JPH06308654A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make possible rapid processing without curing, to enhance sensitivity, to improve pressure resistance, and to obtain a sufficient Dmax by subjecting emulsion grains to selenium sensitization and to spectral sensitization with a specified dyestuff. CONSTITUTION:The emulsion grains is sensitized with a selenium compound and spectrally sensitized with the dyestuff represented by formula I and/or II in which each of Z<1>-Z<3> is an atomic group necessary to form an oxazole, benzoxazole, naphthoxazole, or the like; each of R<1>-R<3> optionally substituted alkyl; R<4> is alkyl, aryl, or the like; X is an acid anion; and n is 0 or 1. This dyestuff may be used alone or in combination of both.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a regular type X-ray silver halide photographic light-sensitive material suitable for non-hard film rapid development processing.

[0002]

2. Description of the Related Art In recent years, with the introduction of an automatic processor, high-temperature rapid processing has become possible. At the present time, dry-to-dry ultra-rapid processing of 45 seconds or less has been developed. On the other hand, it is customary for these systems to undergo a dura mater reaction during the process step in order to impart rapid processability.

Normally, glutaraldehyde is used as a hardener because it is highly reactive in the developer and the hardening reaction is fast. However, glutaraldehyde has an irritating odor, and it cannot be said that it is highly safe when it adheres to the body. Furthermore, due to increasing environmental problems, rapid processing methods without development hardening by glutaraldehyde have been developed.

In order to carry out rapid development processing without relying on such processing hardening, it is necessary to sufficiently harden the silver halide photographic light-sensitive material in advance. However, in the case of a medical silver halide photographic light-sensitive material that requires high sensitivity and high density (Dmax), if the film is sufficiently hardened in advance, a large amount of coated silver is required to obtain the necessary photographic characteristics. A high silver content not only increases the cost but also causes serious obstacles such as deterioration of rapid processability, increase of fog and deterioration of pressure resistance.

In recent years, in the case of silver halide photographic light-sensitive materials for medical use, there has been an increasing shift from a regular system to an ortho (green sensitivity) system combined with a rare earth screen. In this system, a large amount of an ortho sensitizing dye can be adsorbed, a high concentration can be obtained with a smaller amount of silver, and even if the film is sufficiently hardened in advance, the decrease in the density is relatively small, and the processed hardened film is Tabular silver halide emulsions have come to be used because sufficient photographic characteristics can be obtained even if they are not applied. This is for example Research Discl
osure 22534 (January 1983) and the like.

However, the light-sensitive material using the tabular silver halide emulsion is not good in pressure resistance such as blackening of scratches and generation of roller marks due to rapid processing in an automatic processor, and further hardening of the emulsion layer. It is known that the pressure resistance and the processing dependency are further deteriorated by increasing the temperature.

Further, tabular grains are known to have lower intrinsic (blue region) sensitivity than silver halide grains having the same volume such as cubic, octahedron, and sphere, because of the smaller grain thickness. ing. Although a method of increasing the iodide content of the grains is known as one of the improving means, it is very difficult to apply tabular grains to regular (blue-sensitive) type light-sensitive materials because of the deterioration of rapid processability. It was difficult.

On the other hand, there is known a sensitization technique in a specific sensitivity range by using a regular dye, but it is difficult to use it because it has a property of reducing the specific absorption of silver halide depending on the kind of the sensitizing dye. Had.

JP-A-59-55426 discloses a technique in which the processing dependency of tabular grains having an aspect ratio of 3 or more with a regular dye is improved. However, this technology is based on high-temperature rapid processing that contains an aldehyde-based hardening agent (glutaraldehyde) in the developer, and is not a technology related to rapid processing without development hardening, and is a technology for increasing spectral sensitization. not.

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

[0011]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a tabular silver halide photographic light-sensitive material which has a high sensitivity and an improved pressure resistance and has a sufficient Dmax, which enables rapid processing without hardening. That is.

[0012]

The above problems have been solved by the present invention described below. That is, in a silver halide photographic light-sensitive material in which at least one tabular silver halide emulsion layer is coated on at least one side of a support, the emulsion grains are selenium-sensitized and the following general formula (I )
And / or a silver halide photographic light-sensitive material characterized by being spectrally sensitized with at least one of the dyes represented by (II).

[0013]

[Chemical 2]

In the formula, Z ¹ , Z ² and Z ³ represent an atomic group forming oxazoles, benzoxazoles, naphthoxazoles, thiazoles, benzothiazoles and naphthothiazoles, and R ¹ , R ² And R ³ represents an alkyl group or a substituted alkyl group, R ⁴ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, X
Represents an acid anion, and n represents 0 or 1.

Examples of the heterocyclic nucleus completed by Z ¹ or Z ^{2 in the} above general formula (I) include oxazoles (oxazole, 4-methyloxazole, 4,5-dimethyloxazole, etc.), benzoxazoles ( Benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-methoxybenzoxazole, 5-phenylbenzoxazole, 5,6-dimethylbenzoxazole, etc., naphthoxazoles (naphtho [1,2-d] oxazole , Naphtho [2,1-d] oxazole, naphtho [2,3
-d] oxazole etc.), thiazoles, benzothiazoles, naphthothiazoles and the like.

Examples of the alkyl group represented by R ¹ and R ^{2 in} the general formula (I) include methyl, ethyl, n-propyl and n-butyl groups.
The substituted alkyl group for R ¹ and R ² is a hydroxyalkyl group (eg, β-hydroxyalkyl group, specifically 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl group, etc.), acetoxyalkyl group. (For example, β-acetoxyethyl group, γ-acetoxypropyl group, etc.), alkoxyalkyl group (for example, β-methoxyethyl group, γ-methoxypropyl group, etc.), alkoxycarbonylalkyl group (for example, β-methoxycarbonylethyl group) , Γ-methoxycarbonylpropyl group, δ-ethoxycarbonylbutyl group, etc.), carboxyalkyl group (for example, carboxymethyl group, β-carboxyethyl group,
γ-carboxypropyl group, δ-carboxybutyl group, etc.), sulfoalkyl group (for example, β-sulfoethyl group,
γ-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, 2- (3-sulfopropoxy) ethyl group, 2- [2- (3
-Sulfopropoxy) ethoxy] ethyl group), allyl group (for example, vinylmethyl group), cyanoalkyl group (for example, β-cyanoethyl group), carbamoylalkyl group
(Eg, β-carbamoylethyl group), aralkyl group (eg, benzyl group, 2-phenylethyl group, 2- (4-
Sulfophenyl) ethyl group, etc.) and the like. or,
The alkyl group preferably has 1 to 8 carbon atoms, and the substituted alkyl group preferably has 1 to 10 carbon atoms.

Examples of the heterocyclic nucleus completed by Z ³ of the general formula (II) include the same as Z ¹ and Z ² of the general formula (I).

As R ³ , the same groups as R ¹ and R ^{2 in} the general formula (I) can be mentioned.

Examples of the alkyl group represented by R ⁴ in the general formula (II) include methyl, ethyl, n-propyl and n-butyl groups. The substituted alkyl group, a sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-
Sulfobutyl, 4-sulfobutyl group, etc.), carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl group, etc.), hydroxyalkyl group (for example, 2-hydroxyethyl, 3-hydroxy) Propyl, 4-hydroxybutyl group and the like), alkoxyalkyl group (for example, 2-methoxyethyl, 3-methoxypropyl group and the like), acyloxyalkyl group (for example, 2-acetoxyethyl group and the like), alkoxycarbonylalkyl group (for example, Methoxycarbonylmethyl, 2-methoxycarbonylethyl, 4-ethoxycarbonylbutyl group, etc.), substituted alkoxyalkyl group (for example, hydroxymethoxymethyl, 2-hydroxyethoxymethyl, 2- (2-hydroxyethoxy) ethyl, 2- (2 -Acetoxyethoxy) ethyl, acetoxymethoxymeth Group, etc.), dialkylaminoalkyl group (for example, 2-dimethylaminoethyl, 2-diethylaminoethyl, 2-piperidinoethyl, 2-morpholinoethyl group, etc.), N- (N, N-dialkylaminoalkyl) -carbamoylalkyl Group (for example, N- [3- (N, N-dimethylamino) propyl] carbamoylmethyl, N- [2- (N, N-diethylamino) ethyl] carbamoylmethyl, N- [3- (morpholino) propyl] carbamoyl Methyl, N- [3- (piperidino) propyl] carbamoylmethyl group, etc.), N- (N, N, N-trialkylammoniumalkyl) carbamoylalkyl group (for example, N- [3- (N,
N, N-trimethylammonium) propyl] carbamoylmethyl, N- [3- (N, N, N-triethylammonium) propyl] carbamoylmethyl, N- [3- (N-methylpiperidinio) propyl] carbamoylmethyl, etc. ), N, N, N-trialkylammonioalkyl groups (e.g., N, N-diethyl-N-
Methylammonioethyl, N, N, N-triethylammonioethyl group, etc.), cyanoalkyl group (for example, 2-cyanoethyl, 3-cyanopropyl group, etc.), carbamoylalkyl group (for example, 2-carbamoylethyl, 3- Carbamoylpropyl group), heterocyclic-substituted alkyl group (for example, tetrahydrofurfuryl, furfuryl group, etc.), allyl group (for example, vinylmethyl group), aralkyl group (for example,
Benzyl, 2-phenylethyl group, etc., aryl group (for example, phenyl, p-chlorophenyl, p-tolyl, p-methoxyphenyl, p-carboxyphenyl, p-methoxycarbonylphenyl, m-acetylaminophenyl, p-acetyl Examples thereof include aminophenyl, m-dialkylaminophenyl group (for example, m-dimethylaminophenyl group), p-dialkylaminophenyl group (for example, p-dimethylaminophenyl group), etc. The alkyl group has 1 carbon atoms. ~
8. The substituted alkyl group preferably has 1 to 10 carbon atoms. The following are preferred as the substituted alkyl group.
A hydroxyalkyl group, an acetoxyalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group, a carboxyalkyl group, a sulfoalkyl group, an allyl group, a carbamoylalkyl group, an aralkyl group, and a heterocyclic-substituted alkyl group.

As the compound used in the present invention, in the general formula (I), Z ¹ is oxazole, benzoxazole or naphthoxazole, and Z ² is thiazole, benzotheazole or naphthothiazole,
And a compound represented by the general formula (II) are preferred.

Next, typical specific examples of the compounds represented by the general formulas (I) and (II) are shown, but the invention is not limited thereto.

Examples of compounds

[0023]

[Chemical 3]

[0024]

[Chemical 4]

[0025]

[Chemical 5]

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

The sensitizing dyes represented by the general formula (I) and the general formula (II) are known ones, can be easily obtained, and can be easily synthesized based on the description in the following documents. You can

FM Hamer “The chemistry of heterocy”
clic compounds ； The cyanine dyesand related compou
nds ”1964, John Wiley Sons (New York, London)
Pp.58, 536.

The general formula (I) or the general formula (I
The sensitizing dye represented by I) may be used alone or in combination.

The amount of the compound represented by the general formula (I) or the general formula (II) added is 5 × 10 ^-6 to 1 mol of silver halide in the silver halide emulsion layer containing tabular grains. 5 x 10
It is preferably used in the range of ^-3 mol.

The addition time may be at any stage during the production of the silver halide photographic light-sensitive material, but is preferably from after grain formation to the end of chemical sensitization, and more preferably after grain formation and before chemical sensitization. .

The general formula (I) and the general formula (I
The sensitizing dye of I) is preferably added as a dye solution dissolved in a suitable organic solvent such as methanol, phenoxyethanol, phenylethanol, or a mixed solvent of these organic solvents and water or amines.

The average grain size of the tabular silver halide grains is 0.3
˜3.0 μm is preferable, and 0.5 to 1.5 μm is particularly preferable.

The tabular silver halide grains according to the present invention are
The average value of the particle diameter / thickness (called the aspect ratio) (called the average aspect ratio) is 1.2 or more, preferably 1.5.
˜20.0, particularly preferably 2.0 to 10.0.

The average thickness of the tabular silver halide grains according to the present invention is preferably 1.0 μm or less, particularly preferably 0.5 μm.
Or less, and more preferably 0.3 μm or less.

The advantages of such tabular silver halide grains are as follows.
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 a tabular 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 thickness of the tabular silver halide grain is defined as the minimum distance between the two parallel principal planes constituting the tabular silver halide grain.

The thickness of tabular silver halide grains can be determined from an electron micrograph of a shaded silver halide grain 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 according to the present invention is preferably monodisperse, which means that the coefficient of variation of grain size (standard deviation of grain size / average grain size × 10 6).
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 and silver chloroiodobromide, but has high sensitivity. From this point of view, silver iodobromide is preferred, and the average silver iodide content is 0.1 to 4.0 mol%, particularly preferably 0.5 to 3.0 mol%. Further, silver chloroiodobromide can be used from the viewpoint of rapid processability.

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

In the tabular silver halide emulsion according to the present invention, the halogen composition may be uniform within the grain, or silver iodide may be localized. The existing one is preferably used. A method for producing a tabular silver halide emulsion is described in JP-A Nos. 58-113926 and 58-113927.
No. 58-113934, No. 62-1855, European Patent 219,
You can also refer to 849 and 219,850. or,
As a method for producing a monodisperse tabular silver halide emulsion,
Reference can be made to JP-A-61-6643.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, a silver nitrate aqueous solution is added to a gelatin aqueous solution whose pBr is kept at 2 or less, or a silver nitrate aqueous solution and a halide aqueous solution are simultaneously added. To generate twin seed particles and then grow by the double jet method. The size of tabular silver halide grains can be controlled by the temperature at the time of grain formation, the addition rate of silver salt and halide aqueous solution, and the like.

The average silver iodide content and average silver chloride content of the silver halide emulsion according to the present invention (hereinafter referred to as parent grain emulsion) are the compositions of the aqueous halide solution to be added, that is, bromide, iodide and chloride. It can be controlled by changing the ratio of. Further, when producing the silver halide emulsion of the present invention, a silver halide solvent such as ammonia, thioether or thiourea can be used if necessary.

The emulsion may be subjected to a water washing method such as a noodle water washing method or a flocculation sedimentation method in order to remove soluble salts (desalting treatment step). As a preferable washing method, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or aggregating polymer agent exemplified G3, G8 described in JP-A-63-158644, etc. The method used is mentioned as a particularly preferable desalting method.

The silver halide emulsion according to the present invention is selenium sensitized. Selenium-sensitized means that the tabular silver halide grain according to the present invention has a selenium sensitizing nucleus at any site, and particularly preferred sites are the surface of the grain and / or the vicinity of the surface. Is mentioned.

In the present invention, 2 nm or more and 600 nm or less, preferably 5 nm or more and 200 nm from the particle surface closest to the surface vicinity
It means a depth of not more than nm, particularly preferably not less than 8 nm and not more than 70 nm.

As a method for sensitizing selenium at a target site near the surface of the grain of the present invention, for example, the grain growth process is temporarily stopped, a selenium sensitizer is added, and selenium is added to the surface of the shell layer. A method of continuing the growth step again after performing the sensitization treatment is preferable.

Further, the selenium sensitizer may be added in several times with the growth of the silver halide of the present invention, or may be continuously added for a certain period of time.

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

The selenium sensitization according to the present invention 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 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 unstable selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, 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. A combination of an unstable selenium compound and a non-unstable selenium compound is preferred.

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.

Examples of the silver halide solvent that can be used in the present invention include US Pat. Nos. 3,271,157, 3,531,289, and US Pat.
3,574,628, organic thioethers described in JP-A-54-1019, JP-A-54-158917, JP-A-53-82408, JP-A-53-82408,
55-77737 and 55-2982, thiourea derivatives, silver halide having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319 Solvents, imidazoles described in JP-A-54-100717, sulfites, thiocyanates and the like can be mentioned.

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 grains of the silver halide emulsion of the present invention may be subjected to reduction sensitization treatment. Reduction sensitization is
A method of adding a reducing compound, pAg =
It can be applied to the silver halide emulsion by a method of passing a silver ion excess state of 1 to 7 or a method of passing a high pH state of pH = 8 to 11 called high pH thermal synthesis. Further, these two or more methods can be used in combination.

The method of adding a reducing compound is preferable because the degree of reduction sensitization can be finely adjusted.

The reducing compound may be an inorganic or organic compound, such as thiourea dioxide, stannous salt, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds, ascorbic acid and the like. Examples thereof include derivatives and sulfites, and particularly preferable examples include thiourea dioxide, stannous chloride and dimethylamine borane. The addition amount of these reducing compounds varies depending on the reducing property of the compound and the type of silver halide and the emulsion production conditions such as dissolution conditions, but it is 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol per mol of silver halide. The range is appropriate. These reducing compounds are preferably dissolved in water or an organic solvent such as alcohols and added during the growth of silver halide grains.

The silver halide emulsion of the present invention is preferably chemically ripened by a selenium sensitizing method and a chemical sensitizing method other than the selenium sensitizing method after the desalting step.

The temperature of the chemical aging can be arbitrarily determined,
Preferably in the range of 20 ℃ ~ 80 ℃, preferably 30 ℃ ~ 70 ℃,
More preferably, it is 35 ° C to 65 ° C.

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

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, size of silver halide grains, and as a guide, it is 5 × 10 ^{-8 to} 5 per mol of silver in the silver halide emulsion according to the present invention.
× 10 ^-5 mol is preferable.

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 preferably 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol per mol of the silver halide emulsion of the present invention. X 10 ^-6 to 4 x
More preferably 10 ⁻⁴ mol.

It is preferable to add a silver halide fine grain emulsion to the silver halide emulsion of the present invention after grain formation.

Examples of the fine silver halide grains include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodochloride, silver iodobromide, and silver chloroiodobromide. Silver and silver iodide are preferred. The grain size of these fine silver halide grains is 0.12 μm.
The following is preferable and 0.09 μm or less is further preferable, and 0.06 μm
The following are particularly preferred.

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

When fine particles such as AgBr ₉₀ I ₁₀ containing silver bromide, silver chloride or a solid solution mainly composed of rock salt are used in the present invention, these fine particles have substantially no twin planes. A so-called normal crystal or a single twin crystal having one twin plane is preferable.

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

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

The silver halide fine grains may be added in any step from the chemical ripening step to immediately before coating, but the addition is preferably in the chemical ripening step. The term "chemical ripening step" as used herein means from the time after the grain formation of the emulsion according to the present invention and when the desalting operation is completed to the time when the chemical sensitizer is added and then the operation for stopping the chemical ripening is performed. Points between As a method of ending the chemical ripening step, a method of lowering the temperature, a method of lowering the pH, a method of using a chemical ripening stopper, etc. are known, but a chemical ripening stopper is used in consideration of the stability of the emulsion. The method is preferred. 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 plural compounds.

The silver halide fine grains may be added in several times with a time interval, or another chemically ripened emulsion may be added after the addition of the silver halide fine grains.

The temperature of the emulsion according to the present invention at the time of adding fine silver halide grains is preferably in the range of 30 to 80 ° C, and particularly preferably in the range of 40 to 65 ° C.

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

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

The silver halide grains of the present invention may contain a Group VIII metal of the periodic table.

The Group VIII metal of the Periodic Table can be contained in the silver halide grains by adding the metal compound as a metal compound at the time of forming the parent grain. You may add.

Further, a method is also preferred in which it is added to a water-soluble silver salt and / or a water-soluble halide solution in advance and the silver halide grains are precipitated by using these aqueous solutions.

Compounds of Group VIII metals of the Periodic Table are iron,
Iridium, platinum, palladium, nickel, rhodium,
Refers to metal compounds derived from osmium, ruthenium and cobalt. Of course, not only as these metal compounds but also as metal ions and metal atoms thereof, they may be contained in the silver halide grain according to the present invention.

The silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer according to the present invention have a dissolution time (melting time) of 5 to 150 minutes, preferably 7 to 9 depending on the hardening agent.
It is hardened for 0 minutes, particularly preferably for 10 to 60 minutes.

The dissolution time is determined by, for example, immersing a sample cut into 5 mm × 20 mm in a 1.5 wt% sodium hydroxide aqueous solution kept at 50 ° C. without stirring, and measuring the time until the hydrophilic colloid layer elutes. Can be found by

In order to obtain a desired dissolution time (melting time), a means for adjusting with a hardener can be used. For this purpose, any of the conventionally known hardeners can be used alone or in combination.

For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3- Dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-2-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-
Dichlor-6-hydroxy-3-triazine, etc.), mucohalogen acids (mucochromic acid, mucophenoxychromic acid, etc.) isoxazoles, dialdehyde starch, 2-chloro
-6-Hydroxytriazinated gelatin, carbamoylpyridinium compound and the like can be used.

With these hardeners, the swelling ratio in water is 200% or less, preferably 160% or less, particularly preferably 12%.
The film is preferably hardened so as to be 0% or less.

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

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 IVB Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 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, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer.

[0104]

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 iodobromide was prepared using the solution shown below.

[A ₁ ] Hydrogen peroxide treated ossein gelatin 40 g Potassium bromide 75.1 g Water was added to 4000 ml [B ₁ ] Silver nitrate 600 g Water was added to 803 ml [C ₁ ] Hydrogen peroxide treated ossein gelatin 16.1 g Potassium bromide 393.7 g Potassium iodide 35.1 g Water was added 803 ml [D ₁ ] Ammonia water (28%) 235 ml Using a device disclosed in Japanese Patent Laid-Open No. 62-160128, a stirring impeller for mixing was used. The number of supply nozzles to the lower part was set to be 6 for each of solution B ₁ and solution C ₁ .

Solution B ₁ and solution C ₁ were added at a flow rate of 62.8 ml / min by a controlled double jet method to solution A ₁ which was stirred at a temperature of 40 ° C. and a rotation speed of 430 rpm at a high speed. 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 changed 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 aging, and in order to remove excess salts, desalting was performed using an aqueous solution of Demol N (manufactured by Kao Atlas) and an aqueous solution of magnesium sulfate. After washing with water, seed emulsion Em-
Got 1.

Observation of Em-1 with an electron microscope revealed that the particles were spherical particles having an average particle size of 0.28 μm and a particle size variation coefficient of 21%.

(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.

(Preparation of Growth Emulsion) The obtained seed emulsion was taken in an amount of 0.027 mol per mol of silver halide in the growth emulsion,
As a defoaming agent, a copolymer of polypropylene oxide (PO) and polyethylene oxide (EO) (EO / PO = 0.33,
It was dissolved and dispersed in a gelatin aqueous solution containing a molecular weight of 1400) at 62 ° C. Subsequently, a 3.5N silver nitrate aqueous solution and a 3.4N potassium bromide aqueous solution were added by a control double jet method over 97 minutes so that the addition rate at the end of the addition was 2.3 times that at the start of the addition. In addition, temperature 62 ℃, pH = 5.8, p
It was kept at Ag = 8.9 from beginning to end. Further, desalting treatment was carried out in the same manner as in the seed emulsion. The obtained emulsion was a tabular silver halide emulsion having an average grain size of 1.30 μm, an average thickness of 0.32 μm and an average aspect ratio of 4.1. This emulsion was designated as EM-1.

(Preparation of silver iodide fine particles) 5000 ml of a 5.2% by weight gelatin solution containing 0.008 mol of potassium iodide, 5000 ml, 1.06
1500 ml each of an aqueous solution containing moles of silver nitrate and potassium iodide were added over a period of 35 minutes under constant flow. 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
It was a mixture of β-AgI and γ-AgI at 0.05 μm.

(Chemical sensitization of emulsion)
The above-mentioned sensitizing dye according to the present invention while maintaining stirring at 0 ° C.
As shown in Table 1, I-6, I-7, I-16, II-1, II-3, and II-13 were added as methanol solutions so that 140 mg per 1 mol of silver of EM-1 was added. , 10 minutes after that, as a chemical sensitizer, 60 mol of ammonium thiocyanate per mol of silver
mg, chloroauric acid 1.45 mg, and sodium thiosulfate 13.8 mg were added, respectively. Further, after 30 minutes, 1.37 × 10 ⁻³ mol of the silver iodide fine grain emulsion was added, and after a certain period of time, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, and 1-Phenyl-5-mercaptotetrazole was added to stabilize and optimally chemically sensitize each. The obtained emulsions were designated as EM-2 to EM-7.

Furthermore, selenium was prepared by the same procedure as EM-2 to EM-7 except that 8 × 10 ⁻⁷ mol of N, N-dimethylselenourea was added together with chloroauric acid as a chemical sensitizer. Sensitive emulsions EM-8 to EM-13 were obtained.

(Preparation of Internal Selenium Sensitized Emulsion) Emulsion EM-
The addition of the silver nitrate aqueous solution and the halide solution of 1 was temporarily stopped in 75 minutes, and 7.8 × 10 ^-6 mol of ammonium thiocyanate and 1.1 × of N, N-dimethylselenourea were added per 1 mol of silver in the finally formed emulsion. The ^mixture was added so as to have a concentration of 10 ^-6 mol, and after 4 minutes, the remaining silver nitrate aqueous solution and the halide solution were added again to form a shell portion having a thickness of 25 nm in the main plane direction.
The shape of the obtained emulsion was EM-
It was almost equal to 1. The resulting emulsion was designated as EM-14.

The sensitizing dye according to the present invention similar to EM-2 to EM-7 was added to EM-14, and further the same chemical sensitizer was added to sensitize the surface of the grain with gold and sulfur. . The resulting emulsions were designated as EM-15 to EM-20.

The resulting chemically aged emulsion EM-2.
EM-7, EM-8 to EM-13, and EM-15 to EM-20 were added to the additives described below to prepare emulsion layer coating solutions. At the same time, a protective layer coating solution described below was also prepared. The coating amount of silver weight of 2.5 g / m ² per side, gelatin with the amount of 1.85 g / m ² and so as to 80m per minute using two slide hopper type coaters
Both sides were simultaneously coated on the support at a speed of 2 minutes and dried for 2 minutes and 20 seconds to obtain coated samples No. 1 to No. 18, respectively. As the support, the copolymer aqueous dispersion obtained by diluting the copolymer consisting of three kinds of monomers of glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%, and butyl methacrylate 40 wt% to 10 wt% is undercoated. Liquid 175
A polyethylene terephthalate film base colored blue with a density of 0.15 for a μm X-ray film was used.

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 82 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 25 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1, Ammonium 3-dihydroxybenzene-4-sulfonate 2.0 g 2-Mercaptobenzimidazole-5-sodium sulfonate 1.5 mg

[0121]

[Chemical 15]

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-decylsulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (area average particle size) Matte agent of 1.2 μm) 0.5 g Ludox AM (DuPont) (colloidal silica) 30 g (CH ₂ = CHSO ₂ CH ₂ ) ₂ O (hardener) 200 mg Glyoxal 40% aqueous solution (hardener) 2.0 ml

[0124]

[Chemical 16]

Sensitometry (Evaluation of Photographic Performance) In sensitometry, a sample was sandwiched between two intensifying screens (NR-160 Konica Corporation), and a tube voltage of 80 kv was applied through an aluminum wedge.
P, tube current 50 mA, X-ray irradiation for 0.05 seconds. Next, using a roller-conveying type automatic developing machine, development and fixing were performed with the developing solution and fixing solution shown below. Shown below.

The processing time was dry to dry for 90 seconds to obtain the sensitivity. The temperature during processing is 32 ° C for development and 33 for fixing.
C., washed with water at 20.degree. C., and dried at 50.degree. Sensitivity is fog +
It was expressed by the reciprocal of the exposure amount giving a density of 0.5, and was shown by the relative sensitivity with the sensitivity of Sample No. 1 being 100.

Evaluation of roller mark property Pressure mark (roller mark) by a roller of an automatic developing machine
Was evaluated as follows. That is, in an unexposed state, processing was carried out by an automatic processor in the same manner as in sensitometry. The roller mark generated at that time can be visually checked to
It was classified into stages and evaluated.

5: No occurrence of roller mark 4: Very slight occurrence 3: Some occurrence (within practical permit) 2: Many occurrences (outside practical permission) 1: Very large occurrence 5mm × 20mm The cut samples No. 1 to 18 were immersed in a 1.5 wt% sodium hydroxide aqueous solution held at 50 ° C., and the melting time was measured to be within 15 to 20 minutes. The drying property was sufficient.

The above results are shown in Table 1 below.

[0130]

[Table 1]

As is clear from Table 1, according to the present invention, it is possible to obtain a light-sensitive material having high sensitivity, low fog and excellent photographic performance with the highest density. Moreover, roller mark resistance was excellent, and almost no roller mark was observed. In terms of photographic performance and roller mark resistance, the selenium sensitized nuclei were better near the grain surface than at 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 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 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 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 with glacial acetic acid.
The H was adjusted to 10.40. This is used as a developing solution.

20 ml / l of the aforesaid starter was added to 1 liter of this developing solution to adjust the pH to 10.26 to prepare a working solution.

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 was used as a fixing solution.

Example 2 (Preparation of hexagonal tabular twin seed emulsion) A hexagonal tabular seed emulsion was prepared by the following method.

[0139] A ₂ ossein gelatin 24.2g Distilled water 9657Ml 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) (10% methanol solution) 6.78ml KBr 10.8g 10% nitric acid 114ml B ₂ 2.5N AgNO ₃ aqueous solution 2825ml C ₂ KBr 824g KI 23.5g Distilled water to 2825ml D ₂ 1.75N KBr aqueous solution Silver potential control below At a temperature of 35 ° C., 464.3 ml of each of solution B ₂ and solution C ₂ was mixed with solution A ₂ using a mixing stirrer shown in Japanese Patent Publication Nos. 58-58288 and 58-58289 for 2 minutes by the simultaneous mixing method. Need to add,
Nucleation was performed.

After stopping the addition of solution B ₂ and solution C ₂ ,
It takes 60 minutes to raise the temperature of solution A ₂ to 60 ° C,
After adjusting the pH to 5.0 with 3% KOH, the solution B ₂ and the solution C were again adjusted.
₂ was added by the double jet method at a flow rate of 55.4 ml / min for 42 minutes. This temperature rise from 35 ° C. to 60 ° C. and solution B ₂ , C ₂
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the re-simultaneous mixing was controlled to +8 mv and +16 mv, respectively, using solution D ₃ .

After the completion of the addition, the pH was adjusted to 6 with 3% KOH, and the mixture was immediately desalted and washed with water. This seed emulsion has a maximum adjacent side ratio of 1.0 to 90% of the total projected area of silver halide grains.
It was found by an electron microscope that the hexagonal tabular grains of 2.0 had an average thickness of 0.06 μm and an average diameter (converted to a circle diameter) of 0.57 μm.

(Preparation of Growth Emulsion) The obtained hexagonal tabular seed emulsion was taken in an amount corresponding to 0.023 mol per mol of silver of the growth emulsion,
After being dissolved and dispersed in a gelatin aqueous solution containing a copolymer of polypropylene oxide (PO) and polyethylene oxide (EO) (EO / PO = 0.33, molecular weight about 1400) at a liquid temperature of 60 ° C, the final The aqueous silver nitrate solution and a halide solution of potassium bromide and potassium iodide, which were prepared so that the average silver iodide content of the grown grains formed in 1, was 1.05 mol%, pH = 5.8, pAg = 9.0, 60 ° C. While being kept at 1, the mixture was added for 107 minutes by the controlled double jet method. A tabular silver iodobromide emulsion EM-21 having an average grain size of 1.51 μm, an average thickness of 0.25 μm and an average aspect ratio of 6.04 was obtained.

The obtained emulsion EM-21 was chemically sensitized while being kept at 50 ° C. 52 mg of ammonium thiocyanate, 1.4 mg of chloroauric acid, and 15.0 mg of sodium thiosulfate pentahydrate were added per 1 mol of silver, and 32 minutes after that, the silver iodide fine grain emulsion of Example 1 was equivalent to 1.80 × 10 ⁻³ mol. Was added. After that, after a certain period of time, 2.34 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to stabilize and optimally perform chemical sensitization.

10 minutes before the start of the chemical sensitization, the sensitizing dyes I-6, I-7, I-16, II-3, II-13, II-23, II- of the present invention were used.
26 of each was added in an amount of 160 mg per mol of silver halide,
Seven emulsions were prepared.

The obtained chemically sensitized emulsions were EM-22 to E.
It was set to M-28.

(Preparation of Internal Selenium Sensitized Emulsion) Emulsion EM-
The addition of the 21 aqueous solution of silver nitrate and the halide solution was temporarily stopped for 95 minutes, and 7 × 10 ⁻⁶ mol of ammonium thiocyanate and 2 × 10 ⁶ of N, N-dimethylselenourea were added per mol of the finally formed emulsion silver. ^-6, and after 4 minutes, the remaining silver nitrate aqueous solution and halide solution were added to form a shell portion having a thickness of 10 nm in the principal plane direction. Immediately after the shell formation, desalting and washing with water gave Emulsion EM-29. The shape of the obtained emulsion grains was almost the same as that of EM-28.

The sensitizing dye according to the present invention similar to EM-22 to EM-28 was added to EM-29, and further the same chemical sensitizer was added to sensitize the surface thereof with gold and sulfur. . The resulting emulsions were designated as EM-30 to EM-36.

Obtained EM-22 to EM-28, EM-30 to
EM-36 was applied in the same manner as in Example 1 to give Sample No. 19
Got ~ 32.

These samples were evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0150]

[Table 2]

As is clear from Table 2, according to the present invention, the tabular silver iodobromide emulsion grown from the hexagonal tabular twin seed emulsion has high sensitivity, low fog, high maximum density and high roller mark resistance. Is also excellent.

[0152]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a regular type silver halide photographic light-sensitive material for regular X-ray suitable for non-hard film rapid development processing.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material in which at least one tabular silver halide emulsion layer is coated on at least one side of a support, the emulsion grains are selenium-sensitized, and A silver halide photographic light-sensitive material, which is spectrally sensitized with at least one of the dyes represented by formula (I) and / or (II). [Chemical 1] [Wherein Z ¹ , Z ² and Z ³ represent a non-metal atom group forming oxazole, benzoxazole, naphthoxazole, thiazole, benzothiazole or naphthothiazole, and R ¹ , R ² and R ³ are alkyl groups. Or a substituted alkyl group, R ⁴ represents an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, X represents an acid anion, and n represents 0 or 1. ]