JP2899840B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent antistatic properties,
The present invention relates to a silver halide photographic material suitable for a scanner using an argon laser as a light source.

[0002]

BACKGROUND OF THE INVENTION Generally, a plastic film support has a strong chargeability, and in many cases, this has imposed many restrictions on use. For example, a support such as polyethylene terephthalate is generally used in a silver halide photographic light-sensitive material, but is easily charged particularly at low humidity such as in winter. In recent years, when a high-sensitivity photographic emulsion is coated at a high speed, or when a high-sensitivity photosensitive material is exposed through an automatic printer, antistatic measures are particularly important.

[0003] When the photosensitive material is charged, the discharge causes a static mark to be formed or a foreign substance such as dust to adhere thereto, thereby generating a pinhole. Workability is reduced. For this reason, photosensitive materials generally use an antistatic agent, and recently, a fluorinated surfactant, a cationic surfactant, an amphoteric surfactant, a surfactant or polymer containing a polyethylene oxide group, a sulfonic acid or Polymers having a phosphate group in the molecule are used.

In particular, the use of a fluorine-based surfactant to adjust the charging sequence or to improve the conductivity by using a conductive polymer has been frequently used, for example, Japanese Patent Application Laid-Open Nos. 49-91165 and 49-91165.
-121523 discloses an example in which an ionic polymer having a dissociating group in the polymer main chain is applied.

However, in these conventional techniques, the antistatic ability is greatly deteriorated by the development processing. This is presumably because the antistatic ability is lost due to the steps of developing with an alkali, fixing with an acid, washing with water, and the like. Therefore, in the case of printing using a processed film further, such as a printing photosensitive material,
Problems such as generation of pinholes due to adhesion of dust occur. For example, JP-A-55-84658 and JP-A-61-174542 disclose a water-soluble conductive polymer having a carboxyl group, a hydrophobic polymer having a carboxyl group and an antistatic layer comprising a polyfunctional aziridine or a conductive material such as tin oxide. Metal oxides have been proposed. These conductive layers are usually provided on the backing layer side opposite to the emulsion layer and the support.
The backing layer contains a dye in order to enhance the safe light resistance against halation or light from the backing layer side. The conductive layer as described above easily adsorbs these dyes, and in particular, the deterioration of the charging performance and the deterioration of the residual color with time were remarkable. However, there is a problem that the dye cannot be removed due to halation or the like.

[0006]

SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide an antistatic layer provided on the backing layer side so that the antistatic ability does not deteriorate even after the treatment, and the image quality due to safelight and halation does not occur. An object of the present invention is to provide a silver halide photographic light-sensitive material for an argon laser, which has little deterioration and little residual color.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to provide a halogenated silver halide emulsion having at least one silver halide emulsion layer on a support and having a conductive layer containing a water-soluble conductive polymer or a conductive metal oxide. This is achieved by a silver halide photographic material, wherein the hydrophilic colloid layer on the side having a conductive layer with respect to the support has an absorbance at 488 nm of 0.3 or more and 2.0 or less. here
The absorbance referred to in the silver halide photographic light-sensitive material
The side opposite to the side with the conductive layer is peeled off
Means the absorbance of the film surface.

Hereinafter, the present invention will be described in detail.

The dye preferably used in the light-sensitive material of the present invention includes a compound represented by the following formula [D].

[0010]

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[In the general formula [D], R ₁ is an alkyl group, specifically, for example, an alkyl group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group,
2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, vinylmethyl, benzyl, phenethyl, n-propyl Group, isopropyl group, n-butyl group and the like. Z is a group of nonmetallic atoms necessary to form a 5- or 6-membered heterocyclic ring, and examples of the heterocyclic ring include a thiazole ring, a selenazole ring, an oxazole ring, a benzothiazole ring, a benzoselenazole ring, Benzoxazole ring, naphthothiazole ring, naphthoselenazole ring, naphthoxazole ring, pyridine ring, quinoline ring and the like,
Further, these heterocycles may have substituents, and these substituents are, for example, halogen atoms (for example, chlorine atoms, bromine atoms, etc.), for example, alkyl groups, preferably having 1 to carbon atoms.
4 alkyl groups (eg, methyl group, ethyl group, n-propyl group, etc.), halogenated alkyl groups (eg, trifluoromethyl group, etc.), alkoxy groups, preferably having 1 to 1 carbon atoms
4 alkoxy groups (eg, methoxy, ethoxy, n-
Propyloxy group, etc.), hydroxy group, aryl group (for example, phenyl group etc.). Q ₁ represents a group of nonmetallic atoms necessary for forming a 5-membered heterocyclic ring. Examples of these heterocyclic rings include a rhodanine ring, a thiohydantoin ring, a thiooxazolidinedione ring, and a thioselenazolidinedione ring. These heterocyclic rings may have a substituent, and these substituents may be an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, an n-propyl group, -Hydroxyethyl group,
2-hydroxyethyloxyethyl group, 2-methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfoethyl Propyl group, 3-sulfobutyl group, 4-sulfobutyl group, benzyl group, phenethyl group, n-propyl group, n-butyl group, etc., aryl group (eg, phenyl group, p-sulfophenyl group, etc.), viridyl group (eg, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 4-methyl-2-pyridyl group, etc.). M represents 1 or 2. The compounds represented by the above general formula [D] include, for example, the following D-1 to D-26
Is mentioned.

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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The compound represented by the general formula [D] used in the present invention can be easily synthesized based on the methods described in, for example, US Pat. No. 2,161,331 and West German Patent No. 936,071. . The above general formula [D]
In order to use the compound represented by, add or dissolve in the coating solution, or dissolve in water or an organic solvent such as methanol, ethanol, acetone, etc. alone or a mixture thereof, and add to the coating solution at any time. I just need.

The emulsion using the compound represented by the formula [D] is desirably desalted with aggregated gelatin.

The agglomerated gelatin used in the present invention is an agglomerated gelatin in which at least 50% of the amino groups of the gelatin molecule are substituted with acyl, carbamoyl, sulfonyl, thiocarbamoyl, alkyl and / or aryl groups. is there. Hereinafter, this aggregated gelatin is referred to as denatured gelatin as necessary.

Examples of the substituent for the amino group of gelatin are as follows:
It is described in U.S. Pat. Nos. 2,691,582, 2,614,928 and 2,525,753.

Examples of useful substituents include (1) acyl groups such as alkylacyl, arylacyl, acetyl and substituted and unsubstituted benzoyl; (2) carbamoyl groups such as alkylcarbamoyl and arylcarbamoyl; and (3) alkylsulfonyl. , A sulfonyl group such as arylsulfonyl, (4) a thiocarbamoyl group such as alkylthiocarbamoyl and arylthiocarbamoyl, (5) a linear or branched alkyl group having 1 to 18 carbon atoms, (6) a substituted or unsubstituted phenyl, And aryl groups such as naphthyl and aromatic heterocycles such as pyridyl and furyl.

Among them, preferred modified gelatin is _one derived from an acyl group (—COR ₁ ) or a carbamoyl group —CON (R ₂ ) R ₁ .

R ₁ is a substituted or unsubstituted aliphatic group (for example, an alkyl group having 1 to 18 carbon atoms, allyl group), an aryl group or an aralkyl group (for example, phenethyl group).
₂ is a hydrogen atom, an aliphatic group, an aryl group, or an aralkyl group.

Particularly preferred are those wherein R ₁ is an aryl group,
R ₂ is a hydrogen atom.

In the following, specific examples of the agglomerated gelatin agent will be exemplified by amino group substituents, but the present invention is not limited thereto.

[0028]

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The aggregating gelatin agent can be used before the desalting step in the silver halide emulsion, but is preferably performed during the desalting step. The amount of the flocculant gelatin agent is not particularly limited, but when used for desalting, after desalting, a substance (preferably gelatin) contained as a protective colloid is used.
An appropriate amount is 0.1 to 10 times (weight), particularly preferably 0.2 to 10 times (weight).
５5 times (weight).

The agglomerated gelatin agent causes the silver halide particles to be agglomerated together with the protective colloid. After the addition of the agglomerated gelatin agent, the pH can be adjusted to agglomerate the silver halide emulsion. PH for coagulation
Is preferably 5.5 or less, particularly preferably 4.8 to 2. The acid used for pH adjustment is not particularly limited, but organic acids such as acetic acid, citric acid and salicylic acid, and inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid are preferably used.

Heavy metal ions such as magnesium ions, cadmium ions, lead ions, zirconium ions and the like may be added in combination with the aggregating gelatin agent.

The removal of dissolved substances (desalting) may be performed once or may be repeated several times. When repeated several times, an agglomerated gelatin agent may be added each time it is removed, or only the agglomerated gelatin agent may be added first.

In the present invention, typical methods for forming the conductive layer include a method using a water-soluble conductive polymer, hydrophobic polymer particles, a curing agent and the like, and a method using a metal oxide. .

The water-soluble conductive polymer of the present invention includes a polymer having at least one conductive group selected from sulfonic acid groups, sulfate groups, quaternary ammonium salts, tertiary ammonium salts, and carboxyl groups. . The conductive groups require at least 5% by weight per polymer molecule. The water-soluble conductive polymer may contain a hydroxy group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, and a vinyl sulfone group.

The molecular weight of the polymer is from 3000 to 100,000, preferably from 3500 to 50,000.

The following are examples of compounds of the water-soluble conductive polymer used in the present invention, but are not limited thereto.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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The hydrophobic polymer particles contained in the water-soluble conductive polymer layer of the present invention are composed of a so-called latex which is substantially insoluble in water. This hydrophobic polymer is obtained by polymerizing a monomer selected in any combination from styrene, a styrene derivative, an alkyl acrylate, an alkyl methacrylate, an olefin derivative, a halogenated ethylene derivative, a vinyl ester derivative, and acrylonitrile. In particular, at least styrene derivatives, alkyl acrylates and alkyl methacrylates
It is preferably contained at 30 mol%. In particular, 50 mol% or more is preferable.

The monomer having an amide group contained in the latex of the present invention is preferably represented by the following general formula [A].

[0045]

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Wherein R represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms. L represents a divalent group, and a represents 0 or 1. R ₁ and R _{2 each} represent a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. Specific examples of the monomer of the present invention will be given.

[0047]

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There are two methods for converting a hydrophobic polymer into a latex by emulsion polymerization, or by dissolving a solid polymer in a low-boiling solvent and finely dispersing it, and then distilling off the solvent. In addition, it is preferable to carry out emulsion polymerization in that a uniform product can be obtained.

The molecular weight of the hydrophobic polymer may be 3000 or more, and there is almost no difference in transparency depending on the molecular weight.

Specific examples of the hydrophobic polymer of the present invention will be given.

The method of introducing a polyalkylene oxide chain into the hydrophobic polymer latex of the present invention is preferably a method of copolymerizing a monomer having a polyalkylene oxide chain.

The monomer is preferably represented by the following general formula [M].

[0053]

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Next, specific examples of these monomers will be described.

[0055]

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[0056]

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[0057]

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[0058]

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The following are specific examples of the latex of the present invention.

[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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As the epoxy compound of the present invention, those having a hydroxy group containing an ether condensation are preferred.

Specific examples of the epoxy compound of the present invention will be given.

[0069]

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[0070]

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[0071] The addition amount of the hydrophobic polymer latex contained in the antistatic layer, the addition amount of preferably 10mgm ² ~1000mg / m ^2, particularly preferably ^{100mg / m 2 ~500mg / m 2} , the water-soluble conductive polymer , amount of preferably ^{50mg / m 2 ~2000mg / m 2} , particularly preferably ^{100mg / m 2 ~1000mg / m 2} , an epoxy compound, preferably ^{10mg / m 2 ~500mg / m 2} , particularly preferably 50mg / m ^{2 to} 300 mg / m ² .

A dispersant can be used in the antistatic layer, and a nonionic activator is used as the dispersant.
Polyalkylene oxide compounds are preferably used.

The polyalkylene oxide compound used in the present invention refers to a compound containing at least 2 and at most 500 or less polyalkylene oxide chains in the molecule, for example, polyalkylene oxide and aliphatic alcohols, phenols and fatty acids. Condensation with aliphatic mercaptans, organic amines, ethylene oxide, propylene oxide, etc. by condensation reaction with compounds having active hydrogen atoms such as aliphatic mercaptans and organic amines, or with polyols such as polypropylene glycol and polyoxytetramethylene polymer Can be synthesized.

The above polyalkylene oxide compound is
The number of polyalkylene oxide chains in the molecule is 2 instead of 1.
It may be a block copolymer divided into two or more places.

At this time, the total polymerization degree of the polyalkylene oxide is preferably 3 or more and 100 or less.

Specific examples of the polyalkylene oxide compound optionally used in the present invention are shown below.

[Exemplary Compound]

[0078]

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[0079]

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[0080]

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[0081]

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Next, a method for forming a conductive layer using a metal oxide will be described.

Preferred as the metal oxide are crystalline metal oxide particles, but those containing oxygen vacancies and those containing a small amount of heteroatoms forming donors for the metal oxide used are generally used. In particular, those having a small amount of hetero atoms forming a donor for the latter metal oxide are particularly preferable because they do not give fog to the silver halide emulsion.

Examples of metal oxides include ZnO ₂ , TiO ₂ , Sn
O ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, M ₀ O ₃ , V ₂ O _{5 and the} like or composite oxides thereof are preferable, and ZnO ₂ , TiO ₂ , Sn
O ₂ is preferred.

As an example containing a heteroatom, for example, addition of Sb or the like to SnO ₂ or addition of Nb or Ta to TiO ₂ is effective. The addition amount of these different atoms is preferably in the range of 0.01 to 30 mol%, and particularly preferably in the range of 0.1 to 10 mol%.

The metal oxide particles used in the present invention are:
It has conductivity and its volume resistivity is 10 ⁷ Ωcm
Below, it is particularly preferred that it is 10 ⁵ Ωcm or less.

This oxide is disclosed in JP-A-56-143431.
Nos. 56-120519 and 58-62647.

The metal oxide particles are used by being dispersed or dissolved in a binder. The binder that can be used is not particularly limited as long as it has a film forming ability,
For example, gelatin, proteins such as casein, carboxymethyl cellulose, hydroxyethyl cellulose, acetyl cellulose, diacetyl cellulose, cellulose compounds such as triacetyl cellulose, dextran, agar,
Sodium alginate, sugars such as starch derivatives, polyvinyl alcohol, polyvinyl acetate, polyacrylate,
Polymethacrylate, polystyrene, polyacrylamide, poly-N-vinylpyrrolidone, polyester,
Examples include synthetic polymers such as polyvinyl chloride and polyacrylic acid.

In particular, gelatin (lime-treated gelatin, acid-treated gelatin, oxygen-degraded gelatin, phthalated gelatin, acetylated gelatin, etc.), acetylcellulose, diacetylcellulose, triacetylcellulose, polyvinyl alcohol, polyvinyl acetate, polybutyl acrylate, Polyacrylamide and dextran are preferred.

In order to use the metal oxide more effectively and lower the resistance of the conductive layer, it is preferable that the volume content of the metal oxide in the conductive layer is higher, but the strength of the layer is not sufficiently increased. Since a binder of at least about 5% is required to have the metal oxide, the volume percentage of the metal oxide is preferably in the range of 5 to 95%.

[0091] The amount of the metal oxide is preferably 0.05 to 10 g / m ^2, more preferably 0.01-5 g / m ^2. Thereby, an antistatic property is obtained.

In the present invention, the conductive layer is provided between the silver halide emulsion layer and the support and / or on the opposite side of the support with respect to the emulsion layer. That is, it may be provided on the photosensitive emulsion side of the transparent support, or may be provided on the opposite side of the transparent support with respect to the photosensitive emulsion surface, that is, on the so-called back surface. On the other side of the body
It is preferably provided on the so-called back surface.

The conductive layer is formed on a transparent support by coating.

The transparent support may be any photographic one, but is preferably polyethylene terephthalate or cellulose triacetate made to transmit at least 90% of visible light.

These transparent supports are prepared by a method well-known to those skilled in the art. In some cases, a slight amount of a dye is added so as not to substantially impede light transmission, and the transparent support may be tinted or blued. You may.

The support may be provided with an undercoat layer containing a latex polymer after the corona discharge treatment. Corona discharge treatment is 1mW ~ 1kw as energy value
/ m ² min is particularly preferably applied. Also particularly preferably,
After applying the latex subbing layer, the corona discharge treatment may be performed again before applying the conductive layer.

[0097]

The dyes used in the backing layer of the present invention include, for example, the following general formulas [Ba], [Bb], [B-
c] and [Bd].

[0099]

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In the formula, R ₁ is an atomic group represented by —OX or —N (X) (Y), wherein X and Y are a hydrogen atom, an alkyl group, a cyanoalkyl group, a carboxyalkyl group, a sulfoalkyl group, A hydroxyalkyl group, a halogenated alkyl group or an optionally substituted alkyl group or a sodium / potassium salt thereof, wherein R ₂ and R ₃ are a hydrogen atom,
A halogen atom, an alkyl group, a hydroxy group, an alkoxy group, an alkylthio group, or a group similar to the aforementioned -OX group, and Q represents at least one halogen atom, a carboxy group, a sulfo group, a sulfoalkyl group or a sodium salt thereof. A phenyl group or a sulfoalkyl group, a sulfoalkoxyalkyl group, a sulfoalkylthioalkyl group substituted with a potassium salt, and L represents a methine group which may be substituted. R ₄ represents an alkyl group, a carboxy group, an alkyloxycarbonyl group or an acyl-substituted or unsubstituted amino group. m represents an integer 1 or 2, and n represents an integer 0 or 1.

[0101]

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In the formula, R ₅ , R ₆ , R ₈ , R ₉ and R ₁₀ are a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group, an amino group, an acylamino group, a carboxyl group or a sulfone group or a sodium salt thereof. · represents a potassium salt, R ₇ represents an alkyl group or a carboxyl group.

[0103]

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In the formula, R ₁₁ and R ₁₂ represent an alkyl group, a substituted alkyl group, an aryl group, an alkoxycarbonyl group or a carboxyl group, and R ₁₃ and R ₁₄ represent an alkyl group or a sulfone substituted with a sulfonic acid group or a carboxyl group. An aryl group substituted with an acid group, a carboxyl group or a sulfonic acid group or a sodium / potassium salt thereof, and L represents a substituted or unsubstituted methine chain. M represents a sodium, potassium or hydrogen atom, and l represents 0 or 1.

[0105]

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In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent an alkyl group, a hydroxyalkyl group, a cyano group, an alkylcyano group, an alkoxy group and a sulfoalkyl group. R ₅ and R ₆ represent a sulfonic acid group or an alkylsulfonic acid group.

The following are typical specific examples of the compounds represented by formulas [Ba] to [Bd].

[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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[0115]

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The silver halide emulsion used in the light-sensitive material of the present invention may be any silver halide emulsion selected from ordinary silver halide emulsions such as silver chloride, silver chlorobromide, silver chloroiodobromide and the like. Can be selected and used, but the emulsion used is preferably a monodisperse emulsion.

The grain size of the silver halide grains in the emulsion was 3 μm.
The following is preferable, and particularly preferably 0.1 μm to 1.0 μm.

The silver halide grains used in the emulsion of the present invention may be added with a compound belonging to Group 8 such as a water-soluble rhodium salt and / or a water-soluble iridium salt in the course of forming the grains, and the inside of the grains and / or It can be included on the particle surface.

The light-sensitive material of the present invention is disclosed in JP-A-1-274131.
Silver halide photosensitive materials described on pages 38 to 46 can be used. Various other techniques known in the photographic industry can be used as needed.

Sulfur sensitization is preferred for chemical ripening in the present invention, but other sensitization methods such as gold sensitization, reduction sensitization, and selenium sensitization may be used in combination with sulfur sensitization. Particularly preferred is a combination of gold sensitization.

In the light-sensitive material of the present invention, various additives can be further used according to the purpose. These additives are more particularly described in Research Disclosure No. 176.
Volume Item17643 (December 1978) and Volume 187 Item18716 (19
(November 1979), and the relevant locations are summarized in the table below.

Additive type RD17643 RD18716 1. Chemical sensitizer, page 23, 648, right column 2. Sensitivity increasing agent Same as above 3. Spectral sensitizer, supersensitizer, 23 to 24, page 648, right column to 649 Right column of page 4. Brightener page 24 5. Antifoggant and stabilizer page 24-25 page 649 right column 6. Light absorber, filter page 25-26 649 right column to 650 left column Dye and ultraviolet absorber 7 Anti-stain agent, page 25, right column, page 650, left to right column 8. Dye image stabilizer, page 25 9. Hardening agent, page 26, page 651, left column 10. Binder, page 26 Same as above 11. Plasticizer / lubricant, page 27, 650 right Column 12.Coating aids / surfactants page 26 to 27 Same as above 13.Static inhibitor page 27 Same as above The photographic processing of the silver halide photographic light-sensitive material according to the present invention is as follows.
Various techniques known in the art can be used.

[0123]

The present invention will be specifically described below with reference to examples. Note that, needless to say, the present invention is not limited to the embodiments described below.

Example 1 (Preparation of Subbing Layer) A support U-1 was prepared by subjecting a 100 μm-thick polyethylene terephthalate to the undercoating treatment described in Example 1 of JP-A-59-19941.

The following formulas A and B were applied to the upper layer of the support U-1 on the backing layer side, respectively.
-3.

[0126]Formula A  Water-soluble conductive polymer A (Table 1) 0.6g / m^Two  Hydrophobic polymer particles B (Table 1) 0.3 g / m^Two  Curing agent E (Table 1) 0.15 g / m
²  Nonionic surfactant (C) 0.06 g / m
²  This is applied, dried at 90 ° C for 2 minutes, and heat-treated at 140 ° C for 90 seconds.
I understood.

[0127]Formula B  Gelatin 35mg / m^Two  SnO_Two/ Sb (8/2) Particle size 0.3μm 250mg / m^Two  Polyalkylene oxide (P) 5mg / m²

[0128]

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(Preparation of Emulsion Layer Coating Solution) Solution A water 9.7 l sodium chloride 20 g gelatin 105 g solution B water 3.8 l sodium chloride 365 g gelatin 94 g potassium bromide 450 g 0.01% aqueous solution of potassium hexachloroiridate 28 ml potassium hexabromorhodate 1.0 ml of 0.01% aqueous solution of salt solution C water 3.8 l silver nitrate 1,700 g solution D flocculant gelatin agent (G8, denaturation rate 90%) 36 g water 300 cc pH 3 and pAg 7.7 in the above solution A kept at 40 ℃ While simultaneously adding the above solution B and solution C functionally over a period of 60 minutes and stirring for another 10 minutes, add solution D and stir for 5 minutes, lower the pH to 4.7 with acetic acid (20%), aggregate the gelatin, After precipitation, the supernatant was drained. After the first desalting, fresh water was added, and the mixture was stirred for 5 minutes. Then, the pH was lowered to 4.7 with acetic acid in the same manner as the first, and the second desalting was performed. . This operation is repeated once, and the desalting is performed for the third time. To this, 3.7 l of water and 141 g of gelatin are added and dispersed at 55 ° C. for 30 minutes. As a result, grains having a silver bromide content of 32 mol% and a silver chloride content of 68 mol% having an average monodispersity of 0.30 μm of 9 are obtained.

2600 ml of this emulsion was weighed, and 40 ml of a 1% aqueous solution of citric acid and 100 ml of an aqueous solution of 5% potassium bromide were added.
The pH and pAg were prepared by adding ml. To the emulsion thus obtained, 30 ml of chloroauric acid and 20 ml of an aqueous solution of 0.1% sodium thiosulfate were added and ripened at 60 ° C. for about 3 hours to obtain the highest sensitivity.

The above emulsion was mixed with 1-mol per mole of silver halide.
25m 0.5% solution of phenyl-5-mercaptotetrazole
1, ripening was stopped by adding 600 ml of a 1% solution of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene as a stabilizer and 960 ml of a 10% aqueous solution of gelatin.

To this emulsion were added 15 ml of a 0.1% solution of the following (I) and 6 ml of an aqueous saponin solution per mol of silver halide.
7 ml of a 20% aqueous solution of hydroquinone, 8.4 g of a polymer latex of ethyl acrylate, 3.5 ml of a 1% aqueous solution of citric acid, 13 ml of a 4% aqueous solution of styrene-maleic acid polymer, and an aqueous solution of 5% potassium bromide PH, pA
g was adjusted.

(Preparation of Coating Solution for Emulsion Protective Layer) Gelatin 60
Dissolve 0 g in 8000 cc of water, 105 ml of 10% potassium bromide aqueous solution
And 1-decyl-2- (3-isopentyl) succinate-
375 ml of a 1% aqueous solution of sodium 2-sulfonate and 9.8 g of amorphous silica having an average particle size of 3 μm are added and dispersed. To the solution thus obtained, 150 cc of a 5% solution of the following compound (II) was added and stirred.

[0134]

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(Preparation of Coating Solution for Backing Layer) Gelatin 70
a 2% aqueous solution of the water-soluble dye a-14,
A 2% aqueous solution of a-19 and a 5% aqueous solution of the following water-soluble dye B were added so as to obtain the amounts shown in Table 5. 20% saponin aqueous solution
21ml butyl acrylate high polymer latex
10.5 g, 20 mg of 82.5 ml of a 0.75% methanol solution of 5-nitroindazole, 20 ml of a 4% aqueous solution of a styrene-maleic acid polymer, and 5 ml of a 7% aqueous solution of citric acid were added and stirred.

(Preparation of Coating Solution for Backing Layer Protective Layer) A 1% aqueous solution of 1% sodium 1-decyl-2- (3-isopentyl) succinate-2-sulfonate was added to an aqueous solution containing 600 g of gelatin.
l, 360ml of 10% aqueous solution of sodium chloride, average particle size 4μ
m of polymethyl methacrylate was added and stirred.

[0137]

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(Preparation of Sample) Of the coating solutions for the emulsion layer, the protective layer on the emulsion layer, the back layer, and the protective layer on the back layer prepared as described above, the coating solution for the protective layer on the emulsion layer To this solution, a sodium salt aqueous solution of formalin and 2,4-dichloro-6-hydroxytriazine was added as a hardening agent, and glyoxal was added as a hardening agent to the coating solution for the back layer, and a coating for the protective layer on the top of the back layer was added. After adding glyoxal as a hardening agent to the solution, the emulsion layer was formed on one side of the undercoated polyethylene terephthalate support so that the silver amount was 4.25 g / m2, and the protective layer was further formed on top of the emulsion layer. Is 1.36 g / m ²
Were applied simultaneously. And on the opposite side of the emulsion layer,
The back surface layer so that the amount of gelatin is 2.26 g / m ^2, as further amount of gelatin protective layer thereon is 1.34 g / m ^2,
Samples 1 to 7 were prepared by simultaneous coating on the supports shown in Table 5.

(Evaluation of Samples) Each of the ten types of sample films thus obtained was exposed to an argon laser.
Developing was performed at 38 ° C. for 20 seconds using the following developing solution and fixing solution with a Konica automatic developing machine GR-27 (manufactured by Konica Corporation).

The unexposed samples of the 10 sample films were placed at a distance of 2 m under a yellow lamp in which a yellow filter SG808II was wound around a 40 W fluorescent lamp with the backing layer facing upward.
The fog density in the case of minutes and in the case of standing for one hour was measured by a conventional method, and expressed by the difference.

Table 5 shows the measurement results of the sensitivity of each sample and the fog density under each condition. The sensitivity was represented by the reciprocal of the exposure at a fog density of +3.0 as a relative sensitivity.

The absorbance of the backing layer was measured at 488 nm using a Shimadzu spectrophotometer UVIDFC-610 after peeling the emulsion layer.
The absorbance at m was measured. The remaining color is the unexposed film as it is, and after the humidity control in the environment of 23 ° C and 55RH%,
After being sealed and left for 1 day in an environment of 50 ° C. to be forcibly deteriorated, five sheets subjected to development processing were superposed and visually evaluated. An evaluation one rank lower than the standard indicates that the film has more residual color than the standard.

The surface resistivity indicates the surface resistivity on the backing layer side of the film after the development processing. At this time, the distance between the electrodes
1 cm and the width of the electrode was 5 cm.

Sharp is SG80 manufactured by Dai Nippon Screen Co., Ltd.
Output 50% dots using 8II, and after developing, 100%
It was visually observed with a loupe and evaluated on a 5-point scale. 1 was the lowest rating and 5 showed the best level.

[Developing solution formulation] Pure water (ion-exchanged water) 800 ml Ethylenediaminetetraacetic acid ditonarium salt 2 g Diethylene glycol 25 g Potassium sulfite 60 g Potassium carbonate 15 g Height perquinone 20 g 5-methylbenzotriazole 300 ml 1-phenyl-5-mercaptotetrazole 60 mg 1- Phenyl-4,4-dimethyl-3-pyrazolidinone 300 mg Potassium bromide 3.5 g 1-Phenyl-3-pyrazolidone 500 mg Used at the end of 1 L when using a developer. pH is about 10.8
Met.

[Formulation of Fixing Solution] (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid (90% W / W aqueous solution) 8.1 ml (composition B) pure water (ion-exchanged water) 17 ml sulfuric acid (50% W / W aqueous solution) 5.8 g aluminum sulfate (Al ₂ O ₃ in terms of content of 8.1% W / W aqueous solution) 26.5 g fixing When the solution was used, the composition A and the composition B were dissolved in 500 ml of water in this order, and the solution was finished to 1 liter. The pH of the fixing solution was about 4.3.

The results are shown in Table 1.

[0148]

[Table 1]

From the results shown in Table 1, it can be seen that the sample of the present invention has antistatic ability even after treatment, has little deterioration in safelight property and sharpness, and has little residual color.

[0150]

According to the present invention, a silver halide photographic light-sensitive material for an argon laser having antistatic ability even after processing, having little deterioration in safelight property and sharpness, and having little residual color can be provided.

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and having a conductive layer containing a water-soluble conductive polymer or a conductive metal oxide. A silver halide photographic material, wherein the hydrophilic colloid layer on the side having a conductive layer with respect to the body has an absorbance at 488 nm of 0.3 to 2.0.