JPH11212213A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material greatly improved in dryness and in cracking occurring at the time of storage in an environment of low humidity and superior in antistatic effect and rapid processing aptitude. SOLUTION: This photographic sensitive material is provided with at least 2 undercoat layers on the same surface of a support and further at least one hydraulic colloidal layer on these layers. In the case, one of the undercoat layers is conductive undercoat layer, the other undercoat layer contains a polymer compd. having a glass transition point Tg of 10 deg.-120 deg.C and also, the hydrophilic colloidal layers contain gelatin in an amount of 0.1-2.0 g/m<2> and further, contain fine inorganic particles and/or composite particles composed of the fine inorganic particles and a hydrophobic polymer in an amount of 0.1-2.0 g/m<2> .

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide light-sensitive material, and more particularly to a silver halide light-sensitive material useful as a printing material for printing plate making.

[0002]

2. Description of the Related Art In recent years, with the increase in the amount of information, in the field of printing and plate making, orders for various kinds and small quantities of printed materials have increased, and shortening of delivery time has been demanded. Also, in the medical field, there is a demand for a reduction in medical treatment time, and it is desired that an X-ray or the like can be used to obtain a test result in a short time.

In order to shorten the delivery time in the field of printing and plate making, and to obtain inspection results by X-rays and the like in a short time in the medical field, a silver halide photographic light-sensitive material to be used is rapidly developed (generally used). , Development, fixing, washing or stabilization, and drying).) It is strongly desired to increase the development processing amount within the same time.

In order to shorten the development processing time, the transport speed of the automatic developing machine must be increased. However, if the transport speed of the automatic developing machine is increased in order to shorten the developing processing time, poor drying of the film occurs. Problems arise.

[0005] In order to improve the drying property, the binder amount of the silver halide photographic material has been reduced. As a method of reducing the amount of the binder of the silver halide photosensitive material, for example, by including rigid inorganic fine particles such as colloidal silica in the hydrophilic binder, to increase the stress generated in the layer, the hydrophilic binder for that A method for reducing the weight is disclosed in Japanese Patent Publication No. 6-85059.

Although this method is an excellent method, stress generated in the hydrophilic binder caused by a change in environmental humidity is concentrated on the interface between the inorganic fine particles and the hydrophilic binder, and cracks are easily generated during storage in a low humidity environment. Therefore, there was naturally a limit to the reduction in the amount of the hydrophilic binder. Also, if the photosensitive material is stored for a long time in a rolled state,
There has been a problem that the internal stress generated by the roll winding is naturally relaxed and curls are generated, so-called curling curls are promoted.

On the other hand, if the conveying speed of the automatic developing machine is increased in order to shorten the development processing time, the contact, friction or contact / separation between the rolls of the automatic developing machine and the silver halide photosensitive material causes Are easily charged, and the charged electrostatic charges are discharged, so that a spot-like or resin-like or feather-like image pattern called a static mark appears on the developed silver halide photographic material, which is fatal. Cause damage.

A silver halide photosensitive material cannot be inspected nondestructively and is a product whose normal quality can only be ascertained after development processing. It must not be done.

[0009] For example, in medical or industrial X-ray photographic films, failures due to static electricity cause erroneous signals and hinder diagnosis. Even in the case of photographic films other than medical or industrial X-ray photographic films, the occurrence of such static marks should not reduce the commercial value.

When the photographic film is charged after the development processing, dust adheres to the surface of the photographic film, and unnecessary points appear on the baked print, which also loses commercial value. Further, in a printing company or the like, when an operator touches a charged film while handling the film, an electrostatic shock is generated, which also poses a threat to the operator.

Regarding the prevention of electrification of a photographic film, for example, JP-A-55-84658 and JP-A-61-1745.
No. 42, (1) a water-soluble conductive polymer having a carboxyl group (for example, a water-soluble conductive copolymer from styrenesulfonic acid sodium salt and a monomer having a functionally bonded carboxyl group), 2) providing an antistatic layer comprising a reaction product of a hydrophobic polymer containing a carboxyl group and (3) a polyfunctional aziridine, or after applying the mixture of the above (1) and (2), ) Is provided thereon to provide an antistatic layer coated thereon, which is disclosed in JP-A-3-256039 and JP-A-3-1922.
No. 52 and No. 3-206444 disclose providing an antistatic layer composed of a water-soluble conductive polymer, a hydrophobic polymer and an epoxy compound. Also,
JP-A-4-124646, JP-A-4-124647, JP-A-4-124649 and JP-A-4-124465.
No. 2 discloses providing an antistatic layer made of a water-soluble conductive polymer having a self-crosslinkable group such as an N-methylol group.

[0012] Although the combination of these techniques can considerably improve the problems of static electricity and drying due to the rapid processing, it is necessary to further reduce the amount of the hydrophilic binder in order to proceed further. Becomes indispensable.

Therefore, even if the amount of the hydrophilic binder is reduced, there is no crack generated during storage in a low-humidity environment, no curl is generated, and excellent in rapid processing suitability which does not cause defective automatic conveyance. The development of silver halide photosensitive materials has been strongly desired.

[0014]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to significantly improve the drying property, improve the cracks generated during storage in a low-humidity environment, have an excellent antistatic performance, and have a rapid processing suitability. It is another object of the present invention to provide a silver halide photographic light-sensitive material which is excellent in the above.

[0015]

The above object of the present invention is attained by the following constitution. (1) In a silver halide photographic material having at least two undercoat layers on the same surface of a support and further having at least one hydrophilic colloid layer thereon, one of the undercoat layers is provided. The layer is a conductive undercoat layer, and another layer of the undercoat layer is a sublayer containing a polymer compound having a Tg of 10 ° C. or more and 120 ° C. or less, and a hydrophilic colloid. 1. The amount of gelatin in the layer is 0.1 g / m ² or more;
0 g / m ² or less, and inorganic fine particles and / or composite particles comprising inorganic fine particles and a hydrophobic polymer compound are contained in the hydrophilic colloid layer in an amount of 0.1 g / m ² or more and 2.0 g / m ² or less. A silver halide photographic light-sensitive material, characterized in that: (2) The silver halide photograph as described in (1) above, wherein the polymer compound of the undercoat layer containing the polymer compound is a polymer compound having a Tg of 30 ° C. or more and 100 ° C. or less. Photosensitive material. (3) The undercoating layer having conductivity contains polymer particles in which a water-soluble polymer having a sulfonic acid group and a carboxylic acid group is arranged on the outer periphery of the polymer particles. The silver halide photographic material according to 1) or 2). (4) The silver halide photographic material as described in any of (1) to (3) above, wherein the conductive undercoat layer contains a conductive metal oxide. (5) The silver halide photographic material as described in any of (1) to (4) above, wherein the inorganic fine particles are colloidal silica. (6) The method according to (1), wherein the hydrophobic polymer compound of the composite particles composed of the inorganic fine particles and the hydrophobic polymer compound is a hydrophobic polymer compound having a repeating unit represented by the general formula (1). The silver halide photographic light-sensitive material according to any one of 1) to (5).

[0016]

Embedded image [In the formula, R ₁ represents a substituent. Hereinafter, the present invention will be described in detail.

As the support of the silver halide photographic light-sensitive material of the present invention, for example, a cellulose nitrate film, a cellulose triacetate (hereinafter abbreviated as TAC) film, a cellulose acetate butyrate film, a cellulose acetate propionate film,
Polyethylene terephthalate (hereinafter abbreviated as PET)
A film, a polyethylene naphthalate (hereinafter abbreviated as PEN) film, a modified polyester film described in JP-A-6-51437, a polycarbonate (hereinafter abbreviated as PC) film, a laminate thereof,
A support such as a paper support coated or laminated with an α-olefin polymer (eg, polyethylene, polypropylene, copoly-ethylene-butene), a syndiotactic polystyrene (hereinafter abbreviated as SPS) film, or the like can be used. Among them, TAC film, PET film, PEN film, polyethylene coated paper support and the like are currently in practical use, and are commercially available and easily available.
In the case where a PET film forming equipment is provided, by using this equipment, the above-mentioned other films can be formed in the same manner as the PET film by an ordinary method. The support for a silver halide photographic light-sensitive material can be widely used without being limited thereto.

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

The thickness of the support for a silver halide photographic light-sensitive material varies depending on the material and the purpose of use.
２００200 μm.

The support of the present invention has at least two undercoat layers on the same surface, and further has at least one hydrophilic colloid layer provided thereon.

At least one of the at least two undercoat layers is a conductive undercoat layer, and at least one other undercoat layer has a Tg of not less than 10 ° C.
This is an undercoat layer containing a polymer compound having a temperature of not more than ° C.

The high molecular compound used for the undercoat layer is one kind of polymer or copolymer, or 2
It is constituted by mixing two or more kinds of polymers and / or copolymers.

The Tg of the polymer is determined by Brand Wrap et al., "Polymer Handbook", pages III-139 to III-1.
It is described on page 79 (1966, Wiley and Sun), and the Tg (コ ポ リ マ ー K) of the copolymer can be calculated by the following equation.

Tg (copolymer) = v ₁ Tg ₁ + v ₂ Tg ₂
+ ... + v _w Tg _w However, in the above _{formula, v 1, v 2 ... v} w represents the weight fraction of monomer in the _{copolymer, Tg 1, Tg 2 ... Tg} w homopolymer of each monomer in the copolymer Tg (゜ K).

Tg calculated according to the above equation is ± 5 ° C.
There is accuracy.

When the polymer compound is a mixture of two or more polymers, the Tg (゜ K) of the mixed polymer can be calculated by the following equation.

Tg (polymer compound) = v ₁ Tg ₁ + v ₂ T
_{g 2 + ... + v w Tg} w However, in the above _{formula, v 1, v 2 ... v} w represents the weight fraction of the polymer or copolymer in the polymer compound, Tg _1, Tg ₂ ...
Tg _w represents Tg (゜ K) of each polymer or copolymer in the polymer compound.

The Tg of the polymer compound used in the undercoat layer is from 10 ° C. to 120 ° C., preferably from 30 ° C. to 100 ° C., and more preferably
40 ° C. or higher and 80 ° C. or lower.

The conductive undercoat layer (hereinafter referred to as a conductive layer) has an antistatic property.

In the present invention, the volume resistivity of the conductive layer is 10 ² Ω · cm in view of the effect of the present invention.
As described above, it is preferable that the resistance is less than 10 ¹⁰ Ω · cm.

The volume resistivity can be measured by using an ordinary method for measuring the resistance of a plastic film. For example, it can be determined by measuring the surface resistivity using a commercially available tetraohmmeter model VE-30 (manufactured by Kawaguchi Electric Co., Ltd.) or the like.

The conductive layer of the present invention preferably comprises an antistatic agent and a polymer binder.

As the antistatic agent, those containing conductive metal oxide particles or conductive particles are preferable.

The conductive metal oxide particles are preferably fine particles having a crystallite size of 1 nm or more and 45 nm or less. When the crystallite size is smaller than 1 nm, sufficient conductivity cannot be obtained. When the crystallite size is larger than 45 nm, transparency is impaired, which is optically undesirable. Crystallite size is 1 nm or more and 20 nm or less, further 1 nm or more, 5 n
When fine particles having a particle size of m or less are used, excellent conductivity is obtained, and the optical characteristics are also improved.

Further, it was found that the use of the fine particles having the above crystallite size did not cause the layer containing the fine particles to crack or become brittle.

In the present invention, the crystallite size (t) is
It is calculated based on Scherrer's formula often used in powder X-ray diffraction.

T = (0.9 × λ) / (BXcos θ _B ) B: Half-width (measured in radians) of a diffraction curve based on reflection of a certain surface of a crystal measured by a powder X-ray diffraction method. X-ray wavelength θ _B : Bragg angle (Agnecarity Co., Ltd.
reference)

Metal oxide in conductive metal oxide particles
Is, for example, Nb_TwoO_{5 + X}Oxygen-excessive oxidation such as
Thing, RhO_2-X, Ir_TwoO_3-XSuch as oxygen-deficient oxides
Or Ni (OH)_XNon-stoichiometric hydroxides such as Hf
O_Two, ThO_Two, ZrO_Two, CeO_Two, ZnO, TiO_Two,
SnO_Two, Al_TwoO_Three, In_TwoO_Three, SiO_Two, MgO, Ba
O, MoO_Two, V_TwoO_FiveOr these composite oxides are preferred.
More preferably, ZnO, TiO_TwoAnd SnO_TwoIs preferred
ぃ. Also, metal oxides containing different types of atoms are preferred.
For example, Al, In, etc. are added to ZnO,
TiO_TwoNb, Ta, etc. are added to_Two
Is to add Sb, Nb, halogen element, etc.
It is effective. The addition amount of these hetero atoms is 0.01 m
ol% to 25 mol% is preferable, but 0.1 mol
A range of 1% to 15 mol% is particularly preferred.

The amount of the conductive metal oxide to be used is preferably 0.00005 to 1 g per m ^{2 of} the photographic material.

The volume resistivity of these conductive metal oxide particles is 10 ¹⁰ Ω or less, preferably 10 ⁷ Ω or less.
In particular, it is preferably at most 10 ⁵ Ω.

The volume resistivity referred to here is that of a large single crystal.
In the case of the resulting oxide, the value of the volume resistivity of the single crystal
If a large single crystal cannot be obtained, form a powder.
It means the volume resistivity of the sintered body obtained by shaping. this
If these values are unknown, apply a constant pressure in the powder state.
The volume resistivity of the compact obtained by^TwoDivided by
adopt. The constant pressure is not particularly limited,
10kg / cm^TwoThe above pressure is good, preferably 10
0kg / cm^TwoThe volume of material molded under the above pressure
10 specific resistance^TwoUse the value divided by. Generally to powder
On the applied pressure and the volume resistivity of the compact
Tends to decrease in volume resistivity as pressure increases
is there. However, 3t / cm^Two Isotropic pressure
Even when multiplied by
No lower value is obtained, but a value that is about 100 times higher. So
Therefore, a molded product obtained by applying a certain pressure in the powder state
Volume resistivity of 10^TwoUse the value divided by.

Next, the conductive particles will be described.

In the present invention, the conductive particles have a structure in which a water-soluble polymer having a sulfonic acid group and a carboxyl group is arranged on the outer periphery of the polymer particle main body. It is used in the form of a dispersion or emulsion dispersed in an aqueous solvent.

First, the water-soluble polymer having a sulfonic acid group and a carboxyl group disposed on the outer periphery of the polymer particle body will be described.

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

Examples of the monomer having a sulfonic acid group include vinyl sulfonic acid and 2-acrylamide-
Examples include 2-methylpropane sulfonic acid, 2-acrylamidoethyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene disulfonic acid, and the like, and salts thereof. Because of the excellent conductivity in these,
It is preferred to use styrene sulfonic acid and its salts.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid,
Monocarboxylic acids or dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid or dicarboxylic anhydrides may be mentioned. Among these, it is preferable to use a dicarboxylic acid, particularly preferably maleic acid, because the adhesion between the formed antistatic layer and the adjacent layer is much better.

As the water-soluble polymer, a monomer having a copolymerizable vinyl group may be used together with a monomer having a sulfonic acid group and a carboxyl group.

The polymerization method of the monomer is not particularly limited, and a conventionally known method can be applied. Specifically, for example, the monomer having a sulfonic acid group and the monomer having a carboxyl group, and further, if necessary, other monomers are dissolved and dispersed in water, and a polymerization initiator ( Polymerization can be carried out by adding, for example, potassium persulfate) and heating the mixture.

The water-soluble polymer of the present invention produces a copolymer by polymerizing a monomer having a carboxyl group and a monomer having no sulfonic acid group, and this copolymer is sulfonated. It can also be obtained by processing.

The monomer having no sulfonic acid group is not particularly restricted but includes, for example, styrene and α-methylstyrene.

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, 1,2-
Chlorohydrocarbons such as dichloroethane, hydrocarbons such as n-hexane and cyclohexane, dioxane and the like are mentioned as good solvents. Among these, dichloroethane, which hardly reacts with the sulfonating agent and does not form a salt upon neutralization, and the like are mentioned as suitable solvents. 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.

The water-soluble polymer is preferable because it can be easily copolymerized in advance using the above-mentioned styrene sulfonic acid and is economical.

In the water-soluble polymer, the ratio of the sulfonic acid group to the carboxyl group is preferably in the range of sulfonic acid group / carboxyl group = 10/90 to 95/5 by mole ratio of the functional group, and more preferably, Acid group / carboxyl group = 20 / 80-80 / 20, particularly preferably sulfonic acid group / carboxyl group = 30 / 70-
It is in the range of 60/40.

When the sulfonic acid group-containing monomer is styrene sulfonic acid and the carboxyl group-containing monomer is maleic acid, the ratio is preferably 40/60 to 95/5, and 50/50 to 95/50. 5 is particularly preferred in terms of ease of production.

The water-soluble polymer has a weight average molecular weight of 1
The range of 000 to 500,000 is preferable.
A range of 000 is preferred.

Next, polymer particles having a water-soluble polymer having a sulfonic acid group and a carboxyl group arranged on the outer periphery will be described.

The polymer particles can be produced by emulsion polymerization or suspension polymerization of a hydrophobic vinyl monomer in an aqueous solution of a water-soluble polymer.

Suitable vinyl monomers for obtaining these polymer particles include, for example, aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene and methoxystyrene; methyl acrylate, ethyl acrylate, Propyl acrylate (n, i), butyl acrylate (n, i)
s, t), 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate (n, i), butyl methacrylate (n, s, t), benzyl acrylate, benzyl methacrylate, hydroxy methacrylate, cyclohexyl Acrylic acid or methacrylic acid esters such as acrylates; Acrylic nitriles such as acrylonitrile; Monocarboxylic or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, or dicarboxylic anhydride Vinyl halides such as vinyl chloride and vinylidene chloride; vinyl esters such as vinyl acetate and vinyl benzoate; and conjugated dienes such as butadiene and isoprene, but are not limited thereto.

In obtaining the polymer particles, other vinyl monomers, for example, a polyfunctional vinyl monomer can be used. As these polyfunctional vinyl monomers, for example, divinylbenzene, trivinylbenzene, diallyl phthalate, allyl acrylate, allyl methacrylate,
Examples include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, trimethylolpropane triacrylate, and the like.

Further, in obtaining the above polymer particles, it is preferable to use a vinyl monomer having a reactive group. Examples of these reactive vinyl monomers include epoxy group-containing vinyl monomers such as glycidyl acrylate and glycidyl methacrylate, and N-methylol acrylamide and the like.
-Methylol group-containing vinyl monomers, oxazole group-containing vinyl monomers such as vinyloxazoline and 2-propenyl-2-oxaborine, and the like, 2-acrylic acid-4,6-dichloro-1,3,5-triazineamide, Examples thereof include, but are not limited to, triazine-based reactive vinyl monomers such as 2-acrylic acid-4,6-dichloro-1,3,5-triazine ester.

The conductive particles of the present invention have a configuration in which a water-soluble polymer having a sulfonic acid group and a carboxyl group is arranged on the outer periphery of the polymer particle main body. The configuration in which the water-soluble polymer having an acid group and a carboxyl group is arranged means that the state is such that it cannot be easily separated, unlike simple mixing. The water-soluble polymer having a polymer particle body and a sulfonic acid group and a carboxyl group may be partially bound to, embedded in, or embedded in the polymer particle body during the synthesis of the water-soluble polymer. It is guessed that it is in a state.

The present inventors have imagined such an embodiment of the conductive particles of the present invention, but have found that the conductive particles of the present invention are different from the mixed state by the following experiment. (1) In order to separate the water-soluble polymer outside the polymer particles from the conductive particles in the form of an emulsion, the water-soluble polymer was extracted with hot water at a temperature at which the polymer particles did not fuse. Alternatively, only a small amount was separated and extracted, and the amount of extraction did not increase no matter how long it took. (2) Even when the conductive particle emulsion was centrifuged, little or no separation of the water-soluble polymer was observed. (3) A mixture of a polymer latex polymerized using a surfactant and a water-soluble polymer was subjected to extraction and centrifugation as described in (1) and (2) above. The particles and the water-soluble polymer were separated intact.

The conductive particles can be produced, for example, by forming the polymer particles by emulsion polymerization or suspension polymerization in an aqueous solution of a water-soluble polymer.

When used in a polymer particle using a reactive vinyl monomer such as glycidyl acrylate, the carboxyl group of the water-soluble polymer may bond to the epoxy group of the polymer particle. In addition, since the bonding state may be developed even after the working liquid of the conductive particles is applied as a film, the use of the reactive vinyl monomer may reduce the adhesiveness and the permanent antistatic effect. Higher and preferred.

The particle size of the conductive particles of the present invention is usually 0.1.
01-2.0 μm, preferably 0.04-0.1 μm
It is. However, in some cases, the particle size may not be clear, but even in this case, it is sufficient to achieve the object of the present invention.

For the undercoating layer having conductivity, a polymer binder can be used.

As these polymer binders, for example,
Gelatin, colloidal albumin, proteins such as casein, carboxymethylcellulose, hydroxyethylcellulose, diacetylcellulose, triacetylcellulose and other cellulose compounds; agar, sodium alginate,
Sugar derivatives such as starch derivatives; synthetic hydrophilic colloids, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives or copolymers of these; natural products such as rosin, silicone, and the like; Derivatives thereof; many other synthetic resins are used. Further, styrene-butadiene copolymer, polyacrylic acid, polyacrylate and derivatives thereof,
Water-dispersible polymers such as polyvinyl acetate, vinyl acetate-acrylate copolymer, polyolefin, and olefin-vinyl acetate copolymer can also be used.

The water-dispersible polymer or the like suitable for the above-mentioned polymer binder is a latex or a particulate polymer compound dispersed in an aqueous solvent. Examples of the polymer compound include C ₁ -C ₁₈ Acrylic or methacrylic acid esters having a linear or branched alkyl group, phenyl group, benzyl group, phenethyl group, cyclohexyl group, glycidyl group, etc .; acrylonitrile; diene monomers such as butadiene, isoprene; C ₁ -C ₁₈ linear or branched alkyl group-substituted N- or N, N-acrylamide; chlorine-based monomers such as vinylidene chloride and vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; Acid-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, and maleic anhydride; styrene, α-methyl Styrene homopolymers or copolymers, such as styrene monomer, such as methoxystyrene, polyester resins, acrylic-modified polyester resin or the like. Preferred polymer compounds include styrene-butadiene copolymer, n-butyl acrylate-n-butyl methacrylate-acrylamide-
Styrene quaternary copolymer, styrene-n-butyl acrylate-acrylic acid terpolymer, vinylidene chloride-methyl acrylate-itaconic acid terpolymer, and the like, but are not limited thereto. Absent.

The water-dispersible polymer can be obtained by a usual latex polymerization method using monomers constituting the polymer. As for a surfactant, a polymerization initiator and the like as an emulsifier, those used in a conventional method may be used.

In the conductive undercoat layer of the present invention,
It is preferable to mix a hardener.

Examples of such hardeners include aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. Nos. 2,732,303 and 3,288,775, and British Patent No. 974,72
Compounds having a reactive halogen, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethyl) urea, 2-hydroxy-, and the like described in JP-A Nos. 3,167,207 and 1,167,207. 4,6-dichloro-1,3,5-triazine, divinyl sulfone,
5-acetyl-1,3-diacryloylhexahydro-
1,3,5-triazine, U.S. Pat. No. 3,232,76
No. 3,3,635,718, British Patent No. 994,809, etc., compounds having a reactive olefin, U.S. Pat. Nos. 3,539,644, 3,642,486, JP-B-49-
Nos. 13568, 53-47271 and 56
-48860, JP-A-53-57257,
JP-A-61-128240, JP-A-62-4275, JP-A-63-53541, and JP-A-63-264572.
No. 2,732,316, a vinyl sulfone compound described in Japanese Patent Application Publication No.
No. 2,586,168 and the like, an N-methylol compound described in U.S. Pat. No. 3,103,437.
Compounds described in U.S. Pat. Nos. 2,983,611 and 3,107,280.
Aziridine compound described in US Pat.
Acid derivatives described in, for example, US Pat. Nos. 725,294 and 2,725,295, US Pat. No. 3,100,7
No. 04, etc., carbodiimide compounds described in U.S. Pat. No. 3,091,537, etc., epoxy compounds described in U.S. Pat. No. 3,091,537, U.S. Pat. Nos. 3,321,313 and 3,543,292. Compounds, halogenocarboxaldehydes such as mucochloric acid, organic hardeners such as dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and chrome pan, zirconium sulfate, and chromium trichloride. And inorganic hardeners. Further, as a hardener having a relatively fast hardening action on gelatin, for example, Japanese Patent Application Laid-Open No.
Compounds having a dihydroquinoline skeleton described in JP-A-38540, JP-A-51-59625, JP-A-62-2.
Nos. 62854, 62-26444, 6
N-carbamoylpyridinium salts described in JP-A-3-1847471, acylimidazoles described in JP-B-55-38655, N-acyloxyimidazoles described in JP-B-53-22089, JP-B-53
A compound having two or more N-acyloxyimino groups in a molecule described in JP-A-22089;
No. 70, an N-sulfonyloxyimide group-containing compound, JP-A-58-113929, a compound having a phosphorus-halogen bond, and JP-A-60-22.
Nos. 5148 and 61-240236 and 63
And chloroformamidinium compounds described in JP-A-41580.

The amount of these hardeners to be added is as follows:
It is preferably 0.001 to 40 g per liter.

Next, the inorganic particles used in the hydrophilic colloid layer and / or the composite particles comprising the inorganic particles and the hydrophobic polymer in the present invention will be described.

Materials constituting the inorganic fine particles used in the present invention include inorganic oxides, nitrides, sulfides and the like, and are preferably inorganic oxides. Specifically, S
i, Na, K, Ca, Ba, Al, Zn, Fe, Cu,
Sn, In, W, Y, Sb, Mn, Ga, V, Nb, T
u, Ag, Bi, B, Mo, Ce, Cd, Mg, Be,
A single or complex oxide such as Pb is preferred. When used in a silver halide emulsion, Sb is preferred from the viewpoint of miscibility with the emulsion.
i, Y, Sn, Ti, Al, V, Sb, In, Mn, C
Single or complex oxides of e and B are preferred.

The inorganic fine particles may be crystalline or amorphous, but are preferably amorphous.

The average particle size of the inorganic fine particles used in the present invention is about 0.5 to 3000 nm, preferably 3 to 500 nm.
nm. The inorganic fine particles are preferably used by dispersing in water and / or a solvent soluble in water.

The amount of the inorganic fine particles added to the hydrophilic colloid layer is about 1 to 2000% by weight, preferably 30 to 1000% by weight, based on the hydrophilic colloid layer.

The following are examples of oxides preferred for use in the present invention. _{SO-1 SiO 2 SO-2} TiO 2 SO-3 ZnO SO-4 SnO 2 SO-5 MnO 2 SO-6 Fe 2 O 3 SO-7 ZnSiO 4 SO-8 Al 2 O 3 SO-9 BeSiO 4 SO- 10 Al ₂ SiO ₅ SO-11 ZrSiO ₄ SO-12 CaWO ₄ SO-13 CaSiO ₃ SO-14 InO ₂ SO-15 SnSbO ₂ SO-16 Sb ₂ O ₅ SO-17 Nb ₂ O ₅ SO-18 Y ₂ O ₃ SO-19 CeO ₂ SO-20 Sb ₂ O ₃

Of these, particularly preferred is S
i, and further, colloidal silica.

The composite particles composed of inorganic fine particles and a hydrophobic polymer compound used in the present invention may be in any form as long as they are composed of inorganic fine particles and a hydrophobic polymer compound.

The composite particles comprising the inorganic fine particles and the hydrophobic polymer can be obtained, for example, by polymerizing a monomer in the presence of the inorganic fine particles to form a hydrophobic polymer.

The hydrophobic polymer composing the composite particles of the present invention preferably has a repeating unit represented by the general formula (1), particularly preferably vinyl pivalate, vinyl acetate, vinyl caproate, It is a polymer of vinyl octylate.

[0085]

Embedded image [In the formula, R ₁ represents a substituent. The polymer may be one obtained by polymerizing a monomer that forms the repeating unit represented by the general formula (1) alone, or one obtained by copolymerizing a plurality of these monomers. It may be copolymerized with another copolymerizable monomer. In the case of copolymerization, 45% by weight of the monomer represented by the general formula (1) is used.
When the above is used, cracking can be effectively prevented.

Examples of the polymerization method include an emulsion polymerization method, a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and a radiation polymerization method.

(Solution Polymerization) In a solvent, an appropriate concentration of a monomer composition (generally 40% by weight or less, preferably about 10 to 25% by weight, based on the solvent) is added in the presence of an initiator. At a temperature of about 10-200C, preferably 30-120C,
Polymerize for about 0.5 to 48 hours, preferably 2 to 20 hours.

Any initiator can be used as long as it is soluble in the polymerization solvent.
S), benzoyl peroxide, azobisisobutyronitrile (AIBN), organic solvent-based initiators such as di-tert-butyl peroxide, potassium peroxide, 2,2'-azobis- (2-amidinopropane) -hydro Examples thereof include water-soluble initiators such as chlorides, and redox-based polymerization initiators obtained by combining these with reducing agents such as Fe ²⁺ salts and sodium bisulfite.

As the solvent, any solvent can be used as long as it can dissolve the monomer composition. For example, water, methanol, ethanol, dimethylsulfoxide, dimethylformamide, dioxane, or a mixture of two or more of these can be used. Solvents and the like can be mentioned. After completion of the polymerization, the reaction mixture is poured into a solvent in which the produced polymer compound is not dissolved, the product is precipitated, and then the unreacted composition is separated and removed by drying.

(Emulsion polymerization) Water is used as a dispersion medium, and 1 to 50% by weight of a monomer based on water and 0.05 to
Using 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a dispersant, a temperature of about 30 to 100 ° C., preferably 60 to 90 ° C.
It is obtained by polymerizing under stirring for ８8 hours.

Examples of the initiator include water-soluble peroxides (potassium persulfate, ammonium persulfate, etc.), water-soluble azo compounds (2,2'-azobis- (2-amidinopropane) -hydrochloride, etc.), Redox-based polymerization initiators in which a reducing agent such as a ²⁺ salt or sodium bisulfite is combined can be used.

Examples of the dispersant include an anionic surfactant,
Any of a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, but an anionic surfactant and a nonionic surfactant are preferable.

Hereinafter, specific examples of the composite particles comprising the inorganic particles of the present invention and a hydrophobic polymer compound will be described.

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[Table 1]

The average particle diameter of the composite particles composed of the inorganic fine particles and the hydrophobic polymer is 0.005 to 3.0 as a weight average particle diameter.
It is preferably 0 μm, and more preferably 0.01 to 0.8 μm.

The silver halide photographic light-sensitive material of the present invention includes black-and-white silver halide photographic light-sensitive materials such as black-and-white films for photography, printing light-sensitive materials, X-ray films, negative color roll films, negative color cut films, and positive color roll films. And any silver halide photographic light-sensitive material such as a color silver halide photographic light-sensitive material such as a positive color cut film.

Hereinafter, the silver halide photographic light-sensitive material of the present invention will be described mainly with respect to a light-sensitive material for printing, but the silver halide photographic light-sensitive material of the present invention is not limited by these descriptions.

The silver halide of the silver halide photographic light-sensitive material of the present invention includes common silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide and silver chloroiodobromide. The silver halide used can be arbitrarily used.

As the silver halide emulsion, those obtained by any method such as an acid method, a neutral method and an ammonia method can be used. Preferred silver halide in the photosensitive material for printing is silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride,
It is a silver chloroiodobromide containing 60 mol% or more of silver chloride.

The silver halide grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer. The particles may be mainly formed 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 silver halide emulsion used for the light-sensitive material for printing is preferably a monodisperse emulsion. Silver halide contained within a grain size range (coefficient of variation) of ± 20% around the average grain size r is preferred. Monodispersed emulsions that are 60% or more of the total silver halide are preferred, and particularly preferred are 70% of the total silver halide.
A monodisperse emulsion having at least 80% of the total silver halide is more preferable. In addition,
The particle size referred to here is the diameter of a spherical silver halide grain, or, in the case of a grain having a shape other than a spherical shape,
This is the diameter when the projected image is converted into a circular image having the same area.
A photographic image in which the particle diameters are highly uniform can be obtained.

Monodispersed emulsions are described in JP-A-55-48521, JP-A-58-49938 and JP-A-60-1229.
It can be obtained with reference to the method described in the specification such as JP-A-35.

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. For example, JP-A-5-20407
The tabular grains obtained by the method described in JP-A No. 0 can be used.

In producing a silver halide emulsion,
As a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like can be used.

A method of forming silver halide grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. A method of maintaining a constant pAg in a liquid phase in which silver halide is formed, as one type of the double jet method;
A so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

In at least one of the steps of forming or growing silver halide grains, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, rhodium salts,
Alternatively, a complex salt containing these elements is preferably added.

For details of the silver halide emulsion and its preparation method, see Research Disclosure 1764.
3, pages 22 to 23 (December 1978) or in the literature cited.

As the silver halide emulsion, a so-called unripened (Primitive) emulsion which is not subjected to chemical sensitization can be used as it is, but it is usually preferable to perform chemical sensitization.

In the silver halide emulsion, various photographic additives can be used before and after physical ripening or chemical ripening.

In the photosensitive material for printing, a silver halide emulsion layer or a non-photosensitive layer contains a high-contrast agent in order to enhance the halftone dot quality, or a high-contrast process is carried out in the developing process. Examples of excellent contrast agents include hydrazine compounds and tetrazonium compounds. Representative examples of these are described below, but are not limited thereto.

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Examples of various photographic additives to be added before and after physical ripening or chemical ripening are, for example, Research Disclosure (RD) 17643 and 18
716 and 308119 (December 1989) can be used.

The photographic additives described in these three Research Disclosures and their locations are listed in Table 2.

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[Table 2]

The photographic additives that can be used are also described in Product Licensing Magazine (Product Le
icensing) 92 Vol. 107-110 (Dec. 1978
Month) can also be referred to.

The photosensitive material for printing is provided with at least one silver halide emulsion layer and one emulsion protective layer on one side of a support, and a back coat layer having a certain function and a back coat layer having a certain function on the other side. At least one protective layer each
It is provided layer by layer. The number of these silver halide emulsion layers and backcoat layers is not particularly limited.

Gelatin is mainly used as a binder for the emulsion layer, protective layer, intermediate layer, back coat layer and the like constituting the silver halide photographic light-sensitive material. This gelatin includes lime-treated, acid-treated, and enzyme-treated gelatin, and those that have also been subjected to decalcification, inertization, inactivation, and the like can 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, sodium styrenesulfonate polymer or copolymer with other monomers, poly-N-vinylpyrrolidone, maleic anhydride copolymer, polyacrylamide and its derivatives, polyacrylic acid and its derivatives and copolymer Stuff,
Synthetic products such as casein, albumin, carboxymethylcellulose, hydroxyethylcellulose, sodium alginate, and processed natural products are used. Further, the polymer latex described in U.S. Pat. No. 3,411,911 can be contained in the photographic component layer.

A function can be imparted to each layer of the back coat layer. For example, functionalized layers include antihalation layers, antiirradiation layers,
There is a magnetic recording layer and the like. These layers may be adjacent to the undercoat layer or on the surface, or the layers may be present at any position depending on the purpose.

In the silver halide photographic material, it is important to balance the curl between the photosensitive layer side and the back coat layer side. Therefore, the ratio of the binder such as gelatin on the back coat layer side to the hydrophilic polymer such as gelatin on the photosensitive layer side (back layer / photosensitive layer side) is preferably 0.1 or more in terms of weight ratio. 0.32 to 1.50 are particularly preferred. 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 the design of the curl balance of the silver photographic light-sensitive material, the developing speed during the developing process, or the drying speed after the process.

In order to provide the back coat layer with a function of preventing sharpness halation and anti-irradiation of the image of the silver halide photographic light-sensitive material, the corresponding antihalation dye described in the section of the dye of Research Disclosure is used. And anti-irradiation dyes.

In order to impart a function of preventing the photosensitive layer of the silver halide photographic material from sticking to the back coat layer, the matting agent and the slipping agent of the above-mentioned Research Disclosure can be used appropriately. The shape and particle size of the matting agent are not limited, but a spherical matting agent having an average particle size of 10 μm or more and 50 μm or less can also be used. As the slipping agent, the following can be used as typical examples in addition to the above research disclosure. For example, US Pat. No. 3,042,522, British Patent No. 955,061, US Pat. No. 3,080,3
No. 17, No. 4,004,927, No. 4,047,958, No. 3,489,576
No. 1,143,118, JP-A-60-140341, and the like, a silicone-based slip agent, U.S. Pat. Nos. 2,454,043 and 2,732. , No. 305, No. 2,976,148
No. 3,206,311, German Patent No. 1,284,295, No. 1,284,29
No. 4, specification, etc., higher fatty acid type, alcohol type, acid amide type slip agents, metal soaps described in British Patent No. 1,263,722, US Pat. No. 3,933,516, etc. U.S. Pat. Nos. 2,588,765 and 3,121,060; British Patent 1,19.
No. 8,387, etc., such as ester-based and ether-based slip agents, and U.S. Pat. Nos. 3,502,437 and 3,042,222, include taurine-based slip agents. You can also.

The development process is described in the Journal of
The American Chemical Society (JournaI of t
he American Chemical Society) Vol. 73, No. 3, 10
Known developers described on page 0 (1951) can be used. The photographic light-sensitive material for printing can be developed by the processing described in, for example, JP-A-5-123292 and JP-A-53-17719.

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EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 << Preparation of antistatic agent >><Synthesis method of conductive metal oxide A> Stannic chloride hydrate 6
5 g was dissolved in 2000 cc of a water / ethanol mixed solution,
A homogeneous solution was obtained. Then, this was boiled to obtain a coprecipitate. The formed precipitate is taken out by decantation, and the precipitate is washed with distilled water many times. Silver nitrate was dropped into distilled water from which the precipitate was washed, and after confirming that there was no reaction of chloride ions, 1000 cc of distilled water was added, and the total amount was 200 ml.
0 cc. Further, 40 cc of 30% aqueous ammonia was added, and the mixture was heated in a water bath to obtain a colloidal gel dispersion. This colloidal gel dispersion is referred to as “conductive metal oxide A”.

On the other hand, water was removed from this dispersion by a spray drying method, and the powder was taken out. The crystallite size was measured by a powder X-ray diffraction method. When spray drying, 7
No heat above 0 ° C was applied. Crystallite size is 2.3
nm, and the volume resistivity was 2.1 × 10 ⁵ Ω · cm.

<Preparation of Conductive Particles A> —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 inlet tube. Then, 465 parts of styrenesulfonic acid sodium salt (hereinafter, may be abbreviated as StSO ₃ Na) and 87.5 parts of maleic acid (hereinafter, may be abbreviated as MA) are dissolved, and while stirring,
Introduce nitrogen gas, fill the container with nitrogen gas, 70 ℃
Heated. Separately, 40 parts of isopropanol and 250 parts
Dissolve 0.5 part of potassium persulfate in a solution consisting of 1 part of water, put it in a dropping funnel, drop it into the reaction vessel not too late, raise the temperature to 75-80 ° C, and heat for 2 hours to give a viscous colorless A clear solution was obtained. The solution was poured into a large amount of acetone to precipitate the polymer, which was washed several times with acetone.
C. to obtain a white solid of the water-soluble polymer (A).
As a result of measuring the molecular weight of the water-soluble polymer (A) by GPC, the weight average molecular weight was about 10,000. The component composition of this water-soluble polymer (A) is StSO ₃ Na: M
A = 3: 1 (molar ratio).

—Synthesis of Conductive Particle A— 700 parts of degassed distilled water was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, and the water-soluble polymer (A) was added thereto. 400 parts were added with stirring to obtain an aqueous solution. Next, nitrogen gas is introduced through the nitrogen introduction pipe, and the inside of the reaction vessel is brought into a nitrogen gas atmosphere.
The dissolved oxygen in the aqueous solution was eliminated. Then, the aqueous solution is
° C. Styrene (St) 90 was added to this aqueous solution.
Parts and 10 parts of butyl acrylate (BA) were separately dropped with 100 parts of a 1% by weight aqueous solution of potassium persulfate, and a polymerization reaction was carried out at 80 ° C. under nitrogen gas reflux to obtain the desired conductive particles [water-soluble Polymer (A): polymer particles = 400: 10
0] was obtained.

Conductive particles Water-soluble polymer (A) Polymer particles StSO ₃ Na: MA = 3: 1 (molar ratio) St-BA

<Preparation of Supports 1 to 10> 100 parts by weight of dimethyl terephthalate and 65 parts by weight of ethylene glycol were mixed with 0.04 g of magnesium acetate hydrate as a transesterification catalyst.
5 parts by weight were added, and a transesterification reaction was performed according to a conventional method. 0.05 parts by weight of antimony trioxide and 0.03 parts by weight of trimethyl phosphate were added to the obtained product. Then, the temperature was gradually raised and reduced to 280 ° C.
Polymerization was carried out at 5 mmHg, intrinsic viscosity 0.65, Tg = 7
5 ° C. polyethylene terephthalate was obtained.

Further, the polyethylene terephthalate was vacuum-dried at 150 ° C. for 8 hours, and then dried using an extruder.
It was melt-extruded at 85 ° C., adhered to a 30 ° C. cooling drum while applying static electricity, cooled and solidified to obtain an unstretched sheet.
This unstretched sheet is heated at 80 ° C. using a roll-type longitudinal stretching machine.
And stretched 3.3 times in the machine direction.

The obtained uniaxially stretched film was stretched in a first stretching zone at 90 ° C. by 50% of the total transverse stretching ratio using a tenter-type transverse stretching machine, and further, at a second stretching zone at 100 ° C., at a total transverse stretching ratio of 3. The film was stretched three times. Then 70
Heat treatment at 2 ° C for 2 seconds, and first heat fixation zone at 150 ° C
For 5 seconds, and heat-setting at 220 ° C. for 15 seconds to obtain a 100 μm-thick biaxially stretched polyethylene terephthalate film.

The surface of the obtained film on which the emulsion layer is to be coated is subjected to a corona discharge treatment of 8 W / (m ² · min), and the following undercoat layer N-1 coating solution and undercoat Layer N-
2 Coating liquids are applied sequentially, and the dry concentration is 0.8μ each.
Undercoat layers N-1 and N-2 of m and 0.1 μm were formed.

<Undercoat layer N-1 coating liquid> A copolymer latex liquid (solids: 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate) 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water 1000 ml

<Undercoat N-2 Coating Solution> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) ) 0.1g Finish with water 1000ml

Then, a corona discharge treatment of 8 / W (m ² · min) was applied to the surface on the side on which the backing layer was applied,
Furthermore, the following undercoating first layer coating liquids A to F shown in Table 3
Was applied so that the dry film thickness became 1.0 μm.

(Undercoat first layer coating solution A) Polymer compound A (copolymer of butyl acrylate 40% by weight, styrene 20% by weight, glycidyl acrylate 40% by weight; Tg = 20 ° C.) latex liquid (solid content 30%) 270 g Compound (UL-1) 0.6 g Compound (UL-5) 5 g Finish with water 1000 ml

(First Undercoating Layer Coating Solution BF) The same as the undercoating first layer coating solution A except that the polymer compound A was changed to the following polymer compounds BF. Polymer B: Copolymer of 60% by weight of styrene and 40% by weight of glycidyl acrylate; Tg = 75 ° C. Polymer C: Copolymer of 55% by weight of butyl acrylate, 5% by weight of styrene, and 40% by weight of glycidyl acrylate; Tg = 0
C Polymer compound D 50% by weight of polymer compound B and 50% by weight of polymer compound C; Tg = 37.5 ° C Polymer compound E 100% by weight of styrene polymer; Tg = 120 ° C Polymer compound F Conductivity Fine particles A; Tg = 80 ° C.

Further, the coating liquids A and B of the second undercoating layer (conductive layer) shown in Table 3 were applied to the coating amounts (g / g) shown in Table 3.
m ² ) to produce Supports 1 to 10.

(Undercoat Second Layer (Conductive Layer) Coating Solution A) Conductive Metal Oxide A Dispersion (Solid Content) 231 g Copolymer Latex Solution of Styrene 60% by Weight and Glycidyl Acrylate 40% by Weight (Solid Content 30) %) 223 g Compound (UL-1) 0.6 g Finish with water 1000 ml

(Undercoating Second Layer (Conductive Layer) Coating Solution B) Conductive Fine Particles A (in Solids) 58 g Copolymerized latex liquid (solids 30%) of styrene 60% by weight and glycidyl acrylate 40% by weight 73 g Average particle size 3 μm silica particles 0.05 g Compound (UL-1) 0.07 g Finish with water 1000 ml

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Embedded image << Preparation of Photographic Material Samples 1 to 10 for Printing >> Halogenation in which a silver halide emulsion layer additive of the following formula 1 was added on the undercoat layer N-2 of supports 1 to 10 shown in Table 3. The silver amount of the silver halide emulsion layer was 2.9 g / m ² by simultaneous multilayer coating of the silver emulsion coating solution and the emulsion protective layer coating solution of the following formula ² .
The emulsion protective layer was formed so that the amount of gelatin became 1.2 g / m ² and the amount of gelatin in the emulsion protective layer became 0.6 g / m ² . On the conductive layer on the opposite side, a coating solution for a backing layer having the following formulation 3 was applied so that the amount of colloidal silica and the amount of gelatin were as shown in Table 3, and photosensitive material samples 1 to 10 for printing were prepared. Produced.

<Formulation 1: Composition of silver halide emulsion layer additive> Sensitizing dye (C-1) 0.6 mg / m ² Hydrazine compound (H-1) 30 mg / m ² Amino compound (C-2) 50 mg / M ² Surfactant (C-3) 100 mg / m ² Latex polymer (C-4) 1.0 g / m ² Hardener (C-5) 30 mg / m ² Sodium-isoamyl-n-decyl sulfosuccinate 0.7 mg / m ² 2-mercapto-6-hydroxypurine 10 mg / m ² EDTA 50 mg / m ²

<Formulation 2: Composition of emulsion protective layer coating solution> Gelatin 0.6 g / m ² sodium-isoamyl-n-decylsulfosuccinate 12 mg / m ² Matting agent: 25 mg of monodisperse silica having an average particle size of 3.5 μm / M ² Hardener (C-6) 30 mg / m ² Surfactant (C-7) 1 mg / m ² Colloidal silica (average particle size 0.05 μm) 20 mg / m ²

<Formulation 3: Composition of backing layer (BC layer) coating liquid> Gelatin Described in Table 3 Zodium-isoamyl-n-decylsulfosuccinate (S-1) 5 mg / m ² latex polymer (C-4) 0.1 g / m ² colloidal silica (average particle diameter 0.05 nm) (in solid content) described in Table 3 Sodium polystyrene sulfonate 20 mg / m ² Compound (C-8) 100 mg / m ² Matting agent: average particle diameter 5 μm Monodispersed polymethyl methacrylate 50 mg / m ² sodium di- (2-ethylhexyl) -sulfosuccinate 10 mg / m ² surfactant (C-7) 1 mg / m ² dye (C-9) 20 mg / m ² dye (C -10) 20mg / m ² dye (C-11) 20mg / m 2 dye (C-12) 20mg / m 2 dye (C-13) 20mg / m 2 dye (C ^{14) 20mg / m 2 H (} OCH 2 CH 2) 68 OH 50mg / m 2 hardener (C-6) gelatin 1g per 0.05m mol hardener (C-15) 0.1m mol hard per gelatin 1g Film agent (C-16) 0.05 mmol / g of gelatin Hardening agent (C-5) 6 mg / m ²

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The photographic light-sensitive material samples for silver halide printing prepared as described above were evaluated by the evaluation methods described below.

The development was performed under the following processing conditions. The developer and fixer used were based on the following formulation.

Processing Conditions (Step) (Temperature) (Time) Developing 38 ° C. 12 seconds Fixing 35 ° C. 10 seconds Washing 40 ° C. 10 seconds Drying 50 ° C. 12 seconds Total 44 seconds

(Composition of developer) Amount per 1 L of working solution Diethyltriamine pentaacetic acid / pentasodium salt 3 g Sodium sulfite 50 g Potassium carbonate 40 g Hydroquinone 21 g 4-methyl-4-hydroxymethyl-1-phenyl-3-hydrazolidone (dimesone S) 0.9 g Potassium bromide 5 g Benzotriazole 0.2 g 5-methyl-benzotriazole 0.13 g Boric acid 8 g Diethylene glycol 40 g 2-Mercapto-6-hydroxypurine 0.06 g Water and potassium hydroxide are added to make 1 L, and the pH is adjusted to 1 L. = 10.2
Adjust to.

(Composition of fixing solution) Amount per 1 L of working solution Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g 25 ml of aluminum sulfate (27% aqueous solution) The pH of the working solution was 4.9.

[Evaluation Method] <Evaluation of Antistatic Performance> (Measurement of Surface Resistivity) The measurement was performed using a Teraohmmeter model VE-30 manufactured by Kawaguchi Electric Co., Ltd.

The undeveloped sample and the developed sample were conditioned for 24 hours in an environmental atmosphere at a temperature of 23 ° C. and a relative humidity of 20%. Is measured.

(Ash adhesion test) Two 10 cm square samples were cut out, and the undeveloped sample and the developed sample were
The test was performed by controlling the humidity for 24 hours in an environment atmosphere of 3 ° C. and 40% RH.

The exposed and developed sample was heated at 23 ° C. and 40% RH.
Under the atmosphere described above, the backing layer (BC layer) side was placed on a rubber plate, and the backing layer (BC layer) side was charged by rotating a rubber roller 10 times. One minute later, the sample surface is kept parallel to the plane of the ash by the worm gear in the upper space of the paper in which the ash of the tobacco is densely spread on average, and
Arrange a device that can move vertically, hold the sample with the clip of insulating material of the device, drop vertically at a speed of 1 cm per minute so that the sample is parallel to the ash surface, and ash adheres to the sample Observed height. The degree of adhesion of the ash was visually observed, and the degree of ash attachment was evaluated according to the following evaluation criteria, and the antistatic effect was observed. In this test, in order to prevent static electricity from leaking from the hand holding the sample, desorption was performed by wearing rubber gloves.

Evaluation Criteria A: The sample does not adhere at all to the ash B: When the sample contacts the ash, the ash adheres to the sample,
When the distance between the sample and the ash is 1 cm, the ash does not adhere at all. C: When the distance between the sample and the ash is 1 cm, the ash adheres.
D: The ash adheres when the distance between the sample and the ash is 2 cm, but 4
E: The ash adheres when the distance between the sample and the ash is 4 cm.
No ash adheres at a distance of 6 cm F: Ash adheres even if the distance between the sample and the ash is 6 cm
G does not adhere at a distance of 10 cm G: Ash adheres even when the distance between the sample and the ash is 8 cm, but 1
Does not adhere at a distance of 0 cm H: Ash adheres even if the distance between sample and ash is 10 cm or more

<Evaluation of Drying Property> In an environmental atmosphere of 30 ° C. and 70% RH, about 20 sheets were continuously developed using an automatic developing machine in which the drying air was set at 45 ° C. under the following processing conditions. . As an automatic processor, an automatic processor for rapid processing (G
R-26SR (manufactured by Konica Corporation)
A heat belt preheating system heated to 0 ° C. was additionally modified, and an automatic developing machine improved so that rapid processing can be performed by changing a conveying speed was used. At the start, a developing solution, a fixing solution and a rinsing solution having the following compositions were charged into the tank of the automatic developing machine.

The line speed of the automatic developing machine was set so that the last twentieth sheet could be obtained by drying. Further, the time required to dry the last twentieth sheet was determined.

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(Developer Composition) Diethyltriamine pentaacetic acid / 5 sodium salt 40% aqueous solution 3.63 g Sodium sulfite 40 g KBr 7 g Potassium carbonate 0.5 mol Sodium carbonate 0.4 mol Hydroquinone 15 g 4-methyl-4-hydroxymethyl- 1-phenyl-3-pyrazolidone (dimazone S) 1.2 g sodium erythrobinate 10 g benzotriazole 0.21 g boric acid 8 g diethylene glycol 40 g 2-mercapto-6-hydroxypurine 60 mg 1-phenyl-5-mercaptotetrazole 0.025 g water And sodium hydroxide were added to make 1 liter of working solution to pH 10.4.

(Fixing solution composition) Ammonium thiosulfate (70% aqueous solution) 200 ml Sodium sulfite 22 g Boric acid 9.8 g Sodium acetate trihydrate 34 g Acetic acid (90% aqueous solution) 14.5 g Tartaric acid 3.0 g Aluminum sulfate (27% aqueous solution) ) 25 ml The pH of the working solution was 4.9.

Water and sulfuric acid were added to make up to 500 ml, and the pH was adjusted to 4.9 when used. At the time of use, 500 ml of water was added to make a 1 liter developer solution.

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(Rinse solution) EDTA · 2Na 40 g KOH 23 g K ₂ CO ₃ 12 g Potassium sulfite 110 g Sanbac-P (San-ai Oil) 20 g

<Evaluation of Curl> The unexposed sample was placed at 23 ° C. for 8 hours.
Leave it for 24 hours in an environmental atmosphere of 0% RH to adjust the humidity.
The sample was moved to an air conditioning room controlled at RH, and the sample was taken out of the hermetically sealed package under this low humidity environment. Then, the curl when left for 5 minutes from the time of removal was measured as curvature. The curvature was indicated by a positive sign when the support was curled with the photosensitive silver halide emulsion layer coated side inside, and a negative sign when the curl was set with the backing layer side inside.

<Evaluation of crack failure>
After leaving for 1 week in an environmental atmosphere at 1 ° C. and 1% RH, cracks were visually observed on the surface of the sample on the side where the backing layer was coated, and evaluated on a scale of 1 to 5. The sample having no crack was evaluated as 5, and as the generation increased, the evaluation was lowered to 4, 3, 2, and 1. Ranks 2 and 1 are practically unfavorable levels.

Table 3 shows the obtained results.

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[Table 3]

As is clear from the results shown in Table 3, when the undercoat layer and the backing layer were applied under the conditions of the present invention, sufficient drying properties could be imparted, and there was no problem in curling and cracking. It also shows that the antistatic performance is excellent.

Example 2 << Preparation of Composite Particles Containing Inorganic Particles and Hydrophobic Polymer Compound >><Production of Composite Particle L-1> A stirrer, a thermometer, a dropping funnel and a nitrogen inlet tube were placed in a 1000 ml four-necked flask. A reflux condenser was attached, and while deoxygenation was performed by introducing nitrogen gas, 360 cc of distilled water and 126 g of a 30% by weight colloidal silica dispersion (average particle size: 12 nm) were added until the internal temperature reached 80 ° C. Heated. The following surfactants 1.
3 g, ammonium persulfate 0.0 g as initiator
23 g are added and then 12.6 g of vinyl pivalate
Was added and reacted for 4 hours. After cooling, the pH was adjusted to 6 with a sodium hydroxide solution to adjust the composite fine particles L-1.
I got

[0180]

Embedded image

<Production of Composite Particle L-2> The same procedure as in Example 1 was repeated except that vinyl pivalate 6.3 g and vinyl caproate 6.3 g were used in place of vinyl pivalate 12.6 g. The composite fine particles L-
2 was obtained.

<Production of Composite Particle L-3> Composite particle L-1 was prepared in the same manner except that vinyl pivalate 6.3 g and vinyl acetate 6.3 g were used instead of vinyl pivalate 12.6 g. In the same manner as in the above, composite fine particles L-3 were obtained.

<Production of Composite Fine Particles L-4> 1000 ml
, A stirrer, a thermometer, a dropping funnel, a nitrogen inlet tube and a reflux condenser were attached to the four-necked flask, and deoxygenation was performed by introducing nitrogen gas. 126 g (average particle size: 12 nm) was added, and the mixture was heated until the internal temperature reached 80 ° C. 1.3 g of dextran sulfate as dispersant, 0.023 g of ammonium persulfate as initiator, then 3.78 g of vinyl pivalate and 8.18 g of vinyl acetate.
82 g was added and reacted for 4 hours. Then cool down,
The pH was adjusted to 6 with a sodium hydroxide solution to obtain composite fine particles L-4.

<< Coating and Production of Photographic Material Sample for Silver Halide Printing >> In Example 1, the undercoating first layer shown in Table 4 was used as the undercoating first layer, and Table 4 was used as the undercoating second layer.
And the amount of the antistatic agent applied (g /
m ² ) Printed in the same manner as in Example 1 except that the fine particles were changed as shown in Table 4 and the above-mentioned composite fine particles shown in Table 4 were used in the amounts shown in Table 4 in place of the colloidal silica of the backing layer. Photosensitive material samples 11 to 20 were prepared, and in the same manner as in Example 1, antistatic performance, drying properties, curling, and crack failure were evaluated. Table 4 shows the obtained results.

[0185]

[Table 4]

As is clear from the results in Table 4, when the undercoat layer and the backing layer were applied under the conditions of the present invention, sufficient drying properties could be imparted, and there was no problem in curling and cracking. It also shows that the antistatic performance is excellent.

[0187]

According to the present invention, the drying property after the water washing treatment is greatly improved, and there is no problem of curling and cracking.
A single-sided photosensitive silver halide photographic material having an excellent antistatic effect was obtained. That is, it is possible to provide a silver halide photographic material which is easy to produce, has a permanent antistatic effect, and is excellent in rapid processing suitability.

Claims (6)

[Claims] 1. A silver halide photographic material having at least two undercoat layers on the same surface of a support and further having at least one hydrophilic colloid layer on the undercoat layers. Is an undercoat layer having conductivity, and another one of the undercoat layers is an undercoat layer containing a polymer compound having a Tg of 10 ° C. or more and 120 ° C. or less;
When the amount of gelatin in the hydrophilic colloid layer is 0.1 g / m ² or more and 2.0 g / m ² or less, inorganic fine particles and / or composite particles comprising inorganic fine particles and a hydrophobic polymer compound are contained in the hydrophilic colloid layer. A silver halide photographic light-sensitive material containing 0.1 g / m ² or more and 2.0 g / m ² or less. 2. The silver halide according to claim 1, wherein the polymer compound of the undercoat layer containing the polymer compound is a polymer compound having a Tg of 30 ° C. or more and 100 ° C. or less. Photosensitive material. 3. The undercoating layer having conductivity contains polymer particles having a water-soluble polymer having a sulfonic acid group and a carboxylic acid group arranged on the outer periphery of the polymer particles. The silver halide photographic light-sensitive material according to claim 1. 4. The silver halide photographic material according to claim 1, wherein the conductive undercoat layer contains a conductive metal oxide. 5. The silver halide photographic material according to claim 1, wherein the inorganic fine particles are colloidal silica. 6. A hydrophobic polymer compound of a composite particle comprising inorganic fine particles and a hydrophobic polymer compound is a hydrophobic polymer compound having a repeating unit represented by the general formula (1). A silver halide photographic material according to any one of claims 1 to 5. Embedded image [In the formula, R ₁ represents a substituent. ]