JPH06175255A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material excellent in preservation stability, improved in pressure resistant property and residual color contamination property and high in sensitivity and image quality. CONSTITUTION:In the silver halide photographic sensitive material having a photosensitive silver halide emulsion layer on at least one side of a supporting body, the photosensitive silver halide emulsion contained in at least one layer of the silver halide emulsion layers is a silver halide emulsion prepared by adding a silver halide particle emulsion which is smaller in solubility product than that of the silver halide emulsion before finishing chemical sensitizing process, previously contains a spectral sensitization dyestuff and has substantially no photosensitivity.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-sensitivity silver halide photographic light-sensitive material which is excellent in storage stability and pressure resistance and has less residual color contamination.

[0002]

BACKGROUND OF THE INVENTION In recent years, along with the development of photographic technology, it has been strongly desired that silver halide photographic light-sensitive materials have high sensitivity and high image quality, and that they are processed rapidly in a short time.

For example, in the field of medical X-ray photographic light-sensitive materials, a rapid increase in the number of diagnoses and an increase in the number of inspection items have led to an increase in the number of images taken and the need to know the diagnosis results as quickly as possible, and thus rapid processing is desired. In contrast imaging and intraoperative imaging, it is necessary to obtain higher quality images in a short time.

In order to meet such demands for higher sensitivity, higher image quality and faster processing, a light-sensitive material comprising tabular silver halide grains has recently been cited. Since the particles have a large specific surface area, a large amount of the spectral sensitizing dye can be adsorbed. Therefore, there is an advantage that the spectral sensitization property can be improved and the crossover light in the X-ray photosensitive material can be reduced, and it has high sensitivity and high sharpness.

However, in general, tabular grains having a large diameter / thickness ratio have a defect that they are weak against external force due to their shape. For example, bending caused during handling of a photosensitive material and mechanical stress during transportation are applied. If given,
In the case of a medical X-ray film, a serious problem such as a blackening in a streak, a fog, a desensitization, etc. is caused, which is a serious problem in diagnosis.

Conventionally, two methods have been roughly proposed as means for preventing the sensitivity of the photographic light-sensitive material to external pressure. One is a method of physically relaxing the force transmitted to the silver halide grains when an external pressure is applied to the emulsion film, and the other is a method of reducing the pressure sensitivity of the silver halide crystal itself. is there.

As the former method, for example, the technique of using gelatin, hydrophilic polymer, latex or the like which is a binder component of the emulsion layer, or the technique of using a plasticizer of gelatin or an adsorbing compound for silver halide grains is used. All of them have been disclosed, and methods for coating the crystal surface have been proposed. However, these techniques are not preferable because they slow down the developing rate and the drying rate and run counter to the demands of the times.

As the latter approach from the side of silver halide crystals, for example, JP-A-59-99433 which improves the pressure resistance by providing a high silver iodide layer inside the tabular grains, or tabular grains Japanese Patent Laid-Open No. 61-14636 discloses that the pressure resistance is improved by making the iodide content of the central region higher than that of the outer region.

However, although these methods using iodide show some improvement in pressure resistance, they have a significant effect on developability. For example, if the average silver iodide content of the whole grain is lowered, development becomes excessive, As a result, the problem of deterioration of graininess is caused.

Further, for the purpose of sensitizing a silver halide emulsion, for example, Japanese Patent Laid-Open No. 4-42223 in which fine grain silver iodide is added in a chemical sensitization step is disclosed. In the case of applying to No. 1, the residual color contamination was generated after the rapid processing, and the improvement of the raw storability of the light-sensitive material was not sufficient.

Deterioration of graininess or generation of fog or residual color contamination in photographic light-sensitive materials for X-rays leads to misdiagnosis in the case of medical use, and therefore improvement thereof is important, and new measures are urgently needed. Was wanted.

[0012]

SUMMARY OF THE INVENTION It is, therefore, an object of the present invention to provide a silver halide photographic light-sensitive material having excellent storage stability, high sensitivity, and high image quality which has improved pressure characteristics and residual color.

[0013]

It has been found that the above objects of the present invention can be achieved by the following structures of the present invention.

That is, in a silver halide photographic light-sensitive material having a photosensitive halide emulsion layer on at least one side of a support, the photosensitive silver halide contained in at least one of the silver halide emulsion layers. Prior to the completion of the chemical sensitization step, the addition of a silver halide fine grain emulsion having a solubility product smaller than that of the silver halide emulsion and containing a spectral sensitizing dye in advance and having substantially no photosensitivity. And a silver halide photographic light-sensitive material characterized by being a silver halide emulsion prepared by

The present invention will be described in detail below.

The silver halide emulsion of the silver halide photographic light-sensitive material according to the present invention includes normal crystal grains, that is, all isotropically grown grains such as cubes, octahedrons and tetrahedrons, or spherical grains. It may be a polyhedral crystal type or a twin crystal having a plane defect, or a mixed type or a composite type thereof, but tabular silver halide grains are preferable.

The grain size of these silver halide grains is 0.2 μm.
To 3.0 μm is preferred.

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

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

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

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 monodisperse referred to here, when measuring the average particle diameter by a conventional method,
At least 95% by number or weight of grains are silver halide grains having an average grain size within ± 40%, preferably within ± 30%.

The grain size distribution of 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 be composed of different silver halide compositions inside and outside,
For example, a core / shell type monodisperse emulsion having a clear two-layer structure in which a high silver iodide core portion is covered with a low silver iodide shell layer may be used.

The silver iodide content in the high iodine portion is 20 to 40 mol%,
Particularly preferably, it is 20 to 30 mol%.

A method for producing such a monodisperse emulsion is known, and for example,
J. Phot. Sci, 12.242 to 251, (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, British Patent 1,413,748, US Patents 3,574,628, 3,655,394 and the like. As a method for obtaining the above monodisperse emulsion, for example, a seed crystal may be used, and an emulsion obtained by supplying silver ions and halide ions to grow the seed crystal may be used. The production method of the above core / shell type emulsion is well known, for example, J. Phot. Sci, 24.198. (1976), British patent.
The methods described in 1,027,146, U.S. Pat. Nos. 3,505,068, 4,444,877, and JP-A-60-143331 can be referred to.

The average grain size of the tabular silver halide grains according to the present invention is preferably 0.3 to 3.0 μm, particularly preferably 0.5 to 3.0 μm.
It is 1.5 μm.

The tabular silver halide emulsion of the present invention has an average value of grain diameter / thickness (called aspect ratio) (called average aspect ratio) of 2.0 or more, preferably 2.2 to 2
0.0, particularly preferably 2.5 to 8.0.

The average thickness of the tabular silver halide emulsion of the present invention is preferably 0.5 μm or less, particularly preferably 0.3 μm or less.

The advantages of such tabular grains are as described above.
As an improvement in spectral sensitization efficiency, improvement of image graininess and sharpness, etc. are obtained, for example, British Patent 2,112,157, U.S. Patents 4,439,520, 4,433,048, 4,414,310,
No. 4,434,226 and the like, and the emulsion can be prepared by the methods described in these specifications.

In the present invention, the diameter of the silver halide grain is defined as the diameter of a circle having an area equal to the projected area of the grain from the observation of an electron micrograph of the silver halide grain.

In the present invention, the grain size, that is, the thickness of the silver halide grain is defined as the minimum distance between the two parallel planes constituting the tabular silver halide grain.

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

To obtain the average aspect ratio, the minimum
Measure 100 samples.

In the silver halide emulsion of the present invention, the proportion of tabular silver halide grains in all silver halide grains is 50% or more, preferably 60% or more, particularly preferably 70% or more.

The tabular silver halide emulsion of the present invention is preferably monodisperse, and the average grain size is ±
50% by weight of silver halide grains contained in the 20% grain size range
The above is particularly preferably used.

In the present invention, monodisperse is represented by a value (coefficient of variation) obtained by dividing the variation (standard deviation) of particle diameter by the average particle diameter.

The tabular silver halide emulsion of the present invention may have any halogen composition such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, etc. Silver iodide is preferred, and the average silver iodide content is 0.1 to 5.0 mol%, particularly preferably 0.5 to 3.0 mol%.

Further, the tabular silver halide emulsion of the present invention comprises
The halogen composition may be uniform within the grain or silver iodide may be localized, but the one localized on the outermost surface of the grain is preferably used.

The method for producing a tabular silver halide emulsion is described in JP-A Nos. 58-113926, 58-113927, 58-113934 and 6-113.
It is also possible to refer to 2-1855, European Patents 219,849, 219,850 and the like.

Further, JP-A-61-6643 can be referred to as a method for producing a monodisperse tabular silver halide emulsion.

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

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

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

Further, during the production of tabular silver halide grains,
If necessary, a silver halide solvent such as ammonia, thioether or thiourea can be used.

The silver halide emulsion according to the present invention includes
Core / shell type or double structure type grains having a silver halide composition whose surface is different from the grain interior are preferably used. As a method for obtaining a core / shell type emulsion, for example, US Pat. Nos. 3,505,068 and 4,444,877, and British Patent 1,02
No. 7,146, JP-A-60-14331 and the like. In the core / shell type grains of the silver halide emulsion according to the present invention, the silver iodide content of the outermost shell layer of the grains is less than 5 mol%, preferably less than 3 mol%.

The silver iodide content of the outermost shell layer of the silver halide grains according to the present invention can be detected by various surface elemental analysis means. XPS (X-ray Photoelectron Spectroscop
It is useful to use methods such as y), Auger electron spectroscopy, and ISS. X is the simplest and most accurate means
There is PS, and the silver iodide content of the outermost shell layer of the present invention can be defined by the value measured by this method.

The depth analyzed by the XPS surface analysis method is said to be about 10Å. Regarding the principle of the XPS method used for the analysis of iodine content near the surface of silver halide grains, see Aihara Soichi et al. "Electron spectroscopy" (Kyoritsu Library 1
6, published by Kyoritsu Shuppan, 1978).

The above-mentioned emulsion is either a surface latent image type emulsion forming a latent image on the grain surface, an internal latent image type emulsion forming a latent image inside the grain, or a type emulsion forming a latent image on the surface and inside. You may. These emulsions may be prepared by using an iron salt, a cadmium salt, a lead salt, a zinc salt, a thallium salt, a ruthenium salt, an osmium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof at the stage of physical ripening or grain preparation. Good.

The emulsion may be subjected to a water washing method such as a Noudel water washing method or a flocculation sedimentation method in order to remove soluble salts. A preferred washing method is, for example, Japanese Patent Publication Sho
Particularly preferable desalting method is a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-A-35-16086 or a method using G3, G8, etc., as an aggregation polymer agent described in JP-A-63-158644. Can be mentioned.

The silver halide emulsion of the present invention is preferably combined with chalcogen sensitization and gold sensitization as sensitizing methods.
Particularly, the combined use of gold sensitization and sulfur sensitization is preferable because not only the sensitizing effect is remarkable but also the fog suppressing effect is obtained.

For sulfur sensitization, sensitizers such as thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine can be used. Other U.S. Patents 1,574,944
No. 3,656,955, German Patent 1,422,869, Japanese Patent Sho 56
The sulfur sensitizers described in JP-A-24937 and JP-A-55-45016 can also be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion. This amount can be varied over a wide range under various conditions such as pH, temperature and size of silver halide grains, but as a guide, it is preferably 10 ^-7 to 10 ^-1 mol per mol of silver halide.

For gold sensitization, gold sensitizers such as chloroauric acid salt, gold thiourea complex salt, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric amide and ammonium auro are used. Examples thereof include thiocyanate and pyridyl trichlorogold. The addition amount of these gold sensitizers can be varied over a wide range under various conditions, but as a guide, it is 5 × 10 ^{-7 to} 5 per mol of silver halide.
It is preferably ^{x10 -3} mol, more preferably 2x10 ^-6 to 4x10 ^-4 mol.

In the present invention, reduction sensitization and hydrogen sensitization methods can be used. Stannous salt as a reduction sensitizer,
Amines, formamine disulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives can be used.

The addition amount of the reduction sensitizer varies depending on the reducibility of the compound and the emulsion production conditions such as the type of silver halide and the dissolution conditions, but it is 1 × 10 ^-8 to 1 × per mol of silver halide.
A range of 10 ⁻² mol is suitable.

Further, selenium sensitization is preferably used in the present invention. In particular, it is preferable to use it in combination with the above-mentioned other sensitizing method.

Here, the selenium sensitization is carried out by a conventionally known method. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
It is carried out by stirring the emulsion at a high temperature, preferably 40 ° C. or higher for a certain time. Selenium sensitization using the unstable selenium sensitizer described in JP-B-44-15748 is preferably used. Specific examples of the unstable selenium sensitizer include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenamides,
There are selenocarboxylic acids and esters, and selenophosphates. Particularly preferred unstable selenium compounds are shown below.

Colloidal Metal Selenium Organic Selenium Compound (Selenium Atom Double Bonded to Carbon Atom of Organic Compound by Covalent Bond) a. Isoselenocyanates Aliphatic isoselenocyanates such as allyl isoselenocyanates b. Selenoureas (including enol type) For example, selenoureas, and methyl, ethyl, propyl,
Isopropyl, butyl, hexyl, octyl, dioctyl, tetramethyl, N- (βcarboxyethyl) -N, N'-
Aliphatic selenoureas such as dimethyl, N, N-dimethyl, diethyl, dimethyl, etc .; Aromatic selenoureas having one or more aromatic groups such as phenyl, tolyl, etc .; Heterocycles having heterocyclic groups such as pyridyl, benzothiazolyl, etc. Cyclic selenoureas.

Particularly preferred selenoureas are N, N′-
It is a 4-substituted selenourea. Preferred substituents are R, RC
O-, ArCO-, R is an alkyl group or a perfluoroalkyl group (C number of 1 to 7 is preferable),
Ar is halogen or a phenyl group which may be substituted with a lower alkoxy group.

C. Selenoketones, for example, selenoacetone, selenoacetophenone, selenoketone having an alkyl group bonded to = C = Se, selenobenzophenone, d. Selenoamides For example, selenoamide e. Selenocarboxylic acids and esters For example, 2-selenopropionic acid, 3-selenobutyric acid, methyl
-3-Selenobutyrate Other a. Selenides For example, diethyl selenide, diethyl diselenide,
Triphenylphosphine selenide b. Selenophosphates For example, preferred types of tri-p-triselenophosphate, tri-n-butylselenophosphate labile selenium compounds are mentioned above, but these are not limiting. Stable selenium compounds as sensitizers for photographic emulsions are known to those skilled in the art, as long as selenium is unstable, the structure of the compounds is not so important, and organic compounds of selenium sensitizer molecules are not important. It is generally understood that the moieties carry selenium and have no role other than allowing it to be present in the emulsion in an unstable form. In the present invention, such a broad concept of unstable selenium compounds is advantageously used.

Selenium sensitization using the non-labile selenium sensitizers described in JP-B-46-4553, JP-B-52-34492 and JP-B-52-34491 can also be used. Examples of the non-labile selenium compound include selenious acid, potassium selenocyanide, selenazoles, quaternary ammonium salts of selenazoles,
Diaryl selenide, diaryl diselenide, 2-thioselenazolidinedione, 2-selenooxazolidinedione 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 at the time of chemical sensitization. The selenium sensitizer used is not limited to one type, and two or more types of the above selenium sensitizers can be used in combination. An unstable selenium compound and a non-unstable selenium compound can be preferably used in combination.

The addition amount of the selenium sensitizer used in the present invention varies depending on the activity of the selenium sensitizer used, the kind and size of silver halide, the temperature and time of ripening, etc.
It is preferably 1 × 10 ⁻⁸ mol or more per mol of silver halide. It is more preferably 1 × 10 ⁻⁷ mol or more and 5 × 10 ⁻⁵ mol or less.

Selenium sensitization is more effective when carried out in the presence of a silver halide solvent.

The silver halide solvent that can be used in the present invention is, for example, US Pat. Nos. 3,271,157 and 3,531,289.
No. 3,574,628, JP-A-54-1019, and JP-A-54-158917.
(A) Organic thioethers described in Japanese Patent Publication No. Sho 53
-82408, 55-77737, 55-2982 and the like (b) thiourea derivatives, and (c) oxygen or sulfur and nitrogen atoms described in JP-A-53-144319. Silver halide solvent having pinched thiocarbonyl group, JP-A-54
-100717 (d) imidazoles, (e)
Examples thereof include sulfite and (f) thiocyanate.

Particularly preferred solvents are thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the type, for example, in the case of thiocyanate, the preferable amount is 1 × per mol of silver halide.
It is 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less.

The chemical ripening temperature of the emulsion according to the present invention is arbitrarily determined, but is preferably in the range of 20 to 90 ° C, preferably 30 to 80 ° C, and more preferably 35 to 70 ° C.

When a selenium sensitizer is used, the temperature is preferably 45 ° C or higher.

In the present invention, a silver halide fine grain emulsion having a solubility product smaller than that of the parent grain emulsion is preferably added before the end of the chemical sensitization step of the silver halide emulsion (hereinafter referred to as parent grain emulsion). .

A solubility product smaller than that of the parent grain emulsion means that
When the solubility product is represented by K _SP , K _SP = [Ag ⁺ ] · [X ⁻ ] where [Ag ⁺ ] represents the silver ion concentration and [X ⁻ ] represents the halogen ion concentration. Therefore, when the parent grain is silver chloride, the fine grain silver halide is silver bromide or silver iodide.

Of course, a mixed crystal of these halogen ions may be used as long as the value of K _SP is smaller in the fine silver halide grains than in the parent grains.

The types of silver halide fine grains according to the present invention include AgBr, AgI, AgClBr and AgBr.
There are I, AgClI and AgClBrI, but silver halide fine grains having substantially no photosensitivity are preferable.

The grain size of the fine silver halide grains is preferably 0.1 μm or less, more preferably 0.07 μm or less, and particularly preferably 0.05 μm.

The silver halide fine grain emulsion according to the present invention contains a spectral sensitizing dye. Examples of the spectral sensitizing dye include oxacarbocyanine, benzimidazolocarbocyanine, and benzimidazolo-oxacarbocyanine as described in Japanese Patent Application No. 3-95310. Further, dyes having a sensitizing property in the blue light region described in JP-A-59-119344 and JP-A-4-234031 can also be preferably used. These spectral sensitizing dyes can be used alone or in combination.

The spectral sensitizing dye may be added to the parent grain emulsion after being contained in the above silver halide fine grain emulsion.
Alternatively, it may be added separately in a solution dissolved in an organic solvent such as methanol.

When the spectral sensitizing dye is added to the silver halide fine grain emulsion, the emulsion temperature during the addition is preferably 20 ° C. to 80 ° C., depending on the kind of the spectral sensitizing dye.
35 ° C to 50 ° C is preferable. The pH during addition is preferably 2.0 to 11.5, and particularly preferably 4.0 to 9.0. The pAg is preferably 5.0 to 11.0, and more preferably 7.5 to 10.0.

The spectral sensitizing dye according to the present invention can be added to the silver halide grains in the presence of a silver halide solvent. Examples of the silver halide solvent include those similar to the silver halide solvent that can be used at the time of sensitizing selenium, and thiocyanate is particularly preferably used.

The addition amount of the spectral sensitizing dye is not uniform depending on the type of dye and the emulsion conditions, but it is preferably 10 to 900 mg, and particularly preferably 60 to 400 mg per mol of silver in the parent grain emulsion.

The silver halide fine particles containing the spectral sensitizing dye are preferably added before the end of the chemical sensitization step,
It may be added in several times before the end of the chemical sensitization step.
More preferably, after the growth step of the parent grain and before the completion of the chemical sensitization step, the addition of the silver halide fine grain emulsion containing the spectral sensitizing dye according to the present invention is preferably at the start of chemical sensitization.

As the silver halide fine particles containing the spectral sensitizing dye according to the present invention, silver iodide fine particles are preferably used.

With respect to silver iodide, generally cubic γ-
Although AgI and hexagonal β-AgI are known, the silver iodide fine grains used in the present invention may have any crystal structure or a mixture thereof.

When silver bromide, silver chloride or a solid solution mainly composed of these rock salt structures is used as the silver halide fine particles according to the present invention, for example, when fine particles such as AgBr ₉₀ I ₁₀ are used, these The fine particles are preferably twin-free so-called normal crystals having substantially no twin planes, or single twin crystals having one twin plane.

The silver halide fine grains used in the present invention preferably have good monodispersibility, and are preferably prepared by the double jet method while controlling the temperature, pH and pAg.

The addition amount of fine silver halide grains is preferably 1/100 dmol or less per 1 mol of the parent grain emulsion, and more preferably 1 mol of the parent grain emulsion, when the average grain size of the parent grain emulsion is d (μm). It is preferably in the range of 1 / 20,000 d to 1/300 d mol, and most preferably 1/5000 d to 1/500 d mol per 1 mol of the parent grain emulsion.

In the present invention, in order to stop the chemical sensitization (chemical ripening), a method using a chemical ripening terminator is preferable in consideration of the stability of the emulsion. Examples of the chemical aging inhibitor include halides (eg potassium bromide, sodium chloride, etc.), organic compounds known as antifoggants or stabilizers (eg 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene, etc.) is known. These are used alone or in combination of a plurality of compounds.

Further, as described above, the addition of silver halide fine grains may be carried out in several times at intervals, or after the addition of silver halide fine grains, another chemically ripened emulsion is added. May be.

The temperature of the parent grain emulsion when adding the fine silver halide grains is preferably in the range of 30 to 80 ° C., more preferably 40 ° C.
A range of up to 65 ° C is particularly preferred.

Further, the present invention is preferably carried out under the condition that after the addition of the silver halide fine particles to be added, and before the coating, a part or all of the silver halide fine particles disappears. More preferable conditions are the added silver halide fine particles. 20% or more of the above has disappeared just before coating.

The disappearance amount is quantified by centrifuging the emulsion or coating solution after addition of the silver halide fine particles under appropriate conditions and then measuring the absorption spectrum of the supernatant to obtain silver halide fine particles having a known concentration. It can be performed by comparing with the absorption spectrum of.

In the emulsion according to the present invention, various photographic additives can be used in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure (RD) No. 17643 (December 1978),
No. 18716 (November 1979) and No. 308119 (December 1989)
Month). The following table lists the types of compounds and the locations where they are described in these three Research Disclosures.

Additives RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25 to 26 VIII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Supports that can be used in the light-sensitive material of the present invention include, for example, RD-17643, page 28 and RD-308119, 100.
Examples include those described on page 9.

A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge, or ultraviolet irradiation in order to improve the adhesion of the coating layer.

[0092]

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 (Preparation of tabular silver halide emulsion) A seed emulsion composed of silver bromide was prepared using the solution shown below.

[A ₁ ] Hydrogen peroxide treated ossein gelatin 40 g Potassium bromide 75.1 g Water added 4000 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 added 803 ml [D ₁ ] Ammonia water (28%) 235 ml Using the device disclosed in Japanese Patent Laid-Open No. 62-160128, a supply nozzle to the lower part of the stirring impeller for mixing Of the solution B ₁ and solution C ₁ .

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. With potassium bromide solution (3.5N), adding
The pBr was kept at 1.3.

After the addition was completed, the temperature of the mixed solution was raised to 20 ° C for 10 minutes.
And the stirring speed was 460 rpm, and the solution D ₁
Was added for 20 seconds, and Ostwald ripening was performed 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 became 5.6 to neutralize the mixture to stop the ripening, and in order to remove excess salts, demineralized (Kao Atlas) aqueous solution and magnesium sulfate aqueous solution were used for demineralized water washing. Seed emulsion Em-1
Got

Observation of Em-1 with an electron microscope revealed that the particles were spherical particles having an average particle size of 0.32 μm and a particle size variation coefficient of 17%.

(Growth of Seed Emulsion) Subsequently, comparative seed emulsion E was prepared.
Using m-1 and the following three kinds of solutions, a silver halide parent grain emulsion mainly composed of tabular twin crystals according to the present invention was prepared.

[A ₂ ] ossein gelatin 114.5 g propyleneoxy polyethyleneoxy disuccinate disodium salt (10% methanol solution) 20 ml with water added 10330 ml [B ₂ ] ossein gelatin 29.8 g potassium bromide 1893.5 g Potassium iodide 40.5 g Water was added 5430 ml [C ₂ ] Silver nitrate 2771.5 g Water was added 5430 ml Seed emulsion Em-1 0.54 mole equivalent Solution A ₂ stirred vigorously at a liquid temperature of 65 ° C. was added with seed emulsion Em-1. The solution was put in and well dispersed, and solution B ₂ and solution C ₂ were added by a controlled double jet method in 40 minutes. Meanwhile, p
H was kept at 6.5 with acetic acid and pAg was kept at 9.1 throughout. In addition,
The addition rates of solution B ₂ and solution C ₂ were linearly increased so that the rate at the end of addition was 2.3 times the rate at the start of addition.

Immediately after the 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 demole (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate, and gelatin was added. PAg at ℃ 8.
Redispersion was carried out under the conditions of pH 5.85 to obtain parent grain emulsion EM-1.

Observation of the obtained emulsion with an electron microscope revealed that the average grain size was 0.96 μm, the variation coefficient of the grain size was 19%, the average thickness was 0.35 μm, and the average aspect ratio was 2.74.

(Preparation of silver iodide fine grain emulsion) 5000 ml of a 5.2% by weight gelatin solution containing 0.008 mol of potassium iodide
And an aqueous solution containing 1.06 mol of silver nitrate and potassium iodide.
1500 ml was added in a constant amount over 35 minutes. The temperature during the preparation of the microparticles was kept at 40 ° C. When the obtained silver iodide fine grains were confirmed by an electron micrograph at a magnification of 60,000, the average grain size was 0.05 μm and it was a mixture of β-AgI and γ-AgI.

(Chemical Sensitization of Emulsion) Obtained Parent Emulsion E
M-1 is used in an amount equivalent to 1 mol of silver, and 210 mg of the following spectral sensitizing dyes (a) and (b) are added while stirring at a temperature of 48 ° C, and
1.5 mg was added. 20 minutes after adding the sensitizing dye, ammonium thiocyanate 52 mg, chloroauric acid 1.56 mg, as a chemical sensitizer
14 mg of sodium thiosulfate were added respectively.

40 minutes later, 1.67 × 10 ^-3 mol of the above silver iodide fine grain emulsion was added.

Then, 4-hydroxy-6-methyl-1,3,3a, 7
-Stabilized by adding tetrazaindene for optimum chemical sensitization.

This emulsion thus obtained was designated as EM-2.

Sensitizing dye (a) 5,5'-dichloro-9-ethyl-
3,3'-Di- (3-sulfopropyl) oxacarboxyanine sodium salt Anhydrous Sensitizing dye (b) 5,5'-di- (butoxycarbonyl) -1,1'-
Diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt Anhydrous spectral sensitizing dyes (a) and (b) before addition of chemical sensitizer
Just before adding silver iodide fine particles to 0 mg and 1.0 mg (a)
EM-2 except that 70 mg and 0.5 mg of (b) were added.
Emulsion EM-3 was prepared in exactly the same manner as in.

The spectral sensitizing dyes (a) and (b) before addition of the chemical sensitizer were adjusted to 140 mg and 1.0 mg, and a silver iodide fine grain emulsion 1.67 was added.
× 10 ^-3 mol equivalent with respect to (i) and (ii) a 70mg and 0.
Immediately after preparation, an aqueous solution prepared to have a concentration of 5 mg was added to the silver iodide fine grain emulsion, and then strongly stirred at 45 ° C. for 30 minutes to prepare a silver iodide fine grain emulsion in which these spectral sensitizing dyes were sufficiently adsorbed. , EM-2 except that it was added to the parent grain emulsion EM-1
Emulsion EM-4 was prepared in exactly the same manner as in.

Emulsion EM-5 was prepared in exactly the same manner as EM-2 except that the silver iodide fine grain emulsion was added immediately after addition of (a) and (b), not 40 minutes after addition of the chemical sensitizer. did.

Immediately after the preparation of an aqueous solution prepared by adjusting the amounts of (a) and (b) to 210 mg and 1.5 mg per equivalent of 1.67 × 10 ⁻³ mol of silver iodide fine grain emulsion, Stir vigorously at 45 ° C for 30 minutes, add the silver iodide fine grain emulsion in which these spectral sensitizing dyes are sufficiently adsorbed, instead of adding the sensitizing dye before chemical sensitization, and 20 minutes after that, perform chemical sensitization. Emulsion EM-in the same manner as EM-5 except that a sensitizer was added.
6 was prepared.

N, N-as a chemical sensitizer together with chloroauric acid
Dimethylselenourea 1.12 × 10 ^-7 E
Emulsion EM-7 was prepared in exactly the same manner as M-5.

As a chemical sensitizer, N, with silver chloride, etc.
N-dimethylselenourea 1.12 × 10 ^-7 mol was added, except
Emulsion EM-8 was prepared in exactly the same manner as EM-6.

Emulsion EM was prepared in the same manner as EM-8 except that 1.12 × 10 ⁻⁶ mol of N, N-dimethylselenourea was added.
-9 was prepared.

As the selenium sensitizer, EM- except that N, N-dimethylselenourea was changed to selenium sensitizer I described later.
Emulsion EM-10 was prepared in the same manner as in No. 7.

Emulsion EM-11 was prepared in the same manner as EM-8 except that selenium sensitizer I was used instead of N, N-dimethylselenourea as the selenium sensitizer.

Emulsion EM-12 was prepared in exactly the same manner as EM-9 except that N, N-dimethylselenourea was changed to selenium sensitizer I as the selenium sensitizer.

Emulsion EM-in the same manner as in EM-7 except that N, N-dimethylselenourea was changed to selenium sensitizer II described later as a selenium sensitizer and 7.4 × 10 ^-7 mol was added.
13 was prepared.

Emulsion EM-14 was prepared in exactly the same manner as EM-8 except that N, N-dimethylselenourea was changed to selenium sensitizer II as the selenium sensitizer and 7.4 × 10 ^-7 mol was added. Prepared.

Emulsion EM-15 was prepared in exactly the same manner as EM-8 except that N, N-dimethylselenourea was changed to selenium sensitizer II as the selenium sensitizer and 7.4 × 10 ^-6 mol was added. Prepared.

[0121]

[Chemical 1]

The emulsions EM-2 to EM-15 thus obtained were added with the additives described below to prepare emulsion layer coating solutions. At the same time, a protective layer coating solution described below was also prepared. In addition, the coating amount was 2.0 g / m ² per side and the amount with gelatin was 3.1 g / m ² , using two slide hopper type coaters at a speed of 80 m / min on both sides of the support simultaneously. Application was performed and drying was performed for 2 minutes and 20 seconds to obtain a sample. Glycidyl methacrylate as support
The concentration of the copolymer consisting of three kinds of monomers of 50 wt%, methyl acrylate 10 wt% and butyl methacrylate 40 wt% is 10
A polyethylene terephthalate film base colored blue at a concentration of 0.15 for a 175 μm X-ray film was used as an undercoating solution of the copolymer aqueous dispersion obtained by diluting the copolymer to a wt%.

The additives used in the emulsion are as follows.
The addition amount is indicated by the amount per mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-Butyl-catechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1 Ammonium 3,3-dihydroxybenzene-4-sulfonate 4g 2-Sodium mercaptobenzimidazole-5-sulfonate 1.5g

[0125]

[Chemical 2]

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 Next, the following was prepared as a protective layer coating liquid. 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-decyl sulfosuccinate 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 (DuPont) (colloidal silica) 30 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardening agent) 8.5 mg Glyoxal 40% aqueous solution (hardening agent) 2.0 ml Dye Emulsion dispersion 1.2g

[0128]

[Chemical 3]

Method for Preparing Dye Emulsion Dispersion 100 g of the following dye was dissolved in a solvent consisting of 280 ml of tricresyl phosphate and 850 ml of ethyl acetate at 55 ° C. This is called an oil solution.

On the other hand, an anionic surfactant (AS) was added to 13.5
2.7 l of a 9.3% zetilan aqueous solution containing g was prepared. This is called an aqueous solution. Next, the oil-based solution, the water-based solution, and a dispersion pot were charged, and dispersion was performed while maintaining the liquid temperature at 40 ° C. Phenol and 1,1-dimethylol-bromo-1-nitromethane were added to the obtained dispersion in appropriate amounts, and the mixture was adjusted to 2.4 Kg with water.

[0131]

[Chemical 4]

With respect to the obtained coating sample Nos. 101 to 114,
Sensitometry, pressure resistance and roller marks were evaluated.

(1) Sensitometry (evaluation of photographic performance) In sensitometry, a sample was sandwiched between two intensifying screens (KO-250 Konica Corporation), and a tube voltage of 80 kv was applied via an aluminum wedge.
p, tube current 100 mA, X-ray irradiation for 0.05 seconds. Then, a roller-conveying type automatic developing machine was used to develop and fix the developing solution having the composition shown below and a fixing solution.

The compositions of the developing solution and fixing solution used in the present invention are shown below.

Developer Formulation Part-A (for 12 liter finish) Potassium hydroxide 450g Potassium sulfite (50% solution) 2280g Diethylenetetraamine pentaacetic acid 120g Sodium bicarbonate 132g 5-Methylbenzotriazole 1.2g 1-phenyl-5- Mercaptotetrazole 0.2g Hydroquinone 340g Add water to make 5000ml.

Part-B (for 12 l finishing) 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 Add to make 1.0 liter.

Fixer formulation Part-A (for 18l finish) Ammonium thiosulfate (70wt / vol%) 6000g Sodium sulfite 110g Sodium acetate ・ 3hydrate 450g Sodium citrate 50g Gluconic acid 70g 1- (N, N-dimethylamino) -Ethyl-5-mercaptotetrazole 18g Part-B Aluminum sulfate 800g To prepare a developer, add Part A and Part B to approximately 5 liters of water at the same time, add water while stirring and dissolve, and add 12 liters to finish with glacial acetic acid.
The H was adjusted to 10.40. This is used as a developing solution.

20 ml of the above starter was added to 1 l of this developer.

The fixing solution was prepared by adding Part A and Part B to approximately 5 liters of water.
Was added at the same time, water was added while dissolving with stirring to make 18 l, and the pH was adjusted to 4.6 using sulfuric acid and NaOH. This is the fixer.

The processing time is dry to dry for 45 seconds (development
(35 ° C., fixing 33 ° C., water washing 20 ° C., drying 50 ° C.), and sensitivity was determined. The sensitivity was represented by the reciprocal of the exposure amount that gives a density of fog +0.5, and was represented by the relative sensitivity with the sensitivity of Sample No. 101 as 100.

(2) Evaluation of pressure resistance As a method for evaluating pressure resistance, each sample was kept at a constant temperature and humidity of 25 ° C. and a relative humidity of 50% for about 12 hours, and under this condition, a radius of curvature of 2 cm was applied. Bent at 280 °. After 3 minutes from bending, exposure was performed using an optical wedge, and development was performed in the same manner as in sensitometry. Each wedge blackening density of this sample was measured, and the density difference between the desensitized portion caused by bending and the portion not bent was ΔD, and Δ was calculated at each density D.
D was divided and the average value ΔD / D was calculated, and this value was used as a standard for pressure desensitization. That is, the smaller this value, the better the pressure desensitization resistance.

The obtained sample was treated in the same manner as in sensitometry.

(3) Evaluation of Roller Mark Property The pressure mark = roller mark by the roller of the automatic developing machine was evaluated as follows. That is, the unexposed state was processed by an automatic developing machine having an opposed roller. The roller marks generated at that time were visually evaluated and classified into the following 5 grades.

5: No occurrence of roller mark 4: Very slight occurrence 3: Some occurrence (within practical use permit) 2: Many occurrences (outside practical use permit) 1: Very many occurrences (4) Remaining color Measurement (Evaluation of Contamination) Regarding the degree of residual color contamination, the unexposed sample was developed by a processing method similar to sensitometry, and the sample was visually observed as follows.
The grade was evaluated.

5: No residual color contamination 4: Slight residual color contamination 3: Slight residual color contamination, practical use possible 2: Slight residual color contamination, practical limit: 1: Large residual color contamination, impractical The results thus obtained are shown in Table 1.

[0146]

[Table 1]

<Evaluation of Storage Stability> Each of the coating sample Nos. 101 to 114 obtained in Example 1 was divided into 2 parts, and 1 part was 2 parts.
Store at 3 ℃, 55% RH for 1 day, another copy at 40 ℃, 8
After storing for 5 days under the condition of 0% RH, sensitometry was performed by the same method as (1).

The sensitivity was shown as relative sensitivity with the sensitivity of Sample No. 101 stored at 23 ° C. and 55% RH for 1 day as 100.

The results obtained are shown in Table 2.

[0150]

[Table 2]

Example 2 (Preparation of Monodisperse Normal Crystal Emulsion) A solution shown below was prepared,
A seed emulsion was prepared.

[Liquid A] Water 11.5l Potassium bromide 2.05g Oscein gelatin 100g [Liquid B] Water 2.6l Potassium bromide 65g Potassium iodide 1.8g Ocein gelatin 55g 0.2N sulfuric acid 38.5cc [Liquid C] Water 3.0 l Potassium bromide 950g Potassium iodide 27g Ocein gelatin 75g [D-solution] Water 2.7l Silver nitrate 95g [E-solution] Water 3.2l Silver nitrate 1410g Put solution A into the reaction vessel and keep it at 60 ° C, and the other solutions are 23 Added at ° C. At this time, the solutions B and D were added by the control double jet method over 30 minutes, and then the solutions C and E were added by the control double jet method over 105 minutes. The stirring was performed at 500 rpm. The flow velocity is increased in proportion to the total surface area of the silver halide grains as the grains grow, new growth nuclei do not occur when the additive liquid flows in, and so-called Ostwald ripening occurs, resulting in a grain size distribution. Was added at a flow rate that did not spread. When the silver ionic liquid and the halide ionic liquid were added, the pAg was adjusted to 8.3 ± 0.05 using potassium bromide liquid, and the pH was adjusted to 2 using sulfuric acid.
It was adjusted to 0 ± 0.1.

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

The resulting emulsion had a grain size of 0.30 μm, {111}
The tetrahedral monodisperse grains were in the shape of a cube having 5% of the plane and the other of which were composed of {100} planes and the corners were slightly chipped and the silver iodide content was 2 mol%. This emulsion is designated as Em-2.

(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 5 g Potassium iodide 3 g Gelatin 0.8 g Water 110 ml [solution L] Potassium bromide 90 g Gelatin 2.0g 240ml with water [M solution (0.75N)] AgNO ₃ 9.9g NH ₄ OH 7.0ml 110ml with water [N solution] AgNO ₃ 130g NH ₄ OH 100ml 240ml with water [O solution] potassium bromide 94g 165ml with water [P liquid] AgNo ₃ 9.9 g NH ₄ OH 7.0 ml 110 ml J liquid was kept warm at 40 ° C and stirred at 800 rpm with a stirrer. J
The pH of the solution was adjusted to 9.90 with acetic acid, and 0.119 mol of the comparative seed emulsion Em-2 was sampled and dispersed and suspended therein per mol of silver halide. Then, the P liquid was added at a constant rate over 7 minutes to adjust the pAg to 7.3. Further, Solution K and Solution M were simultaneously added over 20 minutes. At this time, pAg was fixed at 7.30. Further, after adjusting the pH to 8.83 and the pH to 9.0 using potassium bromide solution and acetic acid over 10 minutes, L solution and N solution were simultaneously added 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. Also, L liquid and N liquid are 2 /
When only 3 amounts were added, 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. next,
Excess salt was removed by the same desalting method as in Example 1 to obtain Emulsion EM-16.

The grains were rounded, tetrahedral monodisperse silver iodobromide emulsions having an average grain size of 0.64 μm and a grain size variation coefficient of 16%.

(Chemical sensitization of emulsion) Obtained parent emulsion EM-
An appropriate amount of 16 was taken, and 150 mg and 1.5 mg of the above-mentioned spectral sensitizing dyes (a) and (b) were added with stirring at a temperature of 55 ° C.
20 minutes after adding the sensitizing dye, as a chemical sensitizer, ammonium thiocyanate 52 mg, chloroauric acid 1.0 mg, sodium thiosulfate
7.1 mg each was added.

40 minutes after that, the silver iodide fine grain emulsion prepared in Example 1 was added so as to be 1.52 × 10 ^-3 mol as silver.

Then 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene was added for stabilization and optimal chemical sensitization.

The obtained emulsion was designated as EM-17.

(The addition amount of the above-mentioned sensitizer, sensitizing dye and silver iodide fine grain emulsion is shown by the amount per mol of silver in the parent grain emulsion.) Spectral sensitizing dye before addition of chemical sensitizer (I)
Emulsion EM-18 was prepared in the same manner as EM-17 except that (b) was changed to 100 mg and 1.0 mg, and (i) and (b) were added to 50 mg and 0.5 mg just before the addition of silver iodide fine grains. did.

The spectral sensitizing dyes (a) and (b) added before adding the chemical sensitizer were changed to 100 mg and 1.0 mg,
A solution prepared by adjusting the spectral sensitizing dyes (a) and (b) to 50 mg and 0.5 mg per 1.52 × 10 ^-3 mol of silver iodide fine grain emulsion was immediately added to the silver iodide fine grain emulsion. Then, the silver iodide fine grain emulsion in which these spectral sensitizing dyes are sufficiently adsorbed by vigorously stirring at 45 ° C. for 30 minutes is used as a parent grain emulsion EM.
Emulsion EM-19 was prepared in the same manner as EM-17 except that it was added to -16.

The same method as in EM-17 except that the silver iodide fine grain emulsion was added immediately after addition of (a) and (b) before addition of the chemical sensitizer, not 40 minutes after addition of the chemical sensitizer. To prepare Emulsion EM-20.

Immediately after preparation, an aqueous solution prepared by adjusting the amounts of (a) and (b) to 150 mg and 1.5 mg relative to 1.52 × 10 ⁻³ mol of silver iodide fine grain emulsion was added to the silver iodide fine grain emulsion. After vigorous stirring at 45 ° C for 30 minutes, the silver iodide fine grain emulsion in which these spectral sensitizing dyes are sufficiently adsorbed is added instead of the dye addition before chemical sensitization, and 20 minutes after that, the chemical sensitizer is added. Emulsion EM-21 was prepared in the same manner as EM-20 except that was added.

As the chemical sensitizer, N,
N-Dimethylselenourea 1.12 × 10 ^-7 E
Emulsion EM-22 was prepared in exactly the same manner as M-20.

As the chemical sensitizer, N,
N-Dimethylselenourea 1.12 × 10 ^-7 E
Emulsion EM-23 was prepared in exactly the same manner as M-21.

Emulsion E was prepared in the same manner as in EM-23 except that 1.12 × 10 ^-6 mol of N, N-dimethylselenourea was added.
M-24 was prepared.

As a selenium sensitizer, EM-22 except that N, N-dimethylselenourea was changed to a selenium sensitizer I of the following formula.
Emulsion EM-25 was prepared in exactly the same manner as.

Emulsion EM-26 was prepared in the same manner as EM-23 except that selenium sensitizer I was used instead of N, N-dimethylselenourea as the selenium sensitizer.

Emulsion EM-27 was prepared in the same manner as EM-24 except that selenium sensitizer I was used instead of N, N-dimethylselenourea as a selenium sensitizer.

As the selenium sensitizer, N, N-dimethylselenourea was changed to the selenium sensitizer II described above, and 7.4 × 10 ^-7 mol was added, and the same procedure as for EM-22 was carried out.
-28 was prepared.

As the selenium sensitizer, N, N-dimethylselenourea was changed to selenium sensitizer II, and 7.4 × 10 ^-7 mol was added in the same manner as in EM-23, except that emulsion EM-
29 were prepared.

As the selenium sensitizer, N, N-dimethylselenourea was changed to the selenium sensitizer II and the emulsion EM-30 was prepared in the same manner as in EM-23 except that 7.4 × 10 ^-6 mol was added. Was prepared.

The obtained emulsions EM-17 to EM-30
Was applied in the same manner as in Example 1 to obtain sample Nos. 201 to 214.

Further, in the same manner as in Example 1, sensitometry, roller mark property and residual color contamination were evaluated. The sensitivity is shown as relative sensitivity with the sensitivity of Sample No. 201 set to 100. The results are shown in Table 3.

[0177]

[Table 3]

<Evaluation of Storage Stability> Each of the coated sample Nos. 201 to 214 obtained in Example 2 was divided into 2 parts, and 1 part was stored at 23 ° C. and 55% RH for 1 day. 1 copy is 40
After storing for 5 days at 80 ° C and 80% RH, sensitometry was carried out in the same manner as in Example 1.

The sensitivity is N stored at 23 ° C. and 55% RH for 1 day.
The relative sensitivity is shown with the sensitivity of o.201 as 100.

The results obtained are shown in Table 4.

[0181]

[Table 4]

As is clear from Tables 1 to 4, the light-sensitive material of the present invention has high sensitivity and low fog. Further, the pressure resistance and the residual color property at the time of ultra-rapid treatment were improved, and further, the change in sensitivity after storage and the deterioration of fog were small, and the effect was particularly large when sensitized with selenium.

[0183]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which is excellent in storage stability, has high sensitivity, and has improved pressure resistance and residual color due to ultra-rapid processing.

Claims (1)

[Claims] 1. In a silver halide photographic light-sensitive material having a photosensitive halide emulsion layer on at least one side of a support, the photosensitive silver halide contained in at least one of the silver halide emulsion layers. Prior to the completion of the chemical sensitization step, the addition of a silver halide fine grain emulsion having a solubility product smaller than that of the silver halide emulsion and containing a spectral sensitizing dye in advance and having substantially no photosensitivity. A silver halide photographic light-sensitive material, which is a silver halide emulsion prepared by