitive material is a product that cannot be subjected to so-called non-destructive inspection, which shows that it is of normal quality only after development, and must not be damaged by static electricity in any case. is there. The obstacle is an unnecessary pattern such as a dot-like or resin-like or feather-like image called a static mark, and when these appear on the photographic film, it becomes noise other than the photographic image. For example, in the case of a medical or industrial X-ray photographic film, an erroneous signal is generated, which may cause a false diagnosis and is dangerous. On the other hand, when the photographic film is charged after the development processing, dust adheres to the surface, unnecessary points appear on the printed print, and the commercial value is completely lost. Further, an electrostatic shock from a charged film during handling of the film in a printing company or the like also poses a threat to the worker. When the photosensitive layer or the like is applied, static electricity may be generated due to contact peeling from the roll, resulting in uneven coating such that the coating solution is unevenly applied.

Conventionally, various kinds of antistatic techniques have been proposed, but a surfactant-based antistatic agent has been mainly used for electrostatic damage for X-ray films.
Proposed antistatic techniques include, for example, Japanese Examined Patent Publication Nos. 47-8742, 56-1617, 58-43729, and JP-A-48-19213, 4).
9-10022, 49-47733, 51-3
2322 and 55-7762.

[0006]

However, the antistatic technique for X-ray film is very difficult, and not only the antistatic performance but also the polyethylene oxide type surfactant antistatic agent as described in the above-mentioned patent documents is developed. It is a substance that easily elutes in liquids and the like, and when it elutes, oily properties also appear, and it easily adheres to the walls of equipment, rollers, films, etc. This is called oil sludge. If it adheres to the film, it will hinder development and cause poor fixing, making it unusable.
It is something that cannot be retaken, and it can also affect human life. In addition, as the development process of the film becomes more and more difficult, such as faster development process, lower replenishment of developer due to environmental problems, concentration, replenishment of processing agent with tablets, etc. We are in a situation where we cannot handle it.

On the other hand, with regard to silver halide photographic light-sensitive materials, there is a tendency that electrostatic damage is likely to occur due to high sensitivity, high-speed production, high-speed photography, automatic photography, and change of photographic support. In addition to the problems of development processing, there is an increasing demand for development of antistatic technology that can address these problems.

The SPS-based photographic support has a smaller dielectric loss than the PET photographic support, and therefore has the property that it is difficult to be neutralized once it is charged. In particular, it is important to search for an antistatic technique when the above photographic support is used for a silver halide high-sensitivity photographic light-sensitive material such as an X-ray film.

The present inventor has found the above two problems, that is, X
An attempt was made to achieve both SPS of a photographic support for a linear film and oil-free sludge of an antistatic agent for a high-sensitivity silver halide photographic light-sensitive material.

The object of the present invention is to use a SPS type photographic support as a photographic support, to reduce the weight thereof, to prevent generation of oil sludge during development processing, and to have a permanent antistatic effect which does not deteriorate even after development. To provide a light-sensitive material.

[0011]

According to the present invention, as an antistatic agent for a silver halide photographic light-sensitive material having an SPS type photographic support, the following water-soluble polymer (A) is positioned around the outer periphery of polymer particles. By providing at least one layer of the silver halide photographic light-sensitive material having an antistatic layer containing conductive particles, a silver halide photographic light-sensitive material having a permanent antistatic property was obtained and achieved. Here, the water-soluble polymer (A) is a water-soluble polymer having a sulfonic acid group and a carboxyl group.

Further, the present invention relates to conductive particles in which the sulfonic acid group of the water-soluble polymer (A) is derived from a styrene sulfonic acid monomer; polymer particles derived from an epoxy group-containing monomer. To the copolymer of styrene sulfonic acid and maleic acid; the molar ratio of styrene sulfonic acid and maleic acid is styrene sulfonic acid / maleic acid = 50/50 to 95/5. Within the range; by setting the weight of the water-soluble polymer (A) to 35 to 500% with respect to the weight of the particles made of the polymer, excellent permanent antistatic performance and excellent other properties are obtained. The silver halide photographic light-sensitive material of the present invention was obtained and achieved.

The present invention is described in detail below.

[Photographic Support] The SPS of the present invention will be described. The SPS of the present invention, that is, a polystyrene polymer having a syndiotactic structure means that the stereoregular structure (tacticity) has a syndiotactic structure, that is, a main chain formed from carbon-carbon bonds. On the other hand, it has a steric structure in which phenyl groups and substituted phenyl groups, which are side chains, are alternately located in opposite directions. In SPS, not all styrene units of the main chain have a syndiotactic structure, but a part where several styrene units of syndiotactic structure are connected, and they are overlapped to form a crystal part. It has a structure. This chain is called racemo chain, and SPS is a composition having many polystyrene racemo chains in the main chain. When a plurality of continuous styrene constitutional units is 2, it is called dyad, when it is 3 it is called triad, and when it is 5 it is called pentad, and the styrene-based polymer mainly having a syndiotactic structure in the present invention means , Usually racemic dyad 75% or more, preferably 85% or more, or racemic triad 60%
As described above, it is preferably 75% or more, or 30% or more and 50% or more, racemic pentad. This tacticity is based on the nuclear magnetic resonance method ( ¹³
It can be quantified by C-NMR method.

The SPS polymer of the present invention may be a styrene homopolymer, a composition containing a styrene derivative or other monomer, and may be a styrene homopolymer. Polymerization can be carried out by the method described in JP-A No. 62-117708, and regarding other polymers, JP-A Nos. 1-46912 and 1-17850.
It can be obtained by polymerizing by the method described in No. 5 or the like.

Specific examples of the polymer constituting the SPS composition include styrene, alkylstyrene such as methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene and chlorostyrene, and alkoxy. Examples thereof include styrene and vinyl benzoate.

When the SPS photographic support of the present invention contains a monomer as a styrene derivative other than styrene, it may be contained in an amount of 15% or less, preferably 10% or less. Particularly, 5 to 10% is preferable. In this case, 4-methylstyrene is preferable as the styrene derivative.

The polystyrene-based resin having a syndiotactic structure of the present invention uses the above-mentioned raw material monomers as a polymerization catalyst and is disclosed in JP-A-5-320448, pages 4 to 1.
(A) (a) a transition metal compound and (b) aluminoxane as a main component described on page 0, or (b) an ionic complex that reacts with (a) a transition metal compound and (c) a transition metal compound It can be produced by polymerization using a compound containing a compound capable of forming

In order to produce the styrene polymer used for the SPS photographic support of the present invention, first, the styrene monomer is sufficiently purified and then polymerized in the presence of any of the above catalysts. Let At this time, the polymerization method, polymerization conditions (polymerization temperature, polymerization time), solvent, etc. may be appropriately selected.
Usually, the polymerization is carried out at a temperature of −50 to 200 ° C., preferably 30 to 100 ° C. for 1 second to 10 hours, preferably 1 minute to 6 hours. As the polymerization method, any of a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used, and either continuous polymerization or discontinuous polymerization may be used. Here, in the solution polymerization, as a solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and aliphatic hydrocarbons such as cyclopentane, hexane, heptane, and octane may be used alone or in combination. It can be used in combination. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected. The molecular weight and composition of the polymer may be controlled by a commonly used method. The molecular weight can be controlled by, for example, hydrogen, temperature, monomer concentration and the like. After completion of the polymerization, it is preferably pelletized by a conventional method before use.

SPS used in the photographic support of the present invention
The molecular weight of the polymer is not limited as long as it is formed into a film, but the weight average molecular weight is 10,000 to 300,000.
0 is preferable, and particularly 30,000 to 1500
000 is preferred. The molecular weight distribution (number average molecular weight / weight average molecular weight) at this time is preferably 1.5 to 8. This molecular weight distribution can be adjusted by mixing different molecular weights.

From the viewpoint of stereoregularity, the SPS photographic support of the present invention is preferably an SPS homopolymer, but in addition to the syndiotactic structure, an isotactic main chain is a mesochain. A styrene-based polymer (IPS) having a structure may be mixed, and this can control the crystallization rate and can form a stronger film. When SPS and IPS are mixed, the SPS: IPS ratio is preferably 30:70 to 99: 1, and particularly preferably 50:50 to 98: 2, although it depends on the stereoregularity of each other. .

In the photographic support of the present invention, inorganic fine particles, antioxidants, UV absorbers, antistatic agents, dyes, pigments and dyes are added for the purpose of imparting functionality to the extent that the objects of the present invention are not impaired. Etc. can be contained in the SPS resin pellets.

As the dye used for coloring the photographic support, a dye which is decomposed by heat before being melted at high temperature and extruded cannot be used. Therefore, a dye that can withstand a temperature of 350 ° C. is selected. The method of mixing the dye is a method of sprinkling the dye on the SPS pellets with a stirring mixer, a method of melting the dye together with the pellets with a kneader into master pellets, mixing them with virgin pellets at the time of use and introducing them into an extruder, and mixing. Etc. Either method can be used in the present invention.

The following high-temperature heat-resistant dyes are available, and blue dyes are used in X-ray films. In the case of color films, 2-3 colors are mixed to give a neutral color. Is being done.

1,4-di (2,6-diethylanilino)
Anthraquinone 1,4-di (2,4,6-triethylanilino) anthraquinone 1,4-di (2,6-dimethylanilino) anthraquinone 1,4-di (2,6-diethyl-4-) Methyl anilino)
Anthraquinone 1,4-di (2, methyl-6-isopropylanilino)
Anthraquinone 1,4-di (2,3,4,6-tetramethyl-5-cyclohexylaminosulfonylanilino) mixture of anthraquinone and copper phthalocyanine 120 to 18 before forming the SPS resin pellet of the present invention into a film.
It is preferable to dry at 0 ° C. for 1 to 24 hours under vacuum or under an atmospheric pressure of an inert gas atmosphere such as carbon dioxide or nitrogen.

Film formation of the SPS type photographic support of the present invention will be described. First, a known method can be applied as a method of extruding at the time of film formation, and for example, it is preferable to extrude with a T die. The vacuum-dried SPS pellets are put into an extruder, melt-extruded at 280 to 350 ° C., and cooled and solidified while electrostatically loading on a casting drum to produce an unstretched film.

The stretching method useful in the method for producing the SPS-based photographic support of the present invention includes stretching temperature in the longitudinal and transverse directions, stretching ratio, heat setting temperature, and stretching method (after longitudinal stretching, then transverse stretching. Alternatively, after the horizontal stretching, successive biaxial stretching method in which longitudinal stretching is continued, simultaneous biaxial stretching method in which both longitudinal and transverse directions are simultaneously stretched, longitudinal, transverse, longitudinal stretching, or three stages such as longitudinal, longitudinal and transverse stretching. It depends on the stretching method and the like) and cannot be determined uniquely, but any combination of these methods is also possible.

Although the Young's modulus in the machine direction and the transverse direction of the finished stretched film may be different from each other, as a silver halide photographic light-sensitive material, there are physical properties such as mechanical and thermal characteristics of the SPS photographic support. From the viewpoint of the above, it is preferable that the physical properties in the vertical direction and the physical properties in the horizontal direction are substantially the same, and it is particularly preferable that the waist has the same Young's modulus as possible.

Since stretching in a certain direction cancels orientation in either the longitudinal direction or the transverse direction, it is important to maintain the orientation in both the longitudinal direction and the transverse direction as much as possible. In order to increase the Young's modulus as well, both during the longitudinal stretching and the transverse stretching, the stretching temperature should be lowered as much as possible and the stretching ratio should be increased to the extent that fracture does not occur during the transverse stretching. It is necessary to adopt a fixed temperature.

Generally, when the SPS-based photographic support is formed into a film by a sequential biaxial stretching method, the longitudinal stretching temperature is about 95 ° C. of the glass transition temperature (Tg) of the unstretched sheet, and the longitudinal and transverse stretching temperatures are about 95 ° C. The stretching ratio in the direction is 3.0 to 3.3 times, the longitudinal stretching temperature is 120 to 130 ° C, and the transverse stretching temperature is 5 to 10 ° C higher than the longitudinal stretching temperature in the temperature range of 125 to 140 ° C. , This biaxially stretched film at 250 to 260 ° C.
Then, it is carried out by a film forming method of heat fixing for 3 to 100 seconds. In this case, Young's modulus is at most 400 kgf / mm ²
Since the SPS-based photographic support used in the present invention is tough, it is preferable to use the following film-forming method. That is, the stretching temperature for film formation of the SPS photographic support is (Tg + 3) ° C. to (Tg
+10) ° C., and a specific film forming method is, for example, 4-
In the SPS type film (Tg≈95 ° C.) containing 5 mol% of methylstyrene, the longitudinal stretching temperature is 98 to 1
At 05 ° C, the longitudinal stretching ratio is 3.0 to 5.0 times,
It is preferable to stretch at a stretch ratio of 3.3 to 4.5, and the transverse stretching temperature is 5 to 10 ° C. higher than the longitudinal stretching temperature (T
It is preferable to stretch at g + 8) ° C to (Tg + 20) ° C, that is, it is preferable to stretch at a temperature range of 103 to 115 ° C. The next heat setting temperature is 235 to 260 ° C,
The heat setting time is preferably 3 to 100 seconds. The SPS-based photographic support thus formed has a Young's modulus of 4 in both the longitudinal and lateral directions of the SPS-based photographic support.
60 kgf / mm ² or more, preferably 475 kgf / m
m ² or more is obtained, and it is preferably used as a stiff SPS type photographic support. The upper limit is not particularly limited, but the upper limit is about 540 kgf / mm ² .

The thickness of the SPS-based photographic support of the present invention thus obtained varies depending on the use of the silver halide photographic light-sensitive material, but is 50 to 250 μm of the color film.
The film-forming conditions described above are effective for a film having a thickness of 50 to 250 μm, though the film forming conditions are various, such as 70 to 200 μm for a printing photosensitive material film and 100 to 200 μm for an X-ray film.

[Undercoat Layer] Next, the undercoat treatment of the SPS type photographic support will be described. Before applying the undercoat layer, chemical treatment, mechanical roughening treatment, corona discharge treatment, flame treatment,
Surface treatment such as ultraviolet ray treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment is preferred. By these processes,
The contact angle of water on the surface of the SPS-based photographic support can be set to 65 ° or less, preferably 55 ° or less, which is effective in improving the wettability and adhesiveness during coating of the undercoat layer. is there.

When the above corona treatment is performed, the discharge frequency is 50 Hz to 5000 kHz as the treatment condition.
In addition, it is preferable to set the frequency to 5 kHz to several 100 kHz. If the discharge frequency is too low, stable discharge cannot be obtained, and pinholes are generated in the object to be treated, which is not preferable.
On the other hand, if the frequency is too high, a special device for impedance matching is required, and the cost of the device becomes high, which is not preferable. The processing strength of the object to be treated is 5 to 20 W · min / m ² , and preferably 6 to 15 W · min / m ² for the SPS photographic support. The treatment strength may vary depending on the type of device (gap clearance between electrode and dielectric roll, discharge shape, discharge frequency, waveform, etc.), and the contact angle between the treated surface of the photographic support and water is within the above range. Adjust the device so that

The ultraviolet treatment is preferably performed by a high-pressure mercury lamp or a low-pressure mercury lamp made of a quartz tube and having a spectrum of 180 to 380 nm. The ultraviolet treatment is preferably performed in the film forming step (stretching process, heat setting, after heat setting), and particularly preferably in the latter half of the stretching step or at heat setting. The ultraviolet irradiation method is preferably a high-pressure mercury lamp (generating a spectrum having a main wavelength of 365 nm), and the irradiation light amount is 100 to 1500 (mJ / m ² ).
In the case of a low-pressure mercury lamp (generating a spectrum whose main wavelength is 254 nm), the irradiation light amount is 200 to 1500 (mJ
/ M ² ) is also preferably 400 to 1300 (mJ
/ M ² ) is preferable. Since the processing strength cannot be strictly defined depending on the type of lamp, the type of device, etc., the contact angle between the treated surface of the photographic support and water may be adjusted so as to satisfy the above range.

As the undercoat layer, any of those used in the art can be used.

The undercoating of the SPS-based photographic support of the present invention may be carried out before stretching during film formation, after uniaxial stretching, after biaxial stretching before heat setting, or after biaxial stretching after heat setting, as in the PET film. Can be done in that process. SPS
The support for the photographic system does not hinder sufficient adhesion of the emulsion layer or the like even if the undercoating after the biaxial stretching and heat setting is carried out, but the undercoating before the completion of the oriented crystal is preferred. The drying temperature of the undercoat layer is 80 to 25
It is preferable to carry out in the temperature range of 0 ° C. The above-mentioned treatments such as UV irradiation and corona discharge before and after the undercoating are effective means for improving the adhesiveness to the SPS-based photographic support.

As an undercoat material for the SPS type photographic support of the present invention, methacrylic acid, acrylic acid, itaconic acid,
Unsaturated carboxylic acid or ester such as maleic anhydride (as the ester group, a C ₁ -C ₈ alkyl group, hydroxyethyl group, phenyl group, benzyl group, phenethyl group,
N, N-dimethylaminoethyl group, glycidyl group, etc.),
Acrylamide, N-substituted acrylamide (as a substituent, a C _{1 to} C ₄ alkyl group, phenyl group, sulfopropyl group, benzyl group, N-methylol group, etc.) Styrene, styrenesulfonic acid, vinylidene chloride, vinyl chloride, Examples thereof include polymers or copolymers obtained from monomers such as butadiene. Further, water-dispersed polyester, polyurethane, polyethyleneimine, epoxy resin and the like are also included. Of these, a styrene-butadiene copolymer is preferably used. Specifically, the styrene / butadiene molar ratio is 9/1 to 1 /
The copolymer of 9 is preferred. In addition, the comonomer having a hydrophilic group such as acrylic acid as the third comonomer is 2 to 10% by weight with respect to the styrene / butadiene copolymer.
Copolymerization and inclusion can provide the effect of further improving the adhesiveness between the SPS-based photographic support and the photographic emulsion layer. Another preferred specific example is a copolymer having a water-dispersible polyester and a styrene polymer as constituent elements.

The water-dispersible polyester is a substantially linear polymer obtained by a polycondensation reaction of a polybasic acid or its ester-forming derivative with a polyol or its ester-forming derivative. The polybasic acid component of this polymer includes terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid,
Examples thereof include 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid and dimer acid. Along with these components, unsaturated polybasic acids such as maleic acid, fumaric acid and itaconic acid and hydroxycarboxylic acids such as p-hydroxybenzoic acid and p- (β-hydroxyethoxy) benzoic acid can be used in a small proportion.

As the polyol component, ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, triglyceride. Methylolpropane, poly (ethylene oxide) glycol,
Examples thereof include poly (tetramethylene oxide) glycol.

In order to impart water dispersibility and water solubility to the water-dispersible polyester, introduction of a sulfonate, diethylene glycol, polyalkylene ether glycol or the like is an effective means. In particular, a dicarboxylic acid component having a sulfonic acid salt (a dicarboxylic acid having a sulfonic acid salt and / or
Or an ester-forming derivative thereof) in an amount of from 5 to 15 mol% based on all dicarboxylic acid components in the water-dispersible polyester. As the dicarboxylic acid having a sulfonate and / or an ester-forming derivative thereof, those having an alkali metal sulfonate group are particularly preferable,
For example, alkali metal salts such as 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5- (4-sulfophenoxy) isophthalic acid,
Alternatively, an ester-forming derivative thereof is used, but 5-sulfoisophthalic acid sodium salt or an ester-forming derivative thereof is particularly preferable. The dicarboxylic acid having a sulfonic acid salt and / or an ester-forming derivative thereof is particularly preferably used in an amount of from 6 to 10 mol% based on all dicarboxylic acid components from the viewpoint of water solubility and water resistance.

The water-dispersible polyester and the copolymer having a styrenic (vinyl-based) polymer as a constituent are a method of chain transfer type copolymerization with the water-dispersible polyester, and addition polymerization at the terminal of the water-dispersible polyester. Method of grafting by introducing a possible group and copolymerizing with a monomer of styrene (vinyl) copolymer, styrene (vinyl)
There is a method of introducing a reactive group at the time of condensation polymerization of a water-dispersible polyester such as a carboxylic acid, a glycidyl group or a substituted amino group as a monomer by polymerizing a copolymer. This styrene may be changed to another vinyl-based monomer and reacted.

When the vinyl monomer is copolymerized in the presence of the water-dispersible polyester, it is polymerized in a latex form. In this case, however, a surfactant is not particularly required and the polymerization reaction is possible. is there. However, in order to improve the polymerization stability, a surfactant may be used as an emulsifier in the system, and a general nonionic and anionic surfactant can be used.

The ratio of the water-dispersible polyester to the styrene copolymer is 99/1 to 5/95, preferably 9
7/3 to 50/50, more preferably 95/5 to 80 /
Twenty.

A polymerization initiator is used for these polymerizations.
As the polymerization initiator, persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, peroxides such as hydrogen peroxide, 4,4′-azobis-4-cyanovaleric acid or a salt thereof, 2,2- Azobis compounds such as azobis (2-aminopropane) hydrochloride can be used. Further, peroxides and persulfates can also be used as a redox initiator in combination with a reducing agent such as ferrous chloride, ferrous sulfate, and sodium ammonium ammonthiosulfate.

The SPS-based photographic support of the present invention may be subbed in an aqueous system, an organic solvent-containing aqueous system, or an organic solvent system. Among the organic solvents, the solvent for SPS is benzene, xylene, toluene, ethylbenzene,
There are cyclopentane, hexane, heptane, octane, methyl ethyl ketone, and cyclohexanone, but if too much of these solvents is used as a submersion liquid, the support will be damaged and the flatness will be impaired, so methanol, ethanol, propanol, Cyclohexanol, acetone,
It is preferable to mix a small amount in a poor solvent such as. The amount is preferably 15% or less with respect to the poor solvent.

Further, a polymer latex is often used as an undercoat for the SPS type photographic support of the present invention. Water is used as the undercoat liquid for this purpose, but an organic solvent such as methanol, ethanol or acetone may be mixed therein.

The coating property of the undercoat liquid on the SPS type photographic support can be improved by containing the following water-soluble polymer. Useful water-soluble polymers include hydroxyethyl cellulose (HEC), carboxymethyl cellulose (CMC), methyl cellulose (MC), hydroxypropyl methyl cellulose (H
PMC), ethyl hydroxyethyl cellulose (EHE
C), modified hydroxyethyl cellulose (HMHE
C), polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), xanthan, cationic hydroxyethyl cellulose (CATHEC), hydroxypropyl guar (HP guar), guar, polyvinyl alcohol (PVA), polyacrylamide, sodium alginate, and carbopol. (Carbopol; registered trademark) acrylamide thickening composition and the like, and particularly useful water-soluble polymers include CMC and MC.
Is preferred. For example, CMC-7LX (Aquaron,
Substitution degree = 0.65 to 0.80, viscosity at a concentration of 5% by weight in water is 200 to 1000 mPa.s. Although s) is suitable for the undercoat liquid of the SPS type photographic support, other types, those having various viscosities and those having various degrees of carboxymethyl substitution can be used. MC and H
EC (manufactured by Aqualon), EHEC (manufactured by Bellol and Nobelol, and HPMC (manufactured by Aqualon and Dow Chemical) are also useful as an undercoat liquid for the SPS photographic support.

The coating concentration of the undercoating polymer in the undercoating liquid for the SPS type photographic support of the present invention is preferably 20% by weight or less, and a concentration of 5 to 15% by weight is particularly preferable in view of uniform coating property. .

The coating amount of the undercoat liquid on the SPS photographic support is preferably 1 to 20 g / m ² after drying, and particularly preferably 5 to 15 g / m ² from the viewpoint of coating property and adhesiveness. . The coating amount of the subbing polymer may have a range of 10~3000mg / m ^2, more preferably in the range of 100-1000 mg / m ^2.

By the way, the SPS type photographic support is PE
Compared to that of the T photographic support, the dielectric loss is small, and therefore, there is a property that it is difficult to eliminate the charge once it is charged. Therefore, according to the charge distribution during undercoating,
The way the liquid adheres may change, causing uneven coating. In such a case, it is desirable to forcibly remove the charge before and after applying the subbing liquid. As the static elimination method, a method of grounding the roll in contact with the transport support, a method of spraying water atomized by ultrasonic waves, a method of ionizing the surrounding air with radiation to neutralize the electric charge, and a static elimination brush are used. The method used, the high-voltage application method, the method of producing ion wind and blowing it can be used.

The subbing layer may be a single layer, but it is preferably a multi-layer in order to obtain more functionality and to enhance the adhesive strength. The subbing multilayer method will be described below. In the multilayer method, the undercoat layer is referred to as an undercoat layer, and the undercoat layer described below is referred to as an undercoat upper layer.

The subbing treatment may be carried out after the film formation, but if the subbing composition can be stretched, before the longitudinal stretching which is in the midst of film formation, between the longitudinal stretching and the lateral stretching, It can be performed at any place such as after transverse stretching and before heat treatment.
When stretching is not possible For example, when a polymer having a hydrophilic group is used, it may not be possible to stretch due to strong interaction between hydrophilic polymers, but stretching under steam, polyglycerin as a stretching aid, etc. It becomes possible to stretch by adding.

The subbing upper layer is preferably a hydrophilic binder layer for adhering the photographic emulsion layer well. As a binder constituting the hydrophilic binder layer, gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, water-soluble polymers such as carboxymethyl cellulose and hydroxyethyl cellulose, sodium polystyrene sulfonate Examples include a combination of a copolymer and a hydrophobic latex, and of these gelatin is most preferable.

A hardener is preferably used for the binder layer in the undercoating upper layer to increase the film strength. Examples of such hardener include aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. Second,
732, 303, 3,288,775, British Patents 974,723, 1,167,207 and the like, compounds having a reactive halogen, ketone compounds such as diacetyl and cyclopentanedione. , Bis (2-chloroethyl) urea, 2-hydroxy-4,6-
Dichloro-1,3,5-triazine, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, US Pat.
763, 3,635,718, British Patent No. 99
Compounds having a reactive olefin described in U.S. Pat. No. 4,539,644, U.S. Pat. Nos. 3,539,644 and 3,642.
No. 486, Japanese Patent Publication No. 49-13568, No. 53-472.
71, 56-48860, and JP-A-53-5725.
No. 7, No. 61-128240, No. 62-4275,
Nos. 63-53541 and 63-264572, vinyl sulfone compounds, N-hydroxymethylphthalimide, U.S. Pat. Nos. 2,732,316 and 2,5.
N-methylol compounds described in US Pat. No. 86,168, isocyanate compounds described in US Pat. No. 3,103,437, US Pat. Nos. 2,983,611 and 3,10.
7,280, etc., aziridine compounds, US Pat. Nos. 2,725,294, 2,725,295, etc., acid derivatives, and US Pat. No. 3,100,704, etc., carbodiimides. Compounds, US Pat. No. 3,093
1,537, etc. epoxy compounds, US Pat. Nos. 3,321,313, 3,543,292 etc. isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, dihydroxydioxane. , Organic hardeners such as dioxane derivatives such as dichlorodioxane, and inorganic hardeners such as chrome alum, zirconium sulfate, and chromium trichloride. Further, as a hardener having a relatively fast hardening effect on gelatin, Japanese Patent Application Laid-Open No. 50-
Compounds having a dihydroquinoline skeleton described in JP-A-38540, JP-A-51-59625 and JP-A-62-26285.
No. 4, No. 62-264044, No. 63-184741.
N-carbamoylpyridinium salts described in JP-B No. 55-38655, acylimidazoles described in JP-B No. 55-238655, N-acyloxyimidazoles described in JP-B No. 53-22089, and N-acyloxy compounds described in JP-B No. 53-22089. A compound having two or more imino groups in the molecule,
Compounds having an N-sulfonyloxyimide group described in JP-A-52-93470, JP-A-58-113929
Compounds having a phosphorus-halogen bond described in JP-A-60-225148, JP-A-61-240236 and JP-A-6-240236.
A chloroformamidinium compound described in 3-41580 is known.

The undercoating upper layer preferably contains, as a matting agent, inorganic fine particles such as silicon dioxide and titanium oxide, and an organic matting agent (1 to 10 μm) such as polymethylmethacrylate. In addition to these, various additives such as an antistatic agent, an antihalation agent, a coloring dye, a pigment, and a coating aid may be contained, if necessary.

The coating liquid concentration of the undercoat layer composition is usually 20% by weight or less, preferably 15% by weight or less. The coating amount is 1 to 30 g / m ^{2 in} terms of coating liquid weight, and further 5 to ²
It is preferably 0 g / m ² .

As a method of applying the subbing liquid, a generally well known method is used. For example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or an extrusion coating using a hopper described in US Pat. No. 2,681,294. It can be applied by a method or the like. US Pat. No. 2,7 as required
61, 791, 3,508,947, 2,94
No. 1,898 and No. 3,526,528, Yuji Harazaki, “Coating Engineering”, page 253 (published by Asakura Shoten in 1973), and the like can be used to simultaneously coat two or more layers. .

[Conductive Particles] The conductive particles of the present invention will be described.

The conductive particles of the present invention have a structure in which the water-soluble polymer (A) having a sulfonic acid group and a carboxyl group is located on the outer periphery of the polymer particle main body, and at the time of coating. Usually, it takes the form of a dispersion or emulsion dispersed in an aqueous solvent.

Here, the water-soluble polymer (A) is a water-soluble polymer having a sulfonic acid group and a carboxyl group.

First, the water-soluble polymer (A) will be described.

The water-soluble polymer (A) can be produced, for example, by copolymerizing a monomer having a sulfonic acid and a monomer having a carboxyl group.

Examples of the above-mentioned monomer having a sulfonic acid group include vinyl sulfonic acid, 2-acrylamide-
Examples include 2-methylpropanesulfonic acid, 2-acrylamidoethylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid and the like, and salts thereof. Among these, because of its excellent conductivity,
Preference is given to using styrenesulphonic acid and its salts.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid,
Examples thereof include monocarboxylic acids such as maleic acid, fumaric acid and itaconic acid, dicarboxylic acids or dicarboxylic acid anhydrides. Among these, it is preferable to use a dicarboxylic acid because the adhesiveness between the layer containing the formed conductive particles and its adjacent layer is much better.
Maleic acid is particularly preferable.

In the water-soluble polymer (A) of the present invention, in addition to the monomer having a sulfonic acid group and a carboxyl group, another monomer having a copolymerizable vinyl group may be used. .

The method of polymerizing the above-mentioned monomer is not particularly limited, and a conventionally known method can be applied. Specifically, for example, a monomer having a sulfonic acid group and a monomer having a carboxyl group and, if necessary, other monomers are dissolved in water, and a polymerization initiator (for example, The polymerization can be carried out by adding potassium sulfate or the like and heating the mixture.

Further, the water-soluble polymer (A) of the present invention can be prepared by a method other than the above. That is,
The above water-soluble polymer (A) can also be obtained by polymerizing a monomer having no sulfonic acid group and a monomer having a carboxyl group to prepare a copolymer, and subjecting this copolymer to a sulfonation treatment. Can be obtained.

The monomer having no sulfonic acid group is not particularly limited, and examples thereof include styrene and 4
-Methylstyrene and the like.

Then, a copolymer is prepared by polymerizing with a monomer having a carboxyl group by the above-mentioned method, and the copolymer is subjected to a sulfonation treatment. The method of the sulfonation treatment is not particularly limited, and a conventionally known method can be applied. Specifically, the above copolymer is put into a solvent and a sulfonation treatment is performed using a sulfonating agent.

As the solvent, dichloromethane, 1,
Chlorinated hydrocarbons such as 2-dichloroethane, hydrocarbons such as n-hexane and cyclohexane, dioxane and the like are mentioned as good solvents. Among these, dichloroethane, which does not easily react with the sulfonating agent and does not form a salt upon neutralization, and the like can be mentioned as a suitable solvent. Further, as the sulfonating agent, SO _3, a complex of Lewis acid to SO _3, and the like chlorosulfonic acid. The reaction of the sulfonating agent in the solvent is preferably performed at a low temperature of 30 ° C. or lower.

In the present invention, the method of pre-copolymerizing using the styrene sulfonic acid is preferable because it is easy and economical.

In such a water-soluble polymer (A),
The ratio of the sulfonic acid group to the carboxyl group is sulfonic acid group / carboxyl group = 10 / 90-molar ratio of functional group
95/5, preferably sulfonic acid group / carboxyl group =
20/80 to 80/20, particularly preferably the range of sulfonic acid group / carboxyl group = 30/70 to 60/40. When the sulfonic acid group is styrene sulfonic acid and the carboxyl group is maleic acid, the ratio is 40/60 to 95 /
5 is preferable, and 50/50 to 95/5 is particularly preferable from the viewpoint of easy production.

The above water-soluble polymer (A) preferably has a weight average molecular weight in the range of 1,000 to 500,000, and in particular 2000 to 2000 because the stability of the conductive particles is increased.
A range of 100,000 is preferred.

When the water-soluble polymer (A) is prepared as an antistatic processing liquid and the water-soluble polymer is added to the aqueous solvent, the processing liquid becomes acidic due to sulfonic acid and carboxylic acid. Can be neutralized or can be used as a working fluid without being neutralized. In the case of neutralizing, as a counter ion, a neutralizing agent for a cationic ion such as Na ⁺ , K ⁺ , NH ₄ ⁺ , specifically, NaOH, KOH, LiOH, NH ₄ ⁺
Inorganic or organic alkaline substances such as OH, triethanolamine and 2-amino-2-methylpropanol can be used, and NaOH is preferable.

Next, the above-mentioned polymer particles refer to polymer particles prepared mainly by emulsion polymerization or suspension polymerization of a hydrophobic vinyl monomer in water.

Suitable vinyl monomers for these are aromatic vinyl monomers such as styrene, 4-methylstyrene, vinyltoluene and methoxystyrene; methyl acrylate, ethyl acrylate, propyl acrylate (n,
i), butyl acrylate (n, s, t), acrylic acid-
Acrylic acid or methacrylic acid such as 2-ethylhexyl, methyl methacrylate, ethyl methacrylate, propyl methacrylate (n, i), butyl methacrylate (n, s, t), benzyl acrylate, benzyl methacrylate, hydroxy methacrylate, cyclohexyl acrylate. Esters; Acrylonitrile and other acrylic nitriles; Acrylic acid, methacrylic acid, crotonic acid,
Monocarboxylic or dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, or dicarboxylic acid anhydrides; halogenated vinyl monomers such as vinyl chloride and vinylidene chloride;
Examples thereof include vinyl esters such as vinyl acetate and vinyl benzoate; conjugated dienes such as butadiene and isoprene, but are not limited thereto.

As another vinyl monomer, a polyfunctional vinyl monomer can also be used in the polymer particles of the present invention. For example,
Divinylbenzene, trivinylbenzene, diallyl phthalate, allyl acrylate, allyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane triacrylate, and the like,
It is not limited to these.

Further, it is preferable to use a vinyl monomer having a reactive group by copolymerizing it as the polymer particles of the present invention. Examples of the reactive vinyl monomer include epoxy group-containing vinyl monomers such as glycidyl acrylate and glycidyl methacrylate, N-methylol group-containing vinyl monomers such as N-methylolacrylamide, vinyl oxazoline, 2-
2-acrylic acid-4,6-dichloro- such as oxazole group-containing vinyl monomers such as propenyl-2-oxaborin
1,3,5-triazineamide, 2-acrylic acid-4,
Examples thereof include, but are not limited to, triazine-based reactive vinyl monomers such as 6-dichloro-1,3,5-triazine ester.

Next, the method for producing the conductive particles of the present invention will be described.

The method for producing conductive particles of the present invention is to polymerize (copolymerize) the above-mentioned one or several kinds of hydrophobic vinyl monomers in an aqueous solvent containing the water-soluble polymer (A).
Is what you do. Here, the above-mentioned aqueous solvent usually refers to water, but it may also refer to a mixed solvent obtained by mixing water with an alcohol such as methanol, ethanol or propanol, or another water-compatible organic solvent.

The conductive particles according to the present invention are polymerized by a general emulsion polymerization method, suspension polymerization method, dispersion polymerization method or the like. In the present invention, the emulsion polymerization method is preferred.

First, a water-soluble polymer (A) neutralized with sodium hydroxide was dissolved in the above aqueous solvent, the reaction vessel was replaced with nitrogen gas, and a polymerization initiator was added to this solution. The vinyl monomer forming the polymer particles is dropped into this system, and polymerization is carried out at a temperature of 20 to 95 ° C. to obtain emulsion-type conductive particles.

Regarding the blending ratio of the water-soluble polymer (A) in the conductive particles of the present invention, the weight of the water-soluble polymer (A) is 35 to 50 with respect to the weight of the monomer used for the polymer particles.
0%. In order to improve the conductivity of the conductive particles, 35% or more of water-soluble polymer is required. It is preferably 100 to 400%, and particularly preferably 200 to 300% because of its excellent conductivity and adhesiveness.

When the monomer used for the polymer particles is dropped into the aqueous solvent, the polymerization initiator may be dissolved in the aqueous solvent in advance or dropped at the same time as the monomer.
Alternatively, it may be added after the monomer is added or an appropriate addition method may be adopted. At this time, the polymerization reaction is preferably performed in an atmosphere containing no oxygen such as nitrogen gas.

As the emulsion polymerization initiator, potassium persulfate,
Persulfates such as ammonium persulfate, peroxides such as hydrogen peroxide, 4,4'-azobis-4-cyanovaleric acid or salts thereof, and azobis compounds such as 2,2-azobis (2-aminopropane) hydrochloride Compounds and the like can be used. Also,
Peroxides and persulfates can also be used as redox initiators in combination with reducing agents such as ferrous chloride, ferrous sulfate, ferrous ammonium sulfate, and sodium thiosulfate.

Although the polymerization temperature of the emulsion polymerization varies depending on the initiator used, it is usually carried out at 20 to 95 ° C. as described above. Redox polymerization using a redox initiator is carried out at a relatively low temperature, and a temperature of 20 to 50 ° C is suitable. In the case of an initiator such as a peroxide or a persulfate, the temperature is preferably from 60 to 95C.

In addition, inorganic substances such as sodium acetate, n-
A chain transfer agent such as dodecyl mercaptan can also be blended. A reaction accelerator may be blended in an aqueous solvent for the purpose of accelerating the reaction. Examples of the reaction accelerator include ammonia, water, triethylamine, triethanolamine, triethylammonium chloride and the like.

If necessary, the above-mentioned aqueous solvent may be used within a range that does not affect the performance of the conductive particles as a product.
A surfactant for emulsion polymerization, a seed emulsion, and other water-soluble polymer may be added.

As the surfactant for emulsion polymerization, higher fatty acid sulfonate, alkylbenzene sulfonate,
Examples include anionic surfactants such as higher alcohol sulfate ether salts, and nonionic surfactants such as polyethylene glycol and alkylphenol polyethylene glycol ether.

Examples of the seed emulsion include acrylic emulsion and acrylic / styrene emulsion, and specific examples include styrene / butyl methacrylate / methacrylic acid.

Now, the mode of the conductive particles of the present invention will be described.

In the conductive particles of the present invention, the fact that the water-soluble polymer (A) having a sulfonic acid group and a carboxyl group is located on the outer periphery of the polymer particle body means that a part of the water-soluble polymer (A) is present. During the synthesis is in a state of being bonded to the particle main body or embedded or embedded.

The present inventors envision the conductive particles of the present invention as such an embodiment, but have found that the state of being mixed with the present invention is different by the following operation. That is, in order to verify this state, when the water-soluble polymer (A) outside the polymer particles is separated from the conductive particles in the emulsion form, extraction is performed with hot water at a temperature at which the polymer particles do not fuse. As a result, most or only a small amount of the water-soluble polymer (A) was separated and extracted,
The amount of extraction did not increase over time. As another separation method, even if the conductive particle emulsion was centrifuged, the water-soluble polymer (A) was hardly or little separated. Conversely, a well-mixed latex polymerized with a surfactant and the water-soluble polymer (A) used in the present invention were subjected to extraction and centrifugation in the same manner as described above. The coalesced particles and the water-soluble polymer (A) were separated as they were.

Further, as described above, when a reactive vinyl monomer such as glycidyl acrylate is used as a part of the polymer particles, the conductive particles may have a heavy carboxyl group of the water-soluble polymer during synthesis. The bonded state may be developed due to the epoxy groups of the coalesced particles, and the bonded state may be developed even after the working fluid for these conductive particles is applied as a film. As described above, the use of the reactive vinyl monomer in the polymer particles further enhances the permanent antistatic effect of the present invention, and thus this method is preferable.

The particle size of the conductive particles of the present invention is usually 0.01.
To 2.0 μm, preferably 0.04 to 0.1 μm. However, the particle size may not be clear in some cases, and these are also sufficient to achieve the present invention.

If the conductive particles of the present invention are contained in at least one layer constituting the silver halide photographic light-sensitive material having the SPS type photographic support, the antistatic effect is exerted and the development treatment is carried out. It has a so-called permanent antistatic property in which the antistatic effect does not deteriorate even afterward. The constituent layers of the silver halide photographic light-sensitive material include an undercoat layer, an undercoat upper layer, an antihalation layer, a light shielding layer, an emulsion layer, an intermediate layer, a protective layer,
There are a protective layer upper layer, a back layer, a back layer upper layer, and the like, and the effects of the present invention are exhibited even if they are contained in any of them.

The conductive particles of the present invention can be easily mixed with various additives contained in the above-mentioned constituent layers in each layer liquid without adversely affecting photographic properties or physical properties.

Most of the constituent layers of the silver halide photographic light-sensitive material contain gelatin as a water-soluble binder, and the conductive particles of the present invention are well mixed with gelatin and can be used without any trouble. Examples of water-soluble binders other than gelatin used in the present invention include proteins such as colloidal albumin and casein; carboxymethyl cellulose; hydroxy cellulose; cellulose derivatives such as methyl cellulose; agar, sodium alginate, starch analogs, and similar compounds. Derivatives: polyvinyl alcohol, polyacrylic acid and copolymers thereof, or derivatives thereof, water-soluble polyacrylic acid ester copolymers, and water-soluble polyester resin sugars. Since gelatin is commonly used in silver halide photographic light-sensitive materials, it is particularly preferably used as a water-soluble binder. The types of gelatin include
There are alkali-processed gelatin, acid-processed gelatin, inert gelatin from which an active substance has been removed, inert gelatin, gelatin derivatives and the like, and any of them can be used. Gelatin is made from raw materials such as ossein, hide and pigskin, and any of them is preferably used.

The content of the conductive particles of the present invention varies depending on the properties of the constituent layers and is not particularly limited, but it is preferably 5 to 90% by weight based on the weight of gelatin coated in each layer.
More preferably, it is 10 to 70%, especially 20 to 60% in consideration of coating properties and the like.

By using a water-dispersible polymer such as latex in combination with the conductive particles of the present invention, the film adhesion, the film strength and the like are enhanced. When the conductive particles and the water-dispersible polymer are mixed and used at the same time, the total weight of the water-dispersible polymer and the water-soluble binder is preferably 200% or less with respect to the weight of the conductive particles, It is preferably 150% or less. In particular, 70 to 140% is preferable.

The water-dispersible polymer suitable for use as a mixture with the conductive particles of the present invention is a latex or a granular polymer dispersed in an aqueous solvent, and as a monomer constituting the polymer. For example, acrylic or methacrylic acid esters such as C ₁ -C ₁₈ linear or branched alkyl groups, phenyl groups, benzyl groups, phenethyl groups, cyclohexyl groups, glycidyl groups; acrylonitrile;
Diene monomers such as butadiene and isoprene; acrylamide, N- or N, N-acrylamide of C _{1 to} C ₁₈ linear or branched alkyl groups; vinylidene chloride, vinyl chloride and other chlorine monomers Vinyl esters such as vinyl acetate and vinyl propionate; acid-containing monomers such as acrylic acid, methacrylic acid, itaconic acid and maleic anhydride; styrene-based monomers such as styrene, α-methylstyrene and methoxystyrene Homopolymers or copolymers, polyester resins, acrylic modified polyester resins and the like can be used. Preferred resins include styrene-butadiene copolymer, n-butyl acrylate-
Examples thereof include n-butyl methacrylate-acrylamide-styrene terpolymer, styrene-n-butyl acrylate-acrylic acid terpolymer, vinylidene chloride-methyl acrylate-itaconic acid terpolymer, and the like. It is not limited to these. The water-dispersible polymer is obtained by the usual latex polymerization method using the above-mentioned monomer. As for the surfactant, the polymerization initiator and the like as the emulsifier used here, those used in the usual manner may be used.

The constituent layers of the silver halide photographic light-sensitive material containing the conductive particles of the present invention are characterized in that they are excellent in film attachment even after the development processing, and a permanent antistatic effect is obtained. Recent development processing is often performed under severe conditions such as higher temperature and higher pH. A crosslinking agent may be added in order to further stabilize the constituent layer of the present invention under such conditions, which is preferable. The crosslinking agent is preferably a crosslinking agent that causes a crosslinking reaction with the water-soluble polymer (A) of the conductive particles, and is the same as the hardener used together with the water-soluble binder forming each layer. However, a cross-linking agent that can cross-link the conductive particles with each other may be used. The amount of the cross-linking agent used is 0.01 to 30% with respect to the weight of the conductive particles of the present invention, preferably 0.1.
It is 05 to 20%.

Examples of the cross-linking agent include low molecular weight cross-linking agents such as those described by TH James in “The Theory of.
The Photographic Process (The Theo)
ry of the Photographic Pr
low-molecular-weight crosslinking agents described in the fourth edition, pages 77 to 88, among which those having a vinyl sulfonic acid, an aziridine group, an epoxy group, and a triazine ring are preferably used. Showa 53-41221
And low molecular crosslinking agents described in JP-A-60-225143, and pentaerythritol tri- [β- (N-aziridinyl) described on page 5 of JP-A-55-84658.
Propionate], polyfunctional epoxy compounds described on pages 27 and 28 of JP-A-3-256039, and dichlorotriazine compounds described on pages 12 to 14 of JP-A-6-082961. And the like are preferred. Further, a polymer crosslinking agent is also used in the present invention. For example, a polymer crosslinking agent having an epoxy group described in US Pat. No. 3,623,878, Research Disclosure Magazine (hereinafter abbreviated as RD) 17333
(1978) and the like, a polymer crosslinking agent having a dichlorotriazine group described in JP-A-56-66841, a polymer crosslinking agent having an active ester group described in JP-A-56-66841, and JP-A-56-142.
No. 524, U.S. Pat. No. 4,161,407;
Polymer crosslinking agents having an active vinyl group described in 4-65033, RD16725 (1978) or the like, or a group serving as a precursor thereof are preferable, and particularly, JP-A-56-
As described in JP-A-142524, an active vinyl group or a group having a precursor thereof bonded to a polymer main chain by a long spacer can be used.

<Synthesis Example of Conductive Particles><< Synthesis Example 1-Synthesis of Water-Soluble Polymer (A) >> In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen introducing tube,
Add 1000 parts of degassed distilled water and add styrene sulfonic acid sodium salt (hereinafter sometimes abbreviated as StSO ₃ Na) 46
5 parts and maleic acid (hereinafter sometimes abbreviated as MA) 87.
Five parts were dissolved and, while stirring, nitrogen gas was introduced to fill the inside of the container with nitrogen gas and heated to 70 ° C. Another 40
0.5 parts of potassium persulfate is dissolved in a solution of isopropanol of 250 parts and water of 250 parts, put in a dropping funnel and dropped into a reaction vessel not too slowly, and the temperature is raised to 75 to 80 ° C.
After heating for hours, it becomes a viscous, colorless and transparent solution. This solution was poured into a large amount of acetone to precipitate the polymer, washed several times with acetone, and dried at 50 ° C. to obtain a white solid of the water-soluble polymer (A). As a result of measuring the molecular weight of this product by GPC, the weight average molecular weight was about 10,000.
The composition of this water-soluble polymer (A) is StSO ₃ Na:
MA = 3: 1 (molar ratio). This water-soluble polymer (A) is used. As shown below, StSO ₃ Na
And MA were changed, and the same synthesis was performed. In addition, ratio 1:
A water-soluble polymer having a ratio of MA higher than 1 could not be prepared because MA did not react at a ratio of 1: 1 or more.

Sample No. StSO ₃ Na: MA 3: 1 1: 1 9: 1 Comparison 10: 0 << Synthesis Example 2 / Synthesis of conductive particles 1 >> In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen introducing tube, 700 parts of degassed distilled water was added, and a sodium salt of a copolymer of StSO ₃ Na and MA (StSO ₃ Na of Synthesis Example 1:
An aqueous solution was prepared by stirring 250 parts of (MA ratio was changed as follows). Then, nitrogen gas was introduced through the above-mentioned nitrogen introducing pipe to make the inside of the reaction vessel under a nitrogen gas atmosphere and eliminate dissolved oxygen in the aqueous solution. Then, the aqueous solution was heated to 80 ° C. To this aqueous solution, 90 parts of monomer styrene (St) of polymer particles and 10 parts of other copolymerizable monomers (butyl acrylate (St-BA) and glycidyl methacrylate (GMA)) were added in an amount of 1% by weight. 100 parts of aqueous potassium persulfate solution was added dropwise separately, and the polymerization reaction was carried out at 80 ° C. under reflux of nitrogen gas to obtain the target conductive particles (water-soluble polymer (A): polymer particles = 250: 100).
I got

Water-Soluble Polymer (A) Polymer Particles Synthetic No. StSO ₃ Na: MA-1 3: 1 St-BA-2 3: 1 St-GMA-1 1: 1 St-BA-2 1: 1 St-GMA-1 9: 1 St-BA-2 9: 1 St-GMA Comparison-1 10: 0 St-BA Comparison-2 10: 0 St-GMA << Synthesis Example 3 / Synthesis 2 of conductive particles >> In Synthesis Example 2,
Water-soluble polymer (A) (StSO ₃ Na: MA = 3: 1)
The conductive particles were synthesized by changing the ratio of the polymer particles (St: GMA = 9: 1) to the following.

Compound No. Water-soluble polymer (A): Polymer particles −2 250: 100 −2−2 50: 100 −2−3 150: 100 −2−4 350: 100 −2−5 450: 100 −2 Comparison 1 30 : 100-2-Comparison 2 550: 100 [Silver halide photographic light-sensitive layer, etc.] Next, the light-sensitive layer of the silver halide photographic light-sensitive material will be described.

The silver halide photographic light-sensitive material according to the present invention is a black-and-white film for photography, a light-sensitive material film for printing, a black-and-white silver halide photographic light-sensitive material such as an X-ray film,
There are color silver halide photographic light-sensitive materials such as negative color roll film, negative color cut film, positive color roll film and positive color cut film, and the present invention can be applied to any of these silver halide photographic light-sensitive materials. Here, the X-ray medical silver halide photographic light-sensitive material will be mainly described.

The emulsion used in the X-ray medical photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (hereinafter abbreviated as RD) No. 17
643 (Dec. 1978), pp. 22-23, 1. Emulsion preparation method (Emulsion Preparation a)
nd types), and the same (RD) No. 18716
(November, 1979) -It can be prepared by the method described on page 648.

In addition, T. H. "Thet" by James
heavy of the photographic
process, 4th edition, published by Macmillan (1977), pp. 38-104, GF.
"Photographic Emulsion Chemistry" by Dauffin, "Photogra
pic Emulsion Chemistry ”,
Published by Focal press (1966), P. G
Lafkides "Physics and Chemistry of Photography""Chimi
e et physique photographi
que "Paul Montel company (1967
Year), V. L. Zelikman et al., "Making and Coating of Photographic Emulsions".
photographic Emulsion "Foc
It is prepared by the method described in, for example, al press (1964).

That is, the solution conditions such as the neutral method, the acidic method, the ammonia method, etc., the forward mixing method, the reverse mixing method, the double jet method, the controlled double jet method, etc., the conversion method, the core / shell method, etc. It can be produced using the particle preparation conditions such as and the like and a combination method thereof. One of the embodiments of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains.

In the present invention, tabular grains are preferably used. The tabular silver halide grains have an average grain size of 0.
2 to 2.5 μm is preferable, and particularly preferably 0.5 to
2.0 μm.

The tabular silver halide emulsion has an average value of grain diameter / thickness (referred to as aspect ratio) (referred to as average aspect ratio) of 2 or more, preferably 3 to 20,
Especially preferably, it is 4-12.

The average thickness is preferably 0.4 μm or less, more preferably 0.3 μm or less, and particularly preferably 0.05.
˜0.25 μm.

In the present invention, the diameter of the silver halide grain is defined as the equivalent spherical diameter of the grain from the observation of an electron micrograph of the silver halide grain. The thickness of the silver halide grain is defined as the minimum distance between the two parallel planes forming the tabular silver halide grain.

The thickness of tabular silver halide grains can be determined from electron micrographs of silver halide grains shaded or electron micrographs of sample slices obtained by coating a support with a silver halide emulsion and drying. .

In order to obtain the average aspect ratio, at least 100 samples are measured.

In the silver halide emulsion of the present invention, the proportion of tabular silver halide grains in all silver halide grains is 50% or more, preferably 60% or more, particularly preferably 70% or more.

As the tabular silver halide emulsion, those having monodispersity are preferably used, and those having 50% by weight or more of silver halide grains contained in a grain size range of ± 20% around the average grain size are particularly preferable. It is preferably used.

The tabular silver halide emulsion has an optional halogen composition such as silver chloride, silver bromide, silver chloroiodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., but has a high sensitivity. To silver iodochlorobromide, the average silver iodide content is 0 to 4.0 mol%, particularly preferably 0.2 to 3.0 mol%, and the average silver chloride content is 0 to 5 mol%. Mol%.

In the tabular silver halide emulsion, the halogen composition may be uniform within the grain or silver iodide may be localized, but it is preferably localized in the central portion. Used.

The method for producing a tabular silver halide emulsion is described in JP-A Nos. 58-113926 and 58-113927,
Nos. 58-113934 and 62-1855, European Patents 219,849, and 219,850 can also be referred to. As a method for producing a monodisperse tabular silver halide emulsion, JP-A-61-6643 can be referred to.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, an aqueous silver nitrate solution or an aqueous silver nitrate solution and an aqueous halide solution are simultaneously added to a gelatin aqueous solution having a pBr of 2 or less to form seed crystals. It can be obtained by generating and then growing by the double jet method.

The size of tabular silver halide grains can be controlled by the temperature at the time of grain formation and the rate of addition of an aqueous silver salt and halide solution.

The average silver iodide content of the tabular silver halide emulsion can be controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of bromide to iodide.

Further, when producing tabular silver halide grains, a silver halide solvent such as ammonia, thioether or thiourea can be used if necessary.

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 particularly preferable desalting method is a method using G3, G8, etc. exemplified by Aggregating Polymer Agents described in No. 37.

The emulsion according to the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, RD N
o. No. 17643 (December 1978); 187
16 (November 1979) and No. 16 308119
(December 1989). Table 1 shows the types of compounds and the places where they are described in these three Research Disclosures.

[0129]

[Table 1]

[0130]

【Example】

Examples [Preparation of SPS photographic support] <Preparation of SPS resin pellets> JP-A-3-131843
SPS resin pellets were produced according to the No. From the preparation of the catalyst to the polymerization reaction, all were carried out under a dry argon stream. In a glass container having an inner volume of 500 ml, copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) 17.8 g (71 mmol) purified benzene 200 ml and trimethylaluminum 2
4 ml was put and stirred at 40 ° C. for 8 hours to adjust the catalyst. This was placed under an argon gas flow. After filtering through 3 glass filters, the filtrate was freeze-dried. Take this out,
It was placed in a 2 l stainless steel container, and tributylaluminum and pentacyclopentadiethyl titanium methoxide were further mixed therein, and heated to 90 ° C. Into this, 1 liter of purified styrene containing 5 mol% of purified 4-methylstyrene was added, and the polymerization reaction was continued at this temperature for 8 hours.
Thereafter, the mixture was cooled to room temperature, 1 l of methylene chloride was added, and a methanol solution of sodium methylate was added to the catalyst to deactivate the catalyst while further stirring. The contents were gradually dropped into 20 liters of methanol, and then No. It was filtered with a 3A glass filter, washed with 1 l of methanol three times, dried, and dried under reduced pressure at 150 ° C. for 12 hours to obtain an SPS resin. 1,2,4-trichlorobenzene as a solvent
The weight average molecular weight of this polymer determined from the results of GPC measurement with standard polystyrene at 35 ° C. was 280,000.
It was 0. The melting point of this polymer was 245 ° C. ^{By 13} C-NMR measurement, it was confirmed that the obtained polymer had a syndiotactic structure. This SP
The S resin was introduced into an extruder at 300 ° C., extruded, and pelletized. The Tg of this SPS resin was 95 ° C.

<Preparation of Colored SPS-Based Photographic Support> Some of the obtained SPS-based pellets were vacuum-dried at 150 ° C. for 8 hours, and then the chips were blue dyed at 140 ° C. with moisture being blocked (manufactured by Bayer). Dye Macrolex BlueR
R) with a rotary mixer, melt-mix and color with an extruder at 330 ° C. to melt-extrude in layers from a T-die, and electrostatically load onto a rotating 40 ° C. cooling drum to bring the resin sheet into close contact, It is cooled and solidified to form an unstretched sheet, and then this unstretched sheet is uniaxially stretched at a longitudinal stretching temperature and a longitudinal stretching ratio shown in Table 2 in a roll-type longitudinal stretching step.
Subsequently, the both ends of the uniaxially stretched film are held with clips and sequentially biaxially stretched at the transverse stretching temperature and the transverse stretching ratio shown in Table 2, and further heat-set at 245 ° C. for 10 seconds and cooled,
A 175 μm thick SPS-based photographic support was obtained. At the same time, the stretching temperature was changed to prepare SPS photographic supports for comparison.

<Undercoating of SPS-based photographic support> Both surfaces of the obtained biaxially stretched SPS-based photographic support were continuously subjected to corona discharge under discharge condition 7 (W · min / m ² ). After the treatment, the ion blower (RH-20 type) is used to remove the charge on both surfaces with ionic wind, and both sides are coated with an air doctor type coating machine undercoating solutions a-1 and b-1 (same formulation). Was applied to give a dry film thickness of 1.0 μm and dried at 160 ° C. to obtain subbing layers A-1 and B-1.

Subsequently, the undercoating upper layer coating liquids a-2 and b-2 were similarly coated on the undercoating layer so that the dry film thickness was 0.2 μm, and dried at 140 ° C. to obtain the undercoating upper layer. A-2 and B-
And 2.

<< Undercoating Coating Solutions a-1 and b-1 >> Styrene-butadiene latex (Nippole LX432A, manufactured by Nippon Zeon Co., Ltd.) 25 parts by weight Methylcellulose (10%) 10.0 parts by weight Silica matting agent (average particle size 3. 0 μm) 0.5 parts by weight (C-1) 0.5 parts by weight Pure water 66 parts by weight << Undercoating upper layer coating liquids a-2 and b-2 >> Gelatin aqueous solution (10%) 80 parts by weight Methylcellulose (10%) 20 parts by weight C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ SO ₃ Na 4 parts by weight Proxel 0.3 parts by weight (C-1) 0.5 parts by weight Finish with pure water to 1 liter.

[0135]

Embedded image

[Preparation of silver halide photographic light-sensitive material having SPS-based photographic support] A- of each SPS-based photographic support
The following silver halide emulsion coating solution was applied onto Nos. 2 and B-2 to prepare a silver halide photographic light-sensitive material for X-ray medical treatment.

<Preparation of silver halide photographic light-sensitive material> An ortho silver halide photographic light-sensitive material for X-ray film was prepared using tabular grains and solid fine particle dispersion (AH).

<< Preparation of Solid Particle Dispersion (AH) >> 50
Dried powder of 5 g of dye (AH) was added to 0 ml of water and dispersed using a high-speed impeller disperser described in JP-A-3-288842, and dispersed at 25 ° C. for 1 hour at 15,000 rpm for 8 hours. It was The average particle diameter and distribution of the dispersion were measured with a laser diffraction / scattering type particle size distribution measuring apparatus LA-700 manufactured by Horiba Ltd. Average particle size is 0.2
In μm, the degree of dispersion of particles was within 20% in terms of coefficient of variation.

<< Preparation of Seed Emulsion >> A seed emulsion was prepared as follows.

A1 ossein gelatin 100 g potassium bromide 2.05 g with water 11.5 l B1 ossein gelatin 55 g potassium bromide 65 g potassium iodide 1.8 g 0.2N sulfuric acid 38.5 ml water with 2.6 l C1 silver nitrate 95 g water 2.7 l D1 ossein gelatin 75 g Potassium bromide 950 g Potassium iodide 27 g Water 3.0 l E1 Silver nitrate 1410 g Water 3.2 l To liquid A1 kept at 60 ° C in a reaction kettle Control liquid B1 and liquid C1 It was added by the jet method over 30 minutes, and then D1 liquid and E1 liquid were added by the control double jet method over 105 minutes. 50 stirring
It was performed at 0 rpm. With the growth of particles, new nuclei were not generated, and so-called Ostwald ripening was caused, and they were added at a flow rate at which the particle size distribution did not spread. When the silver ionic liquid and the halide ionic liquid were added, pAg was adjusted to 8.3 ± 0.05 using potassium bromide liquid, and pH was adjusted to 2.0 ± 0.1 using sulfuric acid.

After the addition was completed, the pH was adjusted to 6.0, and then the emulsion was desalted at 40 ° C. with an aqueous solution of Demol N and magnesium sulfate manufactured by Kao Atlas Co., in order to remove excess salts. I went.

When the seed emulsion was observed with an electron microscope, it was a cubic tetrahedral monodisperse seed emulsion having an average grain size of 0.27 μm and a distribution of 17% with slightly rounded corners.

<< Preparation of Emulsion >> The above seed emulsion and the following 4
A seed solution was used to prepare a tabular emulsion having a core / shell structure.

A2 ossein gelatin 11.7 g polypropylene-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol solution) 1.4 ml seed emulsion 0.10 mol silver equivalent Finish with water to 550 ml B2 ossein gelatin 5.9 g potassium bromide 4.6 g Potassium iodide 3.0 g Finish with water to 145 ml C2 Silver nitrate 10.1 g Finish with water to 145 ml D2 Ocein gelatin 6.1 g Potassium bromide 94 g Finish with water to 304 ml E2 Silver nitrate 137 g Finish to 304 ml with water 70 ° C The solution B2 and solution 25 were added to the solution A2, which was vigorously stirred by using the double jet method, over 58 minutes. Next, the D2 liquid and the E2 liquid were added to the same liquid by the double jet method over 48 minutes. During this time, pH was 5.8 and pAg was 8.
It was kept at 7. After the addition was completed, desalting and precipitation were carried out in the same manner as above to obtain an emulsion having a pAg of 8.5 and a pH of 5.85 and an average silver iodide content of about 2.0 mol at 40 ° C.

Observation of the obtained emulsion with an electron microscope revealed that 81% of the projected area has a mean grain size of 0.96 μm, a broad grain size distribution of 18% and a tabular halogenated form with an average aspect ratio of 4.5. It was a silver particle. The average distance between twin planes was 0.007 μm, and the variation coefficient between the planes was 45%.

<< Preparation of X-ray film sample >> The following layer was used as the first layer, the following transverse light-shielding layer, the second layer was an emulsion layer obtained by adding the following additives to the above emulsion, and the third layer was the following protective layer above the emulsion layer. Was simultaneously coated on both surfaces A-2 and B-2 of a 175 μm SPS-based photographic support colored in blue with a slide hopper so that a sample was prepared.

First Layer (Transverse Light Blocking Layer) The following addition amounts are per 1 m ^{2 of} one side of the silver halide photographic light-sensitive material.

Solid fine particle dispersion dye (AH) 180 mg Gelatin 0.2 g Sodium dodecylbenzenesulfonate 5 mg (C-1) 5 mg 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg Colloidal silica (Average grain size 0.014 μm) 10 mg Second layer (emulsion layer) The following additives were added to each emulsion obtained above, the silver amount in the emulsion was 1.65 g / m ² (one side) and the gelatin amount was 1 .2
g / m ² . Emulsion additive is silver 1
It is contained and coated in the following weight per mole.

Hypo 9.2 g KSCN 263 mg Chloroauric acid 6.4 mg 5,5'dichloro-3,3'-di (3-sulfopropyl) -9-ethyloxacarbocyanine sodium salt 700 mg 4-Hydroxy-6- Methyl-1,3,3a, 7-tetrazaindene 4.4g 2-hydroxy-6-methyl-4,6-dichloro-1,3,5-triazine sodium salt 4g polyacrylic acid sodium salt 5g polystyrene sulfonic acid Sodium salt 2 g Alkali-treated gelatin 80 g 1, bis (bisvinylsulfonylacetamide) ethane 2.3 g When conductive particles are used in the emulsion layer, the conductive particles should be added so that the coating amount is as shown in Table 2. Was applied to form an emulsion layer. In addition, (C-2) is a conductive particle 0.6 g / m ²
The amount of 0.012 g / m ² was proportionally increased / decreased according to the change in the amount of the conductive particles.

Third Layer (Protective Layer) As a protective layer, the following various additives were added, and the following weight was applied per 1 m ² .

Alkali-treated gelatin 1.2 g Dextran 500 mg Polyacrylic acid sodium salt 5 g C ₈ F ₁₇ S0 ₃ Na 2 mg 1,2-bis (bisvinylsulfonylacetamide) ethane 33 mg PMMA (3.5 μm) 2 mg Sodium-isoamyl-N -Decylsulfosuccinate 2 mg When the conductive particles are used in the protective layer, the conductive particles were added and coated so that the coating amount was as shown in Table 2 to give a protective layer. In addition, (C-2) is a conductive particle 0.6
was added proportionally increase or decrease the amount of 0.012 g / m ² based on g / m ² depending on the amount change of the conductive particles.

[0152]

Embedded image

Comparative Third Layer (Protective Layer) As a comparative example in which conductive particles were not added to both the second layer and the third layer, the following compounds were added, and the following compounds were added instead of the conductive particles. .

[0154] _{C 8 H 17 -C 6 H 4} -0 (CH 2 CH 2 O) 10 (CH 2 CH (OH) CH 2) 2 H 0.03g / m 2 C 8 H 17 -C 6 H 4 - _{O (CH 2 CH 2 O)} 2 CH 2 CH 2 SO 3 Na 0.01g / m 2 C 8 F 17 -SO 2 N (C 3 H 7) - (CH 2 CH 2 O) 10 - (CH 2 CH ₂ CH ₂ O) ₄ H 0.002 g / m ² << Preparation of treatment liquid >> (Developer) (as a used liquid 1 l) Potassium carbonate 40 g Hydroquinone 35 g Dimezone S 10 g 1-Phenyl-3-pyrazolidone 5 g Diethylbenzotriazole 0. 2 g 1-phenyl-5-mercaptotetrazole 0.15 g 2-mercaptohypoxanthine 0.07 g sodium sulfite 20 g potassium sulfite 40 g diethylene glycol 20 g N-acetyl-d, l-penicillamine 0. _{5g HS-C 2 H 4 -S} -C 2 H 4 -SH 0.3 g of potassium hydroxide was added to this solution, the 1l pH 10.7
The solution was adjusted to 0.

(Fixer) (1 liter was used as a solution) Sodium thiosulfate 42.0 g Potassium thiosulfate 98.0 g Sodium sulfite 15.0 g Boric acid 10.0 g Sodium hydrogen acetate 30.0 g These were dissolved in 400 ml of water. The pH of the used liquid is 4.
Sulfuric acid was added to 50. Finally 500m with pure water
A concentrated solution was prepared by finishing to 1 l. 1 liter of this concentrate with water
To be used as a working solution.

(Developer Starter) Glacial acetic acid 2.98 g Broccoli 4.0 g Water was added to make 1 liter.

At the start of processing (beginning of running), the developing solution was filled in 1 liter of developing solution and added with 20 ml of a starter, and the developing tank was filled with the solution as a starter solution to start the processing. The pH of the developer containing the starter was 10.50. The automatic processor is SRX-503 (Konica Corporation)
Manufactured) and the following evaluations were performed.

[Evaluation Method] <Evaluation of Antistatic Performance><< Measurement of Surface Resistivity >> In an atmosphere where the temperature is adjusted to 23 ° C. and 20% RH, the teraohm meter model VE- manufactured by Kawaguchi Electric Co., Ltd. It was measured using 30.
Under the same conditions, the undeveloped sample and the developed sample are conditioned for 24 hours, and each sample is sandwiched between the stainless electrodes having a measuring electrode gap of 5 cm to measure the value for 1 minute.

<< Static Mark >> Unexposed sample is 2
After conditioning the humidity in a dark room for 2 hours at 5 ° C and 25% RH,
In this room, it was placed on a neoprene rubber plate, and a roller made of neoprene rubber was rubbed 10 times on it to perform rubbing, and the above-mentioned processing such as development was performed to examine the degree of generation of static marks on the entire surface of the sample.

A: Generation of static marks was not recognized at all B: Generation of static marks was recognized only slightly C: Generation of static marks was slightly recognized D: Generation of static marks was considerably recognized E : Generation of static marks was observed almost on the whole surface <Oil sludge test> 1000 sheets of large-size cut samples were prepared as running films, exposed to a density of 0.9, and then automatically developed. Machine SR
Using the above-mentioned treatment liquid in X-503, the 1000 sheets were continuously subjected to running treatment. After the running treatment, the treatment liquid was allowed to stand for 6 hours, then 10 unexposed samples of the same size were continuously treated, and the 10 treated samples were observed. evaluated.

5: No oil sludge was observed over the entire surface of both sides of the sample 4: A slight amount of sludge was generated within 1 cm from the entire end of the sample 3: On the entire surface of the sample, at a portion corresponding to the pitch of the roller It was observed that the sludge was partly thinly generated, and the degree was about 1/10 of the evaluation standard 2. Stripe-shaped oil sludge was spread over the entire surface of the sample along the roller pitch. Occurrence 1: Sludge was generated on the entire surface of the sample, and more than 20 places were generated within an arbitrary 5 cm ² .

[0162]

[Table 2]

[Results] As can be seen from Table 2, the silver halide photographic light-sensitive material having the emulsion layer or emulsion protective layer containing the conductive particles of the present invention on the syndiotactic polystyrene photographic support was Excellent in antistatic property after development of a silver halide photographic light-sensitive material having an emulsion layer or an emulsion protection layer containing no conductive particles and containing a surfactant-like antistatic agent, and does not generate oil sludge during development processing. I found out. Further, in the composition of the conductive particles within the range of the present invention, the decrease in the surface specific resistance after development was small and the permanent antistatic effect was recognized.

[0164]

By incorporating the conductive particles of the present invention into at least one layer constituting a silver halide photographic light-sensitive material, a syndiotactic polystyrene film can be usefully used as a photographic support. It was possible to obtain a reliable silver halide photographic light-sensitive material that is light in weight, reduces the load on logistics, has excellent antistatic performance, does not generate oil sludge during development processing, and has no misdiagnosis. .

Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08J 7/04 CET C08J 7/04 CETG C08L 25/18 LEK C08L 25/18 LEK G03C 1/00 G03C 1/00 A 1/795 1/795 1/89 1/89 // C08F 257/00 MQH C08F 257/00 MQH B29K 25:00

Claims (7)

[Claims] 1. A polymer particle having at least one layer of an antistatic agent containing conductive particles having the following water-soluble polymer (A) positioned on the outer periphery thereof, wherein the weight of the water-soluble polymer (A) is A silver halide photographic light-sensitive material characterized by having a biaxially-stretched syndiotactic polystyrene-based photographic support in an amount of 35 to 500% based on the weight of the polymer particles.
The water-soluble polymer (A) is a water-soluble polymer having a sulfonic acid group and a carboxyl group. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the sulfonic acid group of the water-soluble polymer (A) is a conductive particle derived from a styrenesulfonic acid monomer. material. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the monomer composition of the polymer particles contains an epoxy group-containing monomer. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the water-soluble polymer (A) is a copolymer of styrene sulfonic acid and maleic acid. . 5. A styrenesulfonic acid / maleic acid molar ratio of styrenesulfonic acid / maleic acid = 50/50.
The silver halide photographic light-sensitive material according to claim 4, which is in the range of 95/5. 6. The halogenated product according to claim 1, wherein the weight of the water-soluble polymer (A) is 100 to 400% with respect to the weight of the polymer particles. Silver photographic light-sensitive material. 7. The halogenated product according to claim 1, wherein the weight of the water-soluble polymer (A) is 200 to 300% with respect to the weight of the polymer particles. Silver photographic light-sensitive material.