JP3240537B2 - Silver halide photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having high sensitivity, high image quality and improved scratch resistance.

[0002]

2. Description of the Related Art Tabular silver halide grains are often used in silver halide photographic materials using gelatin as a binder. This is because flattening increases the projected area, increases the amount of received light per unit grain, and allows a large amount of sensitizing dye or the like to be adsorbed, so that higher spectral sensitization is expected.

On the other hand, with the advance of electronics, the shortening of the access time to images has been drastically reduced, and silver halide photographic materials are required to be processed more and more rapidly. For this reason, there is a need for a technique for reducing the amount of gelatin, which is a binder that has protected silver halide grains, and for shortening photographic processing such as development speed, fixing speed, washing speed, and drying speed. As the amount of gelatin used decreases, high-sensitivity silver halide grains become more and more vulnerable to external pressure, and attempts have been made to improve the grain preparation method to overcome this. At the same time, silver halide grains having both high pressure resistance have not been found yet.

On the other hand, it has often been practiced to add a latex which functions softly as a buffer.
However, latex has various adverse effects on silver halide grains as a photoreceptor, and is also used to deteriorate the film properties of a photographic element to make it easily damaged or to deteriorate the stickiness between films during storage. Therefore, the objective was not sufficiently achieved.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material having high sensitivity, high image quality and excellent scratch resistance.

[0006]

The object of the present invention is to provide a silver halide photographic material having at least one photosensitive silver halide emulsion layer and a hydrophilic colloid layer on one side of a support. A silver halide emulsion layer containing tabular silver halide grains having an aspect ratio of 3 or more, and at least one monomer having a solubility in water at 25 ° C. of 0.025% by weight or less in the emulsion layer. Containing at least one polymer latex obtained by polymerizing at least one type of monomer having an epoxy group, and heating at a temperature of 90 ° C. or more at the end of the polymerization reaction of the polymer latex. This is achieved by a silver halide photographic light-sensitive material.

Hereinafter, the present invention will be described specifically.

The emulsion used in the photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No.17643 (December 1978)
Emulsion Preparation and Emulsion Preparation on pages 22-23
types) and (RD) No. 18716 (November 1979) · 648
It can be prepared by the method described on page.

[0009] Also, "Thetheory of the ph" by TH James
otographic process ”4th edition, published by Macmillan (1977)
Years) p. 38-104, GFDauffin, "Photographic Emulsion Chemistry", Focal p.
ress (1966), P. Glafkides, "Physics and Chemistry of Photography", "Chimie et physique photographique", Paul Mon
"Making and Coating photographic Emul," published by tel (1967), VLZelikman et al.
It is prepared by the method described in “sion” Focal press (1964).

That is, mixing conditions such as a forward mixing method, a reverse mixing method, a double jet method, a controlled double jet method, a conversion method, and a core / shell method under solution conditions such as a neutral method, an acidic method, and an ammonia method. The particles can be produced using particle preparation conditions such as those described above and a combination thereof. One embodiment of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains.

In the present invention, tabular grains are preferably used. The average grain size of the tabular silver halide grains is 0.2
It is preferably from 2.5 to 2.5 µm, particularly preferably from 0.5 to 2.0 µm.

The tabular silver halide emulsion has an average value (called an average aspect ratio) of grain diameter / thickness (called as an aspect ratio) of 3 or more, preferably 6 to 60, and more preferably 7 to 6. -50, particularly preferably 8-20.

The average thickness is preferably 0.4 μm or less, more preferably 0.3 μm or less, and particularly preferably 0.05 to 0.25 μm.

In the present invention, the diameter of a silver halide grain is defined as a sphere equivalent diameter of the grain from observation of an electron micrograph of the silver halide grain. The thickness of a silver halide grain is defined as the minimum of the distance between two parallel planes constituting a tabular silver halide grain.

The thickness of the tabular silver halide grains can be determined from an electron micrograph of a silver halide grain having a shadow or an electron micrograph of a sample slice obtained by coating a silver halide emulsion on a support and drying it. .

In order to determine the average aspect ratio, the minimum
Measure 100 samples.

In the silver halide emulsion of the present invention, the ratio of tabular silver halide grains to all silver halide grains is at least 50%, preferably at least 60%, particularly preferably at least 70%.

The tabular silver halide emulsions are preferably monodisperse emulsions, particularly those having 50% by weight or more of silver halide grains within a grain size range of ± 20% around the average grain size. It is preferably used.

The tabular silver halide emulsion may have any halogen composition such as silver chloride, silver bromide, silver chloroiodide, silver chlorobromide, silver iodobromide and silver iodobromide. Thus, silver iodochlorobromide is preferred, the average silver iodide content is 0 to 4.0 mol%, particularly preferably 0.2 to 3.0 mol%, and the average silver chloride content is 0 to 5 mol%.

The process for producing tabular silver halide emulsions is described in JP-A-58-113926, JP-A-58-113927, JP-A-58-113934 and JP-A-58-113934.
2-1855, European Patents 219,849 and 219,850 can also be referred to. As a method for producing a monodisperse tabular silver halide emulsion, JP-A-61-6643 can be referred to.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, an aqueous silver nitrate solution or an aqueous silver nitrate solution and an aqueous halide solution are simultaneously added to an aqueous gelatin solution having a pBr of 2 or less to form seed crystals. And then grown by the double jet method.

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

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

The emulsion may be subjected to a water washing method such as a noodle washing method or a flocculation sedimentation method to remove soluble salts. As a preferred washing method, for example,
A method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-A-16086, or a method using G3, G8, etc., as an aggregating polymer agent described in JP-A-2-7037 is mentioned as a particularly preferred desalting method. .

In the emulsion of the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. Known additives include, for example, RD No. 176
43 (December 1978), No. 18716 (November 1979) and N
o. 308119 (December 1989). The types of compounds shown in these three research disclosures and the locations 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 IV Desensitizing dye 23 IV 998 B 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 Brightener 24 V 998 V Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 right 1006-7 XIII 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 according to the present invention Examples of the support that can be used for the light-sensitive material include the aforementioned RD-17643, page 28, and RD-308119, page 100.
What is described on page 9 is mentioned. A suitable support is a plastic film or the like. On the surface of these supports, an undercoat layer may be provided, or corona discharge, ultraviolet irradiation, etc. may be applied to improve the adhesion of the coating layer.

At least one of the monomers forming the polymer latex used in the present invention has a solubility in water at 25 ° C. of 0.025% by weight or less, preferably 0.015% by weight or less. Such ethylenic monomers include, for example, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, nonyl acrylate, iso-nonyl acrylate, cyclohexyl acrylate, n-stearyl acrylate, lauryl acrylate, tridecyl acrylate, etc. Acrylates, butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, iso-octyl methacrylate, tert-octyl methacrylate, nonyl methacrylate, iso- Esters such as nonyl methacrylate, cyclohexyl methacrylate, n-stearyl methacrylate, lauryl methacrylate, and tridecyl methacrylate S etc. and divinyl benzene.

The solubility of the monomer forming the polymer latex used in the present invention in water at 25 ° C. can be measured by the method described in Basic Experiment 1 of New Experimental Chemistry Course (Maruzen Chemical, 1975). . When measured by this method, the solubility of the monomer of the present invention in water at 25 ° C. is, for example,
It is 0.01% by weight for 2-ethylhexyl acrylate, 0.00% by weight for 2-ethylhexyl methacrylate, and 0.00% by weight for cyclohexyl methacrylate. The comparative monomer was 0.03% by weight for styrene, 0.32% by weight for butyl acrylate, and 0.03% by weight for butyl methacrylate.

At least one of the monomers forming the polymer latex used in the present invention contains an epoxy group as represented by glycidyl methacrylate.

The polymer latex used in the present invention may be copolymerized with other monomer compounds other than the above monomer compounds.
For example, acrylic esters, methacrylic esters, vinyl esters, olefins, styrenes, crotonic esters, itaconic diesters, maleic diesters, fumaric diesters, acrylamides, allyl compounds, vinyl ethers, Examples thereof include monomer compounds selected from one or two or more selected from vinyl ketones, vinyl heterocyclic compounds, glycidyl esters, unsaturated nitriles, polyfunctional monomers, and various unsaturated acids.

More specifically, these monomeric compounds are exemplified by methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and sec-butyl acrylate. , Tert-butyl acrylate, amyl acrylate,
Hexyl acrylate, 2-chloroethyl acrylate,
2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 2- Hydroxyethyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate,
2-iso-propoxy acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-
Examples include methoxypolyethylene glycol acrylate (additional mole number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, and the like.

Examples of methacrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, amyl methacrylate, chlorobenzyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, (3-phenylpropyloxy) ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate,
Tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate , 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate,
2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2-
(2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, ω-methoxy polyethylene glycol methacrylate (additional mole number n =
6), allyl methacrylate, dimethylaminoethyl methyl methacrylate chloride salt and the like.

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

Examples of the olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, and 2,3-dimethylbutadiene. it can.

As styrenes, for example, styrene,
Examples include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, trifluoromethylstyrene, and methyl vinyl benzoate.

Examples of crotonates include butyl crotonate and hexyl crotonate.

Examples of the diethyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

The maleic acid diesters include, for example, diethyl maleate, dimethyl maleate, dibutyl maleate and the like.

As the fumaric acid diesters, for example,
Examples thereof include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate.

As acrylamides, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-
Butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide,
Dimethyl acrylamide, diethyl acrylamide, β
-Cyanoethylacrylamide, N- (2-acetoacetoxyethyl) acrylamide and the like; methacrylamides, for example, methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert-butyl methacrylamide, cyclohexyl methacrylamide , Benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N- (2-acetoacetoxyethyl) methacrylamide Allyl compounds such as allyl acetate, allyl caproate, allyl laurate, allyl benzoate and the like; Le, such as, for example,
Methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc .; vinyl ketones, for example, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, etc .; vinyl heterocyclic compounds, for example, vinyl pyridine, N -Vinylimidazole, N-vinyloxazolidone, N-vinyltriazole,
N-vinylpyrrolidone and the like; glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; unsaturated nitriles such as acrylonitrile and methacrylonitrile; and polyfunctional monomers such as divinylbenzene and methylenebisacrylamide;
Ethylene glycol dimethacrylate and the like.

Further, acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate, for example,
Monomethyl itaconate, monoethyl itaconate, monobutyl itaconate, etc .; monoalkyl maleate such as monomethyl maleate, monoethyl maleate, monobutyl maleate, etc .; citraconic acid, styrene sulfonic acid, vinylbenzyl sulfonic acid, vinyl sulfonic acid, acryloyl Oxyalkylsulfonic acid, for example,
Acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid, acryloyloxypropylsulfonic acid and the like; methacryloyloxyalkylsulfonic acid such as methacryloyloxydimethylsulfonic acid, methacryloyloxyethylsulfonic acid and methacryloyloxypropylsulfonic acid; acrylamidoalkylsulfonic acid For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid and the like; methacrylamidoalkylsulfonic acid, for example, 2-methacrylamido- 2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc .; acryloyloxyalkyl phos Phosphates, for example, acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate, etc .; methacryloyloxyalkyl phosphates, for example, methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate, etc .; 3 having two hydrophilic groups -Naphthyl allyloxy-2-hydroxypropanesulfonate and the like. These acids may be salts of alkali metals (eg, Na, K, etc.) or ammonium ions. Still other monomer compounds, U.S. Pat.Nos. 3,459,790, 3,438,708, 3,554,987,
Crosslinkable monomers described in JP-A-4,215,195, JP-A-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.

Of these monomer compounds, acrylic esters, methacrylic esters, vinyl esters, styrenes, and olefins are preferably used.

The surfactant used in the polymerization of the polymer latex of the present invention includes an anionic surfactant,
Any of a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used, but an anionic surfactant and / or a nonionic surfactant are preferable. As the anionic surfactant and the nonionic surfactant, various compounds known in the art can be used, and an anionic surfactant is particularly preferably used.

The water-soluble polymer used in the polymerization of the polymer latex of the present invention includes, for example, a synthetic polymer and a natural water-soluble polymer, and any of them can be preferably used in the present invention. Among them, synthetic water-soluble polymers include those having a nonionic group in the molecular structure, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group, those having a nonionic Examples include those having a group and a cationic group, those having an anionic group and a cationic group, and the like. Examples of the nonionic group include an ether group, an alkylene oxide group, a hydroxy group, an amide group, and an amino group. Examples of the anionic group include a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, and the like. Examples of the cationic group include a quaternary ammonium base and a tertiary amino group.

Also, natural water-soluble polymers include those having a nonionic group in the molecular structure, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group, Examples include those having a nonionic group and a cationic group, those having an anionic group and a cationic group, and the like.

The water-soluble polymer used in the polymerization of the polymer latex of the present invention may be any of a synthetic water-soluble polymer and a natural water-soluble polymer, including those having an anionic group and those having a nonionic group and an anionic group. Those having the following can be preferably used.

In the present invention, the water-soluble polymer is 20
It is sufficient to dissolve 0.05 g or more in water at 100 ° C., preferably 0.1 g or more.

As the natural water-soluble polymer, a comprehensive technical data collection of water-soluble polymer water-dispersible resins (the ones described in detail in the Management Development Center can be mentioned, but lignin, starch, pullulan, cellulose, dextran are preferable). Dextrin, glycogen, alginic acid, gelatin, collagen, guar gum, gum arabic, laminaran, lichenin, nigran, etc. and derivatives of natural water-soluble polymers such as sulfonation, carboxylation, phosphorylation, sulfo Alkenylated, carboxyalkylated, alkylphosphorylated and salts thereof are preferably used, particularly preferably glucose, gelatin, dextran, cellulose and derivatives thereof.

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, a bulk polymerization, or the like.

In the emulsion polymerization method, water is used as a dispersion medium, and 10 to 50% by weight of a monomer and 0.05 to 5% by weight of a polymerization initiator and 0.1 to 20% by weight of a monomer are used. 90 with dispersant
It is obtained by polymerizing with stirring at a temperature higher than 0 ° C. for 3 to 8 hours. The concentration of the monomer, the amount of the initiator, the reaction temperature, the time and the like can be widely and easily changed.

Examples of the initiator include a water-soluble peroxide (eg, potassium persulfate, ammonium persulfate, etc.) and a water-soluble azo compound (eg, 2,2′-azobis- (2-amidinopropane)-
Hydrochloride, etc.).

Examples of the dispersant include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants in addition to the water-soluble polymer. These may be used alone or in combination. In solution polymerization, which is preferably a combination of a water-soluble polymer and a nonionic or anionic activator, generally a mixture of monomers in a suitable solvent (eg, ethanol, methanol, water, etc.) at a suitable concentration (usually, An appropriate temperature (for example, benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) in the presence of a polymerization initiator (e.g., benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at 40% by weight or less, preferably 10 to 25% by weight based on the solvent. The copolymerization reaction is carried out by heating to 40 to 120 ° C, preferably 50 to 100 ° C). Thereafter, the reaction mixture is poured into a medium that does not dissolve the formed copolymer, the product is allowed to settle, and then the unreacted mixture is separated and removed by drying.

Next, the copolymer is dissolved in a solvent that dissolves but is insoluble in water (eg, ethyl acetate, butanol, etc.), and is vigorously dispersed in the presence of a dispersant (eg, surfactant, water-soluble polymer, etc.). Is distilled off to obtain a polymer latex.

The Tg (glass transition temperature) of the polymer forming the polymer latex used in the present invention is preferably 60 ° C. or less, particularly preferably 40 ° C. or less.

The Tg of many polymers of the ethylenic monomers used in the present invention can be found in Brand Hand, et al., Polymer Handbook, pages III-139 to III-179 (1966).
Year) (Wiley & Sons, Inc.)
The Tg (° K) of the copolymer is represented by the following formula.

[0056] Tg _{(copolymer) = v 1 Tg 1 + v} 2 Tg 2 + ... + vWTgW However Ueshiki in v _1, v ₂ ... vW represents the weight fraction of the monomer in the copolymer, Tg _1, Tg ₂ ... TgW represents the Tg (° K) of the homopolymer of each monomer in the copolymer.

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

Regarding the method of synthesizing the polymer latex used in the present invention, US Pat. Nos. 2,852,386 and 2,853,457,
3,411,911, 3,411,912, 4,197,127, Belgian Patent 688,882, 691,360, 712,823, JP-B-45-5331, JP-A-60-18540, 51-130217, and 58
-137831, 55-50240, etc.

The average particle size of the polymer latex used in the present invention is preferably 0.5 to 300 nm, and any average particle size is particularly preferably 30 to 250 nm.

The particle size of the polymer latex used in the present invention is determined by the following formula:
1973), which can be measured by an electron micrograph, a soap titration method, a light scattering method, or a centrifugal sedimentation method. The light scattering method is preferably used. As an apparatus for the light scattering method, D
LS700 (manufactured by Otsuka Electronics Co., Ltd.) was used.

Although there is no particular limitation on the molecular weight, the total molecular weight is preferably 1,000 to 1,000,000, more preferably 2,000.
0 to 500,000.

The polymer latex used in the present invention can be contained in the photographic constituent layer as it is or after being dispersed in water. The content of the polymer latex is preferably 5 to 70% by weight based on the binder of the photographic constituent layer. The location for addition is limited to the photosensitive layer.

The polymer latex used in the present invention includes a case where a functional polymer such as a polymer coupler or a polymer ultraviolet absorber is added in the form of a latex.

[0064]

The present invention will be described below in more detail with reference to examples.

Example 1 Preparation of One Emulsion A single silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm was prepared by the double jet method while controlling the temperature at 60 ° C., pAg = 8 and pH = 2.0. Dispersed cubic particles were prepared.

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

Preparation of EM-1 Using the seed emulsion described above, grains were grown as follows. First, the seed emulsion is dispersed in an aqueous gelatin solution maintained at 40 ° C.
The pH was adjusted to 9.7 with aqueous ammonia and acetic acid.

An aqueous solution of ammonium nitrate ion and an aqueous solution of potassium bromide and potassium iodide were added to this solution by a double jet method. During the addition, the pAg was controlled to 7.3, the pH was controlled to 9.7, and a layer having a silver iodide content of 35 mol% was formed. Next, an aqueous solution of ammonium silver nitrate and an aqueous solution of potassium bromide were added by a double jet method. The pAg was maintained at 9.0 until 95% of the target particle size, and the pH was continuously changed from 9.0 to 8.0. Thereafter, the pAg was adjusted to 11.0, and the mixture was grown to a target particle size while maintaining the pH at 8.0. Subsequently, the pH was lowered to 6.0 with acetic acid, and
Anhydrous dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt (desensitizing dye GD-
1) was added to 400 mg / mol AgX, desalted using an aqueous solution of Demol N manufactured by Kao Atlas Co., and an aqueous solution of magnesium sulfate, and then redispersed by adding a gelatin solution.

By this method, a monodispersed silver iodobromide emulsion having an average silver iodide content of 2.0 mol, a rounded apex having an average grain size of 0.65 μm, and a variation coefficient (δ / r) of 0.16 each was obtained. Was. This was designated as EM-1.

Preparation of Seed Emulsion 2 Including hydrogen peroxide-treated gelatin stirred vigorously at 40 ° C.
An equimolar aqueous potassium bromide solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin is added to the 05N aqueous potassium bromide solution by the double jet method, and the mixture is heated at 25 ° C over 30 minutes from 1.5 minutes later.
After the temperature of the solution was lowered to 80 ml, 80 ml of aqueous ammonia (28%) was added per mole of silver nitrate, and stirring was continued for 5 minutes.

Thereafter, the pH was adjusted to 6.0 with acetic acid, desalted with an aqueous solution of Demol N manufactured by Kao Atlas Co., and an aqueous solution of magnesium sulfate, and re-dispersed by adding an aqueous solution of gelatin. The resulting seed emulsion has an average particle size of 0.23 μm and a coefficient of variation.
It was a spherical particle of 0.28.

Preparation of EM-2 to EM-5 Using the seed emulsion described above, grains were grown as follows. 75
An aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added to an aqueous solution containing ossein gelatin and propyloxy / polyethylene oxydisuccinate / disodium salt vigorously stirred at ℃ by a double jet method. During this time p
H = 5.8 and pAg = 9.0 were maintained. After the addition was completed, the pH was adjusted to 6.0, and GD-1 was added at 400 mg / mol AgX.

After desalting at 40 ° C. using an aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd., an aqueous solution of gelatin was added to re-disperse. By changing pAg and potassium iodide by this method, the projected area diameter is 0.96 and the average silver iodide content is 1.5 mol%.
Tabular silver iodobromide emulsions having μm, a coefficient of variation of 0.25, and an aspect ratio (projected area diameter / grain thickness) of 2.0, 3.5, 5.0 and 8.0 were obtained. These were respectively referred to as EM-2, EM-3, EM-
4, EM-5.

Production Example 1 (Synthesis of Lx-4) 385 ml of pure water was placed in a 500 ml three-necked flask, and deoxygenated with nitrogen gas. After that, isononyl acrylate 30
g, cyclohexyl acrylate 60 g, and glycidyl methacrylate 10 g, ammonium persulfate 13.8 g was further added as an initiator, and the reaction was continued at the temperature shown in Table 1 for 6 hours. After the reaction is completed, cool to 40 ° C and add 5% NaOH aqueous solution.
Neutralize to pH 6.0 to obtain white crystals.

The white crystals are subjected to Whatman filtration to obtain a polymer latex. The particle size was 180 nm.

Production Example 2 (Synthesis of Comparative Latex L) In 40 liters of water, 0.25 kg of KMDS (dextran sulfate sodium salt) and 0.5% ammonium persulfate manufactured by Meito Sangyo Co., Ltd.
To a solution to which 05 kg was added, a mixture 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 under a nitrogen atmosphere while stirring at a liquid temperature of 81 ° C., and then ammonium persulfate was added at 0.005 kg. kg, and the mixture was further stirred for 1.5 hours, cooled, and adjusted to pH 6 with aqueous ammonia.

The obtained latex solution was washed with Whotman GF.
The mixture was filtered with a / D filter, and finished to 50.5 kg with water to prepare a monodisperse latex (L) having an average particle size of 250 nm.

Hereinafter, specific examples of the polymer latex according to the present invention and the dispersant used in the synthesis thereof will be shown. The suffix of the monomer unit indicates the content percentage of each.

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In the present invention, the amount of the polymer latex to be used is 10% or more and 300% or less, preferably 30% or more and 200% or less by weight based on 100 parts of gelatin.

If the amount of the polymer latex is too small, the effect of the present invention is not sufficiently exerted. If the amount of the polymer latex is too large, sufficient film strength cannot be obtained. Further, the aqueous polymer used in the present invention is a polymer latex 100
0.5% or more and 30% or less, preferably 1% by weight
% Or more and 15% or less.

Preparation of Samples Each of the obtained emulsions EM-1 to EM-5 was subjected to G at 55 ° C.
D-1 and 5,5′-di- (butoxycarbonyl) -1,1′-diethyl-3,3′-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydrous (200: (Weight ratio of 1) EM-1 per mol of silver halide was 600 mg,
500 mg of EM-5 was added.

After 10 minutes, chloroauric acid, sodium thiosulfate,
Ammonium thiocyanate was added for chemical ripening.
Fifteen minutes before the completion of ripening, 200 mg of potassium iodide was added per 1 mol of silver halide, and then 4-hydroxy-6-methyl-1,4-methyl-1-methyl-1,4-methyl-1-methyl-1,4-
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. The ripened five types of emulsions were respectively EM-I to EM
−V. The following additives were added to each of these emulsions. The amount of addition is shown in an amount per mole of silver halide.

1,1-dimethylol-1-bromo-1-nitromethane 70 mg t-butylcatechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g nitrophenyl-triphenylphosphonium chloride 50 mg 1, Ammonium 3-dihydroxybenzene-4-sulfonate 4.0 g 2-mercaptobenzimidazole-5-sodium sulfonate 15 mg 1-phenyl-5-mercaptotetrazole 10 mg trimethylolpropane 10 g C ₄ H ₉ OCH ₂ CH (CH) CH ₂ N (CH ₂ COOH) ₂ 1g

[0087]

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Further, 1.2 g of a dye emulsified dispersion shown below was added to prepare an emulsion coating solution.

Preparation of Dye Emulsion Dispersion 10 kg of the following dye was dissolved at 55 ° C. in a solvent consisting of 28 liters of tricresyl phosphate and 85 liters of ethyl acetate. This is called an oil-based solvent. On the other hand, a 9.3% gelatin aqueous solution containing 1.35 kg of an anionic surfactant (AS) is called an aqueous solvent.

Next, the oil-based solvent and the aqueous-based solvent were placed in a dispersion vessel and dispersed while maintaining the liquid temperature at 40 ° C. An appropriate amount of phenol and 1,1'-dimethylol-1-bromo-1-nitromethane was added to the obtained dispersion, and the dispersion was adjusted to 240 kg with water.

[0091]

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The additives used in the protective layer are as follows. The amount of addition is indicated by the amount per liter of the coating solution.

Coating solution for protective layer Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymer latex of the present invention Amount shown in Table 1 Polymethyl methacrylate (area average particle size 5.0 μg matting agent) 1.1 g Silicon dioxide particles (matting agent having an area average particle diameter of 3.0 μm) 0.5 g Ludox AM (colloidal silica manufactured by DuPont) 30 g Glyoxal 40% aqueous solution (hardening agent) 1.5 ml (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 500 mg C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0094]

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The emulsion layer was 2.0 g / m 2 in terms of silver per one side.
^2. Glycidyl methacrylate-methyl acrylate-butyl with two slide hopper coaters at a speed of 90 m / min so that the gelatin weight is 2.5 g / m ² and the gelatin weight is 0.99 g / m ^2. An emulsion layer was formed on a 175 μm polyethylene terephthalate base on which a copolymer aqueous dispersion obtained by diluting a methacrylate copolymer (50:10:40 wt%) to a concentration of 10 wt% was applied as a subbing liquid, A protective layer was simultaneously coated on both sides and dried in 2 minutes and 15 seconds to obtain a sample.

The following evaluation was performed using the sample thus obtained.

<Sensitometry> The obtained sample was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica Corporation) and the tube voltage was 90 KV.
X-rays of P, 20 mA, 0.05 seconds were irradiated, and a sensitometric curve was created by a distance method to determine the sensitivity. The sensitivity value was calculated as the reciprocal of the X-ray dose required to obtain a density of fog + 1.0. The results were expressed as relative sensitivities when the sensitivity of sample No. 1 was set to 100. The development was performed using an automatic processor SRX-501 (manufactured by Konica Corporation) at a development temperature of 35 ° C, a fixing temperature of 33 ° C, and a wash water of 18 ° C at a supply rate of 3.5 l / min. All processing steps were processed in the following 45 second mode.

[Processing Step] Step Processing temperature (° C) Processing time (seconds) Replenishment amount Insert-1.2 Development + transfer 35 14.6 33cc / four cut Fix + transfer 33 8.2 63cc / four cut Rinse + transfer 18 7.2 3.5l / Min Squeeze 40 5.7 Dry 45 8.1 Total-45.0 Developing solution Potassium sulfite 70 g Hydroxyethylethylenediamine trisodium trisodium 8 g 1,4-Dihydroxybenzene 28 g Boric acid 10 g 5-Methylbenzotriazole 0.04 g 1-Phenyl-5-mercaptotetrazole 0.01 g Sodium metabisulfite 5 g Acetic acid (90%) 13 g Triethylene glycol 15 g 1-Phenyl-3-pyrazolidone 1.2 g 5-Nitroindazole 0.2 g Glutaraldehyde 4 g Dissolve in 1 liter of water and adjust the pH to 10.5 with sodium hydroxide. Liquid.

Fixing solution Sodium thiosulfate pentahydrate 4.5 g Disodium ethylenediaminetetraacetate 0.5 g Ammonium thiosulfate 150 g Anhydrous sodium sulfite 8 g Potassium acetate 16 g Aluminum sulfate 10 to 18 hydrate 10 g Sulfuric acid (50 wt%) 5 g Citric acid 1 g Boric acid 7 g Ice Acetic acid (5 g) was made into an aqueous solution (1 liter) and the solution was adjusted to pH 4.2 with glacial acetic acid.

<Evaluation of abrasion> After rubbing with a load of 100 g / cm ² using a commercially available nylon scourer in a dark room,
The film was developed by the above-mentioned automatic developing machine, and the following four grades of A to D were evaluated.

A: Almost no abrasion B: Level of practically no problem, but slight abrasion C: Scratch occurs to the extent of being noticeable and has practical problems D: Very large abrasion, width of scratch The results are shown in Table 1.

[0102]

[Table 1]

From the results shown in Table 1, it can be seen that the sample of the present invention has a high sensitivity and a high density, and has good abrasion with few scratches.

[0104]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity, high image quality and excellent scratch resistance can be provided.

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and a hydrophilic colloid layer on one side of a support, wherein the silver halide emulsion layer has an aspect ratio of 3 At least one monomer containing the above tabular silver halide grains and having a solubility in water at 25 ° C. of not more than 0.025% by weight and at least one monomer having an epoxy group in the emulsion layer; Containing at least one polymer latex obtained by polymerizing a seed,
And at the end of the polymerization reaction of the polymer latex,
A silver halide photographic material characterized by being heat-treated at a temperature of 90 ° C or higher.