JPH08122955A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide photographic sensitive material small in variation of sensitivity or fogging in preservation with the lapse of time under a high humidity, easy in recycle of the packing material and convenient in handling. CONSTITUTION: At least one of materials for packing the silver halide photographic sensitive material is a polyethylene sheet having <=150μm thickness and containing a polyethylene >=0.95g/cm<3> in density and the silver halide photographic sensitive material is provided with at least one layer of a photosensitive silver halide emulsion layer on one side of the supporting body, and at least one layer of a non-photosensitive hydrophilic colloid layer on the opposite surface to the surface coated with the emulsion layer on the supporting body and a hydrophobic polymer layer on a position far from the supporting body to the layer are provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as a photographic light-sensitive material or a light-sensitive material), and more specifically, it can be used as a packaging material without using a sheet material laminated with aluminum foil. It relates to a light-sensitive material packaged using a laminated polyethylene single material.

[0002]

2. Description of the Related Art A silver halide grain, which is a constituent of a photographic light-sensitive material, undergoes physical ripening in the presence of a protective gelatin such as gelatin, and its crystal grows to give high photosensitivity through chemical ripening. Therefore, oxidation during storage is a major cause of deterioration of photographic characteristics.

Usually, a photographic light-sensitive material is packaged by, for example, a sheet-shaped film such as an X-ray light-sensitive material for diagnosis, which is gripped by interleaf paper made of thin paper folded one by one. Either a predetermined number of sheets are sandwiched between U-shaped cardboards to form a packaging unit, or the packaging unit excluding the folded interleaf paper is sandwiched between cardboards to protect it from external impacts and to protect it from light. It is kept in a light-tight state by suction and deaeration in a barrier bag made of polyethylene sheet in which black is dispersed.

[0004] The barrier bag is used by making a polyethylene sheet by vapor-depositing or laminating aluminum, and is a composite material rather than a single material. It had to be separated, and the number of steps for recycling was high.

In a single material packaging of a polyethylene sheet which is not vapor-deposited or laminated with aluminum, the moisture permeability of the polyethylene sheet causes the photosensitive material to be affected by humidity, and the photographic characteristics such as a decrease in sensitivity and an increase in fog after storage are affected. . If the thickness of the sheet is increased in order to suppress the moisture permeability of polyethylene, the flexibility of the packaging form is impaired and the handling becomes inconvenient.

Therefore, there has been a demand for a photographic light-sensitive material which can be easily recycled as a packaging material without deterioration of photographic characteristics upon storage.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks and provides a photographic light-sensitive material in which sensitivity and fogging do not fluctuate even during storage of the light-sensitive material with time and under high humidity, and the packaging material can be easily recycled and handled. Is.

[0008]

[Means for Solving the Problems] At least one of the materials for packaging the photosensitive material has a thickness of 15
A polyethylene sheet having a size of 0 μm or less, the polyethylene sheet containing polyethylene having a density of 0.95 g / cm ³ or more, and the light-sensitive material has at least one light-sensitive silver halide emulsion layer on one side of the support. This support has at least one non-photosensitive hydrophilic colloid layer on the surface opposite to the surface on which the emulsion layer is coated, and a hydrophobic polymer layer at a position farther from the support than the layer. A light-sensitive material comprising:

At least one of the materials for packaging the light-sensitive material is a polyethylene sheet having a thickness of 150 μm or less, and the polyethylene sheet contains polyethylene having a density of 0.95 g / cm ³ or more, and the light-sensitive material is one of the supports. Has at least one light-sensitive silver halide emulsion layer on its side, and the water-soluble polymer contained in the light-sensitive material is
It was achieved by a light-sensitive material which is 0.15 g / m ² or less and the emulsion layer is hardened with a carboxyl group-activating type hardener.

The present invention will be described in detail below.

The polyethylene sheet used for packaging the light-sensitive material of the present invention is a polyester such as polyethylene terephthalate, which is a high density polyethylene film containing polyethylene having a polyethylene density of 0.95 g / cm ³ or more and imparts light-shielding property. Therefore, the carbon black powder is dispersed and processed into a sheet.

The thickness of the polyethylene sheet is preferably 12
It is 0 μm or less, and more preferably 100 μm or less.

The density of polyethylene of the polyethylene sheet of the present invention is 0.95 g / cm ³ or more, but two or more polyethylene sheets having different densities may be laminated to form one sheet. However, the composition of the sheet at that time is that the density of at least one polyethylene sheet of the structural unit is 0.95.
It should be g / cm ³ or more.

The polyethylene sheet of the present invention can be manufactured by a conventional method.

A preferred packaging form of the light-sensitive material of the present invention is
Using 50 or more sheets of photosensitive material cut into a certain size as one packaging unit, the polyethylene sheet of the present invention is used for bag making, packaging and vacuum suction to keep the inside of the polyethylene bag anaerobically and light-tightly sealed. At this time, it is preferable that nothing other than the photosensitive material is enclosed in the polyethylene bag, but an oxygen absorber or the like may be enclosed.

A packaging unit in which a predetermined number of sheets are formed into a U-shaped cardboard and protected by U-shaped cardboard, and a single leaf interleaf sheet is applied only to the surface in contact with the cardboard, so-called no-interleaf packaging, may be used. Alternatively, interleaf packaging may be used in which one sheet is held by interleaf paper made of thin paper folded back and a predetermined number of the held sheets are sandwiched by U-shaped cardboard. Further, it is preferable to store these photosensitive material packages in an outer box made of cardboard from the viewpoint of preventing external pressure.

Gelatin is preferably used as the non-photosensitive colloid layer coated on the same side as the hydrophobic polymer layer of the present invention. As the gelatin, so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives and modified gelatin, and any of those commonly used in the art can be used. Among these gelatins, lime-processed gelatin and acid-processed gelatin are most preferably used.

As the hydrophobic colloid other than gelatin,
Colloidal albumin, protein such as casein, agar, sodium alginate, sugar derivative such as starch derivative, cellulose compound such as carboxymethyl cellulose and hydroxymethyl cellulose, polyvinyl alcohol, poly-N
-Synthetic hydrophilic compounds such as vinylpyrrolidone and polyacrylamide can be mentioned. In the case of a synthetic hydrophilic compound, other components may be copolymerized, but when the amount of the hydrophobic copolymerizing component is too large, the moisture absorption amount and moisture absorption rate of the back layer become small, which is not suitable from the viewpoint of curling. These hydrophobic colloids may be used alone or in combination of two or more.

In the back layer of the present invention, other than the binder, a matting agent, a surfactant, a dye, a cross-linking agent, a thickener, an antiseptic,
Photographic additives such as UV absorbers and inorganic fine particles such as colloidal silica may be used, and these can be referred to, for example, Research Disclosure (RD) 176, 17643.

A polymer latex may be further added to the surface of the support of the present invention opposite to the surface on which the emulsion layer is coated (hereinafter referred to as the back layer). The polymer latex used in the present invention is an aqueous dispersion of a water-soluble polymer having an average particle size of 20 μm to 200 μm, and the amount used is preferably 0.01 to 1.0 by dry weight ratio to 1.0 of the binder, and particularly preferably 0.1 to 0.8. . Preferred examples of the polymer latex used in the present invention have an alkyl ester of acrylic acid, a hydroxyalkyl ester or a glycidyl ester, or an alkyl ester of methacrylic acid, a hydroxyalkyl ester or a glycidyl ester, styrene or a derivative thereof as a monomer unit. Is mentioned.

The hydrophobic polymer layer of the present invention is a layer having a hydrophobic polymer as a binder, and the polymer used for the polymer layer includes polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, Fluorinated resins such as polyvinyl acetate, urethane resin, urea resin, melamine resin, phenol resin, epoxy resin, tetrafluoroethylene, polyvinylidene fluoride, butadiene rubber, chloroprene rubber, rubbers such as natural rubber, polymethylmethacrylate, poly Acrylic acid or methacrylic acid ester such as ethyl acrylate, polyester resin such as polyethylene phthalate, polyamide resin such as nylon 6, nylon 66, cellulose resin such as cellulose triacetate, water such as silicone resin. Mention may be made of a polymer or derivatives thereof insoluble. Further, a copolymer composed of one kind of monomer may be used as a binder for the polymer layer. Particularly preferable binders are copolymers of alkyl acrylates or alkyl methacrylates with acrylic acid or methacrylic acid (acrylic acid or methacrylic acid is preferably 5 mol% or less), styrene-butadiene copolymers, styrene-butadiene-acrylic acid copolymers (acrylic acid is 5 mol% or less). Mol or less), styrene-butadiene-divinylbenzene-methacrylic acid copolymer (methacrylic acid is preferably 5 mol% or less), vinyl acetate-ethylene-acrylic acid copolymer (acrylic acid is 5 mol% or less), vinylidene chloride-acrylonitrilo. -Methyl methacrylate-Ethyl acrylate-Acrylic acid copolymer (acrylic acid 5 mol% or less), ethyl acrylate
-Glycidyl methacrylate-acrylic acid copolymer. These may be used alone or in combination of two or more.

Specific examples of the aqueous dispersion of acrylic polymer are shown below, but the present invention is not limited thereto.

A-1 methyl methacrylate: butyl acrylate: styrene: methacrylic acid = 55: 20: 24: 1
Latex (Mw. = 150000) A-2 methyl methacrylate: 2-ethyl-hexyl acrylate: styrene = 70: 15: 15 latex (Mw.1200
00) A-3 Latex of styrene: butadiene: divinylbenzene: methacrylic acid = 20: 40: 37: 3 (Mw.80000) In the hydrophobic polymer layer of the present invention, a matting agent, a surfactant, and A photographic additive such as a dye, a slip agent, a cross-linking agent, a thickener, an ultraviolet absorber, and inorganic fine particles such as colloidal silica may be added. As for these additives, Research Disclosure (RD) Volume 176, 17643 mentioned above.
(December 1978), etc. can be referred to.

The polymer layer of the present invention may be one layer or two or more layers. The thickness of the polymer layer of the present invention is not particularly limited. However, if the thickness of the polymer layer is too small, the water resistance of the polymer layer will be insufficient and the back layer will swell in the treatment liquid, which is unsuitable. On the other hand, if the thickness of the polymer layer is too large, the water vapor permeability of the polymer layer will be insufficient, and the moisture absorption / desorption of the hydrophilic colloid layer of the back layer will be impeded, resulting in poor curling. Of course, the thickness of the polymer layer depends on the physical properties of the binder used.
Therefore, the thickness of the polymer layer needs to be determined in consideration of both factors. The preferable thickness of the polymer layer depends on the kind of the binder of the polymer layer, but is 0.05 to 10 μm, and more preferably 0.1 to 5 μm. When the polymer layer of the present invention is composed of two or more kinds, the sum of the thicknesses of all the polymer layers is the thickness of the polymer layer of the photosensitive material of the present invention.

The method of applying the hydrophobic polymer layer of the present invention is not particularly limited. After coating and drying the back layer, the hydrophobic polymer layer of the present invention may be coated and dried on the back layer, or the back layer and the polymer layer may be simultaneously coated and then dried.

The polymer layer may be dissolved in the solvent of the binder polymer of the polymer layer and applied in a solvent system, or may be applied in an aqueous system using an aqueous dispersion of the polymer.

The method for applying the back layer of the present invention is not particularly limited. Conventionally known methods of coating a hydrophilic colloid layer of a light-sensitive material can be used. For example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or an extrusion method using a hopper described in US Patent No. 2,681,294, or US Patent No. 2,761,418, The multi-layer simultaneous coating method described in Nos. 3,508,947 and 2,761,791 can be used.

The back layer of the present invention may be composed of one layer or may be composed of two or more layers. When the back layer is composed of two or more layers, at least one layer of the back layer is located at a position far from the support. As a result, it is necessary that the layer is composed of the hydrophobic polymer layer of the present invention.

The total amount of the hydrophilic colloids in the back layer of the present invention is the total amount of the hydrophilic colloids on the surface coated with the silver halide emulsion (Side A) (the total amount of the hydrophilic colloids on the emulsion surface).
0.1 times or more (weight ratio) is preferable, and 0.3 is more preferable.
More than double. The appropriate value of the ratio of total hydrophilic colloid of back layer / total hydrophilic colloid of emulsion surface (weight ratio) varies depending on the total amount of hydrophilic colloid of the light-sensitive material, coated silver amount, and support thickness. The curl becomes bad.

In the light-sensitive material of the present invention, it is preferable to provide a conductive layer containing a conductive substance. Examples of the conductive substance include a conductive polymer compound and a conductive metal oxide.

In the light-sensitive material of the present invention, in order to improve the adhesion between the hydrophilic colloid layer of the emulsion layer or the back layer and the support, a corona discharge or an undercoat treatment such as an undercoat layer is applied. preferable. As the undercoat layer, a polymer dispersion, for example, a butadiene-styrene polymer latex, an acrylic acid ester polymer latex, a methacrylic acid ester latex, a vinylidene chloride latex / polyester resin-based latex, etc. Layers are preferred. These undercoat layers may be provided after the support is formed into a film, or may be formed during the support film formation process. Either method may be used.

The support used for the photographic material of the present invention may be a known support known as a photographic material support, such as a polyester-based or triacetate-based support, but is not particularly limited.

In the case of a light-sensitive material having two or more hydrophilic colloid layers, the water-soluble polymer of the present invention may be contained in all the hydrophilic colloid layers, and if at least one layer is contained. It may not be contained in other layers. Further, the amount of the polymer in each layer when the polymer of the present invention is applied to two or more hydrophilic colloid layers can be optionally changed.

Specific examples of the water-soluble polymer used in the present invention will be given below, but the present invention is not limited thereto. The numbers in parentheses represent mol% or acid value.

P-1 Polyacrylic acid (100 mol%) P-2 Polymethacrylic acid (100 mol%) P-3 Acrylic acid / methyl acrylate copolymer (80
Mol%) P-4 acrylic acid / ethyl acrylate copolymer (60
Mol%) P-5 acrylic acid / butyl acrylate copolymer (40 mol%) P-6 acrylic acid / methyl methacrylate copolymer (2
0 mol%) P-7 acrylic acid / butyl acrylate copolymer (15 mol%) P-8 acrylic acid / acrylamide copolymer (60 mol%) P-9 acrylic acid / methyl acrylate / hydroxyethyl acrylate (80 Mol%) P-10 methacrylic acid / methyl methacrylate copolymer (80 mol%) P-11 methacrylic acid / ethyl acrylate copolymer (6
0 mol%) P-12 methacrylic acid / butyl methacrylate copolymer (40 mol%) P-13 methacrylic acid / cyclohexyl methacrylate copolymer (20 mol%) P-14 methacrylic acid / phenyl methacrylate copolymer (15 mol %) P-15 methacrylic acid / styrene copolymer (60 mol%) P-16 methacrylic acid / methyl acrylate / hydroxyethyl acrylate copolymer (40 mol%) P-17 methacrylic acid / ethyl acrylate / acrylonitrile copolymer (30 mol%) P-18 maleic acid / styrene copolymer (50 mol%) P-19 maleic acid / iso-butene copolymer (50 mol%) P-20 itaconic acid / iso-butene copolymer ( 50 mol%) P-21 polyacrylamide propionic acid (100 mol%) P-22 polystyrene sulfonic acid (100 mol%) P-23 poly (3-acrylamide Ropansuruhon acid) (1
00 mol%) P-24 2-acrylamido-2-methylpropanesulfonic acid / acrylamide copolymer (60 mol%) P-25 maleated gelatin (1.5 meq / g) P-26 succinylated gelatin (2.0 meq / g) ) P-27 Carboxymethylcellulose (4.0meq / g) P-28 Polyvinyl alcohol Block copolymer of acrylic acid (2.0meq / g) P-29 Polyvinyl alcohol Graft copolymer of acrylic acid (2.0meq / g)

[0036]

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The molecular weight of these water-soluble polymers is preferably 5 × 10 ³ or more, particularly preferably 1 × 10 ^{4 to} 5 × 10 ^6.
(All are weight average molecular weights).

The amount of the water-soluble polymer added is 0.15 g / m ² or less, preferably 0.1 g / m ² or less.

In the case of a light-sensitive material having two or more hydrophilic colloid layers, the polymer may be contained in all the hydrophilic colloid layers or may be contained in at least one layer and the other layers may not be contained. Further, the amount of the polymer in each layer when the polymer described in the present invention is applied to two or more hydrophilic colloid layers can be arbitrarily changed.

Next, the hardener which acts by activating the carboxyl group of the present invention will be described.

The hardener which acts by activating a carboxyl group in the present invention (hereinafter referred to as a carboxyl group active type hardener) means a hardener which reacts with the carboxyl group in the binder.

Examples of the hardener in the present invention include compounds represented by the following general formulas [1] to [8].

[0043]

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In the formula, R ¹ and R ² are an alkyl group (eg, methyl group, ethyl group, benzyl group, phenethyl group, 2-ethylhexyl group, etc.) or aryl group (eg, phenyl group,
It is also preferable that they represent a naphthyl group) and are bonded to each other to form a heterocycle with a nitrogen atom. Examples of the heterocycle include a pyrrolidine ring, a piperazine ring, a morpholine ring and the like.

R ³ is a substituent such as —NR ⁴ R ⁵ (R ⁴ and R ⁵
Is synonymous with R ¹ and R ² , a halogen atom, a carbamoyl group,
It represents a sulfo group, a ureido group, an alkoxy group, an alkyl group or the like. R ³ includes those having a substituent, and examples of the substituent include a halogen atom, an alkyl group, a carbamoyl group,
Examples thereof include sulfo group, sulfooxy group and ureido group.

[0046] m ¹ represents an 0-5, when the m ¹ ≧ 2, a plurality of R ³ may be different from each other be the same.

[0047] X ^1- represents an anion, preferably halide ions Examples, sulfate ion, sulfonate _{^{ion, ClO 4 -, BF 4 -}} , PF 6 - and the like. l is 0 or 1
The stands, n ¹ represents 0 to 2, the n ¹ when an intramolecular salt is formed 0.

The compound represented by the general formula [1] is more preferable, and the compound represented by the general formula [1a] is more preferable.

[0049]

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In the formula, R ^11a represents a hydrogen atom or an optionally substituted alkyl group or alkoxy group, and R ^11a
12a represents an alkyl group which may have a substituent, an acyl group or an acylamino group, X ^11a- represents an anion, and y ^11a
Is 1 or 2 and forms an inner salt when y ^11a is 1.

In the above formula [1a], R ^12a is an alkylene sulfonic acid or an acylamino group.

In the general formula [1a], R ^{12a is-.
_{(-CH 2 -) m 11a -SO}} 3 -, -NR 13a COR 14a, - (- CH 2 -) p-
CONR ^17a R ^18a , − (− CH ₂ −) q −NR ^19a R ^110a , − (CH ₂ −) s
-CH- (LR ^112a ) -R ^111a , R ^13a represents a hydrogen atom or an alkyl group which may have a substituent, R ^14a represents an alkyl group which may have a substituent, an alkoxyl group, O − (−
CH ₂ −) n ^11a −SO ₃ ⁻ , −NR ^15a R ^16a , − (− CH ₂ −) n ^11a −SO
₃ ^- represents, R ^15a, R ^16a is a hydrogen atom or a substituent alkyl group which may have _{a, - (- CH 2 -)} n 11a -SO 3 - represents, R
^17a represents a hydrogen atom, or an alkyl group or aryl group which may have a substituent, R ^18a represents a hydrogen atom, an alkyl group which may have a substituent, or R ^17a and a 5- or 6-membered aliphatic group R ^19a represents a group forming a ring, R ^19a represents a hydrogen atom, an alkyl group which may have a substituent, or —COR ^14a ,
^110a is a hydrogen atom or an optionally substituted alkyl group, or _{- (- CH 2 -) r} -SO 3 - represents, L is -O- or -NR ^113a
R ^111a represents a hydrogen atom or an alkyl group which may have a substituent, R ^112a represents a hydrogen atom or an alkyl group which may have a substituent, —COR ^114a , —CONHR ^115a , R ^112a
113a , R ^114a and R ^115a represent a hydrogen atom or an alkyl group which may have a substituent, m ^11a is 0 or 2 to 4, n ^11a is 1 to 3, p is 0 to 2, q and r are 1-3 and s are 2-3.

In the above general formula [1a], R ^11a is a hydrogen atom or an alkyl group or an alkoxy group which may have a substituent, and R ^12a is — (— CH ₂ —) m —SO ₃ ^— or NR ^13a. COR
^14a .

[0054]

[Chemical 4]

In the formula, R ²¹ and R ²² are a cycloalkyl group (eg, cyclohexyl group) or an alkyl group (eg, methyl group, ethyl group, 2-ethylhexyl group, etc.), an alkoxyalkyl group such as methoxyethyl group, benzyl. Group, aralkyl group such as phenethyl group, —R ²³ —N
⁺ Represents a group represented by (R ²⁴ ) (R ²⁵ ) (R ²⁶ ) (X ^21- ) m ²¹ .
Here, R ²³ represents an alkylene group (eg ethylene group, propylene group, trimethylene group etc.), R ²⁴ , R ²⁵ and R ²⁶ represent an alkyl group (eg methyl group, ethyl group etc.), and R ^{24 to} R ²⁶ Two of them combine with each other to form a heterocycle (for example, a pyrrolidine ring, a piperazine ring, a formolin ring, etc.) with a nitrogen atom, and a case where it has a substituent.

Preferred examples of the substituent include a carbamoyl group such as diethylcarbamoyl and piperidinocarbamoyl, a sulfo group and the like. m ²¹ represents 0 or 1, and X ^21-
Represents an anion, and a halide ion, a sulfonate ion, a sulfate ion, ClO ₄ −, BF ₄ −, PF ₆ ^{− and the} like are preferable. When forming an intramolecular salt, m ²¹ is 0.

[0057]

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In the formula, R ³¹ represents an alkyl group (for example, a methyl group, an ethyl group, a butyl group, etc., or an aralkyl group such as a benzyl group, a phenethyl group, etc.) or an aryl group (for example, a phenyl group, a naphthyl group, etc.). . These groups include those further having a substituent, and examples of the substituent include a carbamoyl group, a sulfamoyl group and a sulfo group. R ³² and R ³³ represent a hydrogen atom or a substituent, for example, a silver halide atom, an acylamide group, a nitro group, a carbamoyl group, a ureido group, an alkoxy group, an alkyl group, an alkenyl group, an aryl group, an aralkyl group and the like, R ³² And R
^It is also preferable that ³³ is bonded to form a condensed ring together with the pyridinium ring skeleton.

X ³¹ represents a group capable of leaving when the compound represented by the general formula [3] reacts as a nucleophile. Preferred examples include a halogen atom, a sulfonyloxy group, a sulfoalkyl group or a group represented by -OPO (OR ³⁵ ) ₂ (R ³⁵ represents an alkyl group or an aryl group).

When X ³¹ represents a sulfonyloxy group, it is also preferable that X ³¹ and R ³¹ are bonded.

[0061] Y ^31- represents an anion, halide ions, sulfonate ions, sulfate ion, CCl ₄ ^-, B
F ₄ ^-, PF ₆ ^- and the like are preferable. m ³¹ represents 0 or 1, and m ³¹ is 0 when forming an intramolecular salt.

[0062]

[Chemical 6]

In the formula, the definitions of R ⁴¹ and R ⁴² are exactly the same as the definitions of R ¹ and R ² in the general formula [1], and R ⁴³ is an alkyl group (eg, methyl group, ethyl group, butyl group, etc.). other,
It represents an aralkyl group such as a benzyl group or a phenethyl group) or an aryl group (for example, a phenyl group or a naphthyl group).

[0064] X ^41- represents an anion, halide ions, sulfonate ions, sulfate ion, CCl ₄ ^-, B
F ₄ ^-, PF ₆ ^- and the like are preferable.

[0065]

[Chemical 7]

In the formula, the definitions of R ⁵¹ , R ⁵² and R ⁵³ , R ⁵⁴ are exactly the same as the definitions of R ¹ and R ² in the general formula [1], and R ⁵¹ and R ⁵³ form a ring. May be. X ⁵¹ represents a group capable of leaving upon reaction with a nucleophile, preferably a halogen atom, a sulfonyloxy group (preferably an alkylsulfonyloxy group, an arylsulfonyloxy group),
Examples thereof include a 1-pyridinium group, an imidyloxy group (for example, a phthalimidyloxy group, a succinimidyloxy group, a glutarimidyloxy group), an azolyloxy group and an ammonio group.

As the anion represented by Y ^51- , for example, a halogen ion, a sulfonate ion, a sulfate ion,
Examples include CCl ₄ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ phosphonate ion, and phosphate ion.

[0068]

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In the formula, R ⁶¹ and R ⁶² are an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aromatic heterocyclic group or —NR ⁶³ R ⁶⁴ (R ⁶³ and R ⁶⁴ are bonded to form a ring. (Including things). X ⁶¹ has the same definition as X ^{51 in} the general formula [5].

[0070]

[Chemical 9]

Wherein R ⁷¹ , R ⁷² and R ⁷⁴ and R ⁷⁵ , R ⁷⁶
Is the same as the definition of R ¹ and R ² in the general formula [1],
X ⁷¹ is the same as X ⁵¹ in the general formula [5], and Y ⁷¹ is the same as the definition of Y ^51- in the general formula [5].

[0072]

[Chemical 10]

In the formula, R ⁸¹ represents an aryl group, Z ⁸¹ represents a group of non-metal atoms necessary for forming an aromatic heterocycle, and the ring formed by R ⁸¹ and Z includes those having a substituent. .

Y ⁸¹ represents an anion, m ⁸¹ represents O or 1, and when forming an intramolecular salt, m ⁸¹ is 0.

In addition to these compounds, JP-A-50-38540,
52-93470, 56-43353, 58-113929, JP-A-1
-178959, 3-213849, 4-323648, U.S. Patent 3,3
The compounds described in No. 21,313 are also preferably used.

Specific examples of the carboxyl group-activating type hardener used in the present invention are set forth below.
Examples HI-1 to HI-15 described in JP-A-3-213849 and examples 1 to 17 of general formula [1] described in JP-A-4-323648
Compounds described in JP-A-3-213849, H-II-1 to
H-II-7, H-III-1 to H-III-6, H-IV-1 to
H-IV-3, H-V-1 to H-V-12, H-VI-1 to H
-VI-5, H-VII-1 to H-VII-3, H-VIII-1 to
The compound of H-VIII-4 can be preferably used.

Typical compounds among these compounds are shown below, but the present invention is not limited thereto.

[0078]

[Chemical 11]

[0079]

[Chemical 12]

[0080]

[Chemical 13]

[0081]

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[0082]

[Chemical 15]

[0083]

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[0084]

[Chemical 17]

The average grain size of the silver halide grains used in the present invention is preferably 0.1 to 2.0 μm, particularly preferably 0.2.
~ 1.0 μm.

The grain size of silver halide grains is defined as the equivalent spherical diameter to the volume of grains from the observation of electron micrographs.

The emulsion used in the present invention may be a single emulsion or a mixture of two or more kinds of emulsions.
The emulsions to be mixed may be the emulsions according to the present invention, normal crystals, or a mixture of two or more kinds of emulsions.

As the silver halide emulsion of the present invention, those which are monodisperse are preferably used, and the variation coefficient of the average grain size is 20%.
It is preferably 20% or less, more preferably 20% or less.

Silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide are used in the silver halide emulsion of the present invention.
The silver iodide content is preferably 0.5 mol% or less, more preferably 0.3 mol% or less.
At this time, silver iodide may be present uniformly in the grain, but it is preferable that it is localized on the grain surface.

The method for producing a tabular silver halide emulsion is described in JP-A-58-113926, JP-A-58-113927, JP-A-58-113934 and JP-A-58-113926.
It is also possible to refer to 2-1855, European Patents 219,849, 219,850 and the like. Further, JP-A-61-6643 can be referred to as a method for producing a monodisperse tabular silver halide emulsion.

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

Grains may be grown by supplying an aqueous solution containing silver ions and an aqueous solution containing halogen ions, but may be supplied as fine particles of silver halide. In this case, a combination of silver iodide, silver iodobromide, silver bromide, silver chlorobromide, silver chloride, a halogen ion-containing solution, a silver ion-containing solution and the like can be supplied.

The silver halide emulsion according to the present invention includes
Core / shell type or double structure type grains having a silver halide composition whose surface is different from the inside of the grain are also preferably used. Regarding the core / shell type particles, see JP-A-59-17753.
Particles can be prepared by the methods described in No. 5, No. 59-178447, No. 60-35726, No. 60-147727, and the like.

The emulsion may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method in order to remove soluble salts. A preferred washing method is, for example, Japanese Patent Publication Sho
The method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-A No. 35-16086 or the method using G3, G-8, etc., as an aggregation polymer agent described in JP-A-2-7037 is particularly preferable. The salt method can be mentioned.

The chemical sensitization method includes so-called sulfur sensitization,
Gold sensitization, noble metals of Group VIII of the periodic table (eg Pd, Pt, I
The sensitization method can be used by sensitization by (e.g. r) and a combination thereof. Of these, a combination of gold sensitization and a selenium compound is preferable. The addition amount of the selenium compound can be set arbitrarily, but it is preferable to use it together with sodium thiosulfate in the chemical sensitization. More preferably, the molar ratio of the selenium compound and sodium thiosulfate is 2:
It is preferable to use it in a molar ratio of 1 or less, more preferably 1: 1 or less. Further, it is also preferable to use it in combination with reduction sensitization.

It is preferable to supply iodine ions at the time of chemical sensitization or at the end of chemical sensitization, from the viewpoints of sensitivity and dye adsorption. A method of adding in the form of fine grains of silver iodide is particularly preferable.

It is also preferable to carry out chemical sensitization in the presence of a compound having adsorptivity to silver halide. The compound is particularly preferably an azole, a diazole, a triazole, a tetrazole, an indazole, a thiazole, a pyridine, an azaindene, particularly a compound having a mercapto group or a compound having a benzene ring.

The silver halide emulsion according to the present invention may be subjected to reduction treatment, so-called reduction sensitization. As the reduction sensitization method, a reducing compound is added, pAg called silver ripening is passed through a silver ion excess state of 1 to 7, and pH called high pH ripening is performed at a high pH state of 8 to 11. A rubbing method may be applied to the silver halide emulsion.

It is also possible to use two or more of these methods together.

The method of adding a reducing compound is preferable because the degree of reduction sensitization can be finely adjusted. The reducing compound may be an inorganic or organic compound, thiourea dioxide, stannous salt, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives,
Examples thereof include sulfite, and particularly preferable examples include thiourea dioxide, stannous chloride, and dimethylaminoborane.
The addition amount of these reducing compounds varies depending on the reducing property of the compound and the production conditions of the emulsion such as the type of silver halide and the dissolution conditions, but it is 1 × 10 ^-8 to 1 mol per silver halide.
A range of 1 × 10 ^-2 mol is suitable. These reducing compounds are dissolved in water or an organic solvent such as alcohols and added during the growth of silver halide grains.

The sensitizing dyes may be used alone or in combination. Examples of using a combination of sensitizing dyes, U.S. Patent Nos. 2,688,545 and 2,977,299.
Issue 3,397,060, 3,522,052, 3,527,641,
3,617,293, 3,628,964, 3,666,480, 3,6
79,428, 3,703,377, 3,837,862, British Patent 1,
No. 344,281 and Japanese Patent Publication No. 43-4936.

The sensitizing dye may be added at any time during grain formation, before and after chemical sensitization, during the sensitization, and before coating, but it is preferably added before the completion of chemical sensitization. Of course, it can be added to several places.

The preferred addition amount is 40 mg / mol Ag to 400 mg /
Molar Ag is preferably used. More preferably, it is 80 mg / mol Ag to 200 mg / mol Ag.

Gelatin is preferably used as the hydrophilic colloid or binder used in the light-sensitive material of the present invention, but other hydrophilic colloid layers can be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sugar derivatives such as sodium alginate, dextrin and starch derivatives. Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. In particular, it is preferable to use dextran or polyacrylamide having an average molecular weight of 5,000 to 100,000 together with gelatin. Examples of these are, for example, JP-A-1-307738, 2-62532, 2-624748,
No. 2-44445, No. 1-66031, JP-A No. 64-65540, No. 63-1
No. 01841, 63-153538, etc.

Examples of gelatin include lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin as described in Bull. Soc. Phot. Japan, No. 16, p. Halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, those obtained by reacting various compounds such as epoxy compounds) Included.

The emulsion according to the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure (RD) 17643 (December 1978), (RD) 18716 (1
(November 979) and (RD) 308119 (December 1989). The types of compounds shown in these three (RD) and the places where they are described are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 right 1006 to 7 XIII plasticizer 27 XII 650 right 1006 XII slip agent 27 XII matting agent 28 XVI 650 right 1008 to 9 XVI binder 26 XXII 1003 to 4 IX support 28 XVII 1009 XVII according to the present invention Examples of the support that can be used in the light-sensitive material include those described in the above RD. A suitable support is a polyethylene terephthalate film or the like, and the surface of these supports may be provided with an undercoat layer or subjected to corona discharge or ultraviolet irradiation in order to improve the adhesion of the coating layer.

Photographic processing of the light-sensitive material of the present invention is carried out, for example, in RD-17643, XX to XXI, pages 29 to 30 or 308, 119, XX to XX.
Treatment with a treatment solution as described in XXI, pp. 1011-1012 may be performed. This process may be a black and white photographic process that forms a silver image. Processing temperature is usually 18 ℃ ~ 50
It is processed in the range of ℃.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-P-aminophenol).
Etc. can be used alone or in combination.
It should be noted that the developer may be a known one such as preservative, alkaline agent, p
An H buffer, an antifoggant, a development accelerator, a surfactant, an antifoaming agent, a toning agent, a water softener, a solubilizing agent, a viscosity imparting agent and the like may be used if necessary.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution, and a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be contained as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0112]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples described below.

Example 1 Using a silver bromide seed emulsion having an average grain size of 0.1 μm, an aqueous ammoniacal silver nitrate solution, an aqueous potassium bromide solution and an aqueous potassium iodide solution were appropriately mixed, and then added by a double jet method. A cubic monodisperse emulsion having a silver halide content of 0.1 mol% and an average grain size of 0.25 μm was grown.

After the addition was completed, the pH was adjusted to 6.0, followed by precipitation desalting using an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate, followed by washing with water.

Further, a gelatin solution containing 23 g of ossein gelatin was added and the above emulsion was redispersed. The emulsion had a potential of 50 mV at 50 ° C and a pH of 5.85.

The 200 particles thus obtained were arbitrarily selected, and the particle size was measured with an electron microscope to obtain the coefficient of variation of the particle size of 0.15.
Met.

To the above emulsion, 5.2 ml of 1% ammonium thiocyanate, 0.78 ml of 0.2% chloroauric acid and 0.25 mol of silver per mol of silver were added.
A chemical sensitizer consisting of 5.6 ml of% sodium thiosulfate and 3.5 ml of 0.6% triphenylphosphine selenide was added. Immediately before the addition of these additives, the spectral sensitizing dyes (A), (B), (C) and (D) in the following amounts were added per 1 mol of silver and chemically sensitized at 48 ° C.

[0118]

Embedded image

At the time when the increase in fog reached 0.02, 2.4 g of 4-hydroxy-6-methyl-1,3.3a, 7-tetrazaindene, which was 1 mol of silver halide, was added, and the temperature was lowered to give a chemical composition. Aging was stopped.

Further, this emulsion was mixed with an unchemically sensitized emulsion prepared by the following method so that the ratio with the chemically sensitized emulsion was 9: 1.

Preparation of unchemically sensitized emulsion A silver bromide seed emulsion having an average grain size of 0.3 μm was used to grow a monodisperse emulsion having an average grain size of 1.1 μm by the ammonia method. Coefficient of variation of grain size of this emulsion grain When measured in the same manner as above, 0.
It was 15.

The following compounds were added to 1 mol of silver in the emulsion prepared above to prepare an emulsion coating solution.

1-phenyl-5-mercaptotetrazole 10 mg 1-trimethylolpropane 14 g t-butylcatechol 68 mg polyvinylpyrrolidone (molecular weight 10.000) 850 mg styrene-maleic anhydride copolymer 2.0 g nitrophenyl-triphenyl-phosphonium chloride 50 mg 1 1,3-Dihydroxybenzene-4-sulfonic acid 1.7g 1,1 Dimethylol-1-bromo-1-nitromethane 6.2mg nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 700mg

[0124]

[Chemical 19]

The additives used in the protective layer of the emulsion are as follows. The added amount is shown as an amount per 1 g of gelatin.

Matting agent composed of polymethylmethacrylate having an average particle size of 5 μm 21 mg Matting agent composed of polymethylmethacrylate having an average particle size of 3 μm 28 mg Glyoxal 10 mg Formalin 8 mg

[0127]

Embedded image

Preparation of Backing Layer 100 g Gelatin 4 g of the following antihalation dyes 4 g Potassium nitrate 1 g Glyoxal 2 g Water

[0129]

[Chemical 21]

Preparation of protective layer for backing layer Using the binders and hardeners shown in Table 1, the following additives were added to each formulation per 1 m ² .

Matting agent consisting of polymethylmethacrylate having an average particle size of 6 μm 30 mg C ₁₃ H ₂₃ CONH (CH2 ₂ O) ₅ H 0.1 g Emulsion coating solution prepared above, emulsion protective layer solution, backing layer solution, backing protection The film solution was simultaneously applied to the undercoated base.

The amount of silver on the emulsion layer side was 2.0 g / m ² ,
The amount of gelatin on the emulsion layer side was 1.8 g / m ² of the emulsion layer,
The emulsion protective layer is 0.8 g / m ² . The amount of gelatin attached to the backing layer was 2 g / m ^{2 of} the backing layer, and the protective layer of the backing was the amount shown in Table 1.

The obtained sample was cut into four pieces and left in an atmosphere of 40% RH and 40 ° C. for 12 hours.
In the environment of ℃, 50% RH, 100 sheets of packaging is used to make a no-interleaf package, and the thickness is 100 μm and the density is 1.0 g.
/ Cm ³ , a moisture-proof polyethylene polyethylene bag in which carbon black was dispersed as a light-shielding agent was vacuum-sealed under a depressurized pressure of 50 mmHg for light-tight packaging.

The obtained sample was evaluated by processing it using the developing solution and fixing solution shown below.

Developer Formulation Part-A (for finishing 10.8 liters) Potassium hydroxide 340 g Potassium sulfite (50% solution) 2150 g Diethylenetriamine pentaacetic acid 32.3 g Sodium hydrogencarbonate 108 g 5-Methylbenzotriazole 150 mg 1-Phenyl-5-mercaptotetrazole 15mg Hydroquinone 280g Part-B (10.8L for finishing) Glacial acetic acid 158g Triethylene glycol 114g 1-Phenyl-3-pyrazolidone 19.5g 5-Nitroindazole 0.32g n-Acetyl-D, L-penicillamine 0.11g Part-A and B Were mixed and water was added to make 10.8 liters.

Starter solution formulation (for finishing 1 liter) Glacial acetic acid 138 g Potassium bromide 325 g 5-Methylbenzotriazole 1.5 g CH ₃ N (C ₃ H ₆ NHCONHC ₂ H ₄ SC ₂ H ₅ ) ₂ 20 mg Add water 1 Finish to liters.

The amount of the starter added was 20 ml per liter of the developing solution.

Fixer Formulation Part-A (for finishing 16.4 liters) Ammonium thiosulfate (70 wt / vol%) 3460 g Sodium sulfite 150 g Sodium acetate trihydrate 350 g Sodium citrate 43 g Gluconic acid 33 g Boric acid 26 g Glacial acetic acid 120 g Part-B (16.4 (For liter finishing) Aluminum sulfate 56 g Sulfuric acid (50 wt%) 91 g Part-A and B were mixed, and finished to 16.4 liters with water.

Processing Step Processing Temperature (° C) Processing Time (sec) Insertion-0.7 Development + Crossover 35 8.0 Fixing + Crossover 33 5.8 Washing + Crossover 18 5.6 Squeeze 40 2.5 Dry 50 4.3 Total-24.9 Each of the automatic processors used The tank capacity is 16 liters for the developing tank, 10 liters for the fixing layer, and 10 liters for the washing tank.
200 g of Clinker 205 (manufactured and sold by NIPPON R & D Laboratories, Inc.) was filled in a bag sewn with a 20-mesh polyethylene woven fabric, and immersed in the vicinity of the flush water supply section of the flush tank. For drying, an infrared heater (heater temperature 220 ° C) and warm air (60 ° C) were used together.

Regarding the replenishment amount, an area replenishment system using an infrared sensor detection mechanism was used to detect the area of 10 sheets of quadrant and replenish.

Replenishment amount of developer and fixer is 300 ml each
/ M ² .

Evaluation of Sensitivity and Fog Two types of samples were prepared: one that was left in the environment of 23 ° C. and 80% RH for 3 months, and one that was left in the environment of 23 ° C. and 50% RH for 3 months. did. The sample was opened in a dark room at 23 ° C. and 50% RH, the sample on the outermost side was taken out, subjected to wedge exposure using a tungsten light source, and subjected to the developing treatment, and the sensitivity was DG (Davis Givson) filter (Davis-Gibson. A tungsten tube with a color temperature of 5000 ° K that passed through a filter was used as a light source for wedge exposure, and the sensitivity was defined as the reciprocal of the irradiation energy required to give a density of fog +1.0, and the sensitivity and fog were evaluated.

[0143]

[Table 1]

Note: H in the table is

[0145]

[Chemical formula 22]

From the results shown in Table 1, the formulation containing the hydrophobic polymer layer in the backing layer shows less deterioration in sensitivity and fog even when stored in high humidity.

Example 2 Preparation of Seed Emulsion A seed emulsion Em-a having a high degree of monodispersity was prepared by the following method.

Liquid A1 Hydrogen peroxide treated ossein gelatin 11.3 g Potassium bromide 6.72 g DF-1 1.2 ml (Copolymer of polypropylene oxide and polyethylene oxide MW = 1500 [10% methanol solution]) 1.13 liters with water Solution B1 solution 170 g of silver nitrate make 227.5 ml with water C1 solution ossein gelatin 4.56 g potassium bromine 119 g make 227.5 liter with water solution D1 ammonia water (28%) 66.5 ml solution A1 vigorously stirred at 40 ° C, solution B1 And C1 liquid were added by the double jet method to generate nuclei. After the addition, lower the temperature of the mixed solution to 20 ° C, adjust the potential to 40 mV, and add D1 solution.
It was added in 20 seconds and aged for 5 minutes.

Then, modified gelatin (substitution rate 80%) in which the amino group of gelatin was substituted with a phenylcarbamoyl group was used.
After adding 30 g and stirring, the pH was lowered to 3.0 to cause aggregation, and the supernatant was decanted. Add 2000 ml of water again and adjust the pH to 6.0.
Then, the mixture was dispersed by stirring. Then, the pH was lowered to 3.0 and the decantation was performed in the same manner.

Further, the above seed emulsion washed with water using 23 g of ossein gelatin was redispersed.

When this seed emulsion was observed with an electron microscope, it was a monodisperse silver bromide emulsion having an average grain size of 0.28 μm and a distribution width of 20%.

Preparation of tabular grains A silver halide emulsion Em-1 mainly composed of tabular twin crystals was prepared using the seed emulsion Em-a and the solution shown below.

E1 solution Ocein gelatin 6.49 g DF-1 1.2 ml Equivalent to the above seed emulsion 0.62 mol F1 solution Ocein gelatin 1.69 g Potassium bromide 107.2 g Potassium iodide 2.30 g Water 504 ml G1 solution Silver nitrate 170 g Water The solution F1 and solution G1 were added to the solution E1 which was vigorously stirred at 65 ° C. to 504 ml by the controlled double jet method. The addition flow rate was controlled to 80% of the flow rate at which new nuclei were generated. Also,
During the addition, the potential was 65 ° C using a control potassium bromide solution.
And kept at -10 mV.

After the completion of addition, the pH was adjusted to 6.0, and then 283 mg of the spectral sensitizing dye (Chemical Formula 15) used in Example 1 was added per mol of silver halide, and after sufficient adsorption, a demol N aqueous solution was added. Precipitation desalting and washing with water were performed using (Kao Atlas Co., Ltd.) and an aqueous magnesium sulfate solution.

Further, the above emulsion washed with 23 g of ossein gelatin was redispersed. The potential of the emulsion at 50 ° C. was 50 mV, and the pH was 5.85.

Approximately 3000 particles of Em-1 were observed and measured by an electron microscope, and the shape was analyzed. The results are as follows.

Ratio of hexagonal plate to total projected area; 80% Average particle diameter of hexagonal plate (converted to a circle); 1.40 μm Average particle thickness of hexagonal plate; 0.7 μm Average aspect ratio of hexagonal plate; 2.0 Monodisperse of hexagonal plate Degree: 15% The amount of the seed emulsion used was adjusted, and otherwise, Em-2 and Em-3 were prepared in the same manner as the preparation of Em-1. However, the amount of the sensitizing dye added before desalting was adjusted to an amount proportional to the calculated surface area of the particles.

3000 particles of Em-2 and Em-3 were observed and measured with an electron microscope to analyze the shape. The results were as follows.

The ratio of hexagonal tabular grains to the total projected area is 80%, and the average grain diameter (converted to a circle) of hexagonal tabular crystals is 1.1 μm for Em-2 and 0.6 μm for Em-3.
And the average grain thickness of the hexagonal tabular crystal is 0.55 for Em-2.
μm and Em-3 were 0.3 μm, the average aspect ratio of the hexagonal plate crystal was 2.0, and the monodispersity was 15%.

Chemical Sensitization of Tabular Emulsion Em-1 After the spectral sensitizing dyes shown in Table 1 were added to Em-1 prepared above, 1 ml of ammonium thiocyanate (5.2 ml, 0.2%) was added per mol of silver. A chemical sensitizer consisting of 0.78 ml of chloroauric acid and 0.25% sodium thiosulfate was added and chemically sensitized at 48 ° C.

30 minutes after the start of chemical sensitization, the average particle size was 0.04 μm.
0.002 mol of silver iodide fine grains was added per mol of silver halide. After further 20 minutes of chemical ripening, 4-hydroxy
-6-Methyl 1,3,3a, 7-tetrazaindene as silver halide 1
2.4 g was added per mol and the temperature was lowered to stop the chemical ripening.

With respect to Em-2 and Em-3, a chemical sensitizer and a sensitizing dye in proportion to the surface area of the grain were added and chemical ripening was performed in the same manner as Em-1.

Emulsions Em-1 and Em that have been chemically ripened as described above.
-2 and Em-3 were mixed at a ratio of 30:50:20, and then Table 2
To prepare a emulsion coating solution by adding the water-soluble polymer of the present invention, a hardener, and the following various additives, and uniformly coat both sides on a polyethylene terephthalate base which has been subjected to an undercoating treatment, followed by drying to form a sample film. It was created. The coated silver amount was 2.5 g / m ² per side and the gelatin amount was 3.2 g / m ² .

1-Phenyl-5-mercaptotetrazole 10 mg 1-Trimethylolpropane 14 g t-Butylcatechol 68 mg Water-soluble polymer Amount shown in Table 2 Nitrophenyl-triphenyl-phosphonium chloride 50 mg 1,3-Dihydroxybenzene-4-sulfone Ammonium acid 1.7 g 1,1-Dimethylol-1-bromo-1-nitromethane 6.2 mg nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 700 mg As used in Example 1, ) And the same compound was added in the same amount.

The additives used in the emulsion protective layer solution are as follows. The added amount is shown as an amount per 1 g of gelatin.

A matting agent composed of polymethylmethacrylate having an average particle size of 5 μm 21 mg A matting agent composed of polymethylmethacrylate having an average particle size of 3 μm 28 mg The same amount of the same compound as the chemical formula 20 used in Example 1 was added.

Hardening agents shown in Table 2 The obtained samples were packaged and evaluated in the same manner as in Example 1.

The results are shown in Table 2.

[0169]

[Table 2]

As shown in Table 2, it can be seen that the use of the water-soluble polymer of the present invention and the hardening agent improved the storability under high humidity.

[0171]

According to the present invention, there is provided a silver halide photographic light-sensitive material packaged in a packaging form which is less susceptible to fluctuations in sensitivity and fog after storage under high humidity, is easy to handle, and is easy to recycle. Was obtained.

Claims (2)

[Claims] 1. At least one of the materials for packaging the silver halide photographic light-sensitive material is a polyethylene sheet having a thickness of 150 μm or less, and the polyethylene sheet has a density of 0.95 g /
contain cm ³ or more polyethylene, further, a silver halide photographic light-sensitive material has a light-sensitive silver halide emulsion layer at least one layer on one side of the support, the Coating of the emulsion layer of the support Silver halide photographic light-sensitive material, characterized in that it has at least one non-photosensitive hydrophilic colloid layer on the surface opposite to the surface on which it is provided, and a hydrophobic polymer layer at a position farther from the support with respect to the layer. . 2. At least one of the materials for packaging the silver halide photographic light-sensitive material is a polyethylene sheet having a thickness of 150 μm or less, and the polyethylene sheet has a density of 0.95 g /
The silver halide photographic light-sensitive material contains at least one light-sensitive silver halide emulsion layer on one side of the support, and contains at least one cm ³ of polyethylene. Water-soluble polymer content is 0.15g
/ M ² or less, and the emulsion layer is hardened with a carboxyl group-activating type hardener, and a silver halide photographic light-sensitive material.