JPH07281340A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material which is free from gradation fluctuation in rapid processing with low replenishment and has a high sensitivity, high gradation and good preservable property. CONSTITUTION:This silver halide photographic material contains at least one kind of silver halide particles having an average silver iodide content <3mol, >=2 sheets of twin crystal planes parallel with each other and an aspect ratio <2 and a polymer latex consisting of a monomer having solubility <=0.025wt.% in water at 25 deg.C as a monomer. The silver/gelatin ratio in the emulsion layer of the photosensitive material is ;1.3. The content ratio of a polyhydric alcohol to the photosensitive emulsion of the silver halide photographic sensitive material is <=0.20 by the weigh ratio the gelatin.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having good processing stability and long-term storage stability.

[0002]

2. Description of the Related Art In recent years, with the development of photographic technology, there has been a strong demand for higher sensitivity and higher image quality of silver halide photographic light-sensitive materials. Further, with the increase in the consumption of the light-sensitive material, rapid processing in a short time is strongly desired. On the other hand, as interest in environmental protection increases, it is desired to reduce the amount of replenishment of processing liquid in order to reduce the amount of processing liquid waste.

However, when rapid processing with low replenishment is performed, it has been difficult to obtain stable photographic performance in conventional light-sensitive materials because the gradation varies greatly due to an increase in the number of processed sheets and a change in processing temperature.

In order to improve such processing fluctuation, for example, JP-A-2-110542 discloses an attempt to improve by using a tabular silver halide emulsion and a normal crystal core / shell type silver halide emulsion. However, the performance achieved is not yet fully satisfactory. Further, improvement studies have been made on the treating agent, but it is not sufficient. Further, silver halide photographic light-sensitive materials, especially high-sensitivity light-sensitive materials, have a high fog density due to long-term storage, which adversely affects diagnosis in X-ray diagnostic photographs, for example. Therefore, there has been a demand for a silver halide photographic light-sensitive material capable of obtaining stable photographic performance without gradation change by low-replenishment rapid processing and having little fog during long-term storage.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide stable photographic performance without gradation change in low replenishment and ultra-rapid processing of a high-sensitivity and high-quality silver halide photographic light-sensitive material. Another object of the present invention is to provide a silver halide photographic light-sensitive material excellent in long-term storage stability.

[0006]

Means for Solving the Problems In a silver halide photographic light-sensitive material having one or more silver halide emulsion layers on a support, the average silver iodide content in the silver halide emulsion layers is 3 mol%. At least one silver halide grain having two or more twin planes parallel to each other and having an aspect ratio of less than 2, and at least one kind having a solubility in water at 25 ° C. of 0.025% by weight or less A silver halide photographic light-sensitive material comprising at least one polymer latex having a body as a monomer unit.

In the above, the silver halide photographic light-sensitive material is characterized in that the silver / gelatin weight ratio in the silver halide emulsion layer is 1.3 or less.

In the above, the melting point of the silver halide emulsion layer is 40 ° C. or higher, and at least 2 is present in the molecule.
It has been achieved by a silver halide photographic light-sensitive material containing a polyhydric alcohol having three or more hydroxyl groups, and the content of the compound is 0.20 or less by weight ratio to the total gelatin amount.

The present invention will be described in detail below.

The silver halide grain of the present invention is a twin grain having two or more twin planes parallel to each other, preferably an even number, and more preferably two twin planes.

Twin grains mean silver halide grains having one or more twin planes, and the morphology of twins is classified by Klein and Moiser in the report “Photographisch Korrespon”.
denz ”99, 99, 100, 57.

In the present invention, the number of twin grains having two or more twin planes parallel to each other contained in the emulsion of the present invention is 50% or more, preferably 60 when counted from the large grains.
% Or more, and more preferably 70% or more.

The shape of the silver halide grains according to the present invention is
It may have a regular crystal form such as a cube, an octahedron, or a tetrahedron, or may have an irregular crystal form such as a sphere, a plate, or a potato, and it may be a mixed type or a composite type thereof. Good.

The emulsion used in the silver halide photographic light-sensitive material according to the present invention can be produced by a known method. For example, Research Disclosure (RD) No.17643 (December 1978)
Mon) ・ Pages 22-23 1. Emulsion manufacturing method “Emulsion Preparati
on and types ”emulsion method or same (RD) No.1
8716 (November, 1979) -It can be prepared with reference to the method described on page 648.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is described, for example, in "The theory" by TH James.
of the photographic process, 4th edition, published by Macmillan (1977), pages 38-104, GF Daufin, "Photographic Emulsion Chemistry" Foc
Published by al press (1966), P. Glafkides "Physics and Chemistry of Photography""Chimie et physique photographique" Paul
Published by Montel (1967), VL Zelikman et al. "Making and Coating photographic"
It is prepared by the method described in Emulsion ”Focal press (1964).

[0016] That is, in a neutral condition, an acidic method, an ammonia method and the like, a solution mixing condition such as a forward mixing method, a back mixing method, a double jet method, a controlled double jet method and the like, a conversion method, a core / shell method, etc. It can be produced using the particle preparation conditions such as and the like and a combination method thereof.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains.

The term "monodisperse emulsion" as used herein means that when the average grain size is measured from a photomicrograph of silver halide grains, at least 95% of grains or grains by weight are ± 30% of the average grain size.
Within, preferably within ± 20%.

The term "monodispersity" as used herein refers to JP-A-60-16224.
As defined in 4, the coefficient of variation for particle size is 0.20 or less.

The crystal structure of silver halide may have a silver halide composition in which the inside and the outside are different. That is, the core and the core have a core / shell structure composed of at least one shell having different silver halide compositions. The silver iodide content of the high iodine portion is 5 to 40 mol%,
Particularly preferably, it is 5 to 30 mol%.

A method for producing such a monodisperse emulsion is known, and for example, "J. Phot. Sci. 12 vol. 242-251 (1963), JP-A-48-36.
No. 890, No. 52-16364, No. 55-142329, No. 58-49938,
British Patent 1,413,748, U.S. Patents 3,574,628, 3,655,
It is described in detail in No. 394.

As a method for obtaining the monodisperse emulsion, for example, a method of using a seed crystal and supplying silver ions and halide ions as growth nuclei to grow the seed crystal is particularly preferable.

A method for producing a core / shell type emulsion is well known, for example, British Patent No. 1,027,146 and US Pat. No. 3,505,068.
No. 4,444,877 or JP-A-60-143331 can be referred to.

The silver halide emulsion according to the present invention may have any halogen composition such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodobromide, but has high sensitivity. From this point of view, silver iodobromide is preferable, and the average silver iodide content is less than 3.0 mol%, particularly preferably less than 2.5 mol.

The silver halide grains in the present invention are, for example, silver halide grains having an average silver iodide content of less than 3.0 mol%. The silver iodide content of each silver halide grain is
For example, it can be measured by analyzing the composition of each silver halide grain using an X-ray microanalyzer.

As the coefficient of variation of the silver iodide content of each grain, the standard deviation of the silver iodide content when measuring the silver iodide content of at least 100 emulsion grains is the average silver iodide content. It is the value obtained by multiplying the value divided by.

The Journal of the Photographic Society of Japan, Vol. 53, No. 2, 125-1
On page 28 (1990), the results of measuring the silver iodide content for each internal structure of each silver halide by an analytical electron microscope are reported. See also the Journal of Imaging Science vo
l.31 No.1 pp. 15-26 (1987) describes the halogen composition of tabular grains by the low-temperature emission method of fine grain structure.
It has been reported to make observations using ratur eluminescence microscopy). Furthermore, the Journal of Imaging Sci
ence vol.32 No.4, pages 160 to 177 (1988), when silver chloride was precipitated on silver iodide having a silver iodide distribution in the grain, silver iodide determined the deposition site of silver chloride (site Direct) has been reported.

Furthermore, the Journal of the Photographic Society of Japan, Vol. 53, No. 3, (199
It is reported on page 213 of (Year 0) that the nonuniformity of the halogen composition in the grains can be observed by directly observing the grains at a low temperature using a transmission electron microscope.

As described above, the fine structure of the silver halide composition of each silver halide grain can be observed.

The average silver iodide content near the outermost surface of the silver halide grain according to the present invention is preferably less than 10.0 mol%.

The vicinity of the outermost surface of the silver halide grain means that when the average silver iodide content on the surface of the silver halide grain is measured by the XPS method, the X-ray penetrates from the surface of the silver halide grain. It refers to a silver halide phase existing in a region that reaches the area, and usually corresponds to a region of about 50 Å including the grain surface in the outermost layer that constitutes a silver halide grain.

The average silver iodide content in the vicinity of the outermost surface of the silver halide grains in the present invention is XPS when a sample prepared from the silver halide grains is cooled to -110 ° C or lower.
The value measured using the method is shown.

Prior to the XPS method, the silver halide emulsion is pretreated as follows. First, a 0.05% by weight aqueous solution of proteolytic enzyme (protease) is added and gelatin is decomposed by stirring at 45 ° C for 30 minutes. Next, the silver halide grains are settled by centrifugation to remove the supernatant, and then distilled water is added to disperse the silver halide grains in distilled water, followed by centrifugation to remove the supernatant. The remaining silver halide grains are dispersed again in distilled water, and a thin film is applied on a mirror-polished silicon wafer to obtain a measurement sample.

Using the sample thus prepared, XP
The average silver iodide content in the vicinity of the outermost surface of the silver halide grain is measured by the S method. To prevent the sample from being destroyed by X-ray irradiation, the sample is liquid nitrogen in an XPS measurement chamber.
Alternatively, it is cooled to −110 ° C. to −120 ° C. using helium gas. As the probe line, Mg-K line is X-ray source voltage 15kV,
Irradiate with an X-ray source current of 40 mA.

In order to obtain the halide composition near the outermost surface of the silver halide grain, Ag3d and I3d3 / 2 electrons are detected.
The composition ratio is calculated by measuring the average silver iodide content in the vicinity of the outermost surface of the silver halide from the intensity ratio obtained by correcting the integrated intensity of each measured peak with a sensitivity factor (Sensitivty Factor).

The total silver iodide content of the halogen emulsion according to the present invention
50 mol% or more is due to the supply of fine grain silver iodide,
It is preferably 70 mol% or more, more preferably 90 mol% or more.

Since the grain size of fine grain silver iodide governs the supply rate of iodide ions, the preferred grain size varies depending on the grain size and halogen composition of the silver halide grain serving as a host, but the average spherical equivalent diameter is 0.1 μm. The following are preferred.

Further, in order for the fine grain silver iodide to form a solid solution in the host grain of the present invention to be recrystallized, the grain size of the fine grain silver iodide is preferably smaller than the spherical equivalent diameter of the host grain. For silver iodide, generally cubic γ-A
Although gI and hexagonal β-AgI are known, the fine grain silver iodide used in the present invention may have any crystal structure or a mixture thereof.

The fine grain silver iodide used in the present invention preferably has good monodispersibility, and is preferably prepared by the double jet method while controlling the temperature, pH and pAg.

The method for producing twin grains having two or more twin planes parallel to each other according to the present invention includes adding an aqueous solution of silver nitrate to an aqueous solution of gelatin whose pBr is kept at 3.0 or less, or an aqueous solution of silver nitrate and halogen. Compound aqueous solution is added at the same time to generate twin seed particles, and then grown by the double jet method.

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

The average silver iodide content and the average silver chloride content of the silver halide emulsion according to the present invention are determined by changing the composition of the aqueous halide solution to be added, that is, the ratio of bromide to iodide and chloride. It can be controlled, and a silver halide solvent such as ammonia, thioether, thiourea or the like can be used at the time of producing the emulsion, if necessary.

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

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugars such as sodium alginate, dextran and starch derivatives. Various synthetic hydrophilic polymer substances such as derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. In particular, it is preferable to use dextran or polyacrylamide having an average molecular weight of 5000 to 10,000 together with gelatin. Examples of these are, for example, JP-A-1-307738, 2-62532, 2-24748,
2-44445, 1-66031, JP-A-64-65540, 63-101
It is disclosed in gazettes such as 841 and 63-153538.

For gelatin, lime-processed gelatin, acid-processed gelatin, Bull.Soc.Sci.Phot.Japan, No. 1630 page (1966)
In addition to the enzyme-treated gelatin as described in 1., gelatin derivatives (eg gelatin include acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkanesultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides, etc. And those obtained by reacting various compounds such as epoxy compounds.

As the hydrophilic colloid according to the present invention, gelatin is preferred, and the amount of gelatin used is preferably a silver / gelatin weight ratio in the silver halide layer of 1.
It is 5 or less, and more preferably 1.3 or less.

The emulsion of the present invention may be subjected to a water washing method such as a Nudel water washing method or a flocculation sedimentation method in order to remove soluble salts (desalting treatment step). As a preferred washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or aggregating polymer agents exemplified as G-3 and G- in JP-A-2-7037 is used. 8
As a particularly preferable desalting method, a method using, etc. is mentioned.

In the silver halide photographic light-sensitive material of the present invention, a hydrophilic colloid is provided at a position farthest from the support as a protective layer for the silver halide light-sensitive emulsion layer. Examples of these colloids include hydrophilic colloids generally used in the field of photography such as gelatin, colloidal albumin, polysaccharides, cellulose derivatives, synthetic resins such as polyvinyl compounds containing polyvinyl alcohol derivatives and acrylamide polymers. it can.

The coating amount of gelatin as the hydrophilic colloid layer of the protective layer of the silver halide emulsion in the present invention is 1.5 g / m.
² or less. When it is 1.5 g / m ² or more, scratch resistance and pressure desensitization are improved, but poor fixing and dryness are deteriorated. The preferable gelatin coating amount is 1.2 to 0.5 g / m ² .

At least one of the monomers forming the polymer latex used in the present invention has a solubility in water at 25 ° C. of not more than 0.25% by weight, preferably not more than 0.015% by weight. Examples of such ethylenic monomers include 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. Acrylic acid esters, butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, hexyl metallate, 2-ethylhexyl metallate, octyl metallate, iso-octyl methacrylate, tert-octyl metallate, nonyl metallate, iso- Methacrylic acid ester such as nonyl metalylate, cyclohexyl metalylate, n-stearyl metalylate, lauryl methacrylate, 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 New Experimental Chemistry Course Basic Operation 1 (Maruzen Kagaku, 1975). . The solubility of the monomer of the present invention in water at 25 ° C. measured by this method is, for example,
2-ethylhexyl acrylate is 0.01% by weight, 2-ethylhexyl methacrylate is 0.01% by weight, and cyclohexyl methacrylate is 0.01% by weight. The comparative monomer was 0.03 wt% for styrene, 0.32 wt% for butyl acrylate and 0.03 wt% for butyl methacrylate.

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

More specific examples of these monomer compounds include acrylic acid esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, 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 thereof include methoxypolyethylene glycol acrylate (addition mol number n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate.

Examples of methacrylic acid esters are methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, amyl methacrylate, chlorobenzyl methacrylate, sulfopropyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, 2- (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-methoxypolyethylene glycol methacrylate (additional mol number n =
6), allyl methacrylate, dimethylaminoethyl methyl methacrylate salt of methacrylic acid and the like.

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

Examples of styrenes include styrene,
Examples thereof include methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromstyrene, trifluoromethylstyrene, and vinylbenzoic acid methyl ester.

Examples of crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.

Examples of the diethyl itaconates include dimethyl itaconate, diethyl itaconate and dibutyl itaconate. Examples of maleic acid diesters include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumarate diesters include diethyl fumarate, dimethyl fumarate, dibutyl fumarate and the like. Examples of acrylamides include acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, Diethyl acrylamide, β-cyanoethyl acrylamide, N- (2-acetoacetoxyethyl) acrylamide, etc .; methacrylamides such as 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 etc .; allyl compounds, eg
Allyl acetate, allyl caproate, allyl laurate, allyl benzoate, etc .; vinyl ethers such as methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc .; vinyl ketones such as methyl vinyl ketone, phenyl Vinyl ketone, methoxyethyl vinyl ketone, etc .; vinyl heterocyclic compound,
For example, vinylpyridine, 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; polyfunctional monomers such as divinylbenzene, methylenebisacrylamide and ethylene glycol dimethacrylate.

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, vinyl benzyl sulfonic acid, vinyl sulfonic acid, acryloyl Oxyalkyl sulfonic acids, for example
Acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid, etc .; methacryloyloxyalkyl sulfonic acid, such as methacryloyloxydimethyl sulfonic acid, methacryloyloxyethyl sulfonic acid, methacryloyloxypropyl sulfonic acid; , For example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid, etc .; methacrylamide alkyl sulfonic acid, for example, 2-methacrylamide- 2-Methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylbutanesulfonic acid, etc .; acryloyloxyalkylphosphine , For example, acryloyloxyethyl phosphate, 3-acryloyloxypropyl-2-phosphate and the like; methacryloyloxyalkyl phosphate, for example, methacryloyloxyethyl phosphate, 3-methacryloyloxypropyl-2-phosphate and the like; 3 having two hydrophilic groups 3 Examples include naphthyl-allyloxy-2-hydroxypropanesulfonate. These acids may be salts of alkali metals (eg Na, K, etc.) or ammonium ions. Further 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, JP-A-57-205735 and the like can be used. Specific examples of such crosslinkable monomers include N- (2-acetoacetoxyethyl) acrylamide, N- {2- (2-acetoacetoxyethoxy) ethyl} acrylamide and the like.

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

As the surfactant used in the polymerization of the polymer latex of the present invention, an anionic surfactant,
Although any of nonionic surfactants, cationic surfactants and amphoteric surfactants can be used, anionic surfactants and / or nonionic surfactants are preferred. As the anionic surfactant and the nonionic surfactant, various compounds known in the art can be used, but the anionic surfactant is particularly preferably used.

Examples of the water-soluble polymer used in the polymerization of the polymer latex of the present invention include synthetic polymers and natural water-soluble polymers, both of which are preferably used in the present invention. Among them, the synthetic water-soluble polymer, for example, 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, nonionic Examples thereof 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.

As the natural water-soluble polymer, for example, those having a nonionic group, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group in the molecular structure, Examples thereof 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 includes synthetic water-soluble polymers, those having an anionic group in both cases of natural water-soluble, and nonionic groups and anionic groups. Those having a group can be preferably used.

In the present invention, the water-soluble polymer is 20
It may be dissolved in 0.05 g or more with respect to 100 g of water at 0 ° C., preferably 0.1 g or more.

As the natural water-soluble polymer, water-soluble polymer water-dispersible resin comprehensive technical data collection (Management Development Center)
, But preferably includes lignin, starch, pullulan, cellulose, dextran, dextrin, glycogen, alginic acid, gelatin, collagen, guar gum, gum arabic, laminaran, lichenin, nigran, etc. and derivatives thereof. is there. As the natural water-soluble polymer derivative, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkylphosphorylated and salts thereof are preferably used. Particularly preferred are 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 are an emulsion polymerization method, a solution polymerization method, a method of redispersing a polymer obtained by bulk polymerization, and the like.

In the emulsion polymerization method, water is used as the dispersion medium, 10 to 50% by weight of the monomer relative to water, 0.05 to 5% by weight of the polymerization initiator relative to the monomer, and 0.1 to 20% by weight of the monomer. About 3 with dispersant
It can be obtained by polymerizing with stirring at 0 to 100 ° C, preferably 60 to 90 ° C for 3 to 8 hours. The concentration of the monomer, the amount of the initiator, the reaction temperature, the time, etc. can be changed widely and easily.

As the initiator, water-soluble peroxides (eg potassium persulfate, ammonium persulfate, etc.), water-soluble azo compounds (eg 2,2′-azobis- (2-amidinopropane)-) are used.
Hydrochloride etc.) and the like.

Examples of the dispersant include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants in addition to water-soluble polymers, and these may be used alone or in combination. , Preferably a combination of a water-soluble polymer and a nonionic or anionic activator. In solution polymerization, a mixture of monomers at a suitable concentration in a suitable solvent (eg, ethanol, methanol, water, etc.) (generally, A mixture of 40% by weight or less, preferably 10 to 25% by weight with respect to the solvent) in the presence of a polymerization initiator (eg, benzoyl peroxide, azobisisobutyronitrile, ammonium persulfate, etc.) at an appropriate temperature (eg, The copolymerization reaction is carried out by heating to 40 to 120 ° C, preferably 50 to 100 ° C. After that, the reaction mixture is poured into a medium in which the produced copolymer is not dissolved, 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 in which water is insoluble but insoluble in water (for example, ethyl acetate, butanol, etc.), and is vigorously dispersed in the presence of a dispersant (for example, surfactant, water-soluble polymer, etc.), and then the solvent is used. Is distilled off to obtain a polymer latex.

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

The Tg of many polymers of ethylenic monomers used in the present invention are determined by Brand Wrap et al., "Polymer Handbook", pages III-139 to III-179 (1966).
Year) (Wiley and Sons Edition),
The Tg (° K) of the copolymer is represented by the following formula.

Tg (copolymer) = v ₁ Tg ₁ + v ₂ Tg ₂ + ... + vw Tgw In the above formula, v ₁ , v ₂ ... vw represent the weight fraction of the monomer in the copolymer, and Tg ₁ , Tg ₂ · ··· Tgw represents the Tg (° K) of the homopolymer of each monomer in the copolymer.

The Tg calculated according to the above equation is ± 5 ° C.
There is a precision of.

Regarding the method of synthesizing the polymer latex used in the present invention, US Pat. Nos. 2,852,386 and 2,853,457,
No. 3,411,911, No. 3,411,912, No. 4,197,127, Belgium Patents 688,882, No. 691,360, No. 712,823, Japanese Patent Publication No. 45-5331, No. 60-18540, No. 51-130217, No. 58.
-137831, 55-50240 and so on.

Any polymer latex having an average particle size of 0.5 to 300 nm can be preferably used, and 30 to 250 nm is particularly preferable.

The particle size of the polymer latex used in the present invention is determined by "polymer latex chemistry" (Polymer Publishing Society,
Although it can be measured by an electron micrograph, a soap titration method, a light scattering method, and a centrifugal sedimentation method described in 1973), the light scattering method is preferably used. As a light scattering device, D
LS700 (manufactured by Otsuka Electronics Co., Ltd.) was used.

The molecular weight is not specified, but the total molecular weight is preferably 1,000 to 1,000,000, more preferably 2,000.
It is 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 addition place may be a photosensitive layer or a non-photosensitive layer.

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

Specific examples of the polymer latex according to the present invention and the dispersant used for its synthesis are shown below. The suffixes of the monomer units indicate the respective content percentages, but the present invention is not limited thereto.

[0084]

[Chemical 1]

[0085]

[Chemical 2]

[0086]

[Chemical 3]

[0087]

[Chemical 4]

[0088]

[Chemical 5]

[0089]

[Chemical 6]

In the present invention, the amount of polymer latex used is such that the amount of gelatin in the hydrophilic colloid layer according to the present invention is 100.
10% or more and 200% or less by weight ratio, preferably 25
% Or more and 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
It refers to a polymer latex obtained by polymerizing at least one monomer having a solubility in water at 0 ° C. of not more than 0.25% by weight.

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 polyhydric alcohol having a melting point of 40 ° C. or higher and having at least two hydroxyl groups in the molecule according to the present invention has 2 to 12 hydroxyl groups in the molecule and has 2 carbon atoms.
It is preferably an alcohol having 20 to 20 hydroxyl groups and a hydroxyl group not conjugated with a conjugated chain, that is, an oxidized form cannot be drawn, and a melting point of 50 ° C. or more and 300 ° C. or less.

Preferred specific examples of the polyhydric alcohol will be given below, but the compound is not limited to the following examples, and compounds described in JP-A-2-87138 can be used as other compounds.

No. Compound Name 1 2,3,3-Tetramethyl-2,4-pentanediol 2 2,2-Dimethyl-1,3-pentanediol 3 Decanediol 4 2-Butyne-1,4-diol 5 2,5-Dimethyl-3-hexyne-2,5-diol 6 2,4-Dimethyl-2,3,4-hexanetriol 7 2,2-dihydroxymethyl-1-butanol 8 Erythritol 9 1,2,3, 4-Pentanetetrol 10 3-hexyl-1,2,5,6-tetrol 11 D-arabitol 12 rac-trait The above compounds, and the polyhydric alcohols described in JP-A-2-87138 are silver halide emulsion layers. The amount added is not particularly limited, but is 0.20% or less by weight ratio to gelatin,
It is preferably 0.15% or less, particularly preferably 0.05 to 0.15%.

The time of addition is arbitrary, but it is added after the chemical sensitization and during the coating of the emulsion layer. As an addition method, it may be dispersed directly in the hydrophilic colloid, or may be added after being dissolved in an organic solvent such as methanol or acetone.

In carrying out the present invention, the silver halide emulsion may be chemically sensitized. For chemical sensitization, usual sulfur sensitization, reduction sensitization, noble metal sensitization, and a combination thereof are used. Specifically, sensitization with a selenium compound,
Sensitization with a tellurium compound, gold sensitization, sensitization with a noble metal of Group VIII of the periodic table (for example, Pd, Pt, Ir, etc.), and a sensitization method using a combination thereof can be used.

It is also preferable to carry out the chemical sensitization in the presence of a compound having adsorptivity to silver halide. Particularly preferred compounds are azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, particularly compounds having a mercapto group and compounds having a benzene ring.

Further, they may be spectrally sensitized with cyanine dyes and the like, and the sensitizing dyes may be used alone or in combination thereof. Particularly, the combination of sensitizing dyes is often used for the purpose of supersensitization. To be

The emulsion according to the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure (RD) No. 17643 (December 1978),
The compounds described in No. 18716 (November 1979) and No. 308119 (December 1989) are mentioned. The types of compounds and the places where they are described in these three Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IVA Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 VIII Plasticizer 27 VII 650 Right 1006 XII Sliding agent 27 VII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IV Support 28 IVII 1009 IVII The silver halide photographic light-sensitive material of the present invention has at least one photosensitive layer on the support, and optionally an undercoat layer, an antihalation layer, an intermediate layer and a protective layer. You may.

Examples of the support that can be used in the silver halide photographic light-sensitive material of the present invention include the above-mentioned RD-1.
Examples include those described in 7643, 28 and RD-308119, page 1009. A suitable support is a polyethylene terephthalate film or the like, and an undercoat layer may be provided on the surface of these supports in order to improve the adhesion of the coating layer, or corona discharge or ultraviolet irradiation may be applied.

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.
~ XXI, treatments with treatment solutions as described on pages 1011-1012 may be performed. This process may be a black and white photographic process that forms a silver image. Processing temperature is usually from 18 ℃
It is processed in the range of 50 ℃.

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

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

Preferred processing conditions for the silver halide photographic light-sensitive material of the present invention are as follows: developing temperature 20 to 40 ° C., fixing temperature 15 to 45 ° C.
The processing time is less than 45 seconds in Dry to Dry. Say here
Dryto Dry is the time from when the film to be processed is applied to the sensor at the tip of the insertion port of the automatic processor to when it reaches the sensor at the film ejection port, and the total processing time is less than 45 seconds. Is 20 to 33 seconds, more preferably 23 to 30 seconds.

The replenisher used in the present invention comprises the same components for both the developing solution and the fixing solution, and the replenishment is for processing fatigue and oxidation fatigue. As a replenishment method, JP-A-55-126
Replenishment according to width and feeding speed described in Japanese Patent No. 243, JP-A-60-104946
The area replenishment described in JP-A No. 1-149156 and the controlled area replenishment according to the number of continuously processed sheets described in JP-A-1-149156 may be used, and the preferable replenishment rate is 500 to 150 ml / m ² .

Drying is usually 35 to 100 ° C., preferably 40 to 8
The automatic developing machine may be provided with a drying zone in which a hot air of 0 ° C. is blown or a heating means by far infrared rays is provided.

Further, the automatic developing machine has a function of applying water or a rinse solution of an acidic solution having no fixing ability to the light-sensitive material during the respective steps of developing, fixing and washing with water. 3-264953) may be used. Further, the automatic developing machine may include a device capable of preparing a developing solution and a fixing solution.

[0110]

EXAMPLES Examples of the present invention will be described below. However, as a matter of course, the present invention is not limited to the examples described below.

Example 1 A seed emulsion A made of silver bromide was prepared using the solution shown below.

[0112] [A _1] ossein gelatin 40g Potassium bromide 75.1 g HO that hydrogen peroxide treatment _{(CH 2 CH 2 O) m-} (CH (CH 3) CH 2 O) 17 - (CH 2 CH 2 O) n-H (m + n≈5.7) (10% methanol solution) 10 ml Water added 400 ml [B ₁ ] Silver nitrate 600 g Water added 803 ml [C ₁ ] Hydrogen peroxide treated ossein gelatin 16.1 g Potassium bromide 420 g Water 803 ml [D ₁ ] Ammonia water (28%) 235 ml Using the apparatus disclosed in JP-A-62-160128, the feed nozzles to the lower part of the mixing impeller for mixing are for solution B ₁ and solution C _It was installed so that it would be 6 pieces for ₁ piece.

Solution B ₁ and solution C ₁ were added to solution A ₁ which was stirred at a temperature of 40 ° C. and a rotation speed of 430 rpm at a high speed by a controlled double jet method at a flow rate of 62.8 ml / min. The flow rate was gradually increased from 4 minutes and 46 seconds after the start of the addition so that the final flow rate was 105 ml / min. Total addition time is 10 minutes
It was 45 seconds. P during addition with potassium bromide solution (3.5N)
Br was kept at 1.3.

After the addition was completed, the temperature of the mixed solution was increased to 20 minutes in 105 minutes.
Solution D
₁ was added for 20 seconds and Ostwald ripening was carried out for 5 minutes. During aging, the bromine ion concentration was 0.025 mol / l, the ammonia concentration was 0.63 mol / l, and the pH was 11.7.

Immediately thereafter, acetic acid was added until the pH reached 5.6 to neutralize the mixture to stop the ripening, and in order to remove excess salts, desalting was performed using an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate. It was washed with water to obtain a seed emulsion A. When the seed emulsion A was observed with an electron microscope, it was found to be spherical grains having an average grain size of 0.24 μm and a grain size variation coefficient of 17%.

(Preparation of silver iodide fine grain emulsion) 5000 ml of a 5.2% by weight gelatin solution containing 0.008 mol of potassium iodide,
An aqueous solution containing 1.06 mol of silver nitrate and potassium iodide was added at a constant flow rate of 1500 ml over 35 minutes. During this time, the temperature was kept at 40 ° C. The obtained silver iodide fine particles had an average particle diameter of 0.043 μm and was a mixture of β-AgI and γ-AgI.

(Growth of Seed Emulsion A, Preparation of EM-1) Subsequently, the seed emulsion A and a solution shown below were used to prepare a silver halide parent emulsion comprising twins according to the present invention.

[A ₂ ] ossein gelatin 42.8 g HO (CH ₂ CH ₂ O) m- (CH (CH ₃ ) CH ₂ O) _17- (CH ₂ CH ₂ O) n-H (M + N≈5.7) ( 10% methanol solution) 9.0 ml 28% aqueous ammonia solution 370 ml 56% acetic acid aqueous solution 530 ml Add water 3700 ml [B ₂ ] ossein gelatin 24.0 g Potassium bromide 2430 g Add water 4800 ml [C ₂ ] Silver nitrate 3530 g 28% aqueous ammonia solution 2880 ml Ammonium nitrate 668 g Water added 5940 ml [D ₂ ] Silver iodide fine grain emulsion 0.298 mol equivalent [E ₂ ] seed emulsion A 0.83 mol equivalent [F ₂ ] 3.5N potassium bromide aqueous solution pAg control [G ₂ ] 56% acetic acid Aqueous solution pH control Solution A ₂ vigorously stirred at a liquid temperature of 75 ° C. was added with E ₂ or seed emulsion A.
, And disperse well, and add solution B ₂ and solutions C ₂ and D ₂ to 197
It was added by the controlled triple jet method in minutes. The addition of D ₂ was completed when 8% of B ₂ was added.

Here, solution B ₂ , solution C ₂ and solution D ₂
The addition rate is changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate, and added at an appropriate addition rate so as not to cause polydispersion due to generation of small particles other than growing seed crystals and Ostwald ripening. did. The solution D _{2, that} is, silver iodide fine grains, is supplied to the core having a multiple structure by changing the rate ratio (molar ratio) with the solution B ₂ or the aqueous ammoniacal silver nitrate solution to 0.33 with respect to the particle diameter (addition time). /
A shell type silver halide emulsion was prepared.

By using the solutions F ₂ and G ₂ ,
It was kept at pHAg8.00 and pH7.0 during grain growth.

Immediately after completion of the addition, the pH was adjusted to 6.0 with acetic acid, and in order to remove excess salts, precipitation desalting was performed using an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate, and gelatin was added. PAg at 40 ℃
Redispersion under conditions of 8.5, pH 5.85, average silver iodide content 0.5
A mol% emulsion EM-1 was obtained.

When the obtained emulsion was observed with a scanning electron microscope, it was found to be cubic grains having 0.97 μm on each side and having two parallel twin planes.

(Preparation of seed emulsion B) A hexagonal tabular seed emulsion having an average silver iodide content of 2.0 mol% was prepared by the following method.

[0124] [A _3] ossein gelatin 24.2g Distilled water _{9657ml HO (CH 2 CH 2 O} ) m- (CH (CH 3) CH 2 O) 17 - (CH 2 CH 2) n-H (m + n ≒ 5.7 ) (molecular weight 1700) (10% methanol solution) 6.78 mL KBr 10.8 g 10% nitric acid 114ml [B _3] 2.5 N AgNO ₃ solution 2825ml [C _3] to 2825ml with KBr 824 g KI 23.5 g distilled water [D _3] 1.75 Aqueous solution of N KBr At the following silver potential control amount of 35 ° C., 464.3 ml of each of solution B ₃ and solution C ₃ was added to solution A ₃ using a mixing stirrer shown in Japanese Patent Publication Nos. 58-58288 and 58-58289. It takes 2 minutes by the simultaneous mixing method to add,
Nucleation was performed.

After stopping the addition of solution B ₃ and solution C ₃ ,
It takes 60 minutes to raise the temperature of solution A ₃ to 60 ° C,
After adjusting the pH to 5.0 with 3% KOH, the solution B ₃ and the solution C were again adjusted.
₃ was added by the double-sided mixing method at a flow rate of 55.4 ml / min for 42 minutes. This temperature rise from 35 ° C. to 60 ° C. and solution B ₃ , C ₃
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the re-simultaneous mixing by the method was controlled to +5 mv and +12 mv, respectively, using the solution D ₃ .

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. In this seed emulsion B, 90% or more of the total projected area of silver halide grains has a maximum adjacent side ratio of 1.0.
It was found by electron microscope that the hexagonal tabular grains had a mean thickness of 0.05 μm and an average diameter (converted to a circle diameter) of 0.55 μm.

[0127] (Preparation of Emulsion EM-2) [A _4] ossein gelatin _{40.5g HO (CH 2 CH 2 O} ) m- (CH (CH 3) CH 2 O) 17 - (CH 2 CH 2) n- H (m + n≈5.7, molecular weight 1700) (10% methanol aqueous solution) 9.0 ml Distilled water to 3700 ml.

[B ₄ ] Oscein gelatin 30.0 g Potassium bromide 2500 g Distilled water up to 6000 ml.

[C ₄ ] Silver nitrate 3500 g Make up to 590 ml with distilled water.

[D ₄ ] 0.82 mol equivalent of silver iodide fine grain emulsion [E ₄ ] 1.18 mol equivalent of seed emulsion B [F ₄ ] 3.5N KBr aqueous solution Silver potential control amount below Solution A ₄ vigorously stirred at a liquid temperature of 75 ° C. , E ₄ or seed emulsion B
, Disperse well, and mix solution B ₄ and solutions C ₄ and D ₄ with 182
It was added by the controlled triple jet method in minutes. The addition of D ₄ was completed when 2% of B ₄ was added.

Here, solution B ₄ , solution C ₄ and solution D ₄
The addition rate is changed in a function-like manner with respect to time so as to be commensurate with the critical growth rate, and added at an appropriate addition rate so as not to cause polydispersion due to generation of small particles other than growing seed crystals and Ostwald ripening. did. The solution D _{4, that} is, the silver iodide fine particles, is supplied by changing the rate ratio (molar ratio) with the solution B ₄ or the aqueous solution of silver nitrate to 2.2 with respect to the particle diameter (addition time) to form a core / shell having a multiple structure. -Type silver halide emulsion was prepared.

Further, by using the solution F ₄ , it was kept at pAg6.2 during grain growth.

After completion of the addition, in order to remove excess salts,
Precipitation desalination was performed using an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate, and gelatin was added.
Redispersion was carried out at 40 ° C. under the conditions of pH 8.5 and pH 5.85 to obtain Emulsion EM-2 having an average silver iodide content of 0.5 mol%.

When the obtained emulsion was observed with a scanning electron microscope, it was found to be cubic grains having 0.95 μm on each side and having two parallel twin planes.

(Preparation of Emulsion EM-3) In the preparation method of EM-1, 108 minutes after the start of addition of the C ₂ solution (completion of 80% of the total amount of silver added), 1800 ml of a 4.37N potassium bromide aqueous solution was kept at a constant flow rate. Add over 8 minutes. During this time, pAg is 7.5 to 10.1
Rose to. EM except for the addition of this potassium bromide solution
EM-3a was obtained by the same preparation method as in -1. Also D
E except for changing the addition amount of the silver iodide fine grain emulsion of the _second liquid
The average silver iodide content is 2.5 by the same preparation method as that for M-3a.
Emulsion EM-3b and EM-3c of mol% and 3.5 mol% were obtained.

EM-3a and EM- with a scanning electron microscope.
When about 200 samples of 3b and EM-3c were observed, two vertices of twin planes parallel to each other were observed as in EM-1 with an average grain size of 0.98 μm and rounded vertices of a cube.

[0137] The (Emulsion EM-4 of Preparation) EM-2 C ₄ solution added after the start 171 minutes in the method of preparing the 4.37N potassium bromide aqueous solution 1800 ml (added 80% completion of the total silver amount), at a constant flow rate Add over 8 minutes. During this time, pAg is 6.2 to 10.0
Rose to. EM except for the addition of this potassium bromide solution
EM-4 was obtained by the same preparation method as that of -2.

Observation of about 200 samples with a scanning electron microscope showed that the average grain size was 0.96 μm and the vertices of the cube were rounded, and two parallel twin planes were observed as in EM-2. It was

(Preparation of emulsion EM-5) In the preparation method of EM-2, p4 was measured after the addition of D _{4, that} is, the silver iodide fine grain emulsion, was completed.
Gradual change from 6.5 to 8.0, pAg until the end of C ₄ addition
Was kept at 8.0 throughout. EM-2 except for changing the pAg value
EM-5 was obtained by the completely same preparation method.

Observation of about 200 samples with a scanning electron microscope revealed that the grains were tabular grains having an average grain size (equivalent circle diameter) of 1.35 μm and an average aspect ratio of 2.7.

(Preparation of Normal Crystal Seed Emulsion C) [Solution A] Water 11.5l Potassium bromide 2.05g Ossein gelatin 100g [Solution B] Water 2.6l Potassium bromide 65g Potassium iodide 1.8g Ossein gelatin 55g 0.2N Sulfuric acid 38.5cc Water C 3.0 g Potassium bromide 950 g Potassium iodide 27 g Ocein gelatin 75 g [D liquid] Water 2.7 l Silver nitrate 95 g [E liquid] Water 3.2 l Silver nitrate 1410 g Put solution A in a reaction kettle at 60 ° C. The solution was kept warm and the other solution was added at 23 ° C. At this time, the solutions B and D were added by the controlled double jet method over 30 minutes, and then the solutions C and E were added by the controlled double jet method over 105 minutes. Agitation was performed at 500 rpm. The flow velocity was increased in proportion to the total surface area of silver halide grains as the grains grew, and new growth nuclei did not occur when the additive solution flowed in, and so-called Ostwald ripening occurred, and the grain size distribution was widened. Added at no flow rate. When the silver ionic liquid and the halide ionic liquid were added, the pAg was adjusted to 8.3 ± 0.05 using potassium bromide, and the pH was adjusted to 2.0 ± using sulfuric acid.
Adjusted to 0.1.

After the addition was completed, the pH was adjusted to 6.0, and then desalting treatment was carried out in the same manner as in Example 1.

The obtained emulsion had a cubic grain size of 0.30 μm, a {111} plane of about 5%, and other {100} planes with a slight lack of corners and a cubic iodide content of 2 mol%. It was a monodisperse particle. This seed emulsion is designated as C.

(Growth of Seed Emulsion) First, the following solutions were prepared. All amounts are given per mol of silver halide.

[Solution J (reaction mother liquor)] Gelatin 10 g Concentrated ammonia water 28 ml Glacial acetic acid 3 ml Water 600 ml [solution K] Potassium bromide 1.7 g Potassium iodide 1.0 g Gelatin 0.27 g Water 37 ml [solution L] Potassium bromide 90 g Gelatin 2.0 g Water 240 ml [M liquid (0.75N)] AgNO ₃ 3.3 g NH ₄ OH 2.3 ml Water 37 ml [N liquid] AgNO ₃ 130 g NH ₄ OH 100 ml Water 240 ml [O liquid] Potassium bromide 94 g Water 165 ml [P liquid] AgNo ₃ 9.9 g NH ₄ OH 7.0 ml 110 ml of water was kept at 40 ° C. with water and stirred at 800 rpm with a stirrer. J
The pH of the solution was adjusted to 9.90 with acetic acid, and seed emulsion C was added to this.
Was dispersed and suspended in an amount of 0.03 mol per mol of silver halide. After that, P liquid was added at a constant speed over 7 minutes.
The pAg was 7.3. Further, the K solution and the M solution were simultaneously added over 8 minutes. At this time, pAg was fixed at 7.30. Furthermore, 10
PH = 8.8 with potassium bromide solution and acetic acid over a period of minutes
3. After adjusting to pAg = 9.0, L solution and N solution were added simultaneously over 30 minutes. At this time, the inflow rate ratio at the start of addition and the end of addition was 1:10, and the flow rate was increased with time. Moreover, the pH was decreased from 8.83 to 8.00 in proportion to the inflow. Further, when the liquid L and the liquid N were added by 2/3 of the total amount, the liquid O was additionally injected and added at a constant rate over 8 minutes. At this time, pAg rose from 9.0 to 11.0. Further, acetic acid was added to adjust the pH to 6.0. Then, an excessive salt was removed by the same desalting method as in Example 1 to obtain an emulsion EM-6.

The grains were rounded tetrahedral monodisperse silver iodobromide emulsions having an average grain size of 0.91 μm and a grain size variation coefficient of 16%.

<Chemical Sensitization of Emulsion> Obtained Emulsion EM-1
~ While maintaining EM-6 at 55 ℃ with stirring, silver halide 1
54 mg of ammonium thiocyanate, 0.4 mg of chloroauric acid, 2.1 mg of sodium thiosulfate, and 1.2 mg of the following selenium compound (1) were added per mol. 65 minutes later 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene and 1-phenyl-5-
The mercaptotetrazole and additional gelatin and the compound according to the invention were added as described in Table 1 and cooled. The pH was adjusted with a 1% KOH aqueous solution before the start of chemical sensitization. Each emulsion before chemical sensitization had a pH of 5.90 and a pH of 8.3 (5
5 ° C).

Selenium compound (1) (C ₆ H ₅ ) ₃ P = Se To each of the obtained emulsions, the additives described below were added to prepare an emulsion layer coating solution. At the same time, a coating solution for protective layer described later was also prepared. For coating, a blue-colored polyethylene terephthalate support having a concentration of 180 μm and a concentration of 0.15 was used. The emulsion layer had two slides so that the amount of silver per side was 2.8 g / m ² and the amount of gelatin was as shown in Table 1. Using a hopper type coater, both sides were simultaneously coated on the support at a speed of 80 m / min and dried for 2 minutes and 20 seconds to obtain a sample.

Thus, as shown in Tables 1 and 2, coated sample Nos. 1 to 26 were obtained.

The amount of the hardener was adjusted so that the obtained sample had a swelling ratio of 200% by the measuring method described in JP-A-63-206750. The addition amount of the polymer latex according to the present invention is shown in Table 1.
As described above, the other emulsion additives and the addition amounts are as shown below per mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-Butyl-catechol 82 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 2.0 g 2-Mercaptobenzimidazole-5-sulfonate 1.5 mg

[0152]

[Chemical 7]

C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1-phenyl-5-mercaptotetrazole 15 mg diethylene glycol 7 g dextran (average molecular weight 60,000) 600 mg sodium polyacrylate (average molecular weight 3.6 2.5 g Protective Layer Solution Next, the following was prepared as a protective layer coating solution. The additive is shown in the amount per liter of coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (area average particle size) Matting agent of 1.2 μm) 0.5 g Ludox AM (manufactured by DuPont) (colloidal silica) 30 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent) Glyoxal 40% aqueous solution (hardening agent) 2.0 ml

[0155]

[Chemical 8]

Evaluation with an automatic developing machine For development, an automatic developing machine SRX-503 and a processing liquid SR-DF (both manufactured by Konica Corporation) were used and processed in the following steps. The process was a modification of the automatic processor SRX-503.

[Treatment Process] Process Process Process Process Process temperature Process time Process time Process time Replenishment amount (℃) (sec) (sec) (sec) Insertion − 1.6 1.2 0.8 Development + crossover 35 19.4 14.6 9.7 270ml / m ² Fixing + Crossover 33 11.0 8.2 5.5 430 ml / m ² Washing with water + Crossover 18 9.6 7.2 4.8 7.0 l / m ² Squeeze 42 7.6 5.7 3.8 Dry 60 10.8 8.1 5.4 Total − 60.0 45.0 30.0 Preparation of processing agent Formulation of developer (15 liter finish) Part-A Potassium hydroxide 470g Potassium sulfite (50% solution) 3000g Sodium hydrogencarbonate 150g Diethylenetriamine pentaacetic acid sodium salt 45g 5-Methylbenzotriazole 2.0g 1-Phenyl-5-mercaptotetrazole 0.2g 1,4-Dihydroxybenzene 390g Water Part-B (for finishing 15 liters) Glycoacetic acid 220g Triethylene glycol 200g 1-Phenyl-3-pyrazolidone 27g 5-Nitroindazole 0.45 g N-acetyl-DL-penicillamine 0.15 g Starter solution formulation (for finishing 1 liter) Glacial acetic acid 138 g Potassium bromide 325 g 5-Methylbenzotriazole 1.5 g Water is added to make 1 liter.

Fixer formulation Part-A (for finishing 19 liters) Ammonium thiosulfate (70 wt / vol%) 4000 g Sodium sulfite 175 g Sodium acetate trihydrate 400 g Sodium citrate 50 g Gluconic acid 38 g Boric acid 30 g Glacial acetic acid 140 g Add water Make it 5 ttles.

Part-B Aluminum sulfate (calculated as anhydrous salt) 65 g Sulfuric acid (50 wt%) 105 g Pure water is added to make 5 liters.

Preparation of Developer Part-A and Part-B were mixed and made up to 15 liters with water. The pH of this developer is 25 ° C with sodium hydroxide and acetic acid.
Adjust to 10.40, then 2 starters per liter
0 ml was added to make a working solution.

Preparation of Fixing Solution Part-A and Part-B were mixed and made up to 19 liters, and then adjusted with acetic acid and sodium hydroxide to a pH of 4.35 at a temperature of 25 ° C. to obtain a working solution. .

Sensitometric Evaluation After the coated sample film was left for 1 day at 23 ° C. and 50% relative humidity, a fluorescent intensifying screen NR-160 for X-ray photography (Konica Corporation)
Product) and irradiated with X-rays through Penetrometer B type (manufactured by Konica Medical Co., Ltd.), and subjected to the above treatment to evaluate sensitivity and gradation. The sensitivity is the reciprocal of the amount of exposure energy required to give a density of fog +1.0, and is shown as a relative value with the sensitivity of Sample No. 1 being 100.

The gradation is indicated by the slope of the characteristic curve between the density of fog +0.25 to fog +2.0.

Further, as an evaluation of storability, 23 ° C. and relative humidity
A sample stored under the condition of 50% for 3 months was similarly exposed and developed to determine the sensitivity and the fog. The obtained results are shown in Tables 1 and 2.

However, the fog (ΔD) in the table is represented by the difference in fog between the sample stored for one day and the sample stored for three months.

[0166]

[Table 1]

[0167]

[Table 2]

Example 2 Emulsions EM-3a and EM-4 to EM- obtained in Example 1
While maintaining 6 with stirring at 55 ° C., 5,5′-dichloro-9-ethyl-3,5 as a spectral sensitizing dye was added per mol of silver halide.
3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride and 5,5'-di- (butoxycarbonyl) -1,
300 mg and 15 mg of 1'-diethyl-3,3 '-(sulfobutyl) -benzimidazolocarbocyanine sodium salt anhydride were added. 10 minutes later, an appropriate amount of ammonium thiocyanate,
Chloroauric acid and sodium thiosulfate were added for chemical ripening. 20 minutes before the end of ripening 0.8mmo per mol of silver halide
1 g of silver iodide fine particles was added, and then 0.03 mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added and dispersed in a gelatin aqueous solution.

The same additives as in Example 1 were added to the obtained emulsion to prepare an emulsion coating solution. A protective layer coating solution was also prepared in the same manner as in Example 1. The coating is on a polyethylene terephthalate base that is blue-colored with a concentration of 0.15 at 170 μm,
Both sides were simultaneously coated at a speed of 100 m / min using two slide hopper type coaters so that the amount of silver was 2.0 g / m ² per side and the amount of gelatin was as shown in Table 3. The amount of the hardener was adjusted so that the obtained sample had a swelling ratio of 190% by the measuring method described in JP-A-63-206750. The amount of the polymer latex according to the present invention added was as shown in Table 3.

Sensitometric Evaluation After the coated sample film was left at 23 ° C. and 50% relative humidity for 1 day, a fluorescent intensifying screen for X-ray photography SRO-250 (Konica Corporation) was used.
After irradiating with X-ray through Penetrometer B type (manufactured by Konica Medical Co., Ltd.), the same treatment as in Example 1 was performed to evaluate sensitivity and gradation. Sensitivity is fog +
The reciprocal of the exposure energy required to give a concentration of 1.0,
The relative value is shown with the sensitivity of Sample No. 1 being 100.

The gradation is shown by the slope of the characteristic curve between the density of fog +0.25 to fog +2.0.

Further, as a storage stability evaluation, 23 ° C. and relative humidity were used.
A sample stored under the condition of 50% for 3 months was similarly exposed and developed to determine the sensitivity and the fog. The obtained results are shown in Tables 3 and 4. However, the fogging (ΔD) in the table is 3
It is represented by the difference in fog of the sample stored for a month.

[0173]

[Table 3]

[0174]

[Table 4]

[0175]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity, no gradation change and excellent long-term storability can be obtained by rapid processing with low replenishment.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having one or more silver halide emulsion layers on a support, wherein the silver halide emulsion layers have an average silver iodide content of less than 3 mol%, A monomer unit containing at least one silver halide grain having two or more parallel twin planes and an aspect ratio of less than 2, and at least one monomer having a solubility in water at 25 ° C. of 0.025% by weight or less. A silver halide photographic light-sensitive material comprising at least one polymer latex of 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver / gelatin weight ratio in the silver halide emulsion layer is 1.3 or less. 3. The silver halide emulsion layer according to claim 2, which has a melting point of 40 ° C. or higher and has at least 2 atoms in the molecule.
A silver halide photographic light-sensitive material comprising a polyhydric alcohol having three or more hydroxyl groups, the content of the compound being 0.20 or less by weight ratio to the total gelatin amount.