JP3393278B2 - Silver halide photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having a novel antistatic layer and having an excellent antistatic effect.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material is generally a composite material composed of a photographic support of a plastic film having an electrically insulating property and a photographic light-sensitive material layer. Therefore, the silver halide photographic light-sensitive material is not easily produced or used, but the surface of the same kind or different kind of material and the silver halide photographic light-sensitive material come into contact with each other and are rubbed or peeled off from each other. The silver halide photographic light-sensitive material is easily charged with static electricity. The electrostatic charge accumulated and accumulated causes fatal damage to the silver halide photographic light-sensitive material when discharged. The silver halide photographic light-sensitive material cannot be subjected to so-called nondestructive inspection, which shows that it is of normal quality only after development processing, and must not be damaged by static electricity in any case. The obstacle is that dot-like or resin-like or feather-like image-like unnecessary patterns called static marks appear on the photographic film and become useless as a photograph.
For example, in the case of a medical or industrial X-ray photographic film, an erroneous signal hinders diagnosis and is dangerous. Not limited to this, such static marks should not occur in the photographic film. On the other hand, after development processing,
When the photographic film is charged, dust adheres to the surface of the photographic film and unnecessary points appear on the printed print, so that 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.

Problems caused by static electricity are more likely to occur due to higher sensitivity of silver halide photographic light-sensitive materials, high-speed production, high-speed photography, high-speed automatic processing, etc., and there is an increasing demand for antistatic technology capable of coping with these problems. It is rising.

Conventionally, various antistatic techniques have been proposed to meet these demands. For example, JP-A-49-9
Nos. 1165 and 49-121523 disclose examples of applying an ionic polymer having a dissociative group in the polymer main chain. Other Japanese Patent Application Laid-Open Nos. 2-9689 and 2-9
Conducting polymers as described in JP-A-182491, JP-A-63-55541 and JP-A-63-148254.
No. 63-148254, No. 63-148256
And inventions relating to a surfactant as described in JP-A-1-134191 are known. However, many of these substances show specificity depending on the type of photographic support and the type of silver halide emulsion layer or non-light-sensitive layer, and often show good results only for specific ones.
Further, in these techniques, the antistatic performance is significantly deteriorated after the development processing.

[0005]

To solve this, for example, Japanese Patent Laid-Open No. 55-84658 or 61-1745.
In No. 42, (1) a water-soluble conductive polymer having a carboxyl group (for example, a water-soluble conductive copolymer of sodium styrenesulfonate and a monomer having a functionally bonded carboxyl group), (2) a carboxyl group An antistatic layer consisting of a reaction product of a hydrophobic polymer containing (3) and (3) polyfunctional aziridine, or after applying a mixture of (1) and (2), a layer containing (3) is formed thereon. A coated antistatic layer is disclosed. In addition, JP-A-3-25603
No. 9, No. 3-192252 and No. 3-206444 disclose an antistatic layer composed of a water-soluble conductive polymer, a hydrophobic polymer and an epoxy compound. Further, JP-A-4-124646, JP-A-4-124647, and JP-A-4-124647
-124649 and 4-124652 disclose an antistatic layer made of a water-soluble conductive polymer having a self-crosslinkable group such as N-methylol.

Although these techniques considerably improve the antistatic property after development processing, the antistatic layer and the layer adjacent thereto are rubbed or peeled off in water during development processing (for example, (While the rollers of the automatic processor are being conveyed),
It was found that peeling may occur due to external force such as peeling with cellophane tape in a dry state after development processing, which is a problem in practical use. Although this phenomenon is not clearly understood, we suspected that some adhesion between layers would be weakened in water.

In some of these methods, quality control in manufacturing is difficult.

An object of the present invention is to provide a silver halide photograph having an antistatic layer which is easy to make, has a permanent antistatic effect, and has a stable and strong film strength with a film before, during and after development. To provide a light-sensitive material.

[0009]

[Means for Solving the Problems]

(1) By providing at least one antistatic layer containing conductive particles in which the following water-soluble polymer (A) is located on the outer periphery of the polymer particles, it has permanent antistatic performance and excellent adhesiveness. A silver halide photographic light-sensitive material was obtained, and the present invention was accomplished.

Water-soluble polymer (A): A water-soluble polymer having a sulfonic acid group and a carboxyl group.

(2) Permanent antistatic property is provided by providing at least one antistatic layer containing conductive particles in which the water-soluble polymer (A) is located and water-dispersible polymer on the outer periphery of the polymer particles. A silver halide photographic light-sensitive material having an antistatic layer having high performance, excellent adhesiveness before, during and after development processing and strong film strength was obtained, and the second aspect of the present invention was achieved.

Further, the sulfonic acid group of the water-soluble polymer (A) is converted into a conductive particle derived from a styrenesulfonic acid monomer; to a polymer particle derived from an epoxy group-containing monomer; The water-soluble polymer (A) is used as a copolymer of styrenesulfonic acid and maleic acid; the molar ratio of styrenesulfonic acid and maleic acid is styrenesulfonic acid / maleic acid =
In the range of 50/50 to 95/5; the weight of the water-soluble polymer (A) is 35 to 500% with respect to the weight of the particles of the polymer; and the weight of the water-dispersible polymer is the conductivity. By setting the content of the photographic particles to 200% or less, the silver halide photographic light-sensitive material of the present invention having excellent permanent antistatic performance and excellent other properties was achieved.

The present invention is described in detail below.

The silver halide photographic light-sensitive material comprises a photographic support, an undercoat layer, an antistatic layer, an emulsion light-sensitive layer, an intermediate layer, a protective layer and a back layer. These will be described.

[Photographic Support] As the photographic support of the silver halide photographic light-sensitive material of the present invention, for example, cellulose nitrate film, cellulose triacetate (hereinafter abbreviated as TAC) film, and cellulose acetate butyrate are used. Rate film, cellulose acetate propionate film, polyethylene terephthalate (hereinafter abbreviated as PET) film, polyethylene naphthalate (hereinafter abbreviated as PEN) film, JP-A-6-51
No. 437, modified polyester, polycarbonate film (hereinafter abbreviated as PC), other laminates thereof, α-olefin polymer (for example, polyethylene, polypropylene, copoly-ethylene-butene) coated or laminated paper support, Photographic supports such as can be used. Among these, a TAC film, a PET film, a polyethylene-coated paper photographic support, and the like are currently in practical use, and are commercially available and easily available. In addition to the above, when the PET film forming equipment is provided, by using this equipment, the above-mentioned film can be formed in the same manner as the PET film by the conventional method. The photographic support is not limited to these and can be widely used.

The photographic support may be colored according to the purpose, but when transparency is particularly required as in a photosensitive material film for printing, an uncolored transparent photographic support is used. A neutral photographic support is used for the color film, and a blue photographic support is used for the X-ray photosensitive material film. The purpose of coloring is to prevent light piping, halation, or for diagnosis.

The thickness of the photographic support varies depending on its material and purpose of use, but is 50 to 200 μm.

[Undercoat Layer] An undercoat layer is provided on the photographic support in order to firmly hold the emulsion layer and the back layer on the photographic support. Below are typical TAC films and PE
The subbing on the T film will be briefly described.

The undercoat layer of the TAC film is obtained by dissolving or dispersing a hydrophilic resin, gelatin or the like in TAC such as acetone or methylene chloride using a good solvent and coating the solution.

The PET film subbing layer is generally coated with a water-based polymer latex before or after stretching during film formation. In addition to this, the organic solvent-based subbing coating as described above and PET are also used. There is also a method of applying an organic solvent-based or water-based undercoat liquid containing a so-called etching solvent (for example, phenol, cresol, resorcin, chloral hydrate, chlorophenol, etc.) that adheres the undercoat material by the anchoring effect after etching the film. . This is PET
Has a regular structure that does not easily adhere, and it is necessary to change this surface structure loosely or chemically. For this purpose, surface activation treatments such as mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone treatment may be performed. After the above treatment, a subbing layer may be provided, and a photographic emulsion layer may be provided thereon to obtain a film. Even for water-based undercoating agents, if the above various treatments are used as pretreatments,
The adhesiveness can be easily improved. For example, a quaternary copolymer latex composed of n-butyl methacrylate: t-butyl methacrylate, styrene and 2-hydroxyethyl methacrylate according to the method described in JP-A-55-67745, JP-A-59-19941 and the like, an interface, By coating with an aqueous subbing solution consisting of an activator and a curing agent, drying, then corona discharge treatment again, and then applying an aqueous gelatin solution such as an antihalation layer or emulsion layer to the photographic emulsion layer side. A photosensitive material having good adhesiveness can be obtained.
The above treatment and the undercoat layer are also effective for adhesion of the antistatic layer of the present invention. The antistatic agent of the present invention may also be used as the undercoat layer.

The subbing layer is applied in an amount of 0.01 to 10 cc, particularly 0.1 to 3 c per m ² in terms of solid content volume of the subbing agent.
It is preferably c.

The drying conditions in the step of drying the applied subbing liquid are generally 120 to 200 ° C. and about 10 seconds to 10 minutes.

If desired, a surfactant, a swelling agent, a matting agent, a crossover dye, an antihalation dye, a pigment, an antifoggant, an antiseptic agent, etc. may be added to the subbing liquid. Phenol, resorcin, cresol, chlorophenol, etc. are used as a swelling agent for PET and PEN, and if added, 1 to 10 g per 1 liter of the subbing liquid
Good. The matting agent is preferably silica, polystyrene spheres, methyl methacrylate spheres or the like having a particle size of 0.1 to 10 μm.

A generally well-known method is used as a method for applying the undercoating liquid or the antistatic processing liquid of the present invention described below. 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. 2,761,791, as required
No. 3, No. 3,508,947, No. 2,941,898 and No. 3,526,528, and Yuji Harasaki, “Coating Engineering”, page 253 (published by Asakura Shoten in 1973). More than one layer can be applied simultaneously.

[Antistatic Layer] The antistatic layer 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.

First, the water-soluble polymer (A) having a sulfonic acid group and a carboxyl group, which is a constituent of the present invention, 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 monomer having a sulfonic acid group include vinyl sulfonic acid, 2-acrylamido-
Examples thereof include 2-methylpropanesulfonic acid, 2-acrylamidoethylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 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, dicarboxylic acid is preferably used, and maleic acid is particularly preferable, because the adhesion between the formed antistatic layer and the adjacent layer is further improved.

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, the above-mentioned monomer having a sulfonic acid group, a monomer having a carboxyl group, and optionally other monomers are dissolved in water to dissolve a polymerization initiator (for example, a peroxide). Polymerization can be carried out by adding potassium sulfate) or the like and heating.

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 above-mentioned monomer having no sulfonic acid group is not particularly limited, and examples thereof include styrene and α.
-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 this 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 and the like which hardly react with a sulfonating agent and do not form a salt during neutralization 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 above solvent is preferably carried out under low temperature conditions of 30 ° C or lower.

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

In such a water-soluble polymer (A),
The ratio between the sulfonic acid group and the carboxyl group is a sulfonic acid group / carboxyl group = 10/90 in terms of the molar ratio of functional groups.
95/5, preferably sulfonic acid group / carboxyl group =
20/80 to 80/20, particularly preferably sulfonic acid group / carboxyl group = 30/70 to 60/40.

When the sulfonic acid 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 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. It may be neutralized or may 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 ⁺ O.
Inorganic or organic alkaline substances such as H, triethanolamine and 2-amino-2-methylpropanol can be used, and NaOH is preferable.

Next, the above-mentioned polymer particles refer to polymer particles produced 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, α-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.

Furthermore, 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-
Oxazole group-containing vinyl monomers such as propenyl-2-oxaborine, 2-acrylic acid-4,6-dichloro-
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).
To 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 method for polymerizing the conductive particles of the present invention is 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.

In order to improve the conductivity of the conductive particles of the present invention, the water-soluble polymer (A) in the conductive particles is used.
Regarding the blending ratio of, the weight of the water-soluble polymer (A) is required to be 35 to 500% with respect to the weight of the monomer used for the polymer particles. It is preferably 100 to 400%, and particularly preferably 200 to 3 because of its excellent conductivity and adhesiveness.
It is 00%.

When the monomer used for the polymer particles is dropped into the aqueous solvent, whether the polymerization initiator is 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 a salt thereof, and azobis compounds such as 2,2-azobis (2-aminopropane) hydrochloride A compound or 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, ammonium ferrous sulfate and sodium thiosulfate.

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

In addition, inorganic substances such as sodium acetate, n-
A chain transfer agent such as dodecyl mercaptan can also be added. A reaction accelerator may be added to the aqueous solvent for the purpose of promoting the reaction. Examples of this 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.
You may mix | blend the surfactant for emulsion polymerization, a seed emulsion, and other water-soluble polymers.

As the surfactant for emulsion polymerization, higher fatty acid sulfonate, alkylbenzene sulfonate,
Examples thereof 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.

Here, 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 one of the water-soluble polymer (A). It means a mode in which the part is in a state of being bonded to the main body of the particle during the synthesis, or embedded or bited.

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, in an attempt to separate the water-soluble polymer (A) on the outside of the polymer particles from the conductive particles in the form of emulsion, hot water at a temperature at which the polymer particles do not fuse As a result, the water-soluble polymer (A) was separated or extracted only in a small amount or in a small amount, and 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. On the contrary,
When a mixture of a latex polymerized with a surfactant and a water-soluble polymer (A) used in the present invention was well mixed and subjected to extraction and centrifugation in the same manner as above, the latex polymer particles and the water-soluble polymer (A) were highly soluble. The molecule (A) was separated as it was.

Further, as described above, when a reactive vinyl monomer such as glycidyl acrylate is used as a part in the polymer particles, the conductive particles have a carboxyl group of the water-soluble polymer during synthesis. There is a possibility that the bonding state due to the epoxy group of the polymer particles may be developed, and the bonding state may be developed even after the working fluid of 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 adhesiveness and 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.
˜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.

A more preferable embodiment of the antistatic layer containing the conductive particles of the present invention is to use a water-dispersible polymer together with the conductive particles of the present invention, and this embodiment is also the present invention. Depending on the type of silver halide photographic light-sensitive material, an antistatic layer may be provided exposed on the surface of the back layer or the uppermost layer of the light-sensitive layer. For example, a color film of a single-sided film, an X-ray film of a double-sided film, and the like have such a structure, but they are now applied to a single-sided photosensitive material film for printing.
As described above, when it is used for the uppermost antistatic layer, a strong film surface is required, and thus the above-mentioned constitution is preferable.
Further, the antistatic layer may be provided in an intermediate layer of the multi-layer structure, and in this case, it is preferable because the whole film is attached and the whole film strength is improved.

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. This water-dispersible polymer is obtained by the usual latex polymerization method using the above-mentioned monomers. 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 amount of the water-dispersible polymer used in the present invention is 200% or less, preferably 150% or less, and particularly 70 to 140, based on the weight of the conductive particles.
% Is preferred.

In the antistatic layer of the present invention, it is preferable to use the above-mentioned water-dispersible polymer in combination with the conductive particles of the present invention in order to enhance the film strength, and particularly the antistatic layer positioned at the uppermost layer. In this case, this combination is preferable.

The antistatic layer containing the conductive particles of the present invention is characterized in that the film is excellently adhered even after the development treatment and the permanent antistatic effect is obtained. Recent development processes are often performed under severe conditions such as high temperature and high pH. In order to further stabilize the antistatic layer of the present invention under such conditions, a crosslinking agent may be added separately, which is preferable.

A water-soluble binder may be added to the system having the conductive particles of the present invention. As a water-soluble binder,
For example, proteins such as gelatin, derivative gelatin, colloidal albumin and casein; carboxymethyl cellulose; hydroxy cellulose; cellulose derivatives such as methyl cellulose; agar, sodium alginate, starch derivative and other polysaccharide analog compound derivatives; polyvinyl alcohol,
Examples thereof include polyacrylic acid and its copolymers or derivatives thereof, water-soluble polyacrylic acid ester copolymers, and water-soluble polyester resin sugars. Of these, gelatin is particularly preferably used as a water-soluble binder because it is commonly used in silver halide photographic light-sensitive materials. Examples of gelatin include alkali-processed gelatin, acid-processed gelatin, inert gelatin from which an active substance has been removed, inert gelatin, and gelatin derivatives. Examples of gelatin species include ossein and pigskin, and any of them is preferably used.

In the system containing the conductive particles of the present invention,
It is preferable to use a cross-linking agent that causes a cross-linking reaction with the water-soluble polymer (A) of the conductive particles, and by doing so, the strength of the film can be further increased. When a hardener which is usually used in a silver halide photographic light-sensitive material is used, the cross-linking agent is also preferably used. The amount of the cross-linking agent used is 0.01 to 30% by weight, preferably 0.05 to 20% by weight, based on the conductive particles.

As the above-mentioned cross-linking agent, for example, as these low molecular weight cross-linking agents, "The Theory of." By TH James can be used.
The Photographic Process (The Theo
ry of the Photographic Pr
)), 4th edition, pp. 77-88, and of these, those having a vinyl sulfonic acid, an aziridine group, an epoxy group, or a triazine ring are preferably used. Sho 53-41221
No. 60-225143, low-molecular cross-linking agents, and pentaerythritol tri- [β- (N-aziridinyl) described on page 5 of the specification of No. 55-84658.
Propionate], a polyfunctional aziridine compound such as those described on pages 27 and 28 of JP-A-3-256039, and a dichlorotriazine type compound described on pages 12 to 14 of JP-A-6-082961. And the like are preferable. Polymer crosslinking agents are also used in the present invention. For example, a polymer crosslinking agent having an epoxy group described in U.S. Pat. No. 3,623,878, Research Disclosure Magazine (hereinafter sometimes abbreviated as RD) 17333
(1978) and the like, a polymer crosslinking agent having a dichlorotriazine group, a polymer crosslinking agent having an active ester group described in JP-A-56-66841, JP-A-56-142.
524, U.S. Pat. No. 4,161,407, JP-A-5
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.

[Silver Halide Photosensitive Layer, etc.] Next, the photosensitive layer of the silver halide photographic material will be described.

The silver halide photographic light-sensitive material according to the present invention includes 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 silver halide photographic light-sensitive material for printing will be mainly described.

As silver halide used in the silver halide photographic light-sensitive material of the present invention, silver bromide, silver chloride, silver iodobromide,
Usual silver halide emulsions of silver chlorobromide and silver chloroiodobromide can be optionally used, and those obtained by any method such as acidic method, neutral method or ammonia method can also be used. Preferred silver halides for printing emulsions are silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride, or silver chloroiodobromide containing 60 mol% or more of silver chloride.

The silver halide grain may be a grain having a uniform silver halide composition distribution within the grain or a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer. The particles may be formed mainly inside the particles.

As the silver halide grains, grains having a single shape may be used, or grains having various shapes may be mixed. Further, those having any particle size distribution may be used, and a polydisperse emulsion or a monodisperse emulsion may be mixed and used.

The emulsion grains of the silver halide photographic light-sensitive material for printing are preferably monodisperse, and the emulsion of monodisperse grains is within a grain size range (variation coefficient) of ± 20% around the average grain size r. The silver halide contained in is 6 of all silver halides.
It is preferably 0% or more, particularly preferably 70%
Or more, and more preferably 80% or more. The term "particle size" as used herein refers to the diameter of spherical silver halide grains, or the diameter of a projected image of a non-spherical grain converted into a circular image of the peripheral area. A highly uniform monodispersion is preferable as a photographic image. Monodisperse emulsion is disclosed in JP-A-5
5-48521, 58-49938 and 60-
It can be obtained by referring to the method described in the specification such as No. 122935.

The shape of the silver halide grains is not limited,
Any shape such as a flat plate shape, a spherical shape, a cubic shape, a 14-sided shape, a regular octahedron shape or the like may be used. For example, JP-A-5-20407
Tabular grains can be obtained by the method described in No. 0 specification.

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like can be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. According to this method, the crystal form is regular. It is possible to obtain a silver halide emulsion having a substantially uniform grain size.

The silver halide grains used in the silver halide emulsion may be cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, or any of these in at least one of the grain forming process and the growing process. It is preferable to add a complex salt containing the above element.

Details of the silver halide emulsion and its preparation method are described in the literature described or cited in RD 176, 17643, pages 22 to 23 (December 1978).

The photosensitive silver halide emulsion can be used as it is as a so-called unripened (Primitive) emulsion without chemical sensitization, but it is usually preferable to carry out chemical sensitization.

In the silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention, main photographic additives can be used in the steps before and after physical ripening or chemical ripening. Examples of the compound used in such a process include the following R
Various compounds described in D can be used.

Among the silver halide photographic light-sensitive materials, in the light-sensitive material for printing, in order to improve the halftone quality, a silver halide emulsion layer or a non-light-sensitive layer may be added with a high-contrast agent, or a high-contrast treatment may be applied in the development processing. Is done. Examples of excellent contrast enhancers include hydrazine compounds and tetrazonium compounds described below. Representative examples of these are given below, but the invention is not limited thereto.

[0085]

[Chemical 1]

[0086]

[Chemical 2]

[0087]

[Chemical 3]

[0088]

[Chemical 4]

[0089]

[Chemical 5]

[0090]

[Chemical 6]

[0091]

[Chemical 7]

The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening.
Examples of the compound used in such a step include R
D17643, RD18716 and RD308119
Various compounds described in (December 1989) can be used.

The types of compounds described in these three RDs and the locations where they are described are listed below.

[0094]

[Table 1]

In addition to this, Product Licensing Magazine (P
product Leicensing) Volume 92 107-
The description on page 110 (December 1978) can also be referred to.

The silver halide photographic light-sensitive material has at least one silver halide emulsion layer and at least one emulsion protective layer on the light-sensitive layer side on the photographic support, and on the opposite side thereof, a layer having a certain function and its layer. There is a back layer provided with at least one protective layer each. There is no particular limitation on the number of silver halide emulsion layers or back layers.

Gelatin is mainly used as the binder used in the emulsion layer or protective layer, intermediate layer, back layer and the like. This gelatin includes lime-treated, acid-treated and enzyme-treated gelatin, and those subjected to decalcification treatment, inertization treatment and inactivation treatment can also be used.
Derivative gelatin such as phthalated gelatin can also be used.
Other water-soluble substances can be mixed in the gelatin binder. For example, a polymer of sodium styrenesulfonate or a copolymer with other monomers, poly-N-
Vinylpyrrolidone, maleic anhydride copolymer, polyacrylamide and its derivatives, polyacrylic acid and its derivatives and copolymers, casein, albumin, carboxymethylcellulose, hydroxyethylcellulose, sodium alginate, etc. Used. Further, the polymer latex described in U.S. Pat. No. 3,411,911 can be incorporated in the photographic constituent layers.

A function can be imparted to each layer of the back layer. For example, the functionalized layer includes an antistatic layer, an antihalation layer, an irradiation prevention layer, a magnetic recording layer and the like. These layers may be adjacent to the subbing layer, may be on the surface, or may be present at any position depending on the purpose.

In the silver halide photographic light-sensitive material for printing, it is important to keep the curl balance between the light-sensitive layer side and the back layer side. Therefore, the ratio of the binder such as gelatin in the back layer to the hydrophilic polymer such as gelatin in the photosensitive layer side (back layer / photosensitive layer side) is preferably 0.1 or more in weight ratio, and practically not more than 0.1. 32-1.50 is particularly preferably designed. This ratio depends on the material and thickness of the photographic support of the silver halide photographic light-sensitive material, the total amount of hydrophilic polymers such as gelatin, the amount of silver or the amount of other additives (eg polymer latex). It is determined by design such as curl balance of the light-sensitive material, development speed during development processing, or drying speed after processing.

The back layer has various functions as described above.

For example, for the function of preventing the sharpness of the image of the silver halide photographic light-sensitive material and the anti-irradiation, it is preferable to use the corresponding anti-halation dye and anti-irradiation dye described in the section of the RD dye. I can.

For the function of preventing sticking between the light-sensitive layer and the back layer of the silver halide photographic light-sensitive material, the matting agent and slipping agent of the above RD can be used appropriately. Shape of matting agent,
The particle size is not limited, but the average particle size is 10 μm or more and 50 μm
The following spherical matting agents can also be used.

As the slip agent, in addition to the above RD, the following agents can be used as typical ones. For example, U.S. Pat. No. 3,042,522 and British Patent No. 95.
5,061, U.S. Pat. Nos. 3,080,317, 4,004,927, 4,047,958, 3,489,576, and British Patent 1,143,118.
No. 2, JP-A-60-140341 and the like, silicone-based lubricants, U.S. Pat. Nos. 2,454,043 and 2,7.
32,305, 2,976,148, 3,20
6,311, German Patents 1,284,295, 1,284,294 and the like, higher fatty acid-based, alcohol-based, acid amide-based lubricants, British Patents 1,263,7
No. 22, metal soaps described in US Pat. No. 3,933,516, US Pat. Nos. 2,588,765 and 3,12.
1,060, Ester-based and ether-based lubricants described in British Patent 1,198,387, etc., and U.S. Pat. No. 3,5.
The taurine-based lubricants described in Nos. 02,437 and 3,042,222 can also be mentioned.

For the development processing, see the Journal of
The American Chemical Society (Journa
I of the American Chemica
73, p. 3,100 (195)
Known developers described in 1) can be used. The silver halide photographic light-sensitive material for printing is, for example,
Development can be carried out by the processes described in JP-A Nos. 5-123292 and 53-17719.

[Synthesis Example] A synthesis example of conductive particles will be described.

<Synthesis Example 1><< Synthesis of water-soluble polymer (A) >> 1000 parts of degassed distilled water was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen introducing tube, and styrene sulfone was added. Acid sodium salt (hereinafter sometimes abbreviated as StSO ₃ Na) 465 parts and maleic acid (hereinafter sometimes abbreviated as MA) 87.5 parts are dissolved, and nitrogen gas is introduced while stirring to introduce a container with nitrogen gas. The interior was filled and heated to 70 ° C. Separately, add 40 parts of isopropanol and 250 parts of water to 0.5 parts of potassium persulfate.
Part is dissolved, placed in a dropping funnel, added dropwise to the reaction vessel not too slowly, and the temperature is raised to 75 to 80 ° C. and heated for 2 hours to give a viscous colorless transparent solution. This solution was poured into a large amount of acetone to precipitate the polymer, washed with acetone several times, 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 component composition of this water-soluble polymer (A) is StSO ₃ Na: MA =
It was 3: 1 (molar ratio). Let this water-soluble polymer (A) be. As shown below, the same synthesis was performed by changing the ratio of StSO ₃ Na and MA. In addition, from the ratio of 1: 1 MA
A water-soluble polymer having a large ratio of MA did not react because MA did not react at 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. Degassed distilled water 700
A portion was added thereto, and 250 parts of a sodium salt of a copolymer of StSO ₃ Na and MA (changing the StSO ₃ Na: MA ratio in Synthesis Example 1 as follows) was stirred to prepare an aqueous solution. 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 at 80 ° C
Rose to. 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 potassium persulfate aqueous solution was added dropwise separately, and under nitrogen gas reflux, 80 ° C.
Polymerization reaction was carried out to obtain the target conductive particles (water-soluble polymer (A): polymer particles = 250: 100).

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 Comparative -1 10: 0 St-BA comparison -2 10: 0 St-GMA in synthesis example 2 "synthesis 2 of conductive particles"<synthesis example 3>, the water-soluble polymer (a) (StSO ₃ Na : MA = 3: 1) and polymer particles (St: GMA = 9: 1) were changed as follows to synthesize conductive particles. Toshi compound No. Water-soluble polymer (A): Polymer particle-2250: 100-2-250: 100-2-3150: 100-2-4350: 100-2-5450: 100-2-Comparative 1 30 : 100-2-Comparative 2 550: 100 <Synthesis Example 4><Water dispersible polymer> Stirrer, reflux condenser, dropping funnel,
300 parts by weight of degassed distilled water was placed in a reaction vessel equipped with a nitrogen introducing tube, nitrogen gas was introduced through the nitrogen introducing tube, the reaction vessel was placed under a nitrogen gas atmosphere, and dissolved oxygen in water was eliminated. After the temperature was raised to 80 ° C., 50 parts by weight of an aqueous solution containing 5 parts by weight of sodium dodecylbenzenesulfonate was added from a dropping funnel, and 100 parts by weight of a monomer having the following composition of the water-dispersible polymer was added from another funnel. , An aqueous solution containing 3 parts by weight of ammonium persulfate from another funnel 5
0 part by weight was added dropwise, and a polymerization reaction was carried out at 80 ° C. for 8 hours under reflux of nitrogen gas to obtain a water-dispersible polymer.

Compound No. Composition St-BA (90:10) St-GMA (90:10) St-AA-BA-AM-tBMA (40: 5: 10: 5: 40) where AA; acrylic acid AM; acrylamide tBMA; Li-Butyl Methacrylate The present invention will be described by way of examples using the conductive particles synthesized above, but it goes without saying that the present invention is not limited to the described examples.

[0110]

【Example】

Example 1 [Preparation of photographic support] <Preparation of undercoat layers A-1 and B-1> Commercially available PET film having a thickness of 100 μm was subjected to a corona discharge treatment of 8 W · min / m ² on one side, The following subbing liquid a-1 at 10 ml / m
^It was applied so as to be ² and dried at 100 ° C. for 1 minute to obtain an undercoat layer A-1. Further, the undercoating liquid b-1 was applied to the surface opposite to the undercoating layer A-1 so as to be 10 ml / m ² , and 100
It was dried at 0 ° C for 1 minute to obtain an undercoat layer B-1.

[0111] << Preparation of Subtraction Liquid a-1 >>     Butyl acrylate 30% by weight,     20% by weight of t-butyl acrylate,     25% by weight of styrene and     25% by weight of 2-hydroxyethyl acrylate   270 g of copolymer latex liquid (solid content 30%)   (C-1) 0.6 g   Hexamethylene-1,6-bis (ethylene urea) 0.8 g   Make up to 1 liter with water.

[0112] << Preparation of subbing liquid b-1 >>     Butyl acrylate 40% by weight,     20% by weight of styrene and     Glycidyl acrylate rate 40% by weight   270 g of copolymer latex liquid (solid content 30%)   (C-1) 0.6 g   Hexamethylene-1,6-bis (ethylene urea) 0.8 g   Make up to 1 liter with water.

<Preparation of Undercoat Upper Layer A-2> Undercoat Layer A-
8 W · min / m ² of corona discharge was applied on 1 to apply 10 ml / m ^{2 of the following} subbing upper layer liquid a-2, and dried at 100 ° C. for 1 minute to obtain a subbing upper layer A-2.

[0114] << Preparation of subbing upper layer liquid a-2 >>   Gelatin 10g   (C-1) 0.2 g   (C-2) 0.2 g   (C-3) 0.1 g   (C-F) 0.1 g   0.1 g of silica particles having an average particle size of 3 μm   Make up to 1 liter with water.

<Preparation of Antistatic Layer B-2> Above Undercoat Layer B
-1 was subjected to a corona discharge of 8 W · min / m ² , and the following antistatic liquid b-2 of the present invention and the comparative example was treated with conductive particles of 600
It was applied with a combination of a roll coater and a wire bar so as to have a mg / m ² and dried at 100 ° C. for 1 minute to obtain an antistatic layer B-2.

[0116] << Preparation of Antistatic Liquid b-2 >>   Conductive particles (-1, -1, -1, described in Synthesis Example 1, comparative -1)                                           (In solid content) 90g   0.1 g of silica particles with an average particle size of 3 μm   (C-1) 0.1 g   (C-4) 12g   Make up to 1.5 l with water.

[0117]

[Chemical 8]

[Preparation of silver halide photographic light-sensitive material] A silver halide emulsion having the following Formulation 1 was coated on the undercoating upper layer B-1 of a photographic support with a silver content of 2.9 g / m ² and a gelatin content of 1.
So that 2 g / m ^2, the amount of gelatin coating solution having the following formulation 2 as a protective layer on it was simultaneously coated in the emulsion layer and the protective layer so as to be 0.6 g / m ² more. On the antistatic layer B-2 on the opposite side, a back layer having the following formulation 3 was added so that the amount of gelatin was 0.6 g / m ^2, and a polymer layer having the following formulation 4 was further provided thereon. A photographic light-sensitive material sample for silver halide printing was obtained by simultaneously simultaneously coating the back layer protective layer of Formulation 5 so that the amount of gelatin was 0.4 g / m ² .

<< Formulation 1, Composition of Silver Halide Emulsion Layer Coating Solution >> (C-5) Sensitizing Dye 0.6 mg / m ² (H-7) Hydrazine Compound 30 mg / m ² (C-6) Amino Compound 50 mg / M ² (C-7) Surfactant 100 mg / m ² (C-8) Latex polymer 1.0 g / m ² (C-9) Hardener 30 mg / m ² Sodium-isoamyl-n-decylsulfosuccinate 0.7 mg / m ² 2-mercapto-6-hydroxy purine ^{10mg / m 2 EDTA 50mg / m} 2 " formulation 2, the composition of the emulsion protective layer" gelatin 0.6 g / m ² Sojuumu - isoamyl -n- decyl sulfosuccinate 12 mg / m ² matting agent: monodisperse silica having an average particle diameter of 3.5 μm 25 mg / m ² (C-10) hardener 30 mg / m ² (C-11) surfactant 1 mg / m ² colloid Dal silica (average particle size 0.05 μm) 20 mg / m ² << Formulation 3, back layer composition >> Gelatin
0.6 g / m ² Sodium-isoamyl-n-decylsulfosuccinate 5 mg / m ² (C-8) latex polymer 0.3 g / m ² colloidal silica (average particle size 0.05 μm) 70 mg / m ² polystyrene sulfonic acid Sodium 20 mg / m ² (C-12) Hardener 100 mg / m ² << Formulation 4, back layer protective layer composition >> Gelatin 0.4 g / m ² Matting agent: Monodisperse polymethyl methacrylate 50 mg / m with an average particle size of 5 μm ² Sodium di (2-ethylhexyl) sulfosuccinate 10 mg / m ² (C-11) surfactant 1 mg / m ² (C-13) dye 20 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² (C-10) Hardener 15 mg / m ² Polysiloxane 0.7 g / m ²

[0120]

[Chemical 9]

<Processing for Development etc.> The silver halide photographic light-sensitive material of the present invention was processed with a developing solution and a fixing solution under the following prescription and conditions.

[0122] << Developer composition >> Amount per 1 liter of solution used   Diethyltriamine pentaacetic acid-5 sodium salt 3g   Sodium sulfite 50g   40 g of potassium carbonate   Hydroquinone 21g   4-methyl-4-hydroxymethyl-1-phenyl         -3-hydrazolidone (Dimeson S) 0.9 g   Potassium bromide 5g   Benzotriazole 0.2g   5-methyl-benzotriazole 0.13 g   Boric acid 8g   40 g of diethylene glycol   2-mercapto-6-hydroxypurine 0.06 g   Water and potassium hydroxide are added to make 1 L, and the pH is adjusted to 10.2.

[0123] <Fixer composition> Amount per 1 liter of solution used   Ammonium thiosulfate (70% aqueous solution) 200 ml   Sodium sulfite 22g   Boric acid 9.8g   Sodium acetate trihydrate 34g   Acetic acid (90% aqueous solution) 14.5 g   Tartaric acid 3.0g   Aluminum sulfate (27% aqueous solution) 25 ml   The pH of the used solution was 4.9.

<Development processing conditions> (Process) (Temperature) (Time) Development 38 ° C 12 seconds Fixing 35 ° C 10 seconds Washing 40 ° C 10 seconds Drying 50 ° C 12 seconds Total 44 seconds [Evaluation method] <Evaluation of antistatic performance <Measurement of surface specific resistance> The temperature was measured using a teraohm meter model VE-30 manufactured by Kawaguchi Electric Co., Ltd. in an atmosphere where the temperature was adjusted to 23 ° C. and the humidity was adjusted to 20% RH.
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.

<< Ash Adhesion Test >> Samples were cut into two pieces of 10 cm square, exposed to light, and subjected to the above-mentioned development treatment under the above-mentioned conditions. These samples were conditioned in an atmosphere of 23 ° C. and 40% RH for 24 hours, It was submitted to the test. The exposed and developed sample was placed on a rubber plate with the emulsion side up, and the emulsion side was charged by rotating the rubber roller 10 times. One minute later, the cigarette ash prepared separately was densely and evenly spread on the paper, and the sample (with the emulsion side facing down) was clamped at both ends with clips of an insulating material in the upper space where it was vertically spread out. The antistatic effect was evaluated by evaluating the degree of adhesion of ash to the sample by using a simple device in which the surface of the sample was positioned parallel to the plane of the ash by the worm gear and lowered in parallel. The sample was lowered at a rate of 1 cm per minute so that it was parallel to the ash surface, and the height at which ash adhered was observed. In this test, the tester wears rubber gloves and removes them to prevent static electricity from leaking from the hand holding the sample.

Evaluation level A: No adhesion when the sample is contacted with ash B: When the sample is contacted with ash, the ash adheres to the sample, but when the distance between the sample and ash is 1 cm, the ash does not exist at all. Level C where no ash adheres: ash adheres when the distance between the sample and ash is 1 cm,
Level D that does not adhere at a distance of 2 cm: Ash adheres when the distance between the sample and ash is 2 cm,
Level E that does not adhere at a distance of 4 cm: Ash adheres when the distance between the sample and ash is 4 cm,
Level F that does not adhere at a distance of 6 cm: Ash adheres even if the distance between the sample and ash is 6 cm,
Level G that does not adhere at a distance of 8 cm: Ash adheres even if the distance between the sample and ash is 8 cm,
Level H that does not adhere at a distance of 10 cm: Level at which ash adheres even if the distance between the sample and ash is 10 cm or more.

<Test with Film> A photographic light-sensitive material sample for silver halide printing was conditioned in a room at 23 ° C. and 55% RH for 24 hours, and the sample was put in a barrier bag laminated with an aluminum foil with a black polyethylene film. After heating in an oven at 40 ° C for 3 weeks, cooling, opening, and taking out the sample, the undeveloped dry film test for the back layer and the processed dry film, and the undeveloped wet film test and the processed wet film, respectively The attached test was conducted. The method of heating with a barrier bag is for accelerating prediction of the performance of the product during its effective period.

<< Test with Dry Film >> 20 cm × 20 cm
Of undeveloped and developed photographic light-sensitive material samples for silver halide printing of a size of 30 mm with a razor that makes the back layer surface at an angle of 45 ° from the horizontal plane, so as to slightly reach the plastic film surface. Wearing. 23 ° C, 8
After conditioning the humidity in an atmosphere of 0% RH for 24 hours, a cellophane tape with a width of 24 mm (cellophane tape manufactured by Nichiban Co., Ltd., a registered trademark) having a length of about 5 is crossed at right angles across the scratched portion.
0mm sticking Rubbing is done with rounded corner plastic to make it adhere. The end of the cellophane tape was held substantially parallel to the surface of the sample on the side opposite to the scratch at 45 °, and was rapidly pulled and peeled off. Regarding the peeled area of the back layer, the peeled area of the film surface was examined and evaluated as follows.

A: No peeling was observed at all B: Some scratches were peeled off, and less than 10% of the total peeling area was peeled off C: Peeling area was peeled 10% to less than 50% D: 50% or more and less than 80% of the peeled area was peeled off E: Peeled so much that the peeled area was 80% or more of the same peeled off F: There was almost no resistance to peeling and the peeling was complete.

Table 2 shows the results with a dry film.

<< Test with Wet Film >> Sample is 20 cm ×
A sample of 20 cm in size is immersed in a developing solution under the above-mentioned conditions for a predetermined time, and the back layer surface is wet before being dried after all the developing processing time has passed. The area of the back layer peeled off was examined by vigorously rubbing it over the entire area of the grid with the fingertips that had scratches on the eyes and were covered with rubber gloves, and evaluated as follows.

A: Not peeled at all B: Peeling around the scratch was very slight C: Peeling around the scratch was 10% or less of the total area D: Peeling area was 10% or more and less than 50% E: The peeled area was 50% or more and less than 80% peeled F: The peeled area was 80% or more peeled to some extent G: The whole area was peeled or more peeled 2 shows the results with a wet film.

[0133]

[Table 2]

[Results] As shown in Table 2, since the water-soluble polymer (A) of the conductive particles of the present invention has a sulfonic acid group and a carboxyl group, the antistatic property and the film-attached property are obtained. It turns out that is excellent.

Example 2 The same formulation as in Example 1 was used except that the antistatic layer was used.
o. A-11 and b- on the PET support, respectively.
11 and a-12 are applied to form A-11 and B-, respectively.
11 and A-12. Instead of the conductive particles of the antistatic layer processing liquid of Example 1, the formulation No. shown in Table 3 was used. −
The antistatic coating solutions b-12 of Nos. 1, -2, Comparative-1, and Comparative-2 were applied on B-11 in the same manner as in Example 1 to give B-12. Further, the same emulsion layer and the like as in Example 1 and a back layer were respectively coated on A-12 and B-12 to prepare samples. Evaluation items and test methods are shown in Example 1.
The results are shown in Table 3.

[0136]

[Table 3]

[Results] As shown in Table 3, the polymer particles of the conductive particles of the present invention have an epoxy group as a conductive particle having a monomer having an epoxy group such as glycidyl methacrylate as a copolymerization component. It can be seen that the film shows slightly better film-forming properties than those without. However, when the water-soluble polymer (A) of the conductive particles does not have a carboxyl group, even if the polymer particles of the conductive particles have an epoxy group, the effect of the present invention may not be exhibited. Recognize.

Example 3 The same formulation as in Example 1 was used except that the antistatic layer was used.
o. By changing the values of a-21 and b- on the PET support, respectively.
21 and a-22 are applied to form A-21 and B-, respectively.
21 and A-22. Instead of the conductive particles of the antistatic layer processing liquid of Example 1, the formulation No. shown in Table 4 was used. −
2, -2-2, -2-3, -2-4, -2-
5, -2-Comparison 1 and -2-Comparison 2 were coated with antistatic coating liquid b-22 on B-21 in the same manner as in Example 1,
It was set to B-22. Further, the same emulsion layers and the like as in Example 1 and a back layer were coated on A-22 and B-22 to prepare samples. The evaluation items and the test method were exactly the same as in Example 1, and the results are shown in Table 4.

[0139]

[Table 4]

[Results] As shown in Table 4, the ratio of the water-soluble polymer (A) to the polymer particles of the electroconductive particles of the present invention is 35 to 500%, which is excellent in antistatic property, and also has film forming property. I found it good. Most preferred embodiment is 250
(200 to 300%). It was found that if it is 30% or less, the antistatic property is remarkably deteriorated, and if it is 500% or more, the film-carrying property is extremely deteriorated.

Example 4 The same formulation as in Example 1 was used except that the antistatic layer was used.
o. A-31 and b- on the PET support, respectively.
31 and a-32 are applied to form A-31 and B-, respectively.
31 and A-32. Instead of the conductive particles of the antistatic layer processing liquid b-2 of Example 1, as shown in Table 5, the conductive particle formulation No. -1 and -2 are antistatic coating liquid b
-32, each of which was applied in the same manner as in Example 1, and for comparison, b-2 was a mixture formulation No. 1 of the water-soluble polymer (A) and the water-dispersible polymer described below. −
And-and the water-soluble polymer (A) is 600 mg / m
^{In the same} manner as above, a roll coater and a wire bar were used to coat the same on B-31 so that the antistatic layer of the present invention and the comparative example was B-32. Further, the same emulsion layer and the like as in Example 1 and a back layer were coated on A-32 and B-32 to prepare a sample. The evaluation items and the test method were the same as in Example 1, and the results are shown in Table 5.

[0142] (Comparative example formulation, -and-)     Water-soluble polymer (A) 60g     Water-dispersible polymer or (solid content 20%) 80 g     Average particle size 3μm Silica particles 0.07g     (C-1) 0.07g     (C-4) 8g   Make up to 1 liter with water.

[0143]

[Table 5]

[Results] As shown in Table 5, the mixture (formulation No. − and −) was different from the conductive particles of the present invention, and the water-dispersible polymer (A) prepared separately in the water-soluble polymer (A) ( It is understood that the mixture is very poor compared with the case where the conductive particles of the present invention hardly deteriorate the antistatic property and the film forming property before and after the development.

Example 5 The same formulation as in Example 1 was used except that the antistatic layer was used.
o. A-41, b- on the PET support, respectively.
41 and a-42 are applied to form A-41 and B-, respectively.
41 and A-42. Formulation No. in which the mixing ratio of the mixture of the conductive particles and the water-dispersible polymer as shown in Table 6 was changed. −
B- of 1-1, -1--2 and -1--3
42, or a mixture of conductive particles (formulation No.-1) and the following water-soluble polymer (A) to water-dispersible polymer (formulation N).
o. B-42 of-) was coated on B-41 in the same manner as in Example 1 so that the conductive particles would be 600 mg / m < ² >, to give B-42.

[0146] (B-42 combined use of conductive particles and water-dispersible polymer)   Conductive particles (in solid content) 90g   Water-dispersible polymer (solid content) (-1--1) 135 g                             (In the case of -1--2) (90g)                             (In the case of -1--3) (198g)   Average particle size 3μm Silica particles 0.1g   (C-1) 0.1 g   (C-4) 12g   Make up to 1.5 l with water.

[0147] (Comparative Example b-42 formulation, −)   Water-soluble polymer (A) 60g   Water-dispersible polymer (solid content) 60 g   Average particle size 3μm Silica particles 0.07g   (C-1) 0.07 g   (C-4) 8g   Make up to 1 liter with water.

In place of the conductive particles of the antistatic layer processing liquid b-2 of Example 1, the conductive particles of the present invention and gelatin or / and a water-dispersible polymer were mixed as shown in Table 6 to prepare Example 1 An antistatic layer was applied in the same manner as above to give B-42. Further, the same back layer and emulsion layer as in Example 1 were coated to prepare a sample. The evaluation items and the test method were exactly the same as in Example 1, and the results are shown in Table 6.

[0149]

[Table 6]

[Results] As shown in Table 6, the conductive particles of the present invention were mixed with a water-soluble binder such as gelatin and a water-dispersible polymer such as latex in an amount of 50% or less.
Alternatively, both the water-soluble binder and the water-dispersible polymer are used together.
It has been found that the present invention, which is used by mixing it in an amount of not more than%, has the most excellent antistatic property and film forming property.

Example 6 b-2 and B-2 of Example 1 were made to have the same formulation as a-2 and A-2, and the subbing solution No. 1 of Example 1 was used. , A-51, b-51, a-52, and b-52, respectively, and coated on a PET support to form A-51, B-5, respectively.
1, A-52 and B-52. Instead of the back layer protective layer (formulation 4) of Example 1, the following formulations 41 and 42 were simultaneously multilayer-coated with the back layer in the same manner as in Example 1 such that gelatin was 400 mg / m ² , and silver halide printing was performed. A photographic light-sensitive material for use was obtained. A film strength test (wet scratch test) during development was newly added, and other evaluation items and test methods were performed in exactly the same manner as in Example 1, and the results are shown in Table 7.

<< Formulation 41, Composition of Conductive Back Layer Protective Layer >> Conductive particles-2 (solid content) 600 mg / m ² gelatin 400 mg / m ² water-dispersible polymer (solid content) 600 mg / m ² matting agent: Monodisperse polymethylmethacrylate having an average particle size of 5 μm 50 mg / m ² Sodium di (2-ethylhexyl) sulfosuccinate 10 mg / m ² (C-11) surfactant 1 mg / m ² (C-13) dye 20 mg / m ² H -(OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² (C-10) Hardener 15 mg / m ² Polysiloxane 0.7 g / m ² (C-4) Crosslinker 12 mg / m ² << Formulation 42, Conductivity Composition of protective backing layer >> Conductive particles-2 (solid content) 600 mg / m ² Gelatin 400 mg / m ² Matting agent: Monodisperse polymethylmethacrylate having average particle diameter of 5 μm 50 mg / m ² Sodium di (2-ethylhexyl) sulfosuccinate 10 mg / m ² (C-11) surfactant 1 mg / m ² (C-13) dye 20 mg / m ² H- (OCH ₂ CH ₂ ) ₆₈ -OH 50 mg / m ² (C-10) Hardener 15 mg / m ² Polysiloxane 0.7 g / m ² (C-4) Crosslinker 12 mg / m ² [Evaluation method] <Film strength test><< Wet scratch test >> 7 at room temperature The sample that had been left for a day was immersed in the developer at 30 ° C for 5 minutes, and then the product was manufactured by Shinto Scientific Co., Ltd.
Using a continuous load type scratch tester HEIDON-18 manufactured by K.K. The minimum load at which scratches were generated on the film surface of the sample was determined. This is represented as a wet scratch load (g). The results are shown in Table 7.

[0153]

[Table 7]

[Results] Even when the conductive particles of the present invention were used in the back layer protective layer, the antistatic property and the film forming property exhibited the same excellent effects as in the above-mentioned Examples. The protective layer in which the conductive particles and the water-dispersible polymer were used in combination had higher wet scratch strength than those in which the conductive particles and the water-dispersible polymer were not used in combination.

[0155]

By the permanent antistatic technique of the present invention, it is possible to eliminate the electrostatic damage of the silver halide photographic light-sensitive material before and after the development processing.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-258749 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/89 G03C 1/85

Claims (16)

(57) [Claims] 1. At least one antistatic layer containing conductive particles having the following water-soluble polymer (A) positioned on the outer periphery of polymer particles, wherein the weight of the water-soluble polymer (A) is A silver halide photographic light-sensitive material characterized in that it is 35 to 500% by weight of the polymer particles. 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. 8. A water-soluble polymer having at least one antistatic layer containing conductive particles having a water-soluble polymer (A) positioned below and a water-dispersible polymer on the outer periphery of the polymer particle. The weight of (A) is 35 to 500 with respect to the weight of the polymer particles.
%, And the weight of the water-dispersible polymer is 200% or less with respect to the weight of the conductive particles. The water-soluble polymer (A) is a water-soluble polymer having a sulfonic acid group and a carboxyl group. 9. The silver halide photographic light-sensitive material according to claim 8, wherein the sulfonic acid group of the water-soluble polymer (A) is a conductive particle derived from a styrenesulfonic acid monomer. material. 10. The silver halide photographic light-sensitive material according to claim 8, wherein the monomer composition of the polymer particles contains an epoxy group-containing monomer. 11. The silver halide photographic light-sensitive material according to claim 8, wherein the water-soluble polymer (A) is a copolymer of styrene sulfonic acid and maleic acid. . 12. The molar ratio of styrenesulfonic acid and maleic acid is styrenesulfonic acid / maleic acid = 50/50.
12. The silver halide photographic light-sensitive material according to claim 11, which is in the range of ˜95 / 5. 13. The halogenation according to any one of claims 8 to 12, 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. 14. The silver halide according to any one of claims 8 to 12, wherein the weight of the water-soluble polymer (A) is 200 to 300% with respect to the weight of the polymer particles. Photographic material. 15. The silver halide photograph according to claim 8, wherein the weight of the water-dispersible polymer is 150% or less with respect to the weight of the conductive particles. Photosensitive material. 16. The silver halide according to claim 8, wherein the weight of the water-dispersible polymer is 70 to 140% with respect to the weight of the conductive particles. Photographic material.