JP2003295374A - Silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high sensitivity and high Dmax, ensuring little stain after processing and exhibiting good performance even in rapid processing. <P>SOLUTION: In the silver halide photographic sensitive material, tabular silver halide grains having an average aspect ratio of ≥12, a compound of formula (I) and a compound of formula (II) are contained in a photosensitive silver halide emulsion and the amount of a sensitizing dye of the formula (I) is 0.2×10<SP>-3</SP>-1.5×10<SP>-3</SP>mol per mol of silver. <P>COPYRIGHT: (C)2004,JPO

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 a silver halide photographic light-sensitive emulsion, and particularly to a medical X-ray halogenation for high-speed processing with high sensitivity and less residual color. The present invention relates to a silver photographic light-sensitive material and a silver halide photographic light-sensitive emulsion.

[0002]

2. Description of the Related Art Tabular silver halide grains (hereinafter referred to as "tabular grains") have the following photographic characteristics: 1) ratio of surface area to volume (hereinafter referred to as specific surface area)
Is large and a large amount of sensitizing dye can be adsorbed on the surface, and thus the color sensitizing sensitivity is relatively high with respect to the intrinsic sensitivity. 2) When an emulsion containing tabular grains is coated and dried, the grains are arranged parallel to the surface of the support, so that the coating layer can be made thin and the photographic light-sensitive material has good sharpness. 3) In a radiographic system, addition of a sensitizing dye to tabular grains can significantly reduce silver halide crossover light and prevent deterioration of image quality. 4) An image with high resolution can be obtained with little light scattering. 5) The covering power (optical density of developed silver per unit amount of silver) is increased, the required amount of silver can be reduced, which is advantageous for rapid processing and reduction of coating chemical amount.

Since the tabular grains having a larger aspect ratio have a larger specific surface area, the advantages of the tabular grains described above can be greatly utilized. That is, by adsorbing more sensitizing dye on a larger surface area, it is possible to obtain high sensitivity by increasing the amount of light absorption per grain. Therefore, many studies have been made on methods for preparing thinner tabular grains. Japanese Patent Publication No. 5-12696 discloses a method of preparing thin tabular grains by using, as a dispersion medium, gelatin in which a methionine group in gelatin is oxidized to be inactivated. Japanese Unexamined Patent Publication (Kokai) No. 8-82883 discloses a method for preparing thin tabular grains by using gelatin in which amino groups and methionine groups are inactivated as a dispersion medium. Further, JP-A-10-148897 discloses a method of chemically modifying amino groups in gelatin to prepare thin tabular grains using gelatin having at least two carboxyl groups introduced as a dispersion medium. .

During processing of color photographic materials, silver halide is removed from the photographic material. In black-and-white photographic materials, unexposed silver halide is removed. In either case, it is desirable that the sensitizing dye be removed as well. Sensitizing dyes that are not removed tend to cause residual color and adversely affect the image recorded on the photographic material. The problem of residual color is
It is exacerbated with increasing use of tabular grain emulsions. The tabular grain emulsion has a large surface area per 1 mol of silver and a large amount of sensitizing dye is added, so that the residual color is relatively large.
Further, when used for rapid processing, the problem of residual color is particularly likely to become apparent.

By adding a sensitizing dye before chemically sensitizing emulsion grains, chemical sensitization can be controlled and sensitivity / fogging ratio can be improved. However, when the aspect ratio is increased, there is a problem that the surface area of the particles is increased, the required amount of the sensitizing dye is increased, and the residual color is deteriorated.

[0006]

Therefore, the problems to be solved by the present invention are high sensitivity, high Dmax, little residual color after processing, and silver halide showing good performance even in rapid processing. To provide a photographic light-sensitive material.

[0007]

The objects of the present invention have been achieved by the following means. That is, (1) a photosensitive silver halide emulsion containing tabular silver halide grains having an average aspect ratio of 12 or more, a compound of the following general formula (I) and a compound of the following general formula (II), A silver halide photographic light-sensitive material characterized in that the addition amount of the sensitizing dye of the general formula (I) is 0.2 × 10 ^-3 mol or more and 1.5 × 10 ^-3 mol or less per 1 mol of silver.

[0008]

[Chemical 3]

[In the general formula (I), Z ₁₁ and Z ₁₂ represent a group of non-metal atoms necessary for forming an oxazole nucleus which may be condensed with an aromatic ring. R ₁₁ and R ₁₂ each represent an alkyl group, and at least one of them represents a sulfoalkyl group. Q represents a hydrogen atom or an alkyl group, and Y represents an ion necessary for balancing charges. n ₁ is 0 or 1, and is 0 when forming an inner salt. ]

[0010]

[Chemical 4]

[In general formula (II), Z ₂₁ and Z ₂₂ are benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, naphthoxazole nucleus, naphthothiazole nucleus, naphthoselenazole nucleus, thiazole nucleus, thiazoline nucleus, It represents a group of non-metal atoms necessary for completing an oxazole nucleus, a selenazole nucleus, a selenazoline nucleus, a pyridine nucleus, a benzimidazole nucleus or a quinoline nucleus. R ₂₁ and R ₂₂ each represent an alkyl group or an aralkyl group. X
₂ is a charge balancing counterion and n ₂ is 0 or 1. (2) A silver halide photographic light-sensitive material for medical X-ray photography, comprising at least one non-light-sensitive layer and one light-sensitive layer containing light-sensitive silver halide emulsion grains on both sides of a transparent support. A tabular silver halide grain having an average aspect ratio of 12 or more, a compound of the general formula (I) and a general formula (I)
X for medical use, which contains the compound of I) and the addition amount of the sensitizing dye of the general formula (I) is 0.2 × 10 ⁻³ mol or more and 1.5 × 10 ⁻³ mol or less per mol of silver. Silver halide photographic light-sensitive material for line photography. (3) The silver halide photographic light-sensitive material as described in (1) or (2) above, wherein the amount of coated silver on one side is 0.3 g / m ² or more and 1.5 g / m ² or less.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The silver halide photographic light-sensitive material of the present invention is spectrally sensitized with a sensitizing dye of the following general formula (I).

[0013]

[Chemical 5]

The general formula (I) will be described in detail below. In the formula, R ₁₁ and R _{12 each} represent a substituted or unsubstituted alkyl group, which has 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, and particularly preferably 1 to 4 carbon atoms, an unsubstituted alkyl group (for example, methyl group). , Ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.), substituted alkyl groups such as aralkyl groups (eg benzyl, 2-phenylethyl etc.), hydroxyalkyl groups (eg 2-hydroxyethyl, 3-
Hydroxypropyl etc.), carboxyalkyl group (eg 2-carboxyethyl, 3-carboxypropyl,
Carboxyethyl, 3-carboxypropyl group, 4-carboxybutyl group, carboxymethyl group, etc., alkoxyalkyl group (for example, 2-methoxyethyl group, 2-
(2-methoxyethoxy) ethyl group and the like), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2
-(3-sulfopropoxy) ethyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group, etc., sulfatoalkyl group (for example, 3
-Sulfatopropyl group, 4-sulfatobutyl group, etc.), heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) ethyl group, tetrahydrofurfuryl group, 2-morpholinoethyl group, etc. ), 2-acetoxyethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group, allyl group, etc.), aryl group (eg, phenyl group, 2-naphthyl group, etc.), substituted aryl group (eg, 4-carboxyphenyl) Group, 4-sulfophenyl group, 3-chlorophenyl group, 3-methylphenyl group, etc.), heterocyclic group (eg, 2-pyridyl group, 2
-Thiazolyl group) and the like, preferably having 1 carbon atom
To 7, particularly preferably a sulfoalkyl group having 1 to 4 carbon atoms, and it is most preferable that at least one of R ₁₁ and R ₁₂ is substituted by this substituent. Y represents an ion necessary for balancing the charges, n ₁ is 0 or 1, and 0 when forming an intramolecular salt. Z ₁₁
And Z ₁₂ may each be the same or different,
Represents a group of non-metal atoms necessary to form an oxazole nucleus which may be fused with an aromatic ring. Examples of the oxazole nucleus formed by Z ₁₁ and Z ₁₂ include the following.

Oxazole, 4-methyloxazole,
4-nitroxazole, 5-methyloxazole, 4
-Phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, etc.), benzoxazole nucleus (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5
-Phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6 -Nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,
6-dimethylbenzoxazole, 5-ethoxybenzoxazole), naphthoxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2-d])
Oxazole, naphtho [2,3-d] oxazole, 5
-Nitronaphtho [2,1-d] oxazole) and the like, and the present invention is particularly effective when it has a substituted or unsubstituted benzoxazole nucleus.

The optionally substituted alkyl group represented by Q has, for example, 1 to 18 carbon atoms, preferably 1 to
7, particularly preferably 1 to 4 alkyl groups (eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group, dodecyl group, octadecyl group), substituted alkyl groups (eg, Aralkyl groups (eg, benzyl group, 2-phenylethyl group),
Hydroxyalkyl group (for example, 2-hydroxyethyl group, 3-hydroxypropyl group), carboxyalkyl group (for example, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, carboxymethyl group), alkoxyalkyl A group (for example, a 2-methoxyethyl group, a 2- (2-methoxyethoxy) ethyl group),
Sulfoalkyl group (for example, 2-sulfoethyl group, 3-
Sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2- [3-sulfopropoxy] ethyl group, 2-
Hydroxy-3-sulfopropyl group, 3-sulfopropoxyethoxyethyl group, sulfatoalkyl group (eg, 3-sulfatopropyl group, 4-sulfatobutyl group), heterocyclic-substituted alkyl group (eg, 2- (pyrrolidine) 2-on-1-yl) ethyl group, tetrahydrofurfuryl group, 2-morpholinoethyl group), 2-acetoxyethyl group, carbomethoxymethyl group, 2-methanesulfonylaminoethyl group, allyl group), and May be a hydrogen atom. The substituent represented by Q preferably has 1 carbon atom.
To 5 alkyl groups, particularly preferably 1 to 3 carbon atoms
The effect is great when it is an alkyl group (methyl group, ethyl group, propyl group).

Specific examples of the dye represented by formula (I) are shown below, but the invention is not limited thereto. (Note that the charge-balancing counterion is omitted. Any possible counterion may exist.)

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

[0022]

[Chemical 10]

The compound of formula (I) of the present invention may be added at any time before the chemical sensitization step. Specifically, a method of adding at the time of silver halide grain formation, a method of adding at a silver halide emulsion desalting step, a method of adding immediately before a silver halide emulsion chemical ripening (chemical sensitization) step, a silver halide emulsion chemistry There is a method of adding at the time of aging, but preferably, the compound of the general formula (I) is added before the gold sensitizer or the chalcogen sensitizer described later, that is, before the chemical sensitization with these compounds. It is also possible to add the compound of the general formula (I) at a temperature of 25 ° C. or higher and lower than 55 ° C., and then raise the temperature to above the addition temperature to carry out chemical ripening so that each halogenated grain can be uniformly attached.

In order to incorporate the spectral sensitizing dye represented by formula (I) used in the present invention into the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion or water. , Methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3, -tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-
1-butanol, 1-methoxy-2-propanol,
It may be added to the emulsion by dissolving it in a solvent such as N, N-dimethylformamide alone or in a mixed solvent. Further, as described in U.S. Pat.No. 3,469,987, a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and the dispersion is added to an emulsion. ,
As described in JP-B-46-24185, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding the dispersion to an emulsion, JP-B-44-23389 and JP-B-44389 44
-27555, Japanese Examined Patent Publication No. 57-22091, etc., the dye is dissolved in an acid, and this solution is added to the emulsion, or an acid or base is coexistent to form an aqueous solution and added to the emulsion. Method, U.S. Patent No. 3,822,135, U.S. Patent No. 4,006,0
No. 25, etc., a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant into the emulsion, JP-A-53-102733, JP-A-58-105141. As described, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion, JP-A-51-746.
As described in No. 24, a method of dissolving a dye using a compound that causes red shift and adding this solution into an emulsion can also be used. Ultrasonic waves can also be used for dissolution.

In the present invention, the compound of the general formula (I)
The addition amount of 0.2 x 10 per mol of silver^-3More than mol 1.
5 x 10^-3It is less than or equal to mol. More preferably 0.2 x
10 ^-3More than mol 1.2 × 10^-3Less than or equal to moles, 0.3
× 10^-3More than mol 1.2 × 10^-3Especially preferred below molar
Yes. Two or more kinds of dyes of the general formula (I) are used even if only one kind is used.
You may use together.

The silver halide emulsion grains used in the silver halide photographic light-sensitive material of the present invention are chemically sensitized in the presence of the compound of the following general formula (II).

[0027]

[Chemical 11]

In the general formula (II), Z_{twenty one}And Z_{twenty two}Are each
Benzoxazole nucleus, benzothiazole nucleus, benzoce
Renazole nucleus, naphthoxazole nucleus, naphthothiazo
Le nucleus, naphthoselenazole nucleus, thiazole nucleus, thiazoly
Nuclei, oxazole nuclei, selenazole nuclei, selenazolines
Nucleus, pyridine nucleus, benzimidazole nucleus or quinoline
Represents a group of non-metal atoms required to complete a nucleus. R_{twenty one}and
R_{twenty two}Each represents an alkyl group or an aralkyl group. X₂
Is a charge balance counterion, n₂Represents 0 or 1
You Here, when the general formula (II) is a radical body,
Is preferably Z_{twenty one}, Z_{twenty two}A group of atoms or R
_{twenty one}, R_{twenty two}One hydrogen atom removed from the group shown in
And especially R_{twenty one}, R_{twenty two}One hydrogen atom was released from
Is preferred. Further, in the general formula (II), a substituent
With oxidation as (eg R _{twenty one}, R_{twenty two}Has an acid group
Alkyl group or aralkyl group)
As such, it can be a compound represented by the general formula (II).

In the general formula (II), Z ₂₁ and Z ₂₂
The heterocycle formed by is preferably a benzoxazole nucleus, a benzothiazole nucleus, a naphthoxazole nucleus,
It is a naphthothiazole nucleus, a thiazole nucleus, or an oxazole nucleus, more preferably a benzoxazole nucleus, a benzothiazole nucleus, or a naphthoxazole nucleus, and most preferably a benzoxazole nucleus or a naphthoxazole nucleus. In the general formula (II), the heterocycle formed by Z ₂₁ or Z ₂₂ may be substituted with at least one substituent, and the substituent may be a halogen atom (for example, fluorine, chlorine, bromine, iodine),
Nitro group, alkyl group (preferably having 1 to 4 carbon atoms, such as methyl group, ethyl group, trifluoromethyl group, benzyl group, phenethyl group), aryl group (eg phenyl group), alkoxy group (preferably having carbon number) 1-4
Examples thereof include methoxy group, ethoxy group, propoxy group, butoxy group), carboxyl group, alkoxycarbonyl group (preferably having 2 to 5 carbon atoms, for example, ethoxycarbonyl group), hydroxy group, cyano group and the like. it can.

With respect to Z ₂₁ and Z ₂₂ in the general formula (II),
Examples of the benzothiazole nucleus include benzothiazole, 5-chlorobenzothiazole, 5-nitrobenzothiazole, 5-methylbenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole and 5-methoxybenzo. Thiazole, 6-methoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-fluorobenzothiazole, 5-chloro-6
-Methylbenzothiazole, 5-trifluoromethylbenzothiazole, and the like, and the naphthothiazole nucleus is, for example, naphtho [1,2-d] thiazole, naphtho [2,1-d] thiazole, naphtho [2,3-d ] Thiazole, 5-methoxynaphtho [1,2-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole, and the like, and examples of the benzoselenazole nucleus include benzoselenazole and 5-chlorobenzoselenazole. , 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 5-chloro-6-methylbenzoselenazole, and the like. Examples of the naphthoselenazole nucleus include naphtho [1,2-d] selenazole and naphtho [2,2]. Examples of the thiazole nucleus include 1-d] selenazole and the like. Tetrazole nucleus, 4-phenyl-benzothiazole nucleus, 4,5-dimethyl benzothiazole nucleus, etc.,
Examples of the thiazoline nucleus include a thiazoline nucleus and a 4-methylthiazoline nucleus.

Regarding Z ₂₁ and Z ₂₂ in the general formula (II), examples of the benzoxazole nucleus include benzoxazole nucleus, 5-chlorobenzoxazole nucleus, 5-
Methylbenzoxazole nucleus, 5-bromobenzoxazole nucleus, 5-fluorobenzoxazole nucleus, 5-phenylbenzoxazole nucleus, 5-methoxybenzoxazole nucleus, 5-ethoxybenzoxazole nucleus, 5-
Trifluoromethylbenzoxazole nucleus, 5-hydroxybenzoxazole nucleus, 5-carboxybenzoxazole nucleus, 6-methylbenzoxazole nucleus, 6-chlorobenzoxazole nucleus, 6-methoxybenzoxazole nucleus, 6-hydroxybenzoxazole nucleus, 5 ，
Examples of the naphthoxoxazole nucleus such as 6-dimethylbenzoxazole nucleus include naphtho [2,1-d] oxazole nucleus, naphtho [1,2-d] oxazole nucleus, naphtho [2,3-d] oxazole nucleus, 5 -Methoxynaphtho [1,2-d] oxazole nucleus, and the like. Further with respect to Z ₂₁ and Z ₂₂ , examples of the oxazole nucleus include an oxazole nucleus, 4-methyloxazole nucleus, 4-phenyloxazole nucleus, 4-methoxyoxazole nucleus, 4,5-dimethyloxazole nucleus, 5-
Examples of pyridine nuclei include phenyloxazole nuclei and 4-methoxyoxazole nuclei, and 2-pyridine nuclei, 4-pyridine nuclei, 5-methyl-2-pyridine nuclei, 3
-Methyl-4-pyridine nucleus and the like, and as the quinoline nucleus, for example, 2-quinoline nucleus, 4-quinoline nucleus, 3-methyl-2-quinoline nucleus, 5-ethyl-2-quinoline nucleus,
8-fluoro-2-quinoline nucleus, 6-methoxy-2-quinoline nucleus, 8-chloro-4-quinoline nucleus, 8-methyl-
4-quinoline nucleus, etc. can be mentioned.

In the general formula (II), R ₂₁ and R ₂₂
The alkyl group represented by includes unsubstituted and substituted alkyl groups, and the unsubstituted alkyl group has 18 carbon atoms.
The following, particularly preferably 8 or less, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-hexyl group,
Examples include n-octadecyl group. Further, the substituted alkyl group preferably has 6 or less carbon atoms in the alkyl portion, particularly preferably 4 or less carbon atoms. For example, an alkyl group substituted with a sulfo group (a sulfo group is They may be bonded via an alkoxy group, an aryl group, etc. For example, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, 2- (3-sulfopropoxy) ethyl group, 2 -[2
-(3-sulfopropoxy) ethoxy] ethyl group, 2-
Hydroxy-3-sulfopropyl group, p-sulfophenethyl group, p-sulfophenylpropyl group, etc.), alkyl group substituted with a carboxy group (carboxy group may be bonded through an alkoxy group, an aryl group, etc.) Good.
For example, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, etc.), hydroxyalkyl group (eg, 2-hydroxyethyl group, 3-hydroxypropyl group, etc.) Acyloxyalkyl Group (for example, 2-acetoxyethyl group, 3-acetoxypropyl group, etc.), alkoxyalkyl group (for example, 2-methoxyethyl group, 3-methoxypropyl group, etc.), alkoxycarbonylalkyl group (for example, 2-methoxycarbonyl group) Ethyl group, 3-methoxycarbonylpropyl group, 4-ethoxycarbonylbutyl group, etc.), vinyl group-substituted alkyl group (eg, allyl group, etc.), cyanoalkyl group (eg, 2-cyanoethyl group, etc.), carbamoylalkyl group (eg, 2-carbamoylethyl group ), Aryloxyalkyl group (e.g., 2-phenoxyethyl group, and 3-phenoxypropyl group), or an aralkyl group (e.g., 2-phenethyl group and a 3-phenylpropyl group).

It is preferable that at least one of the substituents represented by R ₂₁ and R ₂₂ is an alkyl group having a sulfo group or a carboxyl group. The charge balance counter ion X ₂ is any anion capable of canceling out the positive charge generated by the quaternary ammonium salt in the heterocycle, such as bromide ion, chloride ion, iodine ion, p
-Toluenesulfonate ion, ethylsulfonate ion, perchlorate ion, trifluoromethanesulfonate ion, thiocyanate ion and the like. In this case n ₂ is 1
Is. If the heterocyclic quaternary ammonium salt further comprises an anionic substituent such as a sulfoalkyl substituent, the salt can be in the form of betaine, in which case no counterion is required and n ₄ is 0. is there. When the heterocyclic quaternary ammonium salt has two anion substituents, for example two sulfoalkyl groups, X ₄ is an anionic counterion, such as an alkali metal ion (sodium ion, potassium ion, etc.). ) And ammonium salt (triethylammonium).

Specific examples of the compound represented by the general formula (II) are shown below. However, the present invention is not limited to the following compounds. (Note that the charge-balancing counterion is omitted. Any possible counterion may exist.)

[0035]

[Chemical 12]

[0036]

[Chemical 13]

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

[0042]

[Chemical 19]

[0043]

[Chemical 20]

In order to incorporate the spectral sensitizing dye represented by the general formula (II) used in the present invention into the silver halide emulsion of the present invention, they may be dispersed directly in the emulsion or water. , Methanol, ethanol, propanol, acetone, methyl cellosolve, 2,2,3,3, -tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-
1-butanol, 1-methoxy-2-propanol,
It may be added to the emulsion by dissolving it in a solvent such as N, N-dimethylformamide alone or in a mixed solvent. Further, as described in U.S. Pat.No. 3,469,987, the dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and the dispersion is added to an emulsion. As described in JP-B-46-24185 and the like, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding the dispersion to an emulsion, JP-B-44-23389, and JP-B-44-23389. As described in JP-B-44-27555, JP-B-57-22091, etc., a dye is dissolved in an acid and the solution is added to the emulsion, or an acid or a base is allowed to coexist with it to prepare an aqueous solution, and the emulsion is added to the emulsion. Method of addition, U.S. Pat.No. 3,822,135, U.S. Pat.No. 4,006,0
No. 25, etc., a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant into the emulsion, JP-A-53-102733, JP-A-58-105141. As described, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion, JP-A-51-746.
As described in No. 24, a method of dissolving a dye using a compound that causes red shift and adding this solution into an emulsion can also be used. Ultrasonic waves can also be used for dissolution.

The dye represented by the general formula (II) may be added before the chemical sensitization in any of the grain forming step, the water washing step and the dispersing step.
The chalcogen sensitizer is preferably added before the addition, and most preferably, the gold sensitizer and the chalcogen sensitizer are added before the addition and after the chemical sensitization is completed and immediately before coating.

The addition amount of the compound of the general formula (II) of the present invention is 0.1 × 10 ⁻³ mol or more per 10 mol of silver.
× is preferably less than 10 ^-3 mol, more preferably less than 0.2 × 10 ^-3 mol to 3.0 × 10 ^-3 mol, 0.2 × 1
It is particularly preferably from 0 ⁻³ mol to 2.5 × 10 ⁻³ mol.

In the silver halide photographic light-sensitive material of the present invention, a spectral sensitizing dye can be used in combination with the above-mentioned general formulas (I) and (II). Examples of spectral sensitizing dyes that can be used in combination include cyanine dyes, merocyanine dyes, complex cyanine dyes,
Examples thereof include composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful spectral sensitizing dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. As the basic heterocyclic nucleus, any of the nuclei normally used for cyanine dyes can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a selenazoline nucleus, a pyrrole nucleus,
Oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, tellurazole nucleus, etc .; nucleus in which alicyclic hydrocarbon ring is condensed to these nuclei;
And a nucleus in which an aromatic hydrocarbon ring is condensed to these nuclei,
That is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzimidazole nucleus, naphthimidazole nucleus,
A benzothiazole nucleus, a natophthiazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, a quinoline nucleus, a benzoterazole nucleus or the like can be applied. These heterocyclic nuclei may be substituted on carbon atoms.

For the merocyanine dye or the composite merocyanine dye, as the nucleus having a ketomethylene structure, any nucleus generally used for merocyanine dyes can be applied. Particularly useful nuclei include pyrazolin-5-one nuclei, thiohydantoin nuclei, and 2-thiooxazolidine-2,4-
Applying 5-membered and 6-membered heterocyclic nuclei such as dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus and 2-thioselenazolidine-2,4-dione nucleus You can

A combination of sensitizing dyes is often used especially for the purpose of supersensitization. A typical example is US Pat. No. 2,
688,545, 2,977,229, 3,3
97,060, 3,522,052, 3,52
No. 7,641, No. 3,617,293, No. 3,62
8,964, 3,666,480, 3,67
2,898, 3,679,428, 3,70
No. 3,377, No. 3,769,301, No. 3,61
4,609, 3,837,862, 4,02
6,707, British Patent Nos. 1,344,281 and 1,507,803, Japanese Patent Publication No. 43-493.
6, No. 53-12375, JP-A No. 52-11061.
No. 8 and No. 52-109925.

Furthermore, these sensitizing dyes are dyes that do not exhibit a spectral sensitizing effect by themselves, or substances that do not substantially absorb visible light and are combined with a sensitizing dye to significantly enhance the spectral sensitization. It may be used in combination with any compound known to be called a so-called supersensitizer which exhibits an increase. Typical examples of the supersensitizer include bispyridinium salt compounds described in JP-A-59-142541, stilbene derivatives described in JP-B-59-18691, JP-B-49-46932 and the like. Water-soluble bromides such as potassium bromide, potassium iodide, etc., water-soluble iodides, US Pat. No. 3,743,51
Examples thereof include condensates of aromatic compounds and formaldehyde described in No. 0 specification, cadmium salts, azaindene compounds, and the like. The spectral sensitizing dye is added to the emulsion after chemical ripening or before chemical ripening. Most preferably, the spectral sensitizing dye is added to the silver halide grains of the present invention during or before chemical ripening (for example, during grain formation or physical ripening).

The silver halide emulsion of the present invention has any silver halide composition such as silver chloride, silver chlorobromide, silver chloroiodide, silver chloroiodobromide, silver bromide and silver iodobromide. May be Silver iodobromide is preferable in that high sensitivity can be obtained, and silver chloride and silver chlorobromide are preferably used in terms of good fixability. However, the silver iodide content is 1 mol% or less, preferably 0 mol% or more and 0.45 mol% or less.

For the silver halide emulsion of the present invention, the average circle equivalent diameter of the projected areas of silver halide grains is calculated as the average value of all silver halide grains. The average equivalent circle diameter is preferably 0.1 μm or more and 3.0 μm or less, more preferably 0.1 μm or more and 2.5 μm or less, and most preferably 0.3 μm or more and 2.5 μm or less.

The silver halide grains in the silver halide emulsion essentially include tabular silver halide grains, but isotropically grown grains such as cubes, octahedra and tetradecahedrons.
Alternatively, a polyhedral crystal type such as a spherical shape may be used in combination. The tabular silver halide grains are those of tabular grains having parallel twin planes and having a {111} plane as a main plane.
It may be a tabular grain having a 0 plane as the main plane.

The tabular silver halide grains in the present invention will be described in detail. The thickness of the tabular silver halide grains is preferably 0.05 μm or more and 0.25 μm or less, more preferably 0.05 μm or more and 0.2 μm or less.
The aspect ratio of tabular silver halide grains is defined as the value obtained by dividing the equivalent circle diameter of the projected area of one grain by the thickness of the grain, and in the present invention, the average aspect ratio is 12 or more. It is preferably 12 or more and 30 or less, and more preferably 12 or more and 25 or less in terms of good silver color tone and high optical density per unit developed silver amount. The proportion of tabular silver halide grains having an aspect ratio of 12 or more is preferably such that the sum of their projected areas is 50% or more and 100% or less, and more preferably 70% or more and 100%, relative to the sum of the projected areas of all grains. Hereafter, the most preferable range is 90% or more and 100% or less.

The method for producing tabular silver halide grains is as follows:
This can be achieved by appropriately combining methods known in the art. The tabular grains having parallel twin planes and having the {111} plane as the principal plane of the present invention are described in JP-A-58-127927,
JP-A-58-113927, JP-A-58-11392
It can be easily prepared by referring to the method described in No. 8. In addition, while forming a seed crystal in which tabular grains are present in an amount of 40% or more by weight in an atmosphere having a relatively low pBr value of 1.3 or less pBr, while maintaining the same pBr value, silver and halogen solutions are simultaneously added. Obtained by growing seed crystals. In this grain growth process, it is desirable to add a silver and halogen solution so that new crystal nuclei are not generated. The size of tabular silver halide grains can be controlled by controlling the temperature, selecting the type and amount of solvent, the silver salt used during grain growth,
It can be adjusted by controlling the addition rate of halide and the like.

Further, in the present invention, among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. The details of the structure and manufacturing method of the monodisperse hexagonal tabular grains are as described in JP-A-63-151618.

The silver halide emulsion preferably used in the present invention may have a uniform crystal structure, but may have a different halogen composition inside and outside, or may have a layered structure. Further, it is preferable that reduction sensitized silver nuclei are contained during grain formation.

In the present invention, British Patent No. 635841
So-called halogen conversion type (conversion type) particles as described in U.S. Pat. No. 3,622,318 can be used particularly effectively. The amount of halogen conversion is preferably 0.05 mol% to 0.45 mol% and more preferably 0.1 mol% to 0.3 mol% with respect to the amount of silver.

In the silver iodobromide emulsion, grains having a structure having a high iodine layer inside and / or on the surface thereof are particularly preferable. Further, by converting the surface of the tabular silver halide grains preferred in the present invention into a high iodine type, a silver halide emulsion having higher sensitivity can be obtained.

When the halogen conversion is carried out by the above method, the method in which a silver halide solvent is present is particularly effective. Preferred solvents include thioether compounds, thiocyanates and 4-substituted thioureas. Among them, thioether compounds and thiocyanates are particularly effective, and it is preferable to use thiocyanate in an amount of 0.5 g to 5 g and thioether in an amount of 0.2 g to 3 g per mol of silver halide.

The silver halide used in the present invention preferably has a silver chloride content of 20 mol% or more, and 50% or more of the total projected area is more preferably a tabular grain having a {100} plane as a main plane. . For the tabular grains having the {100} plane as the principal plane, see JP-A-5-281640 and JP-A-5-281640.
313273, JP-A-6-59360, JP-A-6-59360
308648, JP-A-6-308649, JP-A-7
-146522, JP-A-7-104430, JP-A-7-225441, JP-A-8-12954, JP-A-8-122953, and Japanese Patent Application No. 8-96883. Can be prepared. The formation of nuclei of tabular grains having the {100} plane as the principal plane is described in JP-A-5-204073, JP-A-51-88017,
JP-A-63-24238, JP-A-7-146522
And Japanese Patent Application No. 6-262590. In the present invention, the nucleation method described in these patent documents can be arbitrarily used.

As a method for growing the silver halide grains of the present invention, any method known so far can be used. That is, the silver salt aqueous solution and the halogen salt aqueous solution are added to the reaction vessel under efficient stirring. The specific method is Chemie et Phisique by P. Glafkides.
Photographique (Paul Montel, 1967), GF
Photographic Emulsion Chemistry (The Foca by Duffin
L Press, 1966), by VL Zelikman et al Maki
ng and Coating Photographic Emulsion (TheFocal Pre
ss, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used. Good.

As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used. Further, British Patent No. 1535016, Japanese Patent Publication Nos. 48-36890 and 52-1636.
No. 4, etc., a method of changing the addition rate of silver nitrate or an alkali halide aqueous solution according to the particle growth rate, US Pat. No. 4,242,445,
It is also preferable to use the method of changing the concentration of the aqueous solution as described in JP-A-55-158124 and the like to rapidly grow in a range not exceeding the critical supersaturation degree.

When the grains of the present invention have the {100} plane as the principal plane, the growth of tabular grains is caused by the addition of Ag ⁺ salt and halogen at the addition rate such that new nuclei are generated and the new nuclei do not grow to the critical fine grains. It is preferable to add salt. The new nucleus is
The number of grains is preferably 2 times or more, more preferably 5 times or more, and particularly preferably 10 times or more with respect to the number of {100} tabular grains. Here, the generation of new nuclei is preferable because the tabular grains are not dissolved by the generation of new nuclei and the anisotropic growth property of the grains can be maintained. In addition, the decrease in the supersaturation degree of the system due to the generation of new nuclei is also a factor for maintaining the anisotropic growth of particles. The generation of new nuclei, the number of new nuclei, and the fact that no particles larger than the critical particle size are generated can be confirmed by the direct method TEM of the sample without centrifugation at the time of sample preparation. The generation of the new nuclei and the addition rate at which the new nuclei do not grow to the critical fine particle size vary depending on the halogen composition added, pH, pAg, gelatin species, gelatin concentration, temperature, AgX solvent concentration, {100} tabular grain size, etc. . Therefore, it is necessary to determine by the trial and error method at various timings of growth. Generally, the addition rate satisfying the conditions can be realized in a wider range of the addition rate as the pCl value increases. The generation of new nuclei is preferably always occurring, but it is sufficient that the generation of new nuclei occurs only when the growth amount of silver is preferably 5% or more, more preferably 10% or more. . However, also in this case, when Ag salt is added,
There must always be a new nuclear nucleus.

When the grains of the present invention have the {100} plane as the principal plane, the tabular grains can be grown by physical ripening (fine grains are dissolved and substrate grains are grown) in the presence of fine silver halide grains. Crystal growth is also preferably performed.

In the fine grain emulsion addition method, the diameter is 0.15 μm or less, preferably 0.1 μm or less, more preferably 0.1 μm or less.
Add an AgX fine grain emulsion having a diameter of 06 to 0.006 μm,
Tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or continuously. The fine grain emulsion can be continuously prepared by supplying the AgNO3 solution and the X-salt solution in a mixer provided near the reaction vessel, and can be continuously added to the reaction vessel immediately or batchwise in another vessel. It is also possible to add continuously or continuously after formulating. Such a fine grain emulsion can be added in the form of a liquid or a dry powder. It is also possible to mix the dry powder with water immediately before addition to liquefy it and add it. The added fine particles are preferably added in such a manner that they disappear within 20 minutes, more preferably 10 seconds to 10 minutes.
When the disappearance time becomes long, ripening occurs between the fine particles and the particle size becomes large, which is not preferable. Therefore, it is preferable not to add the entire amount at once. It is preferable that such fine particles are substantially free of multi-twin grains. Here, the multi-twin grain means a grain having two or more twin planes per grain. The term "substantially free" means that the number ratio of multiple twinned grains is 5% or less, preferably 1% or less, more preferably 0.1% or less. Further, it is preferable that substantially no single twin crystal grains are contained. Furthermore, it is preferable that the screw dislocation is not substantially contained. Here, the term "substantially free" is in accordance with the above-mentioned rules.

The halogen composition of the fine particles is AgCl, A
gBr, AgBrI (I ^- content is preferably 10 mol% or less, more preferably 5 mol% or less) and those 2
It is a mixed crystal of more than one species. For other details, see JP-A-6-593.
The description of No. 60 can be referred to. The total amount of fine grains added should be 20% or more of the total amount of silver halide.
It is preferably 40% or more, and more preferably 50% or more and 98% or less. Cl content of fine particles is 10 mol%
Or more, more preferably 50 mol% or more and 100
It is preferably not more than mol%.

In the step of nucleating tabular silver halide grains, gelatin having a low methionine content described in US Pat. Nos. 4,713,320 and 4,942,120 is used. 4,914,014
Nucleation with high pBr described in Japanese Patent Application Laid-Open No. 2-2
Performing nucleation in a short time as described in No. 22940 is extremely effective in the step of nucleating particles used in the present invention. Particularly, the methionine content is preferably 0 to 50 μm.
Mol / g, more preferably 0 to 40 μmol / g gelatin can be preferably used. When such gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are formed, which is preferable. In the present invention, it is particularly preferable to add the silver nitrate aqueous solution, the halogen aqueous solution and the low molecular weight oxidation-treated gelatin within 1 minute under stirring in the presence of the low-molecular weight oxidation-treated gelatin at a temperature of 20 ° C. to 40 ° C. At this time, the pBr of the system is 2
The above is preferable and the pH is preferably 7 or less. The concentration of the aqueous silver nitrate solution is preferably 0.6 mol / liter or less.
Gelatin having a molecular weight smaller than that of a usual one is preferable, and 10,000 to 50,000 is particularly preferable. 90 amino groups for phthalation, succination, or trimellitization
% Or more modified gelatin and / or oxidatively processed gelatin having a reduced methionine content is particularly preferably used.

Further, the aging step can be carried out in the presence of a low-concentration base described in US Pat. No. 5,254,453, and at a high pH described in US Pat. No. 5,013,641. Is. Also, U.S. Pat. Nos. 5,147,771, 5,147,772,
No. 5,147,773, No. 5,171,659
No. 5,210,013 and No. 5,25
It is possible to add the polyalkylene oxide compound described in No. 2,453 in the aging step or the subsequent growth step. In the present invention, the aging step is preferably 60 ° C.
It is performed at a temperature of 80 ° C or lower. It is preferable to reduce pBr to 2 or less immediately after nucleation or during ripening. Further, additional gelatin is preferably added immediately after nucleation to the end of ripening. Particularly preferred gelatin is one in which 95% or more of the amino groups are modified to be succinic or trimellitic.

The pH during growth by adding fine particles is 2.0.
The above is required, but 6 or more and 10 or less are preferable. The pH is more preferably 6 or more and 9 or less. Further, pCl needs to be 1.0 or more, but 1.6 or more is preferable. More preferably, it is 1.8 or more and 3.0 or less. These growth conditions are particularly preferable for tabular grains having the {100} plane as the main plane.

[0071] Here in pCl, activity of Cl ions in the solution ^- to pCl = -log [Cl] ^- defined by [Cl]. TH James by THE THEORY OF THE RHO
It is described in detail in Chapter 1 of the 4th edition of TOGRAPHIC PROCESS.

When the pH is 2.0 or less, for example, in the case of tabular grains having the {100} plane as the principal plane, lateral growth is suppressed and the aspect ratio is lowered, so that the emulsion covering power is reduced. Tends to be low, and sensitivity becomes low. When the pH is 2.0 or more, the growth rate in the lateral direction becomes high, and an emulsion having a high aspect ratio and a high covering power can be obtained, but fog tends to be high and sensitivity tends to be lowered. When pCl becomes 1.0 or less, for example, {100}
In the case of tabular grains having a plane as the principal plane, growth in the vertical direction is promoted, the aspect ratio is lowered, the covering power of the emulsion is low, and the sensitivity is lowered. pCl is 1.6
When it becomes the above, the aspect ratio is increased and the covering power is increased, but the fog is high and the sensitivity is easily lowered. At this time,
When substrate particles are grown with silver halide fine particles, the pH is
Is 6.0 or more and / or pCl is 1.6 or more, the fog is low, the sensitivity is high, the aspect ratio is high, and the covering power is high.

The tabular grains of the present invention are preferably silver halide grains having dislocation lines. Dislocation lines of tabular grains are, for example, JF Hamilton, Phot. Sci. Eng.,
11, 57, (1967) and T. Shiozawa, J. Soc. Ph.
It can be observed by a direct method using a transmission electron microscope at a low temperature described in ot. Sci. Japan, 35, 213, (1972). That is, the silver halide grains taken out carefully so as not to apply pressure so as to cause dislocation to the grains from the emulsion are placed on a mesh for electron microscope observation,
Observation is performed by the transmission method while the sample is cooled so as to prevent damage (printout, etc.) due to the electron beam. At this time, the thicker the particles, the more difficult it is for an electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV or more for particles having a thickness of 0.25 μ). From the photograph of the grains obtained by such a method, the position and number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be determined.

In the course of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt, etc. are allowed to coexist. Good.

As the chemical sensitization in the present invention, chalcogen sensitization such as sulfur sensitization, selenium sensitization and tellurium sensitization is used in combination with gold sensitization. In sulfur sensitization, unstable sulfur compounds were used, and P. Grafkides, Chimie
etPhysique Photographique (Paul Momtel, 1987
Year, 5th Edition), Research Disclosure, Volume 307, 307
Unstable sulfur compounds described in No. 105 and the like can be used. Specifically, thiosulfates (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-ethyl-N ′-(4-methyl-).
2-thiazolyl) thiourea, carboxymethyltrimethylthiourea), thioamides (for example, thioacetamide), rhodanines (for example, diethyl rhodanine, 5
-Benzylidene-N-ethyl-rhodamine), phosphine sulfides (eg trimethylphosphine sulfide), thiohydantoins, 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg dimorpholine disulfide) , Cystine, lenthionine), mercapto compounds (eg,
Known sulfur compounds such as cystine), polythionate, elemental sulfur, and active gelatin can also be used.

In the selenium sensitization, an unstable selenium compound is used, and Japanese Patent Publication Nos. 43-13489 and 44-157 are used.
48, JP-A-4-25832 and 4-109240.
JP-A-4-271341, JP-A-5-4032
Unstable selenium compounds described in No. 4 can be used. Specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenamides (eg, selenoacetamide, N, N-diethylphenyl selenamide), phosphine selenides (for example, triphenylphosphine selenide, pentafluorophenyltriphenylphosphine selenide), selenophosphates (for example, tri-p-tolyl selenophosphate, Tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids,
Selenoesters and diacyl selenides may be used. Furthermore, Japanese Patent Publications Nos. 46-4553 and 52-3.
The non-unstable selenium compounds described in Japanese Patent No. 4492, such as selenious acid, potassium selenocyanide, selenazoles, and selenides, can also be used.

In tellurium sensitization, an unstable tellurium compound is used, and Canadian Patent No. 800958, British Patent No. 1,
Nos. 295,462 and 1,396,696, JP-A-4-204640 and 4-271341.
The unstable tellurium compounds described in JP-A Nos. 4-333043 and 5-303157 can be used. Specifically, telluroureas (for example, tetramethyl tellurourea, N, N'-dimethylethylene tellurourea, N, N'-diphenylethylene tellurourea), phosphine tellurides (for example, butyl-diisopropylphosphine). Telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxy-
Diphenylphosphine telluride), diacyl (di) tellurides (for example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (N-phenyl-N-benzylcarbamoyl) telluride, bis (ethoxycarbonyl) telluride), isotellocyanates, telluroamides, tellurohydrazides, telluroesters (eg, butylhexyl telluroester), telluroketones (eg, telluro). Acetophenone), colloidal tellurium, (di) tellurides, and other tellurium compounds (potassium telluride, telluropentathionate sodium salt)
Etc. may be used.

Regarding the gold sensitization, the above-mentioned P. Grafkides
By Chimie et Physique Photographique (Paul Momtel
(Published in 1987, 5th edition), Research Disclosure magazine 30
Gold salts described in Vol. 7, No. 307105, etc. can be used. Specifically, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide,
US Patent 2,642,361 in addition to gold selenide
No. 5,049,484, No. 5,049,485, etc. can also be used. Further, a noble metal salt such as platinum, palladium or iridium may be added.

The amount of the chalcogen sensitizer used in the present invention varies depending on the silver halide grains used, the chemical sensitization conditions and the like, but it is 10 ^-8 to 10 per mol of silver halide.
^-2 mol, preferably about 10 ^{-7 to} 5 × 10 ^-3 mol is used.

The amount of the gold sensitizer and the noble metal sensitizer used in the present invention is 10 ^-7 to 1 per mol of silver halide.
Use about 0 ^-2 mol. The conditions of the chemical sensitization in the present invention are not particularly limited, but pAg is preferably 6 to 11, more preferably 7 to 10, and pH is 4 to 4.
10 is preferable, and the temperature is preferably 40 to 95 ° C, more preferably 45 to 85 ° C.

Regarding reduction sensitization, the above-mentioned P. Grafkides
By Chimie et Physique Photographique (Paul Momtel
(Published in 1987, 5th edition), Research Disclosure magazine 30
Known reducing compounds described in Volume 7, No. 307105 and the like can be used. Specifically, aminoiminomethanesulfinic acid (also known as thiourea dioxide), borane compound (eg, dimethylamineborane), hydrazine compound (eg, hydrazine, p-tolylhydrazine), polyamine compound (eg, diethylenetriamine, triethylene). Tetramine), stannous chloride, silane compounds, reductones (eg, ascorbic acid), sulfites, aldehyde compounds, hydrogen gas and the like may be used. Further, reduction sensitization may be carried out in an atmosphere of high pH or silver ion excess (so-called silver ripening).

In the silver halide emulsion of the present invention, the grain surface or a part thereof may be halogen-converted in the chemical sensitization step. As a method of applying halogen conversion,
Water-soluble bromide salts such as potassium bromide and sodium bromide, water-soluble iodide salts such as potassium iodide and the like can be used alone or in combination, and they are added as solids or as an aqueous solution or gelatin dispersion. can do. Further, it is also preferable to add silver bromide, silver iodobromide, and silver halide fine grains of silver iodide, and these can be used alone or in combination. When added in the form of fine particles, the average equivalent spherical diameter of the fine particles is preferably 0.1 μm or less, more preferably 0.05 μm or less. Further, fine particles can be continuously adjusted by supplying an aqueous solution of silver nitrate and an aqueous solution of an alkali halide having an arbitrary composition with a mixer provided in the vicinity of the reaction vessel, and can be immediately added to the reaction vessel, or can be previously added to another vessel. It is also possible to add it after adjusting it in a batch manner. If necessary, the fine silver halide grains may contain ions or compounds of heavy metals such as iridium, rhodium and platinum.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, during chemical sensitization, it is preferable to allow a salt of a metal ion to exist before coating, depending on the purpose. When the grains are doped, they are preferably added during grain formation, after grain formation, or before chemical sensitization, when grain surface modification or as a chemical sensitizer is used. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Mg, Ca, Sr, Ba, Al, S
c, Y, LaCr, Mn, Fe, Co, Ni, Cu, Z
n, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydrates, hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example CdB
_{r 2, CdCl 2, Cd (} NO 3) 2, Pb (NO 3) 2,
Pb (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (NH
₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ R
Examples include hCl ₆ , K ₄ Ru (CN) _{6, and the} like. The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may use two types or a combination of three or more types.

The method of adding a chalcogen compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. In addition to S, Se and Te, cyanide salt,
A thiocyan salt, selenocyanic acid, carbonate, phosphate or acetate may be present.

It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Patent Nos. 2,131,038 and 3,411,914;
No. 3,554,757, JP-A No. 58-126526 and the above-mentioned Daffin's "Photographic Emulsion Chemistry", pages 138-143.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. What is an oxidizing agent for silver?
It refers to a compound that acts on metallic silver to convert it into silver ions. In particular, the extremely fine silver particles produced as a by-product in the process of forming silver halide grains and the chemical sensitization process,
Compounds that convert to silver ions are effective. The silver ion generated here may form a hardly soluble silver salt such as silver halide, silver sulfide, or silver selenide, or may form a readily soluble silver salt such as silver nitrate. Good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidant include ozone, hydrogen peroxide and its adducts (for example, NaBO ₂ · H ₂ O ₂ · 3H ₂ O and 2NaCO _{3).
· 3H 2 O 2, Na 4} P 2 O 7 · 2H 2 O 2, 2Na 2 SO
₄・ H ₂ O ₂・ 2H ₂ O), peroxy acid salt (eg K ₂ S
_{2 O 8, K 2 C 2} O 6, K 2 P 2 O 8), peroxy complex compounds (e.g., K _{2 [Ti (O 2) C 2 O} 4 ] · 3H ₂ O, 4
K ₂ SO ₄ · Ti (O ₂ ) OH · SO ₄ · 2H ₂ O, Na _{3
[VO (O 2) (C 2} H 4) 2 · 6H 2 O), permanganate (e.g., KMnO _4), chromates (e.g., K ₂ Cr
₂ O ₇ ) and other oxyacid salts, halogen elements such as iodine and bromine, perhalogenate salts (eg potassium periodate) salts of high-valent metal (eg potassium hexacyanoferrate) and thiosulfonic acid There is salt etc.

Examples of the organic oxidant include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (for example, N-bromosuccinimide and chloramine T). , Chloramine B). It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . In other words, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
Etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl (1,3,3a, 7) Tetraazaindene), many compounds known as antifoggants or stabilizers such as pentaazaindenes and the like can be added. For example, those described in U.S. Pat. Nos. 3,954,474, 3,982,947 and JP-B-52-28660 can be used.
One of the preferred compounds is the compound described in Japanese Patent Application No. 62-47225. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose.

In the present invention, it is also preferable to coexist with a nucleic acid or a decomposition product thereof before the chemical sensitization for chemical sensitization. Regarding nucleic acid or its degradation product, see Japanese Patent Laid-Open No.
The thing of 2-67541 can be used. The nucleic acid used in the present invention includes deoxyribonucleic acid (D
NA) and ribonucleic acid (RNA), and as nucleic acid degradation products, those in the middle of degradation, adenine, guanine,
Examples include simple substances such as uracil, cytosine and thymine. Adenine is mentioned as a particularly preferable nucleic acid decomposition product. These can be used alone or in combination. In this case, it goes without saying that the nucleic acid and the nucleic acid decomposition product may be used in combination. The amount of the nucleic acid or its decomposition product added varies depending on the kind of the nucleic acid decomposition product, but 20 mg or more per mol of silver halide,
The preferred range is 100 mg to 1 g. When these nucleic acids or nucleic acid decomposition products are used alone or in combination of two or more as described above, the total amount added is sufficient.

In the light-sensitive material of the present invention, a crossover light-cutting layer may be provided between the light-sensitive emulsion layer and the support, if necessary, for the purpose of making an image clear. A dye corresponding to the photosensitive wavelength range is added to the crossover light cut layer. Any dye can be used as long as it does not leave harmful absorption after development processing. A method for adding a dye in a solid fine particle dispersion state is described in JP-A-2-26493.
6, JP-A-3-210553, JP-A-3-2105
54, JP-A-3-238447, and JP-A-4-140.
38, JP-A-4-14039, and JP-A-4-1256.
35, JP-A-4-338747, JP-A-6-275.
89, etc. The dye that can be used is, for example, one of the general formulas (I) to (V described in JP-A-4-211542).
II) Dyes, Compound Examples I-1 to I-37, II-1 to II-
6, III-1 to III-36, IV-1 to IV-16, V-1 to V
-6, VI-1 to VI-13, VII-1 to VII-5. JP-A-8
-73767 dye of the general formula (1), compound example 1
~ 6. General formula (VIII) described in JP-A-8-87091
(XII) Dye, Compound Examples VIII-1 to VIII-5, IX-1
~ IX-10, X-1 to X-21, XI-1 to XI-6, XII-
1 to XII-7.

In addition to these, a known dye is adsorbed on a mordant, a known dye is dissolved in oil and emulsified and dispersed in the form of oil droplets, and a dye described in JP-A-3-5748 is adsorbed on the surface of an inorganic substance. The method, the method of adsorbing the dye described in JP-A-2-298939 to the polymer, and the like can also be used. As a method of adding the crossover light cut layer to the light-sensitive material, those described in each specification can be used.

A dye may be added to the light-sensitive material of the present invention for the purpose of detecting the position of the light-sensitive material. The dye preferably has an absorption spectrum according to the maximum sensitivity wavelength of the detection sensor, and any dye may be used as long as it does not leave harmful absorption after the development processing. Preferably, a dye having an absorption maximum at 700 nm to 1400 nm or a fine particle dispersion thereof is used. For example, (1) water-soluble dyes that are decolorized during treatment include cyanine dyes of general formulas (I) to (IV), pyrylium dyes and aminium dyes described in JP-A-3-211542, compound examples I-1 to I- 6, II-1 to II-4, III-1 to III-
4, IV-1 to IV-5.

(2) As the solid fine particle dispersed dye which is decolorized at the time of treatment, cyanine dyes of formulas (I) to (IV), pyrylium dyes and aminium dyes described in JP-A-3-138640, Compound Example I-1 ~ I ~ 28, II-1
-II-10, III-1 to III-6, IV-1 to IV-7.

(3) As the dye that is not decolorized during the treatment, tricarbocyanine dyes having a carboxyl group of the general formula (I) to the general formula (II) described in Japanese Patent Application No. 6-227983, Compound Examples 1 to 33. Japanese Patent Application No. 6-27929
No. 7, a tetracarbocyan dye having a carboxyl group of the general formula (I) to the general formula (II), compound examples 1 to
19. General formula (1) described in Japanese Patent Application No. 7-208569
Cyanine dyes having no acid group of the general formula (3), compound examples 1 to 63. General [1] described in Japanese Patent Application No. 7-135118
Lake type cyanine dyes, compound examples No. 1 to No. 37.

In addition to these, JP-A-62-299959
Pyrylium dye described in JP-A-63-131135
The light-scattering particles described in JP-A-1-266536.
Anine dye, oxono described in JP-A-2-282244
Solid fine particle dispersion of an organic dye, JP-A-3-136038
Holopolar type cyanine dye described in JP-A-7-253
No. 639, polymer type cyanine dyes, JP-A-7-1
13072, tin-doped indium oxide (IT
O) powder, Yb described in Japanese Patent Application No. 7-151380 ³⁺Compound
Things can also be used.

A dye for the purpose of detecting the position of a light-sensitive material,
As the method of adding to the light-sensitive material, those described in each specification can be used.

A dye may be added to the light-sensitive material of the present invention for the purpose of improving the color tone of a silver image. The dyes are pyrazoloazole dyes, anthraquinone dyes, azo dyes, azomethine dyes, oxonol dyes, carbocyanine dyes,
Among the styryl dyes, triphenylmethane dyes, indoaniline dyes and indophenol dyes, those having a predetermined absorption maximum wavelength are selected. Among them, anthraquinone dyes of general formula (I) described in JP-A-5-34858 and general formula (I) described in JP-A-4-247449.
And the azomethine dyes of the general formula (I) described in JP-A-4-296845, the indoaniline dyes contained in the general formula (I) described in JP-A-5-43809, and the JP-A-5-43809.
The azo dyes described in No. 341441 are useful.

Specific examples of anthraquinone dyes include compounds 1 to 9 described in JP-A-5-341441 and JP-A-5-
Compounds 3-6 to 3-18 and 3 described in 165147
-23 to 3-38 can be used. As the azomethine dye, specifically, compounds 17 to 46 described in JP-A-5-341441 can be used. As the indoaniline dye, specifically, compounds 11 to 19 described in JP-A-5-289227, compound 47 described in JP-A-5-341441 and compounds 2-10 to 2-11 described in JP-A-5-165147 are used. can do. As the azo dye, specifically, compounds 10 to 16 described in JP-A-5-341441 can be used. As a method for adding a dye for the purpose of improving the color tone of a silver image to a light-sensitive material, those described in each specification can be used.

The sensitive material of the present invention may contain colloidal silica. Colloidal silica has an average particle size of 1 to 1000 nm, preferably 5 to 500 nm, more preferably 5 to 100 nm, its main component is silicon dioxide, and it may contain alumina or sodium alginate as a minor component. Good. Specific examples of colloidal silica include Nissan Chemical Co., Ltd. (Tokyo, Japan).
Snowtex 20, Snowtex 30,
Snowtex C, Snowtex O, etc. are mentioned.

The layer containing colloidal silica in the light-sensitive material of the present invention includes a surface protective layer, an intermediate layer, a silver halide emulsion layer, an antihalation layer, an undercoat layer, a filter layer,
Although it may be any hydrophilic colloid layer such as a backing layer,
Especially for the purpose of pressure resistance, it is preferably contained in the surface protective layer or the silver halide emulsion layer. The content of colloidal silica is 1 to 20 with respect to the weight of the hydrophilic colloid in the hydrophilic colloid layer contained.
0% by weight is preferable, and 10 to 100% by weight is particularly preferable.

In the layer containing colloidal silica, it is preferable to contain a plastic polymer latex in combination, if necessary. Any layer of the photographic light-sensitive material of the present invention may contain a polymer latex obtained by polymerizing a poorly water-soluble monomer. Examples of such a monomer include, for example, JP-A-7-230135, page 2, 2
Acrylic acid esters, methacrylic acid esters, divinylbenzene and the like described in the 5th line to 17th line of the stage can be used.

In such a polymer latex, the above-mentioned monomer may be copolymerized with another monomer, and the monomer at this time is, for example, 2 of JP-A-7-230135.
The monomers described on page 2, 2nd line, line 32 to page 1, 1st line, 35th line can be used, and among them, acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes, and olefins are preferable. Used. An example of the polymer latex is, for example, JP-A-7-230.
No. 135, Lx1 to Lx-21.

In the present invention, No. 1 to No. 8 matting agents described in Example 1 of JP-A-6-194779 can be preferably used. Further, preferable compound examples 1 to 9 described in paragraph [0023] of JP-A-6-138572 can be preferably used. Regarding the sizes of these matting agents, etc., see [004 of Japanese Patent Application Laid-Open No. 6-194779].
9] It can be preferably used in the size and the usage amount described in the paragraph. Further, two or more kinds of matting agents having particle sizes can be mixed and used. Regarding the particle size distribution of the matting agent, monodisperse particles having a coefficient of variation of 3 to 30% can be used or polydisperse particles having a coefficient of variation of 30% or more can be used depending on the purpose.

The preferable coating amount of the emulsion of the silver halide photographic light-sensitive material of the present invention is, in terms of silver, per 1 m ^{2 on} one side,
It is 0.3 g or more and 1.5 g or less. Preferably 0.5 g
It is not less than 1.5 g. More preferably 0.8 g
It is not less than 1.5 g.

The coating amount of total gelatin in the hydrophilic colloid layer of the light-sensitive material of the present invention is 2.5 g or less (total coating amount per one side), 0.5 g / m ² or less and 2.5 g / m ² or less. Is preferred. Particularly preferably, 1.0 g / m ² or more and 2.1 g
/ M ² or less. In this case, the gelatin coating amount of the protective layer is preferably 0.2 g / m ² or more and 1.0 g / m ² or less.

In the present invention, the swelling ratio of the light-sensitive material is the swelling value obtained by subtracting the film thickness value in the dry state from the film thickness value after the light-sensitive material was immersed in distilled water at 21 ° C. for 3 minutes. A value obtained by dividing the value by the film thickness value in the dry state is multiplied by 100, and is defined as (%) and can be obtained. The range of the swelling ratio is preferably 20% to 220%, more preferably 40% or more 1
It is 50% or less.

Generally, in a silver halide photographic light-sensitive material, a water-soluble coating solution containing a hydrophilic colloid such as gelatin as a binder is coated on a support and then in a low temperature air having a dry-bulb temperature of -10 to 20 ° C. It is solidified by cooling and then dried at an elevated temperature. The weight ratio of gelatin to water immediately after coating is usually around 3000%.

The coating solution usually contains various additives such as hydrophilic colloid binder, silver halide particles, surfactant, plasticizer such as polymer latex, gelatin hardening agent, dye, sensitizing dye and matting agent. include.

In the present invention, when the hydrophilic colloid layer coating solution is applied and then dried, the water content is 100% or less based on the dry weight of the binder of the entire coating layer on the side having the silver halide emulsion layer. It is preferable to dry at a wet bulb temperature of 20 ° C. or lower, preferably 19 ° C. to 10 ° C. When two or more hydrophilic colloid layers are simultaneously coated and dried (that is, when the coating layer to be dried is two or more layers), the water content is the sum of the water content of all layers and the binder dryness. The amount represents the sum of the dry weight (dry weight) of the binder in all layers.
Wet bulb temperature is the temperature of water droplets in the equilibrium state of moist air,
The lower the humidity of the air, the lower. During the constant rate drying period of the drying step, the wet-bulb temperature of the drying air is almost equal to the surface temperature of the coated sample.

Further, the environmental conditions at the time of winding into a roll after coating and drying are such that the absolute humidity is 1.4% by weight or less, preferably 0.6 to 1.3% by weight, and it is preferable to wind. In the present invention, the product processing of the silver halide photographic light-sensitive material wound up in a roll after coating and drying is performed under an environment where the absolute humidity is 1.4% by weight or less, preferably 0.6 to 1.3% by weight. It is preferably processed. Absolute humidity (wt
%) Represents the state of moist air, and is a percentage of the ratio of the amount of water vapor (kg) in the moist air to the weight (kg) of dry air in the moist air. The silver halide photographic light-sensitive material is put in a moisture-proof package, and its mouth is sealed by heat sealing or the like so that the absolute humidity in the package is 1.4% by weight or less, preferably 1.1 to 0.6. It means that the light-sensitive material is sealed by the method and is in equilibrium at the above absolute humidity.

Further, after processing, the absolute humidity is 1.4% by weight.
It is particularly preferable to perform the seasoning in the following environment and then heat-seal-seal the package in the same environment.

There are no particular restrictions on the various additives used in the silver halide photographic emulsion and the silver halide photographic light-sensitive material of the present invention. For example, those described in the following relevant parts of JP-A-2-68539 are used. be able to.

Item Applicable place 1. Silver halide emulsion and its manufacturing method
No. 539, page 8, lower right column, line 6 from bottom to page 10, upper right column, line 12; 2. Chemical sensitization method: page 13, upper right column, item 13 to lower left column, line 16 of the same. 3. Anti-fogging agent / stabilizer ... ibid., Page 10, lower left column 17
Line 7 to page 11, upper left column, line 7 and page 3, lower left column, line 2 to page 4, lower left column. 4. Spectral sensitizing dye: page 4, lower right column, line 4 to page 8, lower right column. 5. Surfactants / antistatic agents --- Same as page 11, upper left column 1
From line 4 to page 12, upper left column, line 9 6. Matting agent / slip agent / plasticizer ... page 12, upper left column, line 10 to upper right column, line 10 Page 14, lower left column 10
From line 1 to the lower right column, line 1. 7. Hydrophilic colloid: page 12, right upper column, line 11 to left lower column, line 16 of the same. 8. Hardener: From page 12, lower left column, line 17 to first, same
Page 3, upper right column, line 6 9. Support: page 13, upper right column, lines 7 to 20. Ten. Dyes / mordanting agents, page 13, lower right column, line 1 to page 14, lower left column, line 9

The silver halide emulsion of the present invention can be used in all conventionally known photographic light-sensitive materials. Examples of such a silver halide photographic light-sensitive material, including the silver halide photographic light-sensitive material of the present invention, include black and white silver halide photographic light-sensitive materials (for example, X-ray sensitive materials, printing sensitive materials, photographic papers, negatives). Film, micro film, direct positive sensitive material,
Ultrafine particle dry plate sensitive material (for LSI photomask, shadow mask, liquid crystal mask)], color photographic light-sensitive material (eg negative film, photographic paper, reversal film, direct positive color light-sensitive material, silver dye bleaching method photo) be able to. Further, a diffusion transfer type photosensitive material (for example, a color diffusion transfer element, a silver salt diffusion transfer element), a photothermographic material (black and white, color), a high density digital recording light sensitive material, a holographic light sensitive material and the like can be mentioned.

In the photographic light-sensitive material of the present invention, for example, the following phosphors are used as a fluorescent intensifying screen, and X-ray photography can be preferably carried out.

Blue emitting phosphor Y ₂ O ₂ S: Tb, LaOBr: Tb, BaFCl: Eu Green emitting phosphor Gd ₂ O ₂ S: Tb, LaO ₂ S: Tb

As the UV-emitting phosphor, M'phase YTaO is used.
₄ alone or Gd, Bi, Pb, Ce, Se, Al,
Compounds containing Rb, Ca, Cr, Cd, Nb, etc.,
Compounds obtained by adding Gd, Tm, Gd and Tm, Gd and Ce, Tb to LaOBr, HfZr oxide alone or compounds obtained by adding Ge, Ti alkali metal, etc.,
Y ₂ O ₃ alone or a compound to which Gd and Eu are added, Y ₂
Compounds of Gd added to O ₂ S, G as the base material of various phosphors
Examples include compounds using d, Tl, and Ce as activators. Particularly preferred compounds include M'phase YTaO4 alone or a compound added with Gd, Sr, a compound added with Gd, Tm, Gd and Tm to LaOBr, HfZ.
It is a compound to which an oxide of r or Ge, Ti alkali metal or the like is added.

The particle size of the phosphor is preferably 1 μm or more and 20 μm or less, but can be changed depending on the required sensitivity and manufacturing problems. The coating amount is preferably 400 g / mm ² or more and 2000 g / mm ² or less, but it cannot be unequivocally determined depending on the required sensitivity and image quality. A single intensifying screen may be used to provide a particle size distribution from the vicinity of the support to the surface. In this case, it is generally known to increase the size of particles on the surface. The space filling rate of the phosphor is 40% or more, preferably 6
It is 0% or more.

When the phosphor layers are provided on both sides of the photosensitive material for photographing, the coating amount of the phosphor on the X-ray incident side and the opposite side can be changed. It is generally known to reduce the coating amount of the intensifying screen on the X-ray incident side, especially when a high-sensitivity system is required because of shielding by the intensifying screen on the X-ray incident side.

The support used in the screen used in the present invention may be paper, metal plate, polymer sheet or the like, but a flexible sheet such as polyethylene terephthalate is generally used. The support may be added with a reflecting agent or a light absorbing agent, or may be provided as a separate layer on the surface, if necessary.

If necessary, the surface of the support may be slightly uneven, or an adhesive layer for increasing the adhesion to the phosphor layer or a conductive layer may be provided as an undercoat. Examples of the reflecting agent include zinc oxide, titanium oxide, and barium sulfate. Titanium oxide and barium sulfate are preferable because the phosphor has a short emission wavelength. The reflecting agent may be present not only in the support or between the support and the phosphor layer, but also in the phosphor layer. When it is present in the phosphor layer, it is preferably localized near the support.

As the binder used in the screen of the present invention, proteins such as gelatin, polysaccharides such as dextran and corn starch, natural polymer substances such as gum arabic; polyvinyl butyral, polyvinyl acetate, polyurethane, polyalkyl acrylate, chloride Examples include synthetic polymer substances such as vinylidene, nitrocellulose, fluorine-containing polymers, polyesters, and mixtures and copolymers thereof. As a preferable binder,
The basic performance is high transmittance for light emitted from the phosphor. In this respect, gelatin, corn starch, an acrylic polymer, a fluorine-containing olefin polymer, a polymer containing a fluorine-containing olefin as a copolymer component, a styrene / acrylonitrile copolymer and the like can be mentioned. These binders may have functional groups that are crosslinked by the crosslinking agent. Further, depending on the required image quality performance, an absorber for the light emitted from the phosphor may be added to the binder, or a binder having a low transmittance may be used. Examples of the absorber include pigments, dyes, and ultraviolet absorbing compounds. The ratio of phosphor to binder is generally 1: 5 to 50: 1 by volume, preferably 1: 1 to 1: 5: 1. The ratio of the phosphor to the binder may be uniform or non-uniform in the thickness direction.

The phosphor layer is usually formed by a coating method using a coating liquid in which the phosphor is dispersed in a binder solution.
Examples of the solvent for the coating liquid include water, alcohols, chlorine-containing hydrocarbons, organic solvents such as ketones, esters and ether aromatic compounds, and mixtures thereof.

In the coating liquid, dispersion stabilizers such as phthalic acid, stearic acid, caproic acid, and surfactants for phosphor particles, and plasticizers such as phosphoric acid ester, phthalic acid ester, glycolic acid ester, polyester, and polyethylene glycol are used. Agents may be added.

In the screen used in the present invention, a protective layer can be provided on the phosphor layer. As the protective layer, a method of coating on the phosphor layer, or a method of separately preparing and laminating a protective layer film is generally used. In the coating method, the phosphor layer may be coated at the same time, or the phosphor layer may be coated and dried before coating. The protective layer may be the same substance as the binder of the phosphor layer, or may be a different substance. Examples of the substance used for the protective layer include substances listed as the binder for the phosphor layer, as well as cellulose derivatives, polyvinyl chloride, melamine, phenol resins, and epoxy resins.
Preferred materials include gelatin, corn starch, acrylic polymers, olefin polymers containing fluorine, polymers containing olefins containing fluorine as a copolymer component, styrene / acrylonitrile copolymers, and the like. The thickness of the protective layer is generally 1 μm or more 2
It is preferably 0 μm or less and 2 μm or more and 10 μm or less, and 2
More preferably, it is not less than μm and not more than 6 μm. It is preferable to emboss the surface of the protective layer of the present invention. In addition, a matting agent may be present in the protective layer, or a substance having a light-scattering property for light emission depending on the image to be obtained, such as titanium oxide, may be present.

A surface slipperiness may be imparted to the protective layer of the screen used in the present invention. Examples of preferable slip agents include polysiloxane skeleton-containing oligomers and perfluoroalkyl group-containing oligomers.

Conductivity may be imparted to the protective layer of the present invention. Examples of the conductivity imparting agent include white and transparent inorganic conductive substances and organic antistatic agents. Preferred inorganic conductive materials include ZnO powder, whiskers, and SnO.
₂ , ITO, etc. may be mentioned.

The developing method of the present invention is described in US Pat. No. 5,498,511, JP-A-7-16832, JP-A-8-54712, Japanese Patent Application No. 8-168670 and Japanese Patent Application No. 8-198401. Can be used as a reference.

It is preferable to use hydroquinone, ascorbic acid, or erythorbic acid (diastereomer of ascorbic acid) and / or their derivatives in the developer for treating the light-sensitive material of the present invention.

Ascorbic acid and / or derivatives thereof include US Pat. No. 2,688,549 and Japanese Examined Patent Publication No. 36.
-17599, JP-A-3-249756, JP-A-4
-270343 and the like.

Specifically, compounds described in US Pat. No. 2,688,549, page 1, column 1, line 22 to page 1, column 2, line 33, JP-B-36-17.
Pp. 599, page 1, left column, lines 21 to 26, compounds I-1 to I-8 and II-1 to II-4, described in JP-A-3-249756, page 4, Kaihei 4
-270343, page 4, column 5, line 40 to line 5
The compounds described in line 0 can be used.

Of these, ascorbic acid or erythrubic acid (diastereomer of ascorbic acid) and their alkali metal salts such as lithium salt, sodium salt and potassium salt are preferable.

The developing agent is usually 0.01 mol / liter or more.
It is preferably used in an amount of 0.8 mol / l,
It is particularly preferable to use it in an amount of 0.1 mol / liter to 0.4 mol / liter. In the present invention, it is desirable to use together with a developing agent as an auxiliary developing agent exhibiting superadditivity. As an auxiliary developing agent exhibiting superadditivity, there is a 1-phenyl-3-pyrazolidone type auxiliary developing agent.

1-Phenyl-3-pyrazolidones as auxiliary developing agents 1-phenyl-3-pyrazolidone, 1-
Phenyl-3-pyrazolidone, 1-phenyl-4,4-
Dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1
-P-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and so on. Of these, 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone is preferred.

In the present invention, when a 1-phenyl-3-pyrazolidone type auxiliary developing agent is used in combination with the developing agent, 0.001 mol / liter to 0.1 is used.
It is preferably used in an amount of mol / l, particularly preferably the latter in an amount of 0.005 mol / l to 0.05 mol / l.

As an auxiliary developing agent exhibiting superadditivity, there is a p-aminophenol type auxiliary developing agent. N-methyl-p as auxiliary developing agent for p-aminophenols
-Aminophenol, N- (β-hydroxyethyl)-
p-aminophenol, N- (4-hydroxyphenyl) -glycine, 2-methyl-p-aminophenol,
There are p-benzylaminophenol, etc., but especially N
-Methyl-p-aminophenol is preferred.

In the present invention, when a p-aminophenol type auxiliary developing agent is used in combination with the developing agent, it is preferably used in an amount of 0.001 mol / liter to 0.1 mol / liter, particularly the latter. To 0.0
It is preferably used in an amount of 05 mol / liter to 0.05 mol / liter.

As the antifoggant added to the developing solution,
Azole compounds (for example, benzothiazolium, benzimidazolium, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.),
Mercapto compounds (for example, mercaptothiazoles, mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc.) Etc. Especially as benzotriazoles, 5
-Methylbenzotriazole, 5-bromobenzotriazole, 5-chlorobenzotriazole, 5-butylbenzotriazole, benzotriazole and the like. Examples of nitroindazoles include 5-nitroindazole,
6-nitroindazole, 4-nitroindazole, 7
-Nitroindazole, 3-cyano-5-nitroindazole and the like can be used.

In the present invention, as a silver stain preventing agent in a developing solution, JP-B-56-46585 and JP-B-62-4702 are used.
No. 4, Japanese Patent Publication No. 62703/1987, and US Pat. No. 4,225,221.
5, U.S. Pat. No. 3,318,701, JP-A-58-20.
3439, JP-A-62-56959, JP-A-62-
No. 178247, JP-A 1-200249, JP-A-5
The compounds described in JP-A-503179 and JP-A-5-53257 can be used.

As the fixing accelerator, Japanese Examined Patent Publication (Kokoku) No. 45-357.
54, JP-A-58-122535 and JP-A-58-122.
536, thiourea derivatives, alcohols having a triple bond in the molecule, thioethers described in US Pat. No. 4,126,459, or anion-free cyclodextran ethers, crown ethers, diazacycloundecene and di ( Hydroxyethyl) butamine and the like. JP-A-7-5654 and 6-273898.
Can include the mesoionic compound described in No.

As a mildew-proofing means, JP-A-60-2639 is used.
Ultraviolet irradiation method described in No. 39, 60-263940
Using the magnetic field described in No. 61-131632
Method using the ion exchange resin described in No.
The methods using the antibacterial agents described in JP-A-61-115154, JP-A-62-153952, JP-A-61-63030 and JP-A-61-51396 can be used in combination.

Furthermore, LF West "Water Quality Cr
iteria "Photo. Sci. & Eng., Vol.9, (1965), MW
Beach "Microbiological Growth in Motion-picture Pr
ocessing "SMTPE Journal Vol. 85 (1976), RD Dee
gan "Photo Processing Wash Water Biocides" J. Imag
ing Tech., Vol. 10, No. 6 (1984), and JP-A-57.
-8542, 57-58143, 58-105.
No. 145, No. 57-132146, No. 58-1863.
No. 1, 57-97530, 57-157244.
The antibacterial agents, antifungal agents, surfactants and the like described in JP-A Nos. 6-118583 and 8-248589 can be used in combination.

Further, for the washing bath or stabilizing bath, R.
T. Kreinman, J. Image. Tech., 10 (6) 242 (198
4) isothiazoline compounds, Research Dis
Closure Volume 205, No. 20526 (May 1981), Isothiazoline Compounds, Volume 228, N
It is also possible to use the isothiazoline compounds described in No. 22845 (April, 1983), the compounds described in Japanese Patent Application No. 61-51396, etc. together as a bacteriostatic agent (Microbiocide).

In addition, as described in “Chemistry of Antibacterial and Antifungal” by Hiroshi Horiguchi, Mitsui Publishing (Showa 57), “Handbook of Antibacterial and Antifungal Technology”, Japan Society of Antibacterial and Antifungal, Hakuhodo (Showa 61) Various compounds may be included.

Further, some or all of the overflow from the washing or stabilizing bath caused by supplementing the washing or stabilizing bath with antifungal water according to the treatment is described in JP-A-60-235133. As described, it can also be used for the pretreatment step of diluting the processing solution having fixing ability.

In the processing system of the present invention, the carry-out amount of the liquid carried out by the sensitive material from the developing tank to the fixing tank and from the fixing tank to the washing tank is preferably 0.01 cc or more and 2 cc or less per 4 sheets, It is preferably 1 cc or more and 1.2 cc or less, more preferably 0.1 cc or more and 0.8 cc or less.

When the washing tank has multiple stages, the carry-out amount from the washing tank to the washing tank is 0.1 cc per 4 sheets.
2cc or less is preferable and 0.1cc or more and 1.2cc or less is more preferable. More preferably 0.1cc or more and 0.8cc
The following are preferred.

The amount of washing water carried out when entering the drying zone from the washing tank is 0.1 cc or more per 4 sheets of sensitive material cut into 2 pieces.
It is preferably cc or less, more preferably 1 cc or less, still more preferably 0.5 cc or less.

The light-sensitive material of the present invention is suitable for rapid processing, and the total processing time (Dry to Dry) until it is carried into the developing tank and the drying process is completed is 90 seconds or less, further 5 to 60 seconds. Preferably there is.

The development in this case is 5 to 30 at 25 to 40 ° C.
Sec., Fixing at 25-40 ° C. for 5-40 seconds, washing with water 0-40
It is preferable to perform the drying at 40 ° C. for 5 to 30 seconds and the drying at 40 to 120 ° C. for 1 to 30 seconds. Further, the replenishing amount is preferably 30 to 650 ml of developing solution, 30 to 650 ml of fixing solution, and 30 to 50,000 ml of washing water per 1 m ² of the light-sensitive material.

For details of such processing, reference can be made to the description in the above-mentioned Japanese Patent Application No. 8-168670.

[0152]

EXAMPLES The present invention will be described below with reference to examples. Example 1 (Preparation of silver halide emulsion A-1) Aqueous solution 1 containing 0.8 g of KBr and 3.2 g of gelatin having an average molecular weight of 20,000.
178 mL was kept at 35 ° C. and stirred. AgNO ₃ (1.
6 g) aqueous solution, KBr (1.16 g) aqueous solution, and gelatin (1.1 g) aqueous solution having an average molecular weight of 20,000 were added over 45 seconds by the triple jet method. The AgNO ₃ solution had a concentration of 0.3 mol / liter. After that, the temperature was raised to 75 ° C over 20 minutes, and the average molecular weight was 10,000.
26 g of 0 gelatin was added. AgNO ₃ (209
g) 75 while accelerating the flow rate by the control double jet method while keeping the aqueous solution and KBr aqueous solution at pAg 8.5.
Added over minutes. After adding gelatin having an average molecular weight of 100,000, it was desalted in a conventional manner. Then, gelatin with an average molecular weight of 100,000 is added and dispersed, and the temperature is 40 ° C.
The pH was adjusted to 5.8 and pAg 8.0 to prepare an emulsion. This emulsion is a tabular grain containing 1 mol of Ag and 60 g of gelatin per kg of emulsion, having an average equivalent circle diameter of 1.2 μm, a variation coefficient of equivalent circle diameter of 21%, an average thickness of 0.12 μm, and an average aspect ratio of 10. there were. The particle shape was measured by observing a transmission electron micrograph image of a replica of the particles.

(Preparation of silver halide emulsion B-1) KBr
1178 mL of an aqueous solution containing 0.8 g and 3.2 g of an oxidation-treated gelatin having an average molecular weight of 20,000 was kept at 35 ° C. and stirred. AgNO ₃ (1.6 g) aqueous solution and KBr (1.1
6 g) aqueous solution and an oxidation-treated gelatin (1.1 g) aqueous solution having an average molecular weight of 20,000 were added by the triple jet method over 45 seconds. AgNO ₃ solution has a concentration of 0.3 mol
/ Liter of solution was used. 75 ℃ over 20 minutes
The temperature was raised to, and 26 g of gelatin having an average molecular weight of 100,000 was added. An AgNO ₃ (209 g) aqueous solution and a KBr aqueous solution were added over 75 minutes while the flow rate was accelerated by the control double jet method while maintaining the pAg at 8.5.
After adding gelatin having an average molecular weight of 100,000, it was desalted in a conventional manner. Then, gelatin with an average molecular weight of 100,000 was added and dispersed, and the pH was 5.8 at 40 ° C. and pAg.
The emulsion was adjusted to 8.0. This emulsion is emulsion 1k
Contains 1 mol of Ag and 60 g of gelatin per g, the average circle equivalent diameter is 1.5 μm, and the variation coefficient of the circle equivalent diameter is 22.
%, The average thickness was 0.10 μm, and the average aspect ratio was 15.

(Preparation of silver halide emulsion C-1) KBr
Oxidized gelatin with 0.8g and average molecular weight of 20,000
1178 mL of an aqueous solution containing 3.2 g was kept at 35 ° C. and stirred
did. AgNO₃(1.6 g) aqueous solution and KBr (1.1
6g) Aqueous solution and oxidatively treated gelatin with an average molecular weight of 20,000
Solution (1.1g) for 45 seconds by triple jet method
Added over. AgNO₃Solution concentration is 0.3 mol
/ Liter of solution was used. 75 ℃ over 20 minutes
Gelatinized with an average molecular weight of 100,000
26 g was added. AgNO ₃(209 g) aqueous solution and K
Control solution while keeping the Br aqueous solution at pAg 8.5.
The flow rate is accelerated by the bull jet method for 75 minutes.
Added Gelatin with an average molecular weight of 100,000 was added
Then, it was desalted according to a conventional method. After that, the average molecular weight is 100
000 gelatin was added and dispersed, and the pH was adjusted to 5.
8, pAg was adjusted to 8.0 to prepare an emulsion. This emulsion
Is 1 mol of Ag and 60 g of gelatin per kg of emulsion
Containing, average circle equivalent diameter 1.8μm, fluctuation of circle equivalent diameter
22% coefficient, average thickness 0.08 μm, average aspect ratio
It was 23 tabular grains.

(Preparation of silver halide emulsion D-1) KBr
Oxidized gelatin with 0.8g and average molecular weight of 20,000
1178 mL of an aqueous solution containing 3.2 g was kept at 35 ° C. and stirred
did. AgNO₃(1.6 g) aqueous solution and KBr (1.1
6g) Aqueous solution and oxidatively treated gelatin with an average molecular weight of 20,000
Solution (1.1g) for 45 seconds by triple jet method
Added over. AgNO₃Solution concentration is 0.3 mol
/ Liter of solution was used. 75 ℃ over 20 minutes
Gelatinized with an average molecular weight of 100,000
26 g was added. AgNO ₃(209 g) aqueous solution and K
Control solution while keeping the Br aqueous solution at pAg 8.9.
The flow rate is accelerated by the bull jet method for 75 minutes.
Added Gelatin with an average molecular weight of 100,000 was added
Then, it was desalted according to a conventional method. After that, the average molecular weight is 100
000 gelatin was added and dispersed, and the pH was adjusted to 5.
8, pAg was adjusted to 8.0 to prepare an emulsion. This emulsion
Is 1 mol of Ag and 60 g of gelatin per kg of emulsion
Contain, average circle equivalent diameter 2.4μm, fluctuation of circle equivalent diameter
Coefficient 28%, average thickness 0.07 μm, average aspect ratio
It was 34 tabular grains.

(Chemical sensitization) Each emulsion prepared as described above was chemically sensitized while being kept at 57 ° C. with stirring. First, the following thiosulfonic acid compound-1 was added in an amount of 10 ^-4 mol per mol of silver halide, and then AgI fine particles having a diameter of 0.03 μm were added in an amount of 0.15 with respect to the total amount of silver.
Mol% was added. After 3 minutes, add 1 × 10 ^-6 thiourea dioxide.
Mol / mol Ag was added, and the mixture was held for 22 minutes to carry out reduction sensitization. Then 4-hydroxy-6-methyl-1,
3,3a, 7-Tetraazaindene was added in an amount of 3 × 10 ^-4 mol per mol of silver halide, and the dispersion of sensitizing dye I-1 shown in Table 1 was used as the amount of sensitizing dye I-1. 1 × 10 ⁻³ mol equivalent per mol of silver halide, and II-11
Is added as the amount of the sensitizing dye II-11 corresponding to 1 × 10 ⁻³ mol per mol of silver halide, and the following sensitizing dye-S is added to the sensitizing dye I corresponding to 3 × 10 ⁻² mol. Then
Further calcium chloride was added.

Subsequently, sodium thiosulfate was added in an amount of 6 × 10 ^-6 mol per mol of silver halide and selenium compound-1.
^Was added in an amount of 4 × 10 ^-6 mol per mol of silver halide, and then chloroauric acid was equivalent to 1 × 10 ^-5 mol per mol of silver halide and potassium thiocyanate was 2 × 10 ⁻ per mol of silver halide. ³ mol equivalent was added. Further, nucleic acid (manufactured by Sanyo Kokusaku Pulp Co., Ltd .: trade name RNA-F) was added in an amount of 67 mg per mol of silver halide. After 40 minutes, 1 × 1 of water-soluble mercapto compound-1 was added per mol of silver halide.
An amount corresponding to 0 ^-4 mol was added and the mixture was cooled to 35 ° C. Thus, the chemical sensitization of the emulsion was completed.

[0158]

[Chemical 21]

(Preparation of Dispersion of Sensitizing Dye I-1) Water 50
1 g of the sensitizing dye I-1 to pH 7.0 ± 0.
5, using a dissolver at 50 ~ 65 ℃ 2000
Mechanically dispersed in solid fine particles of 1 μm or less at ˜2500 rpm, 50 g of 10% gelatin was added, mixed and cooled.

At the time of chemical sensitization, A- except that each dispersion of sensitizing dyes I and II was added in the amount shown in Table 1.
A silver halide emulsion was prepared in the same manner as in 1 to D-1.
When a plurality of dyes were used in combination, each dispersion was added at the same time. The dispersion was prepared in the same manner as in I-1.

[0161]

[Table 1]

(Preparation of Dye Layer Coating Solution) Each component of the dye layer (crossover cut layer) coated as an emulsion lower layer is
The coating liquid was prepared so that the coating amount was as follows.

(Preparation Method of Crossover Cut Dye) Dye A (solid 10 g) to methanol 150 ml and water 5
The mixture was stirred in 0 ml of a mixed solvent while controlling the temperature at 70 ° C. for 2 hours to prepare a water wet cake dye I-46. as a result,
The dye crystals contained 1 mol of methanol and 2 mol of water with respect to 1 mol of the dye. As a method for confirming the crystal solvent, the wet cake was dried at room temperature for measurement, and 1H-NMR was used.
This confirmed the presence of methanol in the crystals. The presence of water of crystallization could be confirmed by Karl Fischer titration. It was also confirmed that when this crystal was heated at 150 ° C, methanol and water of crystallization in the crystal were released. From this, the solid concentration of dye in the wet cake was 50% by weight.

(Preparation Method of Microcrystalline Aqueous Dispersion of Dye for Crossover Cut) The above wet cake dye was treated as a wet cake without being dried, and 3.0 g of the dye solid was weighed. Water for dispersion and 1.2 g of a 25% by weight solution of DEMOL SNB (manufactured by Kao Corporation) as a dispersant were mixed in advance, and the above dye was added to the mixture so that the total amount became 30 g. After adjustment, they were mixed well to form a slurry. Prepare 120 g of zirconia beads, put them in a vessel together with the slurry, and use a 1/16 gallon sand grinder mill (made by AIMEX Co., Ltd.) at 1500 rpm.
The vessel was dispersed by water rotation while rotating. The average particle size of the zirconia beads was 1 mm, and the dispersion time was 8 hours. After the dispersion is completed, the solid content concentration of the dye
Water was added so that the amount of the dispersion became 5% by weight, and the dispersion was taken out.
This dye dispersion was designated as DP1.

(Method for Preparing Crossover Cut Layer Coating Solution) Each compound was added to the water mother liquor so that the coating amount was as follows. The coating amount of the material per 1 m ^{2 on} one side was described in the order of addition of each compound.・ Gelatin 0.47g ・ DP1 (dispersion of dye for crossover cut) 8.4mg as dye solid content ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 10mg ・ A-15 mg ・ Preservative D 1mg At this time, acetic acid or water The pH of this coating solution was adjusted to 6.0 with a small amount of sodium oxide. The coating amount was 12.4 ml per 1 m ² on one side.

[0166]

[Chemical formula 22]

(Preparation Method of Emulsion O Layer Coating Solution) Each material was added to the emulsion in the following coating amounts. The amount of material applied was 1 m ^{2 on} one side.・ Coated silver amount 0.90g ・ Gelatin 0.85g ・ Dextran (average molecular weight 39,000) 214mg ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 20mg ・ A-2 102mg ・ A-3 1.1mg ・ A-4 0.25mg ・ A -5 1.4mg ・ 1,2-bis (vinylsulfonylacetamide) ethane 25mg At this time, the coating liquid amount of this emulsion layer was 22.6m per 1m ² on one side.
It was l.

(Preparation Method of Emulsion U Layer Coating Solution) Each compound was added to the emulsion in the following coating amounts. One side 1m ²
Material coating amount per unit ・ Coating silver amount 0.35 g ・ Gelatin 0.40 g ・ Dextran (average molecular weight 39,000) 130 mg ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 7 mg ・ A-2 60 mg ・ A-3 0.80 mg ・ A- 4 0.10mg ・ A-5 0.48mg ・ Dye-1 (oil emulsion) 0.33g as dye solids ・ 1,2-bis (vinylsulfonylacetamido) ethane 25mg At this time, the coating amount of this emulsion layer was 1m ² on each side. Per 10.0m
It was l. The compounds in the above were as follows.

[0169]

[Chemical formula 23]

(Preparation Method of Surface Protective Layer Coating Solution) Each compound was added so that the coating amount was as follows. Material application amount per 1 m ^{2 on} one side ・ Gelatin 0.767 g ・ Sodium polyacrylate (average molecular weight 400,000) 80 mg ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.1 mg ・ Mat agent-1 (average particle size 3.7 μm) Solid 70mg ・ A-6 18.1mg ・ A-7 34.5mg ・ A-8 6.8mg ・ A-9 3.2mg ・ A-10 1.4mg ・ A-11 2.1mg ・ A-12 1.0mg ・ Preservative D 0.9 mg.p-benzoquinone 0.7 mg At this time, a small amount of sodium hydroxide was used to adjust the pH of the coating solution for the surface protective layer to 6.8. The coating amount was 10.7 ml per 1 m ² on one side. The compounds in the above were as follows.

[0171]

[Chemical formula 24]

[0172]

[Chemical 25]

[0173]

[Chemical formula 26]

Corona discharge was performed on a biaxially stretched blue dyeing (containing 1,4-bis (2,6-diethylanilinoanthraquinone) polyethylene terephthalate support having a thickness of 175 μm, and the following main components were added. Each of the coating solutions contained was applied to both sides of the support by a wire bar coater in the order of the first undercoat layer and the second undercoat layer.

First Undercoat Layer (Support Side) The amount of coating liquid per 1 m ² on one side of the support was 4.9 ml. The coating amount of each additive material per 1 m ² on one side of the support is as follows.・ Styrene-butadiene copolymer latex (as solid content) 0.31 g ・ 2,4-dichloro-6-hydroxy-s-triazine sodium 8 mg Drying temperature 190 ° C

The amount of coating solution per 1 m ² on one side of the second undercoat layer support was 7.9 ml. The coating amount of each additive material per 1 m ² on one side of the support is as follows.・ Gelatin 80mg ・ C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 1.8mg ・ Preservative D 0.27mg ・ Polymethyl methacrylate average particle size 2.5μm matting agent 2.5mg Drying temperature 185 ℃

(Coating Method for Photographic Material) A dye layer is formed from the support side on the undercoated support prepared as described above.
The emulsion U layer, the emulsion O layer, and the surface protective layer were simultaneously coated on both sides by the simultaneous extrusion method so as to have a constitution and dried.

(Measurement of Swelling Ratio of Photographic Material) First, the photographic material to be measured was aged for 7 days under the conditions of 40 ° C. and relative humidity of 60%. Next, this sensitive material was immersed in distilled water at 21 ° C. for 3 minutes, and this state was frozen and fixed with liquid nitrogen. This photographic material was cut with a microtome so that its cross section was perpendicular to the surface of the photographic material, and then freeze-dried at -90 ° C. The swelled film thickness Tw was obtained by observing the above-mentioned processed material with a scanning electron microscope. On the other hand, the film thickness Td in the dry state was also obtained by observing the cross section using a scanning electron microscope. Tw obtained in this way
The difference between Td and Td was divided by Td and multiplied by 100 to give a swelling ratio (unit:%). When each photographic material was measured by this method, the swelling ratio was 170%.

(Evaluation of Photographic Performance) The photographic material was brought into close contact with both sides by using an X-ray orthoscreen HGM2 manufactured by Fuji Film Co., Ltd., exposed from both sides for 0.05 seconds, and X-ray sensitive. Totometry was performed. The X-ray apparatus used was a trade name DRX-3724HD manufactured by Toshiba Corporation, and a tungsten target was used. A voltage of 80 kVp was applied to the three phases with a pulse generator, and an X-ray that passed through a filter of 7 cm of water having absorption almost equivalent to the human body was used as a light source. The X-ray exposure amount was changed by the distance method, and logE = 0.
Step exposure was performed with a width of 15. After exposure, development processing was performed under the following development processing conditions, and the density was measured with visible light to obtain a characteristic curve.

(Processing) Automatic processor: CEPROS manufactured by FUJIFILM Corporation
-30 Preparation of concentrated solution

[0181] <Developer>   Parts agent A     330 g potassium hydroxide     Potassium sulfite 630 g     Sodium sulfite 255 g     90 g potassium carbonate     Boric acid 45 g     180 g of diethylene glycol     Diethylenetriamine pentaacetic acid 30 g     1- (N, N-diethylamine) ethyl-5-mercapto       Tetrazole 0.75g     Hydroquinone 450 g     4-hydroxymethyl-4-methyl-1-phenyl-3-       Pyrazolidone 60 g     4125 ml with water   Parts agent B     Diethylene glycol 525 g     3,3 'dithiobishydrocinnamic acid 3 g     Glacial acetic acid 102.6g     2-nitroindazole 3.75g     1-phenyl-3-pyrazolidone 34.5 g     750 ml with water   Parts agent C     Glutaraldehyde (50wt / wt%) 150 g     Potassium bromide 15 g     Potassium metabisulfite 105 g     750 ml with water

[0182] <Fixer>     3000 ml ammonium thiosulfate (70 wt / vol%)     Ethylenediaminetetraacetic acid / disodium / dihydrate 0.45 g     Sodium sulfite 225 g     Boric acid 60 g     1- (N, N-diethylamine) -ethyl-5-mercap       Totetrazole 15 g     Tartaric acid 48 g     Glacial acetic acid 675 g     Sodium hydroxide 225 g     Sulfuric acid (36N) 58.5 g     Aluminum sulfate 150 g     6000 ml with water       pH 4.68

(Preparation of Processing Solution) The developer solution was filled in the following containers for each parts agent. In this container, the partial containers of the parts agents A, B and C are connected together by the container itself.

Further, the above-mentioned fixing solution concentration was filled in the same kind of container.

First, 300 ml of an aqueous solution containing 54 g of acetic acid and 55.5 g of potassium bromide was used as a starter in the developing tank.
Was added.

The processing agent-containing container was turned upside down and inserted into the perforating blade of the processing solution stock tank mounted on the side of the developing machine to break the sealing film of the cap and remove each processing agent in the container. The stock tank was filled.

Each of the processing agents was filled in the developing tank and the fixing tank of the automatic developing machine at the following ratios by operating the pumps installed in the automatic developing machine.

Also, every time 8 sheets of the photosensitive material were processed in terms of 4-cut size, the stock solution of the processing agent and water were mixed at this ratio and replenished in the processing tank of the developing machine.

Developer Parts agent A 51 ml Parts agent B 10 ml Parts agent C 10 ml 125 ml water pH 10.50 Fixer Concentrated liquid 80 ml 120 ml water pH 4.62 The wash tank was filled with tap water.

As a water stain preventive agent, 0.4 g of actinomycetes supported on perlite having an average particle size of 100 μm and an average pore size of 3 μm was covered with a polyethylene bottle (the bottle opening was covered with a 300-mesh nylon cloth. Prepare three pieces filled with water and fungi from the cloth), two of them at the bottom of the washing tank, and one at the bottom of the stock tank for washing water (liquid volume 0.2 liters). I sunk each.

The sensitivity is represented by the reciprocal of the exposure amount that gives a density of Fog + 1.0, and the sensitivity of Sample 1 is 1
It was set to 00.

Evaluation of residual color The light-sensitive material was cut into 30.5 cm × 25.4 cm, the washing water was heated to 5 ° C., and the above-mentioned treatment was carried out for 30 seconds in dry to dry. Was visually evaluated according to the following criteria. A: Almost no color remains. ◯: There is a slight residual color, but it does not bother me. Δ: Color remains, but is practically acceptable. X: Many residual colors are not possible. The results are shown in Table 2.

[0193]

[Table 2]

From Table 2, it is understood that the light-sensitive material using the emulsion of the present invention and the light-sensitive material of the present invention are excellent in sensitivity, Dmax and residual color. For example, a sample chemically sensitized without compound II has low sensitivity and high fog,
Increasing the amount of Compound I increases the sensitivity and reduces the fog, but the residual color fails. On the other hand, the sample of the present invention has high sensitivity, low fog, and excellent residual color. Also, for samples with an average aspect ratio of 12 or more,
It is more excellent in terms of sensitivity and Dmax.

Example 2 In the method for preparing the silver halide emulsions A-1 to D-1 of Example 1, A-1 to A-1 were used except that the temperature during grain formation, the gelatin species used, and pAg during growth were adjusted. An emulsion having the grain size shown in Table 3 was prepared in the same manner as in D-1, and the sensitizing dye I-1 was added at 0.5 × 10 ⁻³ mol / molA during chemical sensitization.
Chemical sensitization was carried out in the same manner as in the emulsion of Example 1 except that 0.5 × 10 ⁻³ mol / mol Ag of g and II-11 was added.

Using the obtained emulsion, coating materials were prepared in the same manner as in Example 1, and the sensitivity, fog, Dmax and residual color were evaluated in the same manner as in Example 1. The sensitivity was expressed as a relative value with the sensitivity of Sample 26 being 100. As is clear from Table 3, the embodiments of the present invention can provide good results in the aspect ratio range of the present invention.

[0197]

[Table 3]

[0198]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and high Dmax and suitable for rapid processing with little residual color can be obtained.

Claims (2)

[Claims] 1. A photosensitive silver halide emulsion containing tabular silver halide grains having an average aspect ratio of 12 or more, a compound represented by the following general formula (I) and a compound represented by the following general formula (II), Moreover, the addition amount of the sensitizing dye of the general formula (I) is 1
A silver halide photographic light-sensitive material characterized by being in the range of 0.2 × 10 ⁻³ mol to 1.5 × 10 ⁻³ mol per mol. [Chemical 1] [In the general formula (I), Z ₁₁ and Z ₁₂ represent a non-metal atom group necessary for forming an oxazole nucleus which may be condensed with an aromatic ring. R ₁₁ and R ₁₂ each represent an alkyl group, and at least one of them represents a sulfoalkyl group. Q represents a hydrogen atom or an alkyl group, and Y represents an ion necessary for balancing charges. n ₁ is 0 or 1, and is 0 when forming an inner salt. ] [Chemical 2] [In the general formula (II), Z ₂₁ and Z ₂₂ are each a benzoxazole nucleus, a benzothiazole nucleus, a benzoselenazole nucleus, a naphthoxazole nucleus, a naphthothiazole nucleus, a naphthoselenazole nucleus, a thiazole nucleus, a thiazoline nucleus, an oxazole nucleus, It represents a group of non-metal atoms necessary for completing a selenazole nucleus, a selenazoline nucleus, a pyridine nucleus, a benzimidazole nucleus or a quinoline nucleus. R ₂₁ and R ₂₂ each represent an alkyl group or an aralkyl group. X ₂ is a charge balancing counterion and n ₂ is 0 or 1. ] 2. A silver halide photographic light-sensitive material for medical X-ray photography, comprising at least one non-light-sensitive layer and one light-sensitive layer containing light-sensitive silver halide emulsion grains on both sides of a transparent support. Containing tabular silver halide grains having an average aspect ratio of 12 or more, a compound of the general formula (I) and a compound of the general formula (II), and the addition amount of the sensitizing dye of the general formula (I) is 0.2 × 10 ^-3 mol or more per silver mole 1.5 × 10
^-3 mol or less, a silver halide photographic light-sensitive material for medical X-ray photography, characterized in that