JP2002131857A - Silver halide photographic sensitive material and method of processing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flat shaped silver halide photographic sensitive material capable of carrying out rapid processing without curing and having high sensitivity and improving pressure resistance and also having enough maximum concentration (Dmax). SOLUTION: In the silver halide photographic sensitive material having at least one photosensitive silver halide emulsion layer and at least one non- photosensitive hydrophilic colloidal layer on a substrate, silver halide grains contained in the silver halide emulsion layer has a peak wavelength of <=500 nm in spectralsensitivity and contains at least one selected from a flat platy grain having an aspect ratio of >=8, a flat platy grain having an aspect ratio of <=6 and a normal crystal. Projected area of the flat platy grain having an aspect ratio of >=8/total projected area of total silver halide grains is preferably >=0.2 but <0.7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material (hereinafter, also simply referred to as "photosensitive material"), and more particularly to a regular type X-ray silver halide photographic light-sensitive material suitable for non-hard film rapid development processing. About.

[0002]

2. Description of the Related Art At present, high-speed rapid processing is possible by introducing an automatic developing machine, and ultra-rapid processing of 45 seconds or less by dry-to-dry has been developed. On the other hand, these systems are usually subjected to a hardening reaction during the processing step in order to impart rapid processing suitability.

Normally, glutaraldehyde is used as a hardening agent because of its high reactivity in a developing solution and rapid hardening reaction. However, glutaraldehyde has a pungent odor,
In the case of contact with the body, it was not safe. Further, usually, a hardening substance which suppresses film swelling typified by aluminum sulfate is used in the fixing solution, and it cannot be said that this is also high in safety. Furthermore, due to increasing environmental concerns, a rapid treatment method without a hardening treatment using glutaraldehyde, aluminum sulfate or the like has been developed.

In order to perform rapid development without relying on such a hardened film, it is necessary to sufficiently harden the photosensitive material in advance. However, high sensitivity and high density (Dma
In the case of a medical light-sensitive material requiring x), if the film is sufficiently hardened in advance, a large amount of silver is required to obtain necessary photographic characteristics. A high silver content not only increases the cost but also causes serious obstacles such as a decrease in rapid processing, an increase in fog, and a deterioration in pressure resistance.

[0005] In recent years, there has been an increasing shift in medical photosensitive materials from regular systems to ortho (green sensitivity) systems combined with rare earth screens. In this system, a large amount of ortho-sensitizing dye can be adsorbed, a high concentration can be obtained with a smaller amount of silver,
Furthermore, even if the film is sufficiently hardened in advance, the decrease in concentration is relatively small,
Tabular silver halide emulsions have come to be used because sufficient photographic properties can be obtained even without processing hardening. This is, for example, the case of Research Disclosure (hereinafter RD).
No. 22534 (January 1983) and the like.

However, a photosensitive material using a tabular silver halide emulsion is not good in pressure resistance, such as blackening of abrasion and occurrence of roller marks for rapid processing in an automatic developing machine, and the silver tone is deteriorated. Further, it is known that pressure resistance and processing dependency are further degraded by further increasing the hardness of the emulsion layer.

Further, Japanese Patent Application Laid-Open No. 4-291338 discloses a sensitizing technique using a zero-methine dye. However, not only is the absolute value of the sensitivity low, but the pressure resistance is not improved. If the film is sufficiently hardened in advance for the development processing, there is a problem that the performance is remarkably deteriorated, and further improvement technology has been desired.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a tabular silver halide having a high sensitivity, an improved pressure resistance, and a sufficient maximum density ( _Dmax ), which enables rapid processing without hardening. A photographic light-sensitive material is provided.

[0009]

The above objects of the present invention are as follows.
In a silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support, silver halide grains contained in the silver halide emulsion layer Is achieved by a tabular grain having a peak wavelength of spectral sensitivity of 500 nm or less and an aspect ratio of 8 or more, and a silver halide photographic material containing at least one selected from a tabular grain having an aspect ratio of 6 or less and a normal crystal. You. The ratio of the projected area occupied by tabular grains having an aspect ratio of 8 or more to the total projected area of all silver halide grains is preferably 0.2 or more and less than 0.7.

The silver halide grains contained in the silver halide emulsion layer have a spectral sensitivity peak wavelength of not more than 500 nm and a tabular grain having an aspect ratio of not less than 8 with respect to the total projected area of all silver halide grains. And a polymer latex in at least one of the silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer.
The effect of the present invention can also be obtained by containing a V absorbent, containing an oil compound instead of the polymer latex, and containing carboxynitrocellulose instead of the polymer latex.

Further, one of the constitutions of the present invention is a processing method for processing any one of the above silver halide photographic materials using a developing solution and a fixing solution substantially free of a gelatin hardener.

Hereinafter, the present invention will be described in more detail. The peak wavelength of the spectral sensitivity can be obtained by a known measuring means. The peak wavelength of the spectral sensitivity of the silver halide grains according to the present invention is 500 nm or less, and preferably 300 to 480 n.
m.

The average grain size of the tabular silver halide grains having an aspect ratio of 8 or more according to the present invention is preferably from 0.3 to 10.0 μm, more preferably from 0.4 to 7.0 μm, especially from 0.5 to 7.0 μm.
5.0 μm is preferred. Further, the average thickness is 0.01 to 0.1.
It is preferably 3 μm, more preferably 0.05 to 0.25 μm, particularly preferably 0.07 to 0.2 μm.

The aspect ratio (also referred to as AR) of the tabular silver halide grains according to the present invention is an average value (average aspect ratio) defined by a grain diameter (in terms of a circle diameter) / a grain thickness. The tabular silver halide grains having an aspect ratio of 8 or more according to the present invention are preferably from 8 to 40, and particularly preferably from 10 to 20.

The tabular silver halide grains having an aspect ratio of 6 or less according to the present invention are preferably 1.2 to 5, and particularly preferably 1.2 to 4.

The advantages of such tabular silver halide grains are:
For example, UK Patent No. 2,112,15 discloses that spectral sensitization efficiency, image graininess and sharpness can be improved.
7, U.S. Pat. Nos. 4,439,520 and 4,433,
048, 4,414,310, 4,434,2
No. 26, etc., and can be prepared by the methods described in these specifications.

In the present invention, the diameter of tabular silver halide grains is defined as the diameter of a circle having an area equal to the projected area of the grains from observation of an electron micrograph of the silver halide grains. The thickness of the tabular silver halide grains is defined as the minimum of the distance between two parallel main planes constituting the tabular silver halide grains.

The thickness of the silver halide grains can be determined from an electron micrograph with a shadow of the silver halide grains or an electron micrograph of a sample tomogram obtained by coating a silver halide emulsion on a support and drying.

In order to determine the average aspect ratio, at least 100 samples are measured. In claim 2 of the present invention, the ratio of the projected area occupied by tabular grains having an aspect ratio of 8 or more to the total projected area of all silver halide grains is 0.2.
Is less than 0.7, but preferably 0.3 to 0.6,
0.3-0.5 is more preferred.

Further, in claims 3 to 6, the ratio of the projected area occupied by tabular grains having an aspect ratio of 8 or more to the total projected area of all silver halide grains is 0.3 or more.
0.6 or more is preferable, and 0.8 or more is more preferable.

In the silver halide emulsions according to the present invention, the ratio of tabular silver halide grains having an aspect ratio of 8 or more to all silver halide grains is 20 to 8%.
0%, preferably 30 to 80%, particularly preferably 40 to 70%.

In the silver halide emulsion according to claims 3 to 5, the ratio of tabular silver halide grains having an aspect ratio of 8 or more to all silver halide grains is 30% or more;
It is preferably at least 50%, particularly preferably at least 70%.

In the silver halide emulsions according to claims 1 and 2, the average grain size of the tabular silver halide grains having an aspect ratio of 6 or less is preferably 0.3 to 10.0 μm, more preferably 0.4 to 7.0 μm. 0 μm is preferred, and especially 0.5 to 5.0 μm.
m is preferred.

The average thickness is preferably from 0.15 to 0.7 μm, more preferably from 0.2 to 0.7 μm, and particularly preferably from 0.1 to 0.7 μm.
3-0.6 μm is preferred.

In the silver halide emulsions according to claims 1 and 2, the silver halide composition of the normal crystal silver halide grains is silver chloride, silver bromide, silver chlorobromide, silver iodobromide or a small amount. Silver chloroiodobromide emulsion containing silver chloride. The normal crystal means a silver halide grain having substantially no twin plane, specifically, a cube having a mirror index (100) plane on the outer surface, and a regular octahedron having a (111) plane on the outer surface. ,
An oblique dodecahedron having a (110) plane on its outer surface, (10
0) and (111) regular tetrahedrons having both surfaces on the outer surface.

The silver halide grains may be of any crystal type, for example, single crystals such as cubic, octahedral, and tetrahedral, and polytwin grains having various shapes. It may be.

For the preparation of silver halide, mixing conditions such as a forward mixing method, a reverse mixing method, a double jet method, a control double jet method, and the like are employed under solution conditions such as an acidic method, an ammonia method, and a neutral method. Method, core / shell method and other particle preparation conditions, and combinations thereof.

The grain size distribution of the silver halide may be either a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. The crystal structure of silver halide may have a different silver halide composition between the inside and the outside. For example, a high silver iodide core portion is coated with a low silver iodide shell layer to form a clear two-layer structure. The core / shell type monodisperse emulsion may be used.

A preferred embodiment of the silver halide emulsion used in the light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. The term “monodisperse” as used herein means that when the average particle diameter is measured by an ordinary method, at least 95% of the particles by number or mass are ± 4 of the average particle diameter.
The silver halide grains are within 0%, preferably within ± 30%. As a method for obtaining the above-mentioned monodispersed emulsion, for example, a seed crystal may be used, and an emulsion obtained by supplying silver ions and halide ions using the seed crystal as a growth nucleus may be used.

The tabular silver halide emulsion according to the present invention is preferably monodisperse. Here, the monodispersion means that the coefficient of variation of the grain size (standard deviation of grain size / average grain size × 10
0) is 25% or less, preferably 20% or less, particularly preferably 15% or less.

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, silver chloroiodobromide, etc. Silver iodobromide is preferred in terms of sensitivity, and the average silver iodide content is 0.1 to 4.0.
0 mol%, particularly preferably 0.5 to 3.0 mol%. Further, silver chloroiodobromide can be used from the viewpoint of rapid processing.

When silver chloroiodobromide is used, silver chloride may be contained in any part of the grain, but it is particularly preferred that silver chloride is unevenly distributed on the outermost surface of the grain or in the vicinity thereof.

In the tabular silver halide emulsion according to the present invention, the halogen composition may be uniform within the grains and silver iodide may be localized. Is preferably used. A method for producing a tabular silver halide emulsion is described in JP-A-58-113926.
Nos. 58-113927 and 58-113934
No. 62-1855, European Patent 219,849,
No. 219,850 and the like can be referred to. or,
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 is added to an aqueous gelatin solution having a pBr of 2 or less, or an aqueous silver nitrate solution and an aqueous halide solution are simultaneously added. To generate twin seed particles and then grow them by a double jet method. The size of the silver halide grains can be controlled by the temperature during grain formation, the rate of addition of the silver salt and the aqueous halide solution, and the like.

The average silver iodide content and average silver chloride content of the silver halide emulsion (hereinafter referred to as parent grain emulsion) according to the present invention are determined by the composition of the aqueous halide solution to be added, ie, bromide, iodide and chloride. It can be controlled by changing the ratio of objects. During the production of a silver halide emulsion, a silver halide solvent such as ammonia, thioether or thiourea can be used, if necessary.

The silver halide emulsion may be subjected to a washing method such as a noodle washing method or a flocculation sedimentation method in order to remove soluble salts (desalting treatment step). As a preferred washing method, for example, Japanese Patent Publication No. 35-16086
Or a method using an aggregating polymer agent (exemplified G3, G8, etc.) described in JP-A-63-158644.

The silver halide emulsion according to the present invention has been subjected to selenium sensitization. The selenium sensitizing treatment means that a selenium sensitizing nucleus is present at an arbitrary site of the tabular silver halide grain according to the present invention, and a particularly preferred site is at the surface and / or near the surface of the grain. Can be

In the present invention, “near the surface” means 2 to 600 nm, preferably 5 to 200 n from the nearest particle surface.
m, particularly preferably a depth of 8 to 70 nm.

As a method of selenium sensitizing a target site near the surface of a tabular grain, for example, the grain growth step is temporarily stopped, and a selenium sensitizer is added to selenium sensitize the shell layer surface. A method is preferred in which the growth step is continued again after the sensitization treatment. Also, with the growth of silver halide,
The selenium sensitizer may be added in several portions, or may be added continuously for a fixed time.

The depth of the selenium sensitization nucleus closest to the surface of the finally formed grain is determined by the amount of silver used in the selenium sensitization treatment during the grain growth step and the subsequent regrowth step. Can be changed by

The selenium sensitization can be carried out by a conventionally known method. That is, it is usually carried out by adding an unstable selenium compound and / or a non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Selenium sensitization using an unstable selenium sensitizer described in JP-B-44-15748 is preferably used. Particularly preferred unstable selenium compounds are shown below.

Colloidal metal selenium Organic selenium compound (a selenium atom is double-bonded to a carbon atom of an organic compound by a covalent bond) a. Isoselenocyanates: aliphatic isoselenocyanates such as allyl isoselenocyanate.

B. Selenoureas (including enol type) ...
Selenoureas and methyl, ethyl, propyl, i-propyl, butyl, hexyl, octyl, dioctyl, tetramethyl, N- (β-carboxyethyl) -N, N′-
Aliphatic selenoureas such as dimethyl, N, N-dimethyl, diethyl and dimethyl;
Aromatic selenoureas having one or more aromatic selenoureas; heterocyclic selenoureas having a heterocyclic group such as pyridyl or benzothiazolyl.

Particularly preferred selenoureas include N,
N, N ', N'-4-substituted selenoureas, and preferred substituents are R, RCO-, ArCO- (R is an alkyl group or a perfluoroalkyl group (preferably having 1 to 7 carbon atoms), and Ar is a halogen. A phenyl group which may be substituted with an atom or a lower alkoxy group).

C. Selenoketones: selenoacetone, selenoacetophenone, selenoketone and selenobenzophenone having an alkyl group bonded to = C = Se.

D. Selenoamides ... selenoamides. e. Selenocarboxylic acids and esters thereof: 2-selenopropionic acid, 3-selenobutyric acid, methyl-3-selenobutyrate.

Others a. Selenides: diethyl selenide, diethyl diselenide, triphenylphosphine selenide.

B. Selenophosphates: tri-p-triselenophosphate, tributylselenophosphate.

While the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. Those skilled in the art will recognize that an unstable selenium compound as a sensitizer for a photographic emulsion is not very important as long as selenium is unstable, and the structure of the selenium sensitizer molecule is not important. It is generally understood that the moieties carry selenium and have no role other than to cause them to be present in the emulsion in an unstable manner.

In the present invention, an unstable selenium compound having such a broad concept is advantageously used. Tokiko 46-4
Nos. 553, 52-34491 and 52-3449
Selenium sensitization using the non-labile selenium sensitizer described in No. 2 is also used.

Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles, diaryl selenide, diaryl diselenide, 2-thioselenazolidinedione, 2-seleno Oxazolidinedione and derivatives thereof are included.

The non-labile selenium sensitizer and thioselenazolidinedione compound described in JP-B-52-38408 are also effective.

These selenium sensitizers are dissolved in water or an organic solvent such as methanol or ethanol, alone or in a mixed solvent, and added during chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types can be used in combination. It is preferable to use a combination of an unstable selenium compound and a non-unstable selenium compound.

The amount of the selenium sensitizer to be added depends on the activity of the selenium sensitizer used, the type and size of the silver halide, the ripening temperature and the time, but is preferably 1 × per mol of silver halide. It is at least 10 ^-8 mol. More preferably, it is 1 × 10 ^{−7 to} 5 × 10 ⁻⁵ mol. Selenium sensitization is more effective when performed in the presence of a silver halide solvent.

The silver halide solvents usable in the present invention include those described in US Pat. Nos. 3,271,157 and 3,5,157.
Nos. 31,289 and 3,574,628;
A organic thioethers described in JP-A-10-19 and JP-A-54-158917; b-thiourea derivatives described in JP-A-53-82408, JP-A-55-77737 and JP-A-55-2982; No. 53-144319, a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, described in JP-A-54-144319;
No. 100717, d-imidazoles, e-sulfite, f-thiocyanate and the like. Particularly preferred solvents include thiocyanate and tetramethylthiourea.

The amount of the solvent used varies depending on the kind. For example, in the case of a thiocyanate, the preferred amount is 1 × 10 ^-4 to 1 × 10 ^-2 mol per mol of silver halide.

The inside of the grains of the silver halide emulsion can be subjected to a reduction sensitization treatment. Reduction sensitization includes a method of adding a reducing compound, a method of passing a silver ion excess state called pAg = 1 to 7 called silver ripening, and a high pH state of pH = 8 to 11 called high pH thermoforming. It can be applied to a silver halide emulsion by a method or the like. Further, these two or more methods can be used in combination.

The method of adding a reducing compound is preferred because the degree of reduction sensitization can be finely adjusted. The reducing compound may be any of inorganic or organic compounds, thiourea dioxide, stannous salts, amines and polyamines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives, sulfurous acid And the like. Particularly preferred are thiourea dioxide, stannous chloride and dimethylamine borane.
The addition amount of the reducing compound is reducible and the type of silver halide of the compound varies depending emulsion preparation conditions such as dissolving conditions, per mol of the silver halide 1 × 10 ^-8 ~
A range of 1 × 10 ^-2 mol is suitable. These reducing compounds are preferably dissolved in an organic solvent such as water or alcohols, and added during the growth of silver halide grains.

The silver halide emulsion of the present invention is preferably subjected to chemical ripening by a selenium sensitization method and a chemical sensitization method other than the selenium sensitization method after completion of the desalting step.

The temperature of chemical ripening is arbitrarily determined,
Preferably in the range of 20-80 ° C, preferably 30-70.
° C, more preferably 35-65 ° C.

Chemical sensitization methods other than the selenium sensitization method include:
Although there are noble metal sensitization methods such as chalcogen sensitization method and gold sensitization method, it is preferable to use sulfur sensitization method and gold sensitization method together.

Examples of sensitizers for sulfur sensitization include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like. Other US patents 1,
574,944, 3,656,955, German Patent 1,422,869, JP-B-56-24937,
Sulfur sensitizers described in JP-A-55-45016 can also be used.

The addition amount of the sulfur sensitizer may be sufficient to effectively increase the sensitivity of the emulsion. This amount pH, temperature, may vary widely under various conditions such as the size of the silver halide grains, as a guideline, per mol of silver 5 × 10 ^-8 to 5 of the silver halide emulsion according to the present invention × 10 ^-5 mol is preferred.

Examples of the gold sensitizer in gold sensitization include chloroaurate, gold thiourea complex, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyano auric amide, and ammonium aurothio. Cyanate, pyridyltrichlorogold and the like. The addition amount of these gold sensitizers can be varied over a wide range under various conditions, but as a guide, it is preferably from 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol per mol of the silver halide emulsion of the present invention. , 2 × 1
0 ^-6 to 4 × 10 ^-4 mol is more preferred.

It is preferable to add a silver halide fine grain emulsion after grain formation to the silver halide emulsion of the present invention.
Examples of the silver halide fine grains include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodochloride, silver bromoiodide, and silver chloroiodobromide. Silver is preferred. The particle size of these silver halide fine particles is preferably 0.12 μm or less, more preferably 0.09 μm or less, and 0.06 μm or less.
m or less is particularly preferred.

When silver iodide fine grains are used in the present invention, generally, cubic γ-type silver iodide and hexagonal β-type silver iodide are known for silver iodide. It may have a structure or a mixture thereof.

[0067] The present invention, silver bromide, when using the fine particles such as solid solutions mainly containing silver chloride or their rock salt structure example AgBr ₉₀ I _10, these particles are substantially free of twin planes Musou It is preferably a crystal, a so-called normal crystal, or a single twin having one twin plane.

The silver halide fine grains to be used preferably have good monodispersibility, and are preferably adjusted by a double jet method while controlling the temperature, pH and pAg.

The addition amount of the silver halide fine particles is preferably 1/100 dmol or less per mol of silver of the emulsion of the present invention, when the average particle size of the silver halide grains of the present invention is d (μm). , And 1 / 20000d to 1/30
A range of 0 dmol is preferred, most preferably 1/5000 d to 1/500 dmol per silver mole.

The addition time of the silver halide fine particles may be any of the steps from the chemical ripening step to immediately before coating, but is preferably added in the chemical ripening step. The chemical ripening step referred to here means that after the grain formation of the emulsion according to the present invention and when the desalting operation is completed, a chemical sensitizer is added, and thereafter, the operation for stopping the chemical ripening is performed. Point between.

As a method for terminating the chemical ripening step, a method of lowering the temperature, a method of lowering the pH, a method of using a chemical ripening terminator, and the like are known. A method using a terminator is preferred. Examples of the chemical ripening stopper include halides (potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (4-hydroxy-6).
-Methyl-1,3,3a, 7-tetrazaindene) is known. These are used alone or in combination of a plurality of compounds.

The addition of silver halide fine grains may be carried out several times at intervals, or after the addition of silver halide fine grains, another chemically ripened emulsion may be added. The temperature of the emulsion according to the present invention when silver halide fine grains are added is preferably in the range of 30 to 80 ° C, and more preferably 4 to 80 ° C.
A range from 0 to 65 ° C is preferred.

In the present invention, it is preferable that the silver halide fine grains to be added are partially or wholly disappeared immediately before the coating after the addition, and more preferably, the silver halide fine grains are added. 20 of silver halide fine particles
% Or more disappears immediately before coating.
The amount of disappearance was determined by centrifuging the emulsion or coating solution after adding the silver halide fine particles under appropriate conditions, measuring the absorption spectrum of the supernatant, and measuring the absorption spectrum of the silver halide fine particles of a known concentration. Performed by comparing with

The silver halide grains of the present invention may contain a Group VIII metal of the periodic table. In order to include the Group VIII metal in the silver halide grains, it is usually sufficient that the metal compound is present as a metal compound at the time of forming the parent grains.
Rush addition, continuous addition, or divisional addition may be performed several times. Further, a method is also preferable in which silver halide grains are added to a water-soluble silver salt and / or a water-soluble halide solution in advance, and silver halide grains are precipitated using these aqueous solutions.

Compounds of Group VIII metals of the Periodic Table include iron,
Iridium, platinum, palladium, nickel, rhodium,
Refers to metal compounds derived from osmium, ruthenium, and cobalt. Of course, not only these metal compounds but also their metal ions and metal atoms may be contained in the silver halide grains.

The emulsions according to the present invention can be prepared by adding various photographic additives (chemical sensitizers, sensitizing dyes, desensitizing dyes, dyes, development accelerators, antifoggants) before and after physical ripening or chemical ripening. Stabilizers, brighteners, hardeners, surfactants, antistatic agents, plasticizers, slip agents, matting agents, binders, etc.). Known additives include, for example, RD1
7643 (December 1978), page 23, section III to page 28X
Section VII, RD18716 (November 1979), 648
６５651, RD308119 (December 1989),
Those described in page 996, section III to page 1012, section XXI can be used.

As a support which can be used for the light-sensitive material according to the present invention, for example, the above-mentioned RD17643-28
And those described on page 1009 of RD 308119. As a suitable support, a plastic film or the like may be used, and the surface of the support may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer.

The polymer latex used in the present invention is a latex derived from a polymerizable ethylene compound and a polymerizable diolefin compound, and the raw materials are roughly classified into a hydrophobic monomer and a hydrophilic monomer.

The hydrophobic monomers include methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate,
acrylic acid alkyl esters such as t-butyl acrylate; methyl methacrylate, ethyl methacrylate,
Alkyl methacrylates such as butyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, t-butyl methacrylate, i-propyl methacrylate; glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; styrene, vinyl toluene, α-methyl Alkenylbenzenes such as styrene and chloromethylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and phenyl vinyl ether; vinyl halides such as vinyl chloride, vinyl bromide and vinylidene chloride Amides such as acrylamide and methacrylamide; and diene monomers such as butadiene.

Examples of the hydrophilic monomer include hydroxyalkyl acrylates such as hydroxyethyl acrylate and hydroxypropyl acrylate; hydroxyalkyl methacrylates such as hydroxyethyl methacrylate and hydroxypropyl methacrylate;
Examples include ethylene glycol methacrylates such as tetraethylene glycol and monomethacrylate; and ionic monomers such as acrylic acid, methacrylic acid, itaconic acid, and α-acrylamido-2-methylpropanesulfonic acid.

These monomers (monomers) may be used alone or in combination of two or more. When a hydrophilic monomer is used, a combination with a hydrophobic monomer may be used. Preferably
To obtain a stable latex, it is better not to use a hydrophilic monomer.

The polymer latex may be obtained by an emulsion polymerization method or a suspension polymerization method in which a polymer is polymerized in a dispersion medium from the beginning, or a polymer is separately polymerized, and a polymer is taken out and redispersed to obtain a polymer latex. However, the emulsion polymerization method is preferred from the viewpoints of production cost, dispersion stability and the like.

The polymer latex preferably has a Tg (glass transition temperature) of the polymer of from 0 to 90 ° C., more preferably from 10 to 70 ° C. The Tg of many polymers of the ethylenic monomer used is described in “Polymer Handbook III, pp. 139-179 (1966), Wiley & Sons, Inc.” by Brand Wrap et al. K) is represented by the following equation.

Tg (copolymer) = V ₁ Tg ₁ + V ₂ Tg ₂
+ ... + in V _w Tg _{W type, V 1, V 2 ··· V} W represents the mass fraction of the monomer in the _{copolymer, Tg 1, Tg 2 ··· Tg} W each in the copolymer It represents the Tg (° K) of the homopolymer of the monomer. Tg calculated according to the above equation has an accuracy of ± 5 ° C.

The polymer latex is used for the non-photosensitive hydrophilic colloid layer close to the silver halide emulsion layer.

The ultraviolet absorber preferably used in the present invention has spectral absorption characteristics in the ultraviolet region (200 to 400 nm). Preferred compounds of the ultraviolet absorber include benzotriazole compounds. The ultraviolet absorbers may be used alone or in combination of two or more.

The typical basic skeleton of this compound and examples of the compound are shown below.

[0088]

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In the structural formula, EWG represents an electron-withdrawing substituent (cyano group, ester group, amide group, sulfonyl group, carbonyl group, etc.).

[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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Next, the oil compound of the present invention will be described. Useful oil compounds are preferably those having a boiling point of at least 120 ° C (preferably at least 160 ° C), a solubility in water of at most 10% by mass at 25 ° C, and a liquid at 25 ° C.

The oil compound is used in the state of being dispersed in gelatin as oil droplets. As the average particle size of the dispersed oil droplets of the oil compound, those having a particle size of 0.1 to 0.4 μm preferably have a particle size distribution occupying 75% or more of the whole.

In dispersing the oil droplets, various surfactants can be used. For example, US Pat.
027, 2,801,170, 2,801,1
No. 71, an anionic surfactant is disclosed in JP-B-48-99.
No. 79 discloses an anionic or nonionic surfactant and the like.

Hereinafter, typical specific examples of oil compounds suitable for the present invention will be described. Diethyl adipate, dibutyl adipate, di-i-butyl adipate, di (hexylethyl) adipate, dioctyl adipate, dicyclohexyl azelate, di (2-ethylhexyl) azelate, dioctyl sebacate, di-i-octyl sebacate, dibutyl succinate Octyl stearate, dibenzyl phthalate, tri-o-cresyl phosphate, diphenyl-pt-butylphenyl phosphate, phenyl-di-o-chlorophenyl phosphate,
Butyl-dioctyl phosphate, 2,4-diamylphenol, 2,4-di-t-amylphenol, 4-nonylphenol, 2-methyl-4-octylphenol, N, N-diethylcaprylamido, N, N-diethyllauryl Amide, glycerol tripropionate,
Glycerol tributyrate, glycerol monolactate acetate, triethyl citrate, tributyl citrate, acetyl triethyl citrate, tri (2-
(Ethylhexyl) citrate, acetyl-tributyl citrate, di (2-ethylhexyl) adipate, dioctyl sebacate, di-i-octyl azelate, diethylene glycol dibenzoate, dipropylene glycol benzoate, di-i-decyl-4,5-epoxy -Tetrahydrophthalate, oligovinyl ethyl ether, dibutyl phthalate, di-i-decyl phthalate,
i-octyl phthalate, diamino phthalate, di-octyl phthalate, polyethylene oxide (n> 1
6), glycerol tributyrate, ethylene glycol dipropionate, di (2-ethylhexyl) isobutyrate, butyl laurate, tri (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, silicone oil, dimethyl phthalate, diethyl Phthalate, di-i-propylphthalate, diamylnaphthalene, triamylnaphthalene, monocaprin, monolaurin, monomyristin, monopalmitin, monostearin, monoolein, dicaprin, diproline, dimyristylin, dipalmitin, distearin, diolein, 1-stearoin -2-palmitin, 1-
Palmito-3-stearin, 1-palmito-2-stearin, triacetin, tricaprin, trilaurin, trimyristin, tripalmitin, tristearin, triolein, tripetroserin, trielsin, triricinolein, linoleistearin, oleodielsin,
Linoleodiesercin, palmito oleolinorenin, paraffin; linseed oil, soybean oil, eno oil, tung oil, thistle oil,
Drying oils such as kaya oil, walnut oil, soy sauce oil, poppy oil, sunflower oil, azusa oil, kwai oil, safflower oil; cottonseed oil, corn oil, sesame oil, rapeseed oil, rice bran oil, lotus oil, poppy oil, pumpkin oil And semi-dry oils such as dehydrated castor oil; peanut oil, olive oil, camellia oil, sasanqua flower oil, tea oil, castor oil, hydrogenated castor oil, almont oil, bundling oil, ben oil, large flour oil, etc. .

In addition, JP-A-50-23823, 5
No. 0-62632, No. 51-26035, No. 51-2
Compounds other than those described in JP-A Nos. 6036 and 51-26037 can be used in the same manner.

Among these, adipic acid, phthalic acid, sebacic acid, succinic acid, citric acid, fumaric acid, esters such as mazeleiic acid, isophthalic acid and phosphoric acid, esters of glycerin, paraffin and the like adversely affect the photosensitive material. However, they are suitable because they are easily available, chemically stable and easy to handle. Further, dibutyl phthalate, di-i
-Decyl phthalate, dioctyl phthalate, glycerol tripropionate, dioctyl sebacate, paraffin, silicone oil can be mentioned as particularly preferred oil compounds.

When the oil compound is contained as oil droplets in the hydrophilic layer containing gelatin as a main component, a water-soluble or water-insoluble organic low-boiling solvent such as described below may be used in the oil droplet dispersion, if necessary. It is preferable to use them. These low-boiling solvents evaporate after coating and drying a gelatin coating solution containing an oil droplet dispersion as a hydrophilic layer, and hardly exist in the layer.

Specific examples of the organic low boiling point solvent include methanol, ethanol, propanol, fluorinated alcohol,
Acetonitrile, dimethylformamide, dioxane,
Examples thereof include methyl isobutyl ketone, diethylene glycol monoacetate, chloroform, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexinol, cyclohexane, tetrahydrofuran, and the like.

Oil droplets of the oil compound useful in the present invention include:
A lipophilic photographic color coupler, an ultraviolet absorber, a development inhibitor releasing compound, a hydroquinone derivative, an image fading inhibitor or a dye may be contained according to the purpose.

The oil compound used in the present invention can be dispersed without being mixed with the dispersion medium in the process of dispersing it as oil droplets or in the prepared coating solution, and even when the coating solution is applied and dried. , The dispersed oil droplets must not break, collect, or disappear. For this purpose, a single melting point or a mixture of two or more oil compounds having a melting point of 50 ° C. or less is preferred, and those which are liquid at 25 ° C. are more preferred.

As the oil droplets of the oil compound, one or more oil droplets may be prepared at the same time, or the oil droplets separately emulsified and dispersed may be used as a mixture.

Hereinafter, typical specific examples of the oil dispersion will be described. Oil Compound Dispersion Particle Size (μm) O-1: Tris (i-propylphenyl) phosphate 0.20 O-2: Trixylyl phosphate 0.25 O-3: Tributyl phosphate 0.15 O-4: Dioctyl phthalate ( DOP) 0.15 O-5: dibutyl phthalate (DBP) 0.20 O-6: dihexyl phthalate 0.15 O-7: tricresyl phosphate (TCP) 0.20 O-8: o-acetyltriethyl citrate 0.15 O-9: N, N-dimethyl lauryl amide (DMLA) 0.10 O-10: di-i-decyl phthalate (DIDP) 0.20 The amount of the oil compound added is as follows. preferably per side 10~1500mg / m ^2, more preferably from 20 to 500 mg / m ^2.

The amount of the oil compound used is from 0.02 to 0.1 in mass ratio to the amount of gelatin in the hydrophilic colloid layer.
8 is preferable, and more preferably 0.05 to 0.4.

The carboxyalkyl nitrocellulose used in the present invention is a kind of cellulose derivative. The cellulose derivative in which the hydroxyl group of the cellulose skeleton is substituted by a carboxyalkyl group and a nitrate group, or the carboxyalkyl group of the derivative is neutralized. It is a cellulose derivative.

The carboxyalkyl nitrocellulose is
It is preferable that the substitution degree of the nitrate ester group per anhydroglucose residue is 0.2 or more and the substitution degree of the carboxyalkyl ether group is 0.05 or more. If the nitrate ester substitution degree is less than 0.2, the dispersibility in gelatin is insufficient, and the carboxyalkyl ether group substitution degree is less than 0.0.
If it is less than 5, the solubility in water becomes insufficient. Further, it is preferable that the sum of the nitrate ester group substitution degree and the carboxyalkyl ether group substitution degree does not exceed 2.4. If the sum of both substitution degrees exceeds 2.4, the dispersibility in gelatin becomes insufficient.

The carboxyalkyl ether group mentioned here includes, for example, carboxymethyl ether, carboxyethyl ether, carboxypropyl ether, carboxybutyl ether and the like, and the carboxymethyl ether group is preferable in terms of availability of raw materials. or,
The degree of substitution mentioned here can be measured by the method described in the example of JP-A-5-39302.

Since the function of the light-sensitive material varies depending on the layer, the optimum amount of carboxyalkylnitrocellulose varies depending on the layer of the light-sensitive material, but is preferably 10 to 70% by mass of the total amount of the binder contained in the layer to be added. And 20 to 50% by mass is more preferable. If the addition amount is less than 10% by mass relative to the binder amount, the effect of speeding up the treatment is small, and if it exceeds 70% by mass, the setting property of the binder is deteriorated, so that production becomes difficult.

The cellulose derivative of the present invention may be prepared by any known method. For example, carboxymethylcellulose, carboxyalkylcellulose such as carboxyethylcellulose, or derivatives thereof such as methyl ether, ethyl ether, hydroxypropyl ether, acetate, propionate, butyrate, or salts thereof such as sodium and ammonium as raw materials As sulfuric acid / nitric acid, phosphoric acid / nitric acid, acetic acid / nitric acid,
Alternatively, it can be prepared by a method of nitrification using a mixture of these acid mixtures and water. Thereafter, it is preferable to neutralize the carboxyl groups contained therein. Neutralization here means that all or part of the hydrogen ions of the carboxyl group is an alkali metal ion, an alkaline earth metal ion,
It means that it is substituted with one or a combination of two or more cations such as an ammonium ion or an organic amine to form a salt. When it is not neutralized, the carboxyl group contained therein is insufficiently dissociated and insoluble in water, and the amount of the organic solvent used when dissolving in a mixed solvent increases.

The carboxyalkyl nitrocellulose is
Two or more kinds having different degrees of nitrate ester group substitution and carboxyalkyl ether group substitution may be used in combination. If necessary, cellulose derivatives such as colloidal albumin, casein, carboxymethylcellulose and hydroxyethylcellulose; agar, alginic acid Sugar derivatives such as sodium, dextran and dextrin; may be mixed with synthetic hydrophilic colloid, polyvinyl alcohol, poly-N-pyrrolidone, polyacrylic acid copolymer, polyacrylamide, or derivatives or partial hydrolysates thereof. Of course, these may be used separately for each layer constituting the photosensitive material.

The carboxyalkyl nitrocellulose is
It may be added to the silver halide emulsion layer of the light-sensitive material or may be added to the non-photosensitive colloid layer, but is preferably contained in the emulsion layer.

The method of adding carboxyalkylnitrocellulose to the silver halide emulsion layer may be in accordance with the usual method of adding photographic emulsion additives. For example, it may be added as a solution by dissolving in water or an aqueous mixed solvent mainly composed of water and an aqueous solvent system, or may be added as a powder, but handleability,
It is preferable to use it dissolved from the viewpoint of safety.

In the case of using a mixed solvent of water and an aqueous solvent, examples of the aqueous solvent include one or a mixture of two or more of solvents such as alcohols, cellosolves, ethers and ketones. Preferably, in consideration of the effect on the photographic performance of the photosensitive material, methanol, ethanol,
Preferred are ethylene glycol, i-propanol, butyl cellosolve and the like. In the case of dissolving in a solvent, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the solution.

The carboxyalkyl nitrocellulose is added at the time of the photographic emulsion production step or after the photographic emulsion production.
It may be added at any stage immediately before the application. Among them, the preferred addition time is from the end of silver halide grain formation to the end of coating liquid preparation.

[0118]

Hereinafter, embodiments of the present invention will be described.
Embodiments of the present invention are not limited to these.

Example 1 (Preparation of Hexagonal Tabular Seed Emulsion A) Hexagonal tabular seed emulsion A was prepared by the following method. [A1] Ossein gelatin 24.2 g Distilled water 9657 ml 10% methanol solution of surfactant (AO-1) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml AO-1: H [CH ₂ CH ₂ O] _m [CH (CH ₃ ) CH ₂ O] ₁₇ [CH ₂ CH ₂ O] _n OH (m + n = 5.7, molecular weight 1700) [B1] 2.525 mol / L silver nitrate aqueous solution 2825 ml [C1] potassium bromide 824 g iodine 23.5 g of potassium bromide 2825 ml of distilled water [D1] 1.75 mol / L aqueous solution of potassium bromide The following silver potential control amount at 35 ° C: JP-B-58-58288, 58-5828
Using a mixing stirrer described in No. 9, 464.3 ml of each of the solution B1 and the solution C1 was added to the solution A1 by a simultaneous mixing method over 2 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, it took 60 minutes to raise the temperature of the solution A1 to 60 ° C. and adjust the pH to 5.0 with a 3% aqueous potassium hydroxide solution. The solution B1 and the solution C1 were added again at a flow rate of 55.4 ml / min for 42 minutes by the simultaneous mixing method. The temperature was raised from 35 ° C. to 60 ° C. and solutions B1 and C1
Potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a comparison electrode) during re-simultaneous mixing was adjusted to +8 mV and +16 mV, respectively, using Solution D1. After completion of addition, pH is adjusted with 3% aqueous potassium hydroxide solution.
Was adjusted to 6 and immediately desalted and washed with water.

In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.1 to 2.0. 0
It was found by an electron microscope that the average diameter was 6 μm and the average diameter (in terms of circular diameter) was 0.57 μm.

(Preparation of Growth Emulsion) The obtained hexagonal tabular seed emulsion A was added in an amount of 0.1 g / mol of silver of the growth emulsion Em-1 described below.
Equivalent to 023 mol, copolymer of polypropylene oxide (PO) and polyethylene oxide (EO) at a liquid temperature of 60 ° C (EO / PO = 0.33, molecular weight about 1400)
Silver nitrate aqueous solution and potassium bromide solution prepared by dissolving and dispersing in a gelatin aqueous solution containing the same, so that the finally formed growth grains have a mean silver iodide content of 1.9 mol%. And a halide solution with potassium iodide
H = 5.8, pAg = 9.0, and kept at 60 ° C. throughout the period for 107 minutes by the controlled double jet method.

Average particle size 1.51 μm, average thickness 0.25
Tabular silver iodobromide emulsion E having an average aspect ratio of 6.0 μm
m-1 was obtained. Em-2 and Em-3 were obtained by changing pAg and the addition time in the same manner as in Em-1. Em-2 has an average particle size of 1.69 μm, an average thickness of 0.20 μm, and an average aspect ratio of 8.5, and Em-3 has an average particle size of 2.02 μm.
13. μm, average thickness 0.14 μm, average aspect ratio
It was 4.

Emulsions Em-1, Em-2, Em-
No. 3 was subjected to chemical sensitization while being kept at 50 ° C. 52m ammonium thiocyanate per mole of silver
g, 1.4 mg of chloroauric acid and 15.0 mg of sodium thiosulfate pentahydrate were added. Thereafter, 2.34 g of a stabilizer (ST-1) was added for a certain period of time to stabilize, and optimally subjected to chemical sensitization.

The emulsions obtained after the chemical sensitization were subjected to EM-1 to EM-1.
M-3. ST-1: 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazaindene (Preparation of seed emulsion B) Seed emulsion B was prepared by the following method. [A2] Ossein gelatin treated with hydrogen peroxide 40 g Potassium bromide 75.1 g Add water to 4000 ml [B2] Silver nitrate 600 g Add water 803 ml [C2] Ossein gelatin treated with hydrogen peroxide 16.1 g Potassium bromide 393.7 g Potassium iodide 35.1 g Add water 803 ml [D2] Ammonia water (28%) 235 ml Using the apparatus disclosed in JP-A-62-160128,
The supply nozzle to the lower part of the mixing stirring propeller is for solution B2,
The solution C2 was installed so as to have six tubes each.

The solution B2 and the solution C2 were added to the solution A2 stirred at a high speed of 40 ° C. and a rotation speed of 430 rpm by a controlled double jet method at a flow rate of 62.8 ml / mi.
n. 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 was 10 minutes and 45 seconds. PBr during addition with an aqueous potassium bromide solution (3.5 mol / L)
Was kept at 1.3.

After completion of the addition, the temperature of the mixed solution was raised to 2 for 10 minutes.
The temperature was lowered linearly to 0 ° C., the stirring rotation speed was set to 460 rpm, and the solution D2 was added in 20 seconds, followed by Ostwald ripening for 5 minutes. The bromine ion concentration during aging is 0.02
5 mol / L, ammonia concentration 0.63 mol / L,
pH was 11.7.

Thereafter, acetic acid was added to neutralize the mixture immediately until the pH reached 5.6 to stop ripening. To remove excess salts, an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate were used. Seed emulsion B after desalting and washing
I got

When the seed emulsion B was observed with an electron microscope, it was found to be spherical particles having an average particle size of 0.28 μm and a variation coefficient of the particle size of 21%.

(Growth of Seed Emulsion) Subsequently, using Seed Emulsion B and the following three kinds of solutions, silver halide parent grain emulsions mainly comprising tabular twins were prepared.

(Preparation of Growth Emulsion) The obtained seed emulsion B was added in an amount of 0.1% per mol of silver halide of the growth emulsion Em-4 described below.
011 mol equivalent, copolymer of polypropylene oxide (PO) and polyethylene oxide (EO) as antifoaming agent (EO / PO = 0.33, molecular weight = 1400)
Was dissolved and dispersed in a 62 ° C. aqueous gelatin solution. Subsequently, a halide solution of an aqueous solution of silver nitrate, potassium bromide and potassium iodide prepared so that the average silver iodide content of the finally formed growth grains is 1.9 mol% is obtained by a control double jet method. Was added over 290 minutes so that the addition rate at the end of the addition became 6.9 times that at the start of the addition. The temperature was 62 ° C., pH = 5.8, p
Ag was kept at 8.9 throughout. Further, desalting was carried out in the same manner as for the seed emulsion.

The obtained emulsion had an average particle size of 1.80 μm,
This was a tabular silver halide emulsion having an average thickness of 0.44 μm and an average aspect ratio of 4.1. This emulsion was designated as Em-4.

(Chemical sensitization of emulsion)
The mixture was stirred and maintained at 2 ° C., and as a chemical sensitizer, 60 mg of ammonium thiocyanate per mole of silver and 1.45 of chloroauric acid were used.
mg and 13.8 mg of sodium thiosulfate were added, respectively. After a certain period of time, ST-1 and AF-1 were added for stabilization, and each was optimally chemically sensitized. The obtained emulsion was designated as EM-4.

AF-1: 1-phenyl-5-mercaptotetrazole (Preparation of Seed Emulsion C) Seed emulsion C was prepared as follows. [A3] Ossein gelatin 30.0 g Potassium bromide 1.25 g 0.1 mol / L nitric acid 150 ml Finish to 7700 ml with water [B3] Potassium bromide 6 g Potassium iodide 0.16 g Finish to 740 ml with water [C3] Bromide Potassium 680 g Potassium iodide 20.0 g Finish with water to 2480 ml [D3] Silver nitrate 8.4 g 0.1 mol / L nitric acid 32.0 ml Finish with water to 740 ml [E3] Silver nitrate 991.6 g 0.1 mol / L nitric acid 80.0 ml Make up to 2480 ml with water. Add solution B3 and solution D to solution A3 vigorously stirred at 60 ° C.
3 was added over 10 minutes by the double jet method.
Then, the solution C3 and the solution E3 were added by a double jet method over 140 minutes. At this time, the initial addition flow rate was 1/8 of the final addition flow rate, and was increased linearly with time. During the addition of these solutions, pH = 2, pAg =
Adjusted constant to 8. After the addition, add sodium carbonate
After raising H to 6 and adding 150 g of potassium bromide,
Immediately after desalting and washing with water, a monodispersed cubic seed emulsion C of silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.3 μm was obtained.

According to observation with an electron microscope, the incidence of twins was 1% or less in number. [A4] Ossein gelatin 7.5 g 10% aqueous solution of surfactant (AO-1) in methanol 1.5 ml Seed emulsion C 0.11 mol equivalent Equivalent to 500 ml with water [B4] Silver nitrate 9.52 g Equimolar to silver nitrate [C4] Silver nitrate 141.8 g Add an equimolar amount of silver nitrate and an ammonia solution and distilled water to make 261 ml [D4] Potassium bromide 4.66 g Potassium iodide 79 g. Finish to 106 ml with water. [E4] 99.3 g potassium bromide. Finish to 261 ml with water. Solution A4 was maintained at 40 ° C. in a reaction vessel, and the pH was adjusted to 9.5 by further adding aqueous ammonia and acetic acid. After adjusting the pAg to 7.3 with an ammoniacal silver ion solution, the solution B4 and the solution D4 were added by a double jet method while keeping the pH and the pAg constant, and a silver iodobromide layer containing 30 mol% of silver iodide was added. Was formed. PH was adjusted to 9.0 using acetic acid and potassium bromide, p
After adjusting the Ag to 9.0, the solution C4 and the solution E4 were added at the same time, and after growth, the solution was grown to reach 90% of the particle size.
At this time, the pH was gradually lowered from 9.0 to 8.20. An aqueous solution of potassium bromide was added to adjust the pAg to 11, and then a solution C4 and a solution E4 were further added to grow the solution while gradually lowering the pH to 8, to obtain a silver iodobromide emulsion containing 1.9 mol% of silver iodide. .

After completion of the addition, in order to remove excess salts,
Precipitation and desalting were carried out in the same manner as for seed emulsion C, and a gelatin aqueous solution containing 15 g of ossein gelatin was added to 500 ml, followed by stirring and redispersion to obtain Em-5.

When about 1000 Em-5 particles were observed and measured with an electron microscope and analyzed for shape, the particles were found to be monodisperse spherical particles having an average particle diameter of 0.78 μm and a distribution width of 12%.

(Chemical ripening of emulsion) Silver-5 was added to the above Em-5.
A mixed aqueous solution of 54 mg of ammonium thiocyanate, 0.5 mg of chloroauric acid and 2.8 mg of sodium thiosulfate was added per mole, and chemically sensitized at 50 ° C. After aging, the stabilizer (ST-1) and additional gelatin were added to obtain EM-5.

Emulsions EM-1 to EM-5 thus obtained
When the spectral sensitivity peaks were measured, all were 420 to 4
It was in the range of 60 nm.

<Preparation of photosensitive material sample> Emulsions EM-1 to EM-5 which had been subjected to chemical ripening were mixed at the ratio shown in Table 1, and the following additives were added to prepare emulsion layer coating solutions. At the same time, a protective layer coating solution described below was also prepared. The amount of silver applied per side was 2.2 g / m ² , and the amount of gelatin applied was two slide hoppers so that the emulsion layer was 1.75 g / m ² and the protective layer was 0.85 g / m ^2. 80m / min using a mold coater
At the same speed on both sides of the support, 2 minutes 20 minutes
After drying in seconds, coating samples 1 to 16 were obtained.

As a support, glycidyl methacrylate / methyl acrylate / butyl methacrylate (50
/ 10/40% by mass) A copolymer aqueous dispersion obtained by diluting the copolymer so as to have a concentration of 10% by mass was used as a subbing liquid and had a concentration of 0.15 for a 175 μm X-ray film. A polyethylene terephthalate (PET) film base colored blue was used.

The additives used in the emulsion are as follows. The amount of addition is shown in an amount per mole 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 25 g nitrophenyl-triphenylphosphonium chloride 50 mg Resorcin-4-ammonium ammonium sulfonate 2.0 g 2-Mercaptobensoimidazole-5-sodium sulfonate 1.5 mg Compound A 7.2 mg Compound B 150 mg Compound C 80 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g AF-1 15 mg Diethylene glycol 7 g Dextran (average molecular weight 60,000) 600 mg Sodium polyacrylate (average molecular weight 36,000) 2.5 g

[0144]

Embedded image

Next, the following was prepared as a coating solution for a protective layer. Additives are shown in amounts per liter of coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethyl methacrylate (a matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (Area) 0.5 g Ludox AM (manufactured by DuPont: colloidal silica) 30 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent) 200 mg Glyoxal 40% aqueous solution (hardening agent) 2.0 ml Surfactant SU-1 1.0 g Surfactant SU-2 0.4 g Preservative DF-1 0.1 g

[0147]

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<Evaluation of photographic performance> Photosensitive material samples 1 to 16
The following photographic performances were evaluated.

<< Covering Power (CP) >> A photosensitive material sample which has been exposed sufficiently to obtain the maximum density is subjected to a developing temperature of 32 using an automatic developing machine SRX502 (manufactured by Konica Corporation).
℃, fixing temperature 32 ℃, dry to dry development processing, maximum density (D _max ) and silver amount (g / m ² per both sides)
Can be measured and calculated from the following equation.

CP = {(D _{max -concentration of the} support) / amount of silver} × 100 << Scratch resistance >> The unexposed sample film was heated at 23 ° C./40%
After leaving for 2 hours under RH conditions, rubbing with a commercially available nylon bundle under a load of 100 g / cm ² under the same conditions, the same developing treatment as in the above-mentioned CP evaluation was performed, and visual evaluation was performed. . However, the intermediate level between A and B is "AB",
Intermediate levels between B and C were designated as "BC".

A: Almost no scratches B: Some scratches, but no problem in practical use C: Scratch occurs to the extent of being noticeable, which is a problem in practical use D: Very large scratches, and wide scratches High density << Silver tone >> Large angle size of photosensitive material sample (35.6cm ×
(35.6 cm) was uniformly exposed to a concentration of 1.2, and the same developing treatment as in the above-mentioned CP evaluation was performed. Each of the developed samples was observed on a Schaukasten, and the silver tone due to the transmitted light was visually evaluated according to the following four ranks. A and B
Is an intermediate level of "AB", and an intermediate level of B and C is "B".
C ".

A: Pure black B: Slightly reddish black C: Reddish black D: Yellowish black The results are summarized in Table 1.

[0153]

[Table 1]

As is clear from Table 1, according to the present invention, a photosensitive material having high sensitivity, low fog and excellent photographic performance at the highest density can be obtained. Further, the roller mark resistance was excellent, and almost no roller mark was generated.
In terms of photographic performance and roller mark resistance, the selenium-sensitized nucleus site was better near the grain surface than the grain surface.

The compositions of the developing solution and the fixing solution used in the present invention are shown below. Developer formulation Part-A (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraminepentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g AF-1 0.2 g Hydroquinone 340 g Add water to make 5000 ml. Part-B (for finishing 12 liters) Glacial acetic acid 170 g Triethylene glycol 185 g 1-Phenyl-3-pyrazolidone 22 g 5-Nitroindazole 0.4 g N-acetyl-DL-penicillamine 1.2 g Starter Glacial acetic acid 120 g Potassium bromide 225 g Water And make up to 1.0 liter.

Fixer Formulation Part-A (for finishing 18 liters) Ammonium thiosulfate (70% by mass / volume) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N- Dimethylamino) ethyl-5-mercaptotetrazole 18 g Part-B Aluminum sulfate 800 g The developer was prepared by adding Part-A, Pa
rt-B was added at the same time, and water was added while stirring and dissolving.
Make up to 1 liter and adjust the pH to 10.40 with glacial acetic acid. This is used as a developer.

20 ml of a starter is added to 1 liter of the developing solution, and the pH is adjusted to 10.26 to prepare a working solution.

The fixer was prepared by adding Par.
t-A and Part-B were added, and water was added while stirring and dissolving to make up to 18 liters, and the pH was adjusted to 4.6 using sulfuric acid and sodium hydroxide. This was used as a fixing solution.

Example 2 Example 1 was repeated except that latex was added as described in Table 2.
A photosensitive material sample was prepared in the same manner as described above. In the performance evaluation, in addition to the same CP and abrasion as in Example 1, evaluation of density unevenness was performed. However, the processing conditions used were those obtained by removing aluminum sulfate from the fixing solution.

<< Density Unevenness >> After uniformly exposing the sample to a density of 1.1 ± 0.1, it was developed with the same automatic developing machine as in Example 1, and the density unevenness was visually evaluated in the following five stages. did. The evaluation of the intermediate level is the same as the evaluation of CP and silver tone.

A. No density unevenness B. C. There is slight density unevenness, but not noticeable. There is density unevenness, but practically acceptable level. E. Density unevenness is conspicuous, making it impractical. Table 2 shows the results where the density unevenness is large and is very conspicuous.

[0162]

[Table 2]

[0163]

Embedded image

Example 3 A photosensitive material sample was prepared and evaluated in the same manner as in Example 2. However, a UV absorber described in Table 3 was added instead of the latex. Table 3 shows the results.

(Preparation of UV Absorber Dispersion) In a solution prepared by dissolving 3.0 g of a UV absorber in 3 ml of ethyl acetate, 1.0 g of gelatin was swollen and dissolved in 8 ml of water, and tri-i-propyl-β-naphthalene was further dissolved. After adding a gelatin solution to which 1.2 ml of a 10% aqueous solution of sodium sulfonate was added and stirring,
Water was added to make 20 g of the finished UV absorber dispersion.

[0166]

[Table 3]

Example 4 A photosensitive material sample was prepared and evaluated in the same manner as in Example 2. However, an oil dispersion shown in Table 4 was added in place of the latex. Table 4 shows the results.

[0168]

[Table 4]

Example 5 A photosensitive material sample was prepared and evaluated in the same manner as in Example 2. However, carboxyalkyl nitrocellulose shown in Table 5 was added in place of the latex. Table 5 shows the results.

[0170]

[Table 5]

[0171]

From Tables 1, 2, 3, 4 and 5, it is clear that the sample of the present invention has a high CP, excellent scratch resistance, excellent silver tone, and low density unevenness.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G03C 1/76 501 G03C 1/76 501 1/815 1/815 5/02 5/02 5/29 5/29 5 / 38 5/38 // G03C 1/00 1/00 A

Claims (7)

[Claims] A silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support,
The silver halide grains contained in the silver halide emulsion layer have a peak wavelength of spectral sensitivity of 500 nm or less and have at least one selected from tabular grains having an aspect ratio of 8 or more, tabular grains having an aspect ratio of 6 or less, and normal crystals. A silver halide photographic light-sensitive material comprising: 2. The halogen according to claim 1, wherein the ratio of the projected area occupied by tabular grains having an aspect ratio of 8 or more to the total projected area of all silver halide grains is 0.2 or more and less than 0.7. Silver halide photographic material. 3. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support,
The silver halide grains contained in the silver halide emulsion layer have a peak wavelength of spectral sensitivity of 500 nm or less, and the ratio of tabular grains having an aspect ratio of 8 or more to the total projected area of all silver halide grains is 0.3 or more. And a polymer latex in at least one of the silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer. 4. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support,
The silver halide grains contained in the silver halide emulsion layer have a peak wavelength of spectral sensitivity of 500 nm or less, and the ratio of tabular grains having an aspect ratio of 8 or more to the total projected area of all silver halide grains is 0.3 or more. And a UV absorber is contained in at least one of the silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer. 5. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support,
The silver halide grains contained in the silver halide emulsion layer have a peak wavelength of spectral sensitivity of 500 nm or less, and the ratio of tabular grains having an aspect ratio of 8 or more to the total projected area of all silver halide grains is 0.3 or more. , And at least one of the silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer contains an oil compound. 6. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one non-photosensitive hydrophilic colloid layer on a support,
The silver halide grains contained in the silver halide emulsion layer have a peak wavelength of spectral sensitivity of 500 nm or less, and the ratio of tabular grains having an aspect ratio of 8 or more to the total projected area of all silver halide grains is 0.3 or more. And a carboxynitrocellulose in at least one of the silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer. 7. A halogen, wherein the silver halide photographic light-sensitive material according to claim 1 is processed using a developer and a fixer substantially free of a gelatin hardener. Processing method of silver halide photographic light-sensitive material.