JPH075608A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material improved in scratch-like fog and antitackiness and high in sensitivity and further having antistatickness and a high covering power and capable of forming a pure black tone silver image. CONSTITUTION:The silver halide photographic sensitive material is characterized by containing flat silver halide grains having an aspect ratio of >=3 sensitized with a selenium compound and a polymer latex polymerized from at least one kind of monomer having a solubility of <=0.025weight% in water at 25 deg.C in a hydrophilic colloidal layer located farthest from a support.

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, and more particularly to a high-sensitivity silver halide photographic light-sensitive material having improved scratch resistance, antistatic property, scratches between films, and color tone of image silver. is there.

[0002]

2. Description of the Related Art In recent years, silver halide photographic light-sensitive materials are required to have high sensitivity, high contrast, excellent graininess and sharpness, as well as rapid processing property. In particular, X-ray photographic light-sensitive materials for medical diagnosis are required to be processed rapidly in order to speed up diagnosis. For example, angiographic photography in which a catheter is inserted into a blood vessel and a contrast medium is injected at high pressure, or during surgery. X
Ultra-quick processing of less than 45 seconds with Dry to Dry is an essential requirement for intraoperative radiography such as line photography.

In order to accelerate processing, rapid processing of a light-sensitive material has been attempted along with automation of photographing, transportation, processing and the like. However, problems such as deterioration of image quality due to high temperature (30 ° C. to 40 ° C.) and high pH in rapid processing, poor drying due to high-speed transportation, and increase in carry-over amount due to processing agent are raised.

In recent years, tabular silver halide grains have been increasingly used as a light-sensitive material surface in order to cope with high image quality. Since the tabular silver halide grains have a large specific surface area, the color sensitization efficiency is improved by the spectral sensitizing dye, and so-called covering power (covering power) is improved. Further, in the case of the X-ray photosensitive material, there are advantages that the crossover light is reduced and the light scattering is reduced to obtain an image with high resolution.

Further, as a method for increasing the sensitivity of the tabular emulsion, it is possible to obtain high sensitivity and high contrast by adding a trace amount of a selenium compound to a gold or sulfur sensitizer, for example, US Pat. No. 3,297,446. It is disclosed in No. 3,420,670.

However, the tabular silver halide grains are weaker in pressure resistance against external force such as pressure or bending than others, and streak-like fog is apt to be generated at a contact portion by roller conveyance of an automatic developing machine or the like. It has a serious drawback such as. Conventionally, many methods have been proposed as a method for improving the pressure resistance of a silver halide photographic light-sensitive material. For example, US Pat. No. 3,632,342 using a polymer latex in a constituent layer is disclosed. Although this technology is effective against the external pressure applied to the entire film, it does not have sufficient effect on the pressure resistance due to friction with the roller during film transport, and it has a raw storability in film photographic performance. It had a defect such as deterioration.

Further, the modification of the film surface by the method causes a scratch between the films, and as a result, there is a problem in that two films are transported while being mechanically transported, or static electricity causes static marks. There were problems such as frequent fog.

On the other hand, in the case of a light-sensitive material such as a medical silver halide photographic light-sensitive material in which a silver image is directly observed and diagnosed and evaluated, one of the important factors for an observer is the fog on the physical properties of the film as described above. In addition, the color tone of the silver image is enhanced. If the silver image is discolored or colored, it may not only give an unpleasant impression to the observer but may also lead to misdiagnosis. Therefore, it is desirable that the image is clear and pure black tone.

It has long been known to use a mercapto compound as a color tone improving agent for developed silver, but it cannot be used for a high-speed emulsion because it gives a marked desensitizing property. However, it was unexpected that the color tone of the silver image could be improved to black by using the polymer latex of the present invention in the protective layer.

[0010]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a high-sensitivity silver halide photographic light-sensitive material having improved rubbing fog resistance and scratch resistance without impairing photographic performance. Another object of the present invention is to provide a silver halide photographic light-sensitive material having a high covering power and having an antistatic property and capable of obtaining a silver image having a pure black tone.

[0011]

The above problems have been solved by the present invention described below. That is, in a silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a hydrophilic colloid layer on at least one side of a support, the silver halide grains of the silver halide emulsion layer are selenium. A hydrophilic colloid layer containing tabular silver halide grains sensitized by selenium with an aspect ratio of 3 or more, and having a solubility in water at 25 ° C. of not more than 0.025% by weight in a hydrophilic colloid layer located farthest from the support. It has been achieved by a silver halide photographic light-sensitive material characterized by containing a polymer latex obtained by polymerizing at least one type of monomer.
Hereinafter, the present invention will be described in detail.

In the present invention, a monomer having a solubility in water at 25 ° C. of 0.025% by weight or less, preferably 0.015% by weight or less (hereinafter referred to as a monomer) is an ethylenic monomer such as hexyl acrylate or 2
-Acrylic acid esters such as ethylhexyl acrylate, octyl acrylate, butyl methacrylate,
Examples thereof include methacrylic acid esters such as iso-butyl methacrylate and nonyl metalylate. Examples thereof include methacrylic acid esters such as iso-nonylmetalylate, cyclohexylmetalylate, n-stearylmetalylate, laurylmethacrylate and tridecylmethacrylate, and divinylbenzene.

The above-mentioned monomer compounds may be copolymerized with other monomer compounds, and examples of the copolymerizable ethylenic monomers include acrylic acid esters, methacrylic acid esters, vinyl esters, olefins, styrenes, crotons. Acid esters, itaconic acid diesters,
Maleic acid diesters, fumaric acid diesters, acrylamides, allyl compounds, vinyl ethers, vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers, various unsaturated acids Alternatively, a monomer compound in which two or more kinds are combined can be used.

More specific examples of these monomers include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, and 2-acrylate.
Chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, dimethylaminoethyl acrylate, phenyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 1,1- Examples thereof include dichloro-2-ethoxyethyl acrylate.

Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, N-ethyl
-N-phenylaminoethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, naphthyl methacrylate, 2-methoxyethyl methacrylate, 2- (methoxyethoxy) ethyl methacrylate, ω-methoxy polyethylene glycol methacrylate (additional mol number n = 6) , Allyl methacrylate, and dimethylaminoethyl methyl chloride methacrylic acid salt.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate,
Examples thereof include vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate and the like.

Examples of olefins include cyclopentadiene, ethylene, propylene, isoprene, and 2,3-dimethylbutadiene.

Examples of styrenes include styrene, dimethylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrene, trifluoromethylstyrene, vinylbenzoic acid methyl ester and the like.

Examples of crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.
Examples of itaconic acids include dimethyl itaconate and diethyl itaconate. Examples of maleic acid diesters include diethyl maleate and dibutyl maleate. Examples of fumaric acid diesters include diethyl fumarate, dimethyl fumarate,
Examples include dibutyl fumarate and the like.

Examples of acrylamides include acrylamide, methyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxyethyl acrylamide, phenyl acrylamide and N- (2-acetoxyethyl) acrylamide. Examples of methacrylamides include methacrylamide, methyl methacryl amide. Amide, tert-butylmethacrylamide, phenylmethacrylamide, β-cyanoethylmethacrylamide, etc., allyl compounds such as allyl acetate, allyl laurate, vinyl ethers such as methyl vinyl ether, butyl vinyl ether, dimethylaminoethyl vinyl ether, etc. Examples of vinyl ketones include methyl vinyl ketone, phenyl vinyl ketone, and methoxyethyl vinyl keto. As the vinyl heterocyclic compound, for example, vinyl pyridine, N-vinyl imidazole, N-vinyl oxazolidone, N-vinyl triazole, N-vinyl pyrrolidone, etc., as the glycidyl ester, for example, glycidyl acrylate, glycidyl methacrylate, unsaturated Examples of nitriles include acrylonitrile and methacrylonitrile, and examples of polyfunctional monomers include divinylbenzene, methylenebisacrylonitrile, and ethylene glycol dimethacrylate.

Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate such as monomethyl itaconate, monoethyl itaconate, monomethyl maleate, monoester maleate, citraconic acid,
Styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid, such as acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid, and the like, as methacryloyloxyalkyl sulfonic acid, for example, methacryloyloxydimethyl Examples of the acrylamidoalkylsulfonic acid such as sulfonic acid, methacryloyloxyethylsulfonic acid and methacryloyloxypropylsulfonic acid include 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and 2-acrylamido-acetic acid. Methacrylamide, such as 2-methylbutane sulfonic acid
Alkyl sulfonic acids, such as 2-methacrylamide-2-
Methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, and the like, acryloyloxyalkyl phosphates, for example, acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2- Methacryloyloxyalkyl phosphate, such as phosphate,
For example, methacryloyloxyethyl phosphate, 3-
Methacryloyloxypropyl-2-phosphate etc.,
Examples thereof include naphthyl 3-allyloxy-2-hydroxypropanesulfonate having two hydrophilic groups.

These acids are alkali metal (eg N 2
a, K, etc.) or a salt of ammonium ion. Examples of other monomer compounds include U.S. Patents 3,459,790, 3,438,708, 3,554,987, and
Crosslinkable monomers described in 4,215,195, 4,247,673 and JP-A-57-205735 can be used.

Specific examples of such a crosslinkable monomer include N- (2-acetoacetoxyethyl) acrylamide, N- {2- (2-acetoacetoxyethoxy) ethyl} acrylamide and the like.

Among these monomers, acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes and olefins are preferably used.

Specific examples of the polymer latex formed of the above monomers will be shown below, but the present invention is not limited thereto. The suffix of each monomer unit indicates the content percentage.

[0026]

[Chemical 1]

[0027]

[Chemical 2]

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

In the present invention, the amount of the polymer latex used is 10% or more and 200% or less, preferably 25% by weight based on 100 of gelatin in the hydrophilic colloid layer of the present invention.
Above, 100% or less. If the amount of the polymer latex used is too small, the effect of the present invention will not be sufficiently exhibited, and if the amount used is too large, sufficient film strength will not be obtained. Further, the weight ratio of the water-soluble polymer used in the present invention is 0.5% or more and 30% or less, preferably 1% or more and 15% or less based on 100 of the polymer latex.

The polymer latex used in the present invention is 25
This refers to a polymer latex obtained by polymerizing at least one kind of monomer having a solubility in water at 0 ° C. of 0.025% by weight or less.

The polymer latex used in the present invention can be easily produced by various methods. For example, there is a method of redispersing a polymer obtained by an emulsion polymerization method, a solution polymerization method, a bulk polymerization method, or the like.

The polymer latex used in the present invention can be contained in the hydrophilic colloid layer as it is or after being dispersed in water.

The preparation examples of the polymer latex according to the present invention are shown below.

(Synthesis of Lx-1) A 1,000 cc four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing pipe, and a reflux condenser, and 350 cc of distilled water was introduced while introducing nitrogen gas and performing deoxidation. Was added and heated until the internal temperature reached 80 ° C. 4.5 g of the following compound 1 is added as a dispersant, 0.45 g of ammonium persulfate is further added as an initiator, and then 90 g of ethylhexyl acrylate is added dropwise by a dropping funnel over about 1 hour. After the completion of the dropping, the reaction is continued for 5 hours as it is, and then unreacted monomers are removed by steam distillation. Then, it was cooled and adjusted to pH 6 with aqueous ammonia to obtain a polymer latex. The particle size was 150 nm.

(Synthesis of Lx-2) A 1,000 cc four-necked flask was equipped with a stirrer, a thermometer, a dropping funnel, a nitrogen introducing pipe, and a reflux condenser, and 350 cc of distilled water was introduced while introducing nitrogen gas and performing deoxidation. Was added and heated until the internal temperature reached 80 ° C. 4.5 g of the following compound 2 is added as a dispersant, 0.45 g of ammonium persulfate is further added as an initiator, and 90 g of ethylhexyl acrylate is added dropwise by a dropping funnel over about 1 hour. After the completion of the dropping, the reaction is continued for 5 hours as it is, and then unreacted monomers are removed by steam distillation. Then, it was cooled and adjusted to pH 6 with aqueous ammonia to obtain a polymer latex. The particle size was 200 nm.

(Synthesis of Lx-10) 200 cc of dioxane was put into a 500 cc three-necked flask and deoxygenated with nitrogen gas.
Then, 15 g of isononyl acrylate and 35 g of cyclohexyl acrylate are added, 1.2 g of dimethyl azobisisobutyrate is further added as an initiator, and the reaction is continued at 60 ° C. for 6 hours. After completion of the reaction, the reaction solution was added to 3 liters of distilled water with vigorous stirring to obtain white crystals.

The white crystals were collected by filtration, dried, and then dissolved in 100 cc of ethyl acetate, and 2 g of the following compound 3 was used as a dispersant.
It was added to 500 cc of added distilled water with vigorous stirring, and then ethyl acetate was removed to obtain a polymer latex. The particle size was 180 nm.

(Synthesis of Comparative Latex L) 0.25 kg of KMDS (dextran sulfate sodium salt) manufactured by Meito Sangyo Co., Ltd. and 0.05 k of ammonium persulfate in 40 liters of water.
In a nitrogen atmosphere while stirring at a liquid temperature of 81 ° C., a mixed liquid of 4.51 kg of n-butyl acrylate, 5.49 kg of styrene and 0.1 kg of acrylic acid was added over 1 hour to the liquid to which g was added, and then ammonium persulfate of 0.005 was added. After adding kg and stirring for another 1.5 hours,
It was cooled and adjusted to pH 6 with aqueous ammonia.

The obtained latex liquid was used as GF manufactured by Whotman.
The mixture was filtered with a / D filter and the weight was adjusted to 50.5 kg with water to prepare a monodisperse latex (L) having an average particle diameter of 250 nm.

[0043]

[Chemical 7]

In the silver halide photographic light-sensitive material of the present invention, the hydrophilic colloid layer farthest from the support means, specifically, a photosensitive or substantially non-photosensitive silver halide emulsion layer, a protective layer. A layer, a filter layer, an ultraviolet absorbing layer, an antistatic layer, and the like are the outermost surface layers of the silver halide photographic light-sensitive material constituent layers, and the preferred layer is a protective layer.

In the hydrophilic colloid layer referred to in the present invention, various synthetic polymer compounds including gelatin as a binder or protective colloid can be used in addition to the polymer latex according to the present invention.

As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin or gelatin derivative may be used.

Next, the selenium compound will be described.

As the selenium sensitizer used in the present invention, the selenium compounds disclosed in conventionally known patents can be used. The selenium sensitization is usually carried out by adding an unstable selenium compound and / or a non-unstable selenium compound to a silver halide emulsion and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. As the unstable selenium compound, for example, compounds described in JP-B-44-15748 and JP-B-43-13489 are preferably used. Specific examples of the unstable selenium sensitizer include isoselenocyanates (for example, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenamides, selenocarboxylic acids (for example, 2- Selenopropionic acid, 2-selenobutyric acid), selenoesters, diacylselenides (for example, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates,
Examples include phosphine selenides and colloidal metal selenium.

As the non-unstable selenium compound used in the present invention, for example, compounds described in JP-B-46-4553, JP-B-52-34492 and JP-B-52-34491 are used. Examples of the non-labile selenium compound are selenious acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, Examples include 2-selenooxazolidinethione and derivatives thereof.

Among the selenium compounds, the following general formulas (1) and (2) are preferable.

[0051]

[Chemical 8]

In the formula, Z ₁ and Z ₂ may be the same or different, and are an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl). , Aralkyl groups (eg, benzyl, phenethyl), aryl groups (eg, phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, a-naphthyl), heterocyclic groups (eg, Pyridyl,
Thienyl, furyl, imidazolyl), -NR ₁ (R ₂ ),-
It represents an OR ₃ or -SR _4.

R ₁ , R ₂ , R ₃ and R _{4, which} may be the same or different, each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group or heterocyclic group are the same as those for Z ₁ . However, R ₁ and R ₂ are a hydrogen atom or an acyl group (eg, acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl,
4-nitrobenzoyl, a-naphthoyl, 4-trifluoromethylbenzoyl).

In the general formula (1), preferably Z ₁ represents an alkyl group, an aryl group or --NR ₁ (R ₂ ), and Z ₂ represents-
Represents NR ₅ (R ₆ ). R ₁ , R ₂ , R ₅ and R _{6, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an aryl group or an acyl group.

In the general formula (1), more preferred are N, N-dialkylselenoureas, N, N, N'-trialkyl-N'-acylselenoureas, tetraalkylselenoureas and N, N-dialkyl-arylseleno. Amide, N-alkyl-N-arylselenoamide.

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent, and added at the time of chemical sensitization. It is preferably added before the start of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. The unstable selenium compound and the non-unstable selenium compound may be used in combination. The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the type and size of silver halide, the temperature and time of ripening, and the like. 1x per mole
^10-8 or more. More preferably 1 × 10 ⁻⁷ mol or more 3 ×
It is 10 ^-5 mol or less. The temperature of chemical ripening when the selenium sensitizer is used is preferably 40 ° C. or higher. More preferably, it is 45 ° C or higher and 80 ° C or lower. pAg and pH are arbitrary. For example, the effect of the present invention can be obtained in a wide range of pH from 4 to 9. It is more effective to perform selenium sensitization in the presence of a silver halide solvent.

The silver halide solvent that can be used in the present invention is, for example, US Pat. Nos. 3,271,157 and 3,531,2.
89, 3,574,628, JP-A-54-1019, 54-158917
(A) Organic thioethers described in Japanese Patent Publication No. Sho 53
-82408, 55-77737, 55-2982 and the like (b) thiourea derivatives, and (c) oxygen or sulfur and nitrogen atoms described in JP-A-53-144319. Silver halide solvent having pinched thiocarbonyl group, JP-A-54
-100717 (d) imidazoles, (e)
Examples thereof include sulfite and (f) thiocyanate. Particularly preferred solvents are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ or more and 1 × 10 ⁴ or more per mol of silver halide.
^-2 mol or less. The silver halide emulsion of the present invention can achieve higher sensitivity and lower fog by combined use of sulfur sensitization and / or gold sensitization in chemical sensitization. Sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain period of time. The gold sensitization is usually carried out by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. For sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, thioureas, allyl isothiocyanate,
Examples include cystine, p-toluenethiosulfonate, rhodanine and the like.

[0058]

[Chemical 9]

In the formula, Z ₃ , Z ₄ and Z ₅ may be the same or different and each is an aliphatic group, an aromatic group, a heterocyclic group, -OR ₇ , -NR ₈ (R ₉ ), -SR. ₁₀ , -SeR ₁₁ ,-
Represents X or a hydrogen atom.

R ₇ , R ₁₀ and R ₁₁ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₈ and R ₉ represent an aliphatic group, an aromatic group, a heterocyclic group or hydrogen. Represents an atom, and X represents a halogen atom.

In the general formula (2), Z ₃ , Z ₄ , Z ₅ ,
The aliphatic group represented by R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (for example, methyl, ethyl,
n-propyl, isopropyl, t-butyl, n-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopentyl,
Cyclohexyl, allyl, 2-butenyl, 3-pentenyl,
Propargyl, 3-pentynyl, benzyl, phenethyl)
Represents

The aromatic group represented by Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ is a monocyclic or condensed aryl group (eg, phenyl, pentafluorophenyl). , 4-chlorophenyl, 3-sulfophenyl, a-naphthyl, 4-methylphenyl).

The heterocyclic group represented by Z ₃ , Z ₄ , Z ₅ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ contains at least one of a nitrogen atom, an oxygen atom and a sulfur atom. To a 10-membered saturated or unsaturated heterocyclic group (eg, pyridyl, thienyl, furyl, thiazolyl, imidazolyl, benzimidazolyl).

The cation represented by R ₇ , R ₁₀ and R ₁₁ represents an alkali metal atom or ammonium, and the halogen atom represented by X is, for example, a fluorine atom, a chlorine atom,
Represents a bromine atom or an iodine atom.

Preferably Z ₃ , Z ₄ or Z ₅ represents an aliphatic group, an aromatic group or --OR ₁ , and R ₇ represents an aliphatic group or an aromatic group. In formula (2), more preferably trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate.

Specific examples of the compounds represented by the general formulas (1) and (2) are shown below, but the invention is not limited thereto.

[0067]

[Chemical 10]

[0068]

[Chemical 11]

[0069]

[Chemical 12]

[0070]

[Chemical 13]

[0071]

[Chemical 14]

[0072]

[Chemical 15]

The silver halide composition of the tabular silver halide emulsion used in the present invention may be arbitrary, and any silver halide such as silver chloride, silver bromide, silver iodobromide, silver chloroiodobromide, etc. may be used. Although it may be used, a silver iodochlorobromide emulsion is preferable from the viewpoint of high sensitivity, and the average silver iodide content is 0 to 4.
The content of 0 mol% is particularly preferably 0.2 to 3.0 mol%, and the average silver chloride content is 0 to 5 mol%. A method for producing a tabular silver halide emulsion is described in, for example, JP-A Nos. 58-113927 and 58-113934.
No. 62-1855, European Patents 219,849, 219, 85
It can be prepared with reference to No. 0 and the like.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, an aqueous solution of silver nitrate or an aqueous solution of silver nitrate and an aqueous solution of halide are simultaneously added to a gelatin aqueous solution having a pBr of 2 or less to form seed crystals. It can be obtained by generating and then growing by the double jet method. The size of the tabular silver halide grains can be controlled by the temperature at the time of grain formation, the addition rate of the silver salt and the aqueous solution of silver halide.

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

The emulsion used in the silver halide photographic light-sensitive material of the present invention is described, for example, in "The Theory of the" by TH James.
Photographic process ”4th edition, published by Macmillan (1977
Year) Method described on pages 38-104, GF Duffin, “Photograph
ic Emulsion Chemistry ”, published by Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Published by Paul Montel (1967) or VL Zelikman et al. “Makin
g And Coating Photographic Emulsion "can be prepared by the method described in Focal Press (1964).

That is, the mixing conditions such as the forward mixing method, the reverse mixing method, the double jet method and the control double jet method under the solution conditions such as the acidic method, the ammonia method and the neutral method,
It can be produced using a particle preparation condition such as a conversion method, a core / shell method, or a combination thereof.

The emulsion used in the silver halide photographic light-sensitive material of the present invention has an aspect ratio (grain diameter) / (grain thickness) of 3
The tabular silver halide grains described above, wherein the silver halide grains are at least 50% of the total projected area of the light-sensitive material of the present invention.
It is preferable to occupy%.

The tabular silver halide grains have an aspect ratio of 3 or more, preferably 5 or more, and practically 5 to 8 or more. The ratio of the tabular grains to the total projected area is
50% or more, preferably 70% or more, more preferably 90%
The above is most preferable. The average particle size of the tabular grains is preferably 0.2 to 2.5 μm, particularly preferably 0.5 to 2.0 μm.
Is. The average thickness of the particles is preferably 0.4 μm or less, more preferably 0.3 μm or less and particularly preferably 0.05 to 0.25 μm.
Is.

In the present invention, the diameter of the silver halide grain is defined as the equivalent spherical diameter of the grain from the observation of an electron micrograph of the silver halide grain. The thickness of a silver halide grain is defined as the minimum distance between two parallel planes constituting a tabular silver halide grain. The thickness of the tabular grains can be determined from an electron micrograph of a silver halide grain shaded or an electron micrograph of a sample prepared by coating a silver halide emulsion on a support and drying the support.

To obtain the average aspect ratio, at least 1000 samples are measured. The tabular silver halide emulsion according to the present invention is preferably monodisperse and contains 50% by weight or more of silver halide grains having an average grain size within a grain size range of ± 20%. Is particularly preferable.

The emulsion may be subjected to a noodle washing method, a flocculation sedimentation method or the like to remove soluble salts. Preferred washing methods include, for example, aromatic hydrocarbons containing a sulfo group described in JP-B-35-16086. Examples thereof include a method using a system aldehyde resin and a desalting method using a polymer flocculant such as Exemplified G-3 and G-8 described in JP-A-63-158644.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening.

Examples of the compound used in such a step include the above-mentioned (RD) No. 17643, (RD) No. 18716 and (RD) N.
Various compounds described in o.308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) are listed below.

Additives RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV 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 Hardener 26 X 651 Left 1004-5 X Surfactant 26-27 XI 650 Right 1005-6 XI Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Halogenation of the Invention Examples of the support used for the silver photographic light-sensitive material include those described in RD above,
A suitable support is a polyethylene terephthalate film or the like, and the surface of the support may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or may be subjected to corona discharge or ultraviolet irradiation.

The photographic processing of the light-sensitive material of the present invention can be carried out, for example, by RD-17643, XX to XXI, pages 29 to 30 or 308119, XX to XX.
Treatment with a treatment solution as described in I, pages 1011-1010 may be performed. This processing is a black and white photographic processing for forming a silver image, and the processing temperature is usually in the range of 18 to 50 ° C.

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. For the developer, known agents such as preservatives, alkali agents, pH buffers, antifoggants, hardeners, development accelerators, surfactants,
A defoaming agent, a toning agent, a water softening agent, a dissolution aid, a viscosity imparting agent and the like may be used as 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.

[0089]

EXAMPLES The present invention will be described below with reference to examples.

Example 1 1) Preparation of seed emulsion 1 Silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm by the double jet method while controlling 60 ° C., pAg = 8 and pH = 2.0. Monodisperse cubic crystal particles were prepared.

The resulting reaction solution was desalted at 40 ° C. using an aqueous solution of Demol N and an aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., and was then redispersed by adding an aqueous solution of gelatin to obtain a seed emulsion.

2) Growth from Seed Emulsion 1 Using the above seed emulsion, grains were grown as follows. First
The above seed emulsion was dispersed in a gelatin aqueous solution kept at 40 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid.
To this solution, an aqueous solution of ammoniacal silver nitrate ion and an aqueous solution of potassium bromide and potassium iodide were added by the double jet method. During the addition, pAg = 7.3 and pH were controlled to 9.7 to form a layer having a silver iodide content of 35 mol%. Next, an ammoniacal silver nitrate aqueous solution and a potassium bromide aqueous solution were added by the double jet method. Keep pAg = 9.0 up to 95% of the target particle size, pH 9.0
Continuously changed to ~ 8.0. After that, the pAg was adjusted to 11.0 and the pH was kept at 8.0 to grow the target grain size.
Subsequently, the pH was lowered to 6.0 with acetic acid and then 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt was added in an amount of 400 mg per mol of silver halide, and desalted using the aforementioned demole N aqueous solution and magnesium sulfate aqueous solution. After that, an aqueous gelatin solution was added and redispersed.

By this method, a tetradecahedron having an average silver iodide content of 2.0 mol% and rounded vertices has an average grain size of 0.40 μm and a grain size of 0.4.
65μm, 1.00μm, coefficient of variation 0.17, 0.16, 0.16 respectively
Monodispersed silver iodobromide emulsions (A), (B) and (C) were prepared.

3) Preparation of Seed Emulsion 2 0.1% containing hydrogen peroxide treated gelatin vigorously stirred at 40 ° C.
A double jet method was used to add an equimolar potassium bromide aqueous solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin to a 05N potassium bromide aqueous solution.
After the liquid temperature was lowered to ℃, 80 ml of ammonia water (28%) was added per mol of silver nitrate, and stirring was continued for 5 minutes.

Thereafter, the pH was adjusted to 6.0 with acetic acid, desalting was performed using an aqueous demol N solution and an aqueous magnesium sulfate solution, and then an aqueous gelatin solution was added for redispersion. The resulting seed emulsion was spherical grains having an average grain size of 0.23 μm and a coefficient of variation of 0.28.

4) Growth from Seed Emulsion 2 Grains were grown as follows using the above seed emulsion. 75 ° C
A double jet method was used to add an aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate to an aqueous solution containing ossein gelatin and propyleneoxy-polyethyleneoxy-disuccinate-disodium salt vigorously stirred at. During this period, pH = 5.8 and pH = 9.0 were maintained. After the addition was completed, the pH was adjusted to 6.0, and 400 mg of 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride was added per mol of silver halide. . 40 ° C
After desalting with a demol N aqueous solution, a gelatin aqueous solution was added and redispersed.

By this method, pAg and potassium iodide were changed to obtain a projected area diameter of 0.96 at an average silver iodide content of 1.5 mol%.
μm, coefficient of variation 0.25, aspect ratio 2.0, 3.5, 5.0 8.0
Tabular silver iodobromide emulsions D-1, D-2, D-3 and D-4 were prepared.

Preparation of Samples Obtained Emulsions (A), (B), (C) and (D-1, D-2, D-
3, D-4), 5,5'-dichloro-9-at 55 ℃
Anhydrous of ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt and 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydrous 20
At a weight ratio of 0: 1, (A) is 975 per mol of silver halide.
mg, (B) 600 mg, (C) 390 mg, and (D) 500 mg.

After 10 minutes, appropriate amounts of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added for chemical ripening. 15 minutes before the end of ripening, potassium iodide was added to silver halide
200 mg was added per mol, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 3 × 10 ^-2 mol per mol of silver halide and dispersed in an aqueous solution containing 70 g of gelatin. .

Of the four ripened emulsions, (A), (B) and (C) were mixed in a weight ratio of 15:65:20 to prepare an emulsion (R-
1) and (D-1 to D-4) were used alone.

For each of these emulsions, JP-A-2-
Additives similar to those described in 301744, page 95 line 16 to page 96 line 20 were also added. Furthermore, 1.2 g of the following dye emulsion dispersion was added to prepare an emulsion coating solution.

Preparation Method of Dye Emulsion Dispersion 10 kg of the following dye was dissolved at 55 ° C. in a solvent consisting of 28 l of tricresylphosphite and 85 l of ethyl acetate. This is called an oil solvent. On the other hand, the following anionic activator (AS) was added to 1.
A 9.3% gelatin aqueous solution containing 35 kg was prepared.

Next, the oil-based solvent and this gelatin aqueous solution were placed in a dispersion pot and dispersed while maintaining the liquid temperature at 40 ° C.
Phenol and 1,1'-dimethylol-1- were added to the resulting dispersion.
An appropriate amount of bromine-1-nitromethane was added to make 240 kg with water.

[0104]

[Chemical 16]

The additives used in the protective layer solution are as follows. The addition amount is shown in the amount per 1 liter of the coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymer latex of the invention Amount shown in the table Polymethylmethacrylate (matting agent having an area average particle size of 5.0 μm) 1.1 g Silicon dioxide (matting agent with an area average particle size of 3.0 μm) 0.5 g Ludox AM (DuPont colloidal silica) 30 mg Glyoxal 40% aqueous solution 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O 500 mg

[0107]

[Chemical 17]

Emulsion layer is 2.0 g / silver conversion per side
m ² , the amount of gelatin attached is 2.5 g / m ² , and the protective layer has an amount of gelatin attached of 0.99 g / m ^{2 Using two} slide hopper type coaters, both sides on the support at a speed of 90 m / min. Simultaneous coating was carried out and the sample was obtained by drying in 2 minutes and 20 seconds.

The support used is glycidyl methacrylate.
The concentration of the copolymer consisting of 50 wt%, 10 wt% methyl acrylate and 40 wt% butyl methacrylate
A blue-colored polyethylene terephthalate film base having a thickness of 175 μm was used, which was applied as an undercoat liquid by diluting the resulting copolymer aqueous dispersion to 10 wt%.

<Sensitometry> The obtained sample was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica Corporation), and a tube voltage of 90 KVP, 2
X-rays were irradiated at 0 mA for 0.05 seconds, and a sensitometric curve was created by the distance method to determine sensitivity and gamma. The sensitivity at this time was obtained by the relative value of the reciprocal of the exposure amount required to obtain the density of 1.0 + fog density, and was shown as the relative sensitivity value when the material No. 1 was 100. Also, the gamma value is the density 1.0 and 2.0 on the characteristic curve.
It is shown by the gamma value of the straight line connecting

For the development, an automatic developing machine SRX-501 (manufactured by Konica Corporation) was used.
C., fixing temperature 33.degree. C., washing water was supplied at 18.degree. C. at 3.5 liters per minute, and the whole treatment process was performed in 45 seconds.

(Developer composition) Potassium sulfite 70g Hydroxyethylethylenediamine triacetate trisodium 8g Hydroquinone 28g Boric acid 10g 5-Methylbenzotriazole 0.04g 1-Phenyl-5-mercaptotetrazole 0.01g Sodium metabisulfite 5g Acetic acid (90% ) 13g triethylene glycol 15g 1-phenyl-3-pyrazolidone 1.2g 5-nitroindazole 0.2g glutaraldehyde 4g Dissolve in 1 liter of water and adjust to pH 10.4 with caustic soda.

(Starter) Glacial acetic acid 144 g Potassium bromide 300 g Add water to make 1 liter (add 20 ml starter to 1 liter of the above developer) (fixer composition) sodium thiosulfate pentahydrate 4.5 g Ethylenediaminetetraacetic acid disodium salt 0.5g Ammonium thiosulfate 150g Anhydrous sodium sulfite 8g Potassium acetate 16g Aluminum sulfate (10-18 hydrate) 10g Sulfuric acid (50wt%) 5g Citric acid 1g Boric acid 7g Glacial acetic acid 5g Make pH 4.2 with glacial acetic acid.

<Evaluation of scratch resistance> Temperature 23 ° C., relative humidity
The sample was conditioned for 4 hours under the condition of 48%, rubbed with a nylon scrubber under a load of 100 g / cm ² , and then developed with the above-mentioned developing solution to visually check the degree of scratches. It was judged.

Evaluation Criteria A: Almost no scratches B: Practically no problem, but some scratches C: Scratches are noticeable and practically problematic D: Very many scratches Wide width and high concentration <Surface resistivity> Samples were conditioned under 20% relative humidity for 1 hour, then sandwiched between yellow copper electrodes with an electrode interval of 14 mm and length of 100 mm, and an insulation tester manufactured by Takeda Rika Co., Ltd. It was measured with TR-8651 model at 23 ° C and 20% relative humidity for 1 minute. The larger the value, the better the antistatic property.

<Stick Test> A sample was cut into a size of 13.5 cm × 7 cm, and the humidity was adjusted for 1 hour under a relative humidity of 80%, and two films were superposed on each other and left for 1 day under a load of 1 kg. Adhesion was evaluated from the feel level when the film was peeled off after 3 days.

5: Smoothly attached 4: Slightly adhered 3: Clearly adhered and made a noise when peeled off 2: Adhesive and peeled emulsion 1: 1: 1/2 or more adhered and difficult to peel off <Silver tone> With respect to the sample subjected to the same treatment as the sensitometry, the silver tone property by visual observation was evaluated as follows.

4: Pure black tone 3: Slightly reddish black 2: Slightly yellowish black 1: Yellowish black The above results are shown in the following table.

[0119]

[Table 1]

[0120]

[Table 2]

As is apparent from the table, according to the present invention,
It can be seen that a high-sensitivity and high-gamma photographic light-sensitive material having a pure black tone silver image having improved rubbing fog resistance and scratch resistance and having antistatic performance can be obtained.

[0122]

According to the present invention, a high-sensitivity silver halide photographic light-sensitive material having improved rubbing fog resistance and scratch resistance without impairing photographic performance can be obtained. Furthermore, according to the present invention, a silver halide photographic light-sensitive material having an antistatic property and a high covering power having a pure black tone silver image can be obtained.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer and a hydrophilic colloid layer on at least one side of a support, and the silver halide grains of the silver halide emulsion layer. However, the solubility in water at 25 ° C. at 25 ° C. is 0 in a hydrophilic colloid layer containing tabular silver halide grains selenium sensitized with a selenium compound and having an aspect ratio of 3 or more, and located farthest from the support.
A silver halide photographic light-sensitive material containing a polymer latex obtained by polymerizing at least one kind of a monomer of 25% by weight or less.