JPH0980679A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material in which a silver image can be provided in a short time, and a satisfactory dot image which has low color residue and Dmin by fogging, and is excellent in image quality with high density can be provided particularly by Ar laser exposure. SOLUTION: In a silver halide photosensitive material containing at least a photosensitive silver halide emulsion having silver chloride content ratio of 80 mole % or more, a hydrophilic binder and a basic metal compound hardly soluble to water on a base, it contains a sensitizing pigment represented by the formula. In the formula Z11 and Z12 represent nonmetal atomic group needed to complete a 5-membered or 6-membered nitrogenous heterocyclic nucleus. R11 and R12 each represent alkyl group, substituted alkyl group, or aryl group. n11 and n12 each represent 0 or 1. Z1 represents anion. (m) represents 0 or 1, and m=1 when an intramolecular salt is formed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a silver halide photosensitive material, and more particularly to a photothermographic material capable of obtaining a black and white image having a high density and a low fog quality in a short time.

[0002]

2. Description of the Related Art A photographic method using silver halide is superior to other photographic methods such as electrophotography and diazo photography in photographic characteristics such as sensitivity, gradation control and resolution, and thus has been the most widely used. Has been used for At present, image information has largely changed from black-and-white images to color images because of the large amount of information and ease of expression.
Black and white images are favorably used in medical fields.
Further, in the printing field, plate making materials for color images are also used as black and white images for each printing ink, and there is still a great demand mainly for industrial applications. In recent years, the image formation processing method for photosensitive materials using silver halide has been changed from the conventional wet processing to an instant system containing a developing solution, and dry heat development processing such as heating to easily and quickly produce images. Obtainable systems have been developed, including environmental protection. Regarding such a photothermographic material, “Basics of Photographic Engineering (Non-silver salt photography)” published by Corona Publishing Co., Ltd., pages 242 to 255, JP-B-43-4
921 and JP-B-43-4924. As a product, in the black and white series, 3M's dry silver sensitive material is on sale. Like dry silver,
In a monosheet photosensitive material composed of silver halide, an organic silver salt and a reducing agent, unused silver halide or organic silver salt remains in the image subjected to the heat development treatment. Therefore, when exposed to intense light or stored for a long period of time, the remaining silver halide or organic silver salt is printed out and the white background is colored, and the contrast is lost. Also, a method for obtaining a black color image by dry processing is described in Research Disclosure (hereinafter abbreviated as RD) September 1978 issue 4.
9 to 51 (RD17326), this system also has the same drawbacks as the above because it is an unfixed type containing a silver salt in the color image.

In order to improve these drawbacks, a movable (diffusible) dye is imagewise formed or released by heating, and then this movable dye is used as a dye receiving substance by using various transfer solvents. For example, a method for forming a black and white image with improved storability by transferring to a dye fixing material containing a mordant, a heat-resistant organic polymer, etc. is disclosed in Japanese Patent Publication No. 3-78617.
No. 3,45,820. However, since these methods are methods of transferring after heat development, the number of steps is large and the processing time is long. Furthermore, JP-A-3
-260645 discloses a method of heat development transfer type black and white image formation utilizing a coupling reaction, a method of transferring after development and a method of simultaneously performing development and transfer. However, this method also requires a high temperature and a long time for processing because it does not have an effective development transfer accelerator. JP 6
2-1219848 discloses that a black and white image can be formed with a transferred dye image by heat development using a small amount of water. However, in order to obtain an image at a transmission density of 2 or more required for many black-and-white images in a short time by a dye transfer method, it is necessary to reduce the film thickness of a light-sensitive material, especially the amount of a binder as much as possible, or to use a dye-donating compound. It is necessary to increase the amount. For this reason, there arises a problem that the film quality is reduced and the manufacturing cost is increased. Further, there is a problem that the use is limited because the sharpness is lowered by the transfer. Further, it is difficult to synthesize a black dye-donating compound, and it is also difficult to obtain a neutral gray color image by mixing yellow, magenta, and cyan dye-donating compounds. Further, a method of forming a silver image by heat development silver salt diffusion transfer using a silver halide light-sensitive material is disclosed in JP-A Nos. 62-283332, 63-198050, 60-194448 and the like. However, these methods are also methods using a transferred silver image, and it is difficult to obtain an image having a transmission density of 2 or more and a high sharpness in a short time, and there is a need for improvement.

On the other hand, one of the exposure methods for photographic light-sensitive materials is
An image forming method by a so-called scanner method is known in which an original image is scanned and exposed on a silver halide photographic light-sensitive material based on the image signal to form a negative image or a positive image corresponding to the image of the original image. . There are various recording devices that have practically used the image forming method by the scanner method,
Conventionally, glow lamps, xenon lamps, mercury lamps, and
Tungsten lamps, light emitting diodes, etc. have been used. However, each of these light sources has a practical defect that the output is weak and the life is short. In order to make up for these drawbacks, a method using a laser beam has recently been often used for a color scanner and an image setter, particularly in the printing field. As laser light, gas lasers such as Ar and He-Ne and solid-state lasers such as semiconductor lasers are known. Among these laser lights, Ar lasers are widely used because of their strong output at a short wavelength of 488 nm. Has been done. The photosensitive material is sensitized in accordance with the wavelength of these lasers, and the laser-exposed image is usually output in the form of halftone dots. These sensitizations can be carried out by a widely known means of spectral sensitization using a sensitizing dye, but a high density and low fog image quality can be obtained by using a conventionally known laser exposure device. A photothermographic material capable of obtaining a good black-and-white image in a short time has not yet been provided as a satisfactory material although desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to obtain a silver image in a short time, and Dmin due to residual color and fog.
It is an object of the present invention to provide a silver halide photographic light-sensitive material having a low density, a high density and an excellent image quality, and in particular, an excellent halftone image can be obtained by Ar laser exposure.

[0006]

The above-mentioned object is to contain a photosensitive silver halide emulsion having a silver chloride content of 80 mol% or more, a hydrophilic binder, and a basic metal compound sparingly soluble in water on a support. In the silver halide light-sensitive material
The following general formula (Ia), general formula (Ib), and general formula (Ic)
And a sensitizing dye represented by the general formula (Id), and a silver halide photographic light-sensitive material.

[0007]

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In the formula, Z ₁₁ and Z ₁₂ represent a group of non-metallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₁₁ and R ₁₂ each represent an alkyl group, a substituted alkyl group, or an aryl group. n ₁₁ and n ₁₂ are each 0
Or represents 1. X ₁ represents an anion. m represents 0 or 1, and m = 0 when forming an intramolecular salt.

[0009]

[Chemical 6]

In the formula, Z ₂₁ represents a nonmetallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. Q ₂₁
Is 4-thiazolidinone, 5-thiazolidinone, or 4
Represents a group of non-metal atoms necessary to complete the imidazolidinone nucleus. R ₂₁ and R ₂₂ each represent an alkyl group, a substituted alkyl group, or an aryl group. n ₂₁ is 0 or 1
Represents

[0011]

[Chemical 7]

In the formula, Z ₃₁ represents a non-metal atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₃₁
And R ₃₂ each represent an alkyl group, a substituted alkyl group, or an aryl group. Q ₃₁ represents a non-metallic atomic group necessary for completing a 4-thiazolidinone, a 5-thiazolidinone, or a 4-imidazolidinone nucleus. n ₃₁ is 0 or 1
Represents

[0013]

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In the formula, Z ₄₁ and Z ₄₂ represent a group of nonmetallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₄₁ and R ₄₂ each represent an alkyl group, a substituted alkyl group, or an aryl group. L ₄₁ represents a methine group or a substituted methine group. X ₄ represents an anion. m represents 0 or 1, and m = 0 when forming an intramolecular salt.

Next, general formulas (Ia), (Ib) and (Ic)
And (Id) will be described in more detail. Where:
Z ₁₁ , Z ₁₂ , Z ₂₁ , Z ₃₁ , Z ₄₁ and Z ₄₂ each represent a non-metal atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus, for example, a thiazole nucleus [eg benzo. Thiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole,
5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole,
6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethyl Benzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3]
-D] thiazole, 5-methoxynaphtho [1,2-d]
Thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole,
5-methoxynaphtho [2,3-d] thiazole, etc.],
Selenazole nucleus [for example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [2,1-d] selenazole, naphtho [1, 2-d] selenazole and the like], oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 6-hi B carboxymethyl benzoxazole,
4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,2]
3-d] oxazole etc.], quinoline nucleus [eg 2-
Quinoline, 3-methyl-2-quinoline, 5-ethyl-2
-Quinoline, 6-methyl-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline,
8-fluoro-4-quinoline and the like], 3,3-dialkylindolenine nucleus (eg, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3 , 3-dimethyl-5
Methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-dimethyl-5-chloroindolenine, etc., imidazole nucleus (for example, 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-
Methyl-5-chlorobenzimidazole, 1-ethyl-
5-chlorobenzimidazole, 1-methyl-5,6-
Dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1-methyl-5-cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-methyl- 5-fluorobenzimidazole,
1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho [1,2-d] imidazole), pyridine nucleus (For example, pyridine, 5-
Methyl-2-pyridine, 3-methyl-4-pyridine and the like).

At least one of Z ₁₁ and Z ₁₂ is preferably selected from a naphthothiazole nucleus, a naphthoselenazole nucleus or a quinoline nucleus. Z ₃₁ is preferably selected from a benzothiazole nucleus, a benzoselenazole nucleus, a naphthothiazole nucleus, a naphthoselenazole nucleus, a quinoline nucleus or a pyridine nucleus.

In the formula, R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ ,
R ₃₂ , R ₄₁ and R ₄₂ may be the same or different and each is an alkyl group (preferably having 1 carbon atom).
.About.8, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, etc.). The alkyl group includes a substituted alkyl group, and examples of the substituent include a carboxy group, a sulfo group, a cyano group, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), a hydroxy group, an alkoxycarbonyl group (having 8 carbon atoms). Hereinafter, for example, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group, etc., alkoxy group (having 7 or less carbon atoms, for example, methoxy group, ethoxy group,
Propoxy group, butoxy group, benzyloxy group, etc.),
Aryloxy group (for example, phenoxy group, p-tolyloxy group, etc.), acyloxy group (having 3 or less carbon atoms, for example, acetyloxy group, propionyloxy group, etc.),
Acyl group (C8 or less, for example, acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (for example, carbamoyl group, N, N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.) , A sulfamoyl group (eg, sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), an aryl group (eg, phenyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, α) -Naphthyl group, etc.)
and so on. In the case of a substituted alkyl group, the alkyl portion preferably has 6 or less carbon atoms. In addition, two or more substituents may be combined and substituted with an alkyl group. L ₂₁ , L ₂₂ , and L
₄₁ is a methine group or a substituted methine group (lower alkyl group (eg, methyl group, ethyl group, propyl group, etc.), lower alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), phenyl group, substituted phenyl group Group (for example, carboxyphenyl group, etc.), methine group substituted with benzyl group, etc.].

The general formulas (Ia) and (I
Specific examples of the sensitizing dyes represented by b), (Ic) and (Id) are shown below. However, the present invention is not limited to these specific examples.

[0019]

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[0020]

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[0021]

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[0022]

[Chemical 12]

[0023]

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[0024]

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[0025]

[Chemical 15]

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

[Chemical 21]

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

[Chemical formula 26]

[0037]

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[0038]

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[0039]

[Chemical 29]

[0040]

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[0041]

[Chemical 31]

[0042]

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The above-mentioned sensitizing dyes used in the present invention are 5 × 10 ⁻⁷ to 1 × 10 ⁻² mol per mol of silver halide.
It is preferably contained in the silver halide photographic emulsion in a ratio of 1 × 10 ^-6 mol to 5 × 10 ^-3 mol, particularly preferably 2 × 10 ^-6 mol to 1 × 10 ^-3 mol. The sensitizing dyes used in the present invention can be directly dispersed in the emulsion. In addition, these are first of all suitable solvents such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone,
It may be dissolved in water, pyridine or a mixed solvent thereof and added to the emulsion in the form of a solution. Also,
Ultrasound can also be used for lysis. The method of adding the infrared sensitizing dye is described in US Pat. No. 3,469,
No. 987 etc., the dye is dissolved in a volatile organic solvent and the solution is dispersed in a hydrophilic colloid,
A method of adding this dispersion into an emulsion, JP-B-46-24
No. 185, etc., a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to an emulsion; as described in US Pat. No. 3,822,135. A method in which a dye is dissolved in a surfactant and the solution is added to an emulsion; as described in JP-A-51-74624, a compound for red-shifting is used for dissolution, and the solution is added to the emulsion. Method: JP-A-50-80
A method in which a dye as described in No. 826 is dissolved in an acid containing substantially no water and the solution is added to the emulsion is used. In addition, US Pat.
No. 2,343, No. 3,342,605, No. 2,9
The methods described in Nos. 96,287 and 3,429,835 are also used. In the present invention, the general formula (I
The sensitizing dyes represented by a), (Ib), (Ic) and (Id) are preferably used in combination with at least one of the compounds represented by the following general formula (II). General formula (II)

[Chemical 33] In the formula, Z ₆ represents a group of non-metal atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocycle, for example, thiazolium compounds {eg thiazolium, 4-methylthiazolium, benzothiazolium, 5- Methylbenzothiazolium, 5-
Chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2,1-d] thiazolium, etc. }, Oxazolium {for example, oxazolium, 4-methyloxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5
-Methylbenzoxazolium, naphtho [1,2-d]
Oxazolium, etc.}, imidazoliums (for example, 1-
Methylbenzimidazolium, 1-propyl-5-chlorobenzimidazolium, 1-ethyl-5,6-dichlorobenzimidazolium, 1-allyl-5-trichloromethyl-6-chloro-benzimidazolium, etc.), selenazoliums [Eg, benzoselenazolium, 5-chlorobenzoselenazolium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho [1,2-d] selenazolium, etc.] and the like. R
₆₁ represents a hydrogen atom, an alkyl group (having 8 or less carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like) and an alkenyl group (for example, an allyl group and the like). R ₆₁ is preferably an alkyl group or an alkenyl group. R ₆₂ represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc.). X ₆ is an acid anion (for example, Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , p-toluenesulfonate ion, etc.), and among Z ₆ , preferably thiazolium compounds are advantageously used. More preferably, benzothiazolium or naphthothiazolium (including those having a substituent) is advantageously used. Specific examples of the compound represented by the general formula (II) used in the present invention are shown below. However, the present invention is not limited to these specific examples.

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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The compound represented by the general formula (II) is used in an amount of about 0.01 to 5 g per mol of silver halide.
Advantageously used in quantities of grams. The ratio (weight ratio) of the sensitizing dyes represented by the general formulas (1a), (Ib), (Ic) and (Id) of the present invention to the compound represented by the general formula (II) is as follows. Sensitizing dye / compound represented by the general formula (II) = 10/1 to 1/50 is preferably used, and particularly preferably 5/1 to 1/10. The compound represented by the general formula (II) used in the present invention can be directly dispersed in an emulsion, and a suitable solvent (for example, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.) or It is also possible to dissolve them in a mixed solvent containing a plurality of these solvents and add them to the emulsion. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of addition. The compound represented by the general formula (II) is a compound represented by the general formula (1) of the present invention described above.
It may be added to the emulsion before the addition of the sensitizing dyes represented by a), (Ib), (Ic) and (Id),
It may be added later. Further, the compound of the general formula (II) and the sensitizing dyes represented by the general formulas (1a), (Ib), (Ic) and (Id) are separately dissolved, and these are separately or simultaneously added to the emulsion. Alternatively, they may be mixed and then added into the emulsion. In the present invention, the general formula (1
It is preferable to use the sensitizing dyes represented by a), (Ib), (Ic) and (Id) in combination with at least one compound represented by the following general formula (III). General formula (III)

[0050]

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In the formula, -A- represents a divalent aromatic residue, which is a -SO ₃ M group (where M represents a hydrogen atom or a cation imparting water solubility (for example, sodium, potassium, etc.). ] May be included. As -A-, those selected from the following -A ₁ -or -A _2- are useful. However, when R ₇₁ , R ₇₂ , R ₇₃ or R ₇₄ is -SO ₃ M
When is not included, -A- is selected from the group of -A _1- . -A _1- Example

[0052]

[Chemical 40]

Example of -A _2-

Embedded image R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ are each a hydrogen atom, a hydroxy group, a lower alkyl group (preferably having 1 to 8 carbon atoms. For example, methyl group, ethyl group, n-propyl group, n-
Butyl group, etc.), alkoxy group (1 carbon atom
To 8 are preferable, for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), aryloxy group (for example, phenoxy group, naphthoxy group, o-troxy group, p-sulfophenoxy group, etc.), halogen atom (for example, chlorine atom, Bromine atom etc.), heterocyclic nucleus (eg morpholinyl group, piperidyl group etc.), alkylthio group (eg methylthio group, ethylthio group etc.), heterocyclylthio group (eg benzothiazolylthio group, benzimidazolyl group, phenyltetrazolylthio group etc.) ), Arylthio groups (eg phenylthio group, tolylthio group), amino groups, alkylamino groups (including substituted alkylamino groups)
(For example, methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di- (β-hydroxyethyl) amino group, β-sulfo. Ethylamino group), arylamino groups (including substituted arylamino groups) (eg anilino groups,
o-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, o-toluidino group, m-toluidino group, p-toluidino group, o-carboxyanilino group, m
-Carboxyanilino group, p-carboxyanilino group,
o-chloroanilino group, m-chloroanilino group, p-chloroanilino group, p-aminoanilino group, o-anisino group, m-anisidino group, p-anisino group, o-acetaminoanilino group, hydroxyanilino group, di- Sulfophenylamino group, naphthylamino group, sulfonaphthylamino group, etc.), heterocyclylamino group (eg, 2-benzothiazolylamino group, 2-pyrazyl-amino group, etc.), aralkylamino group (including substituted aralkylamino group) (Eg, benzylamino group, o-anisylamino group, m-anisylamino group, p-anisylamino group, etc.), aryl group (eg, phenyl group), and mercapto group.

R ₇₁ , R ₇₂ , R ₇₃ and R ₇₄ may be the same or different from each other. When —A— is selected from the group of —A ₂ —, at least one of R ₇₁ , R ₇₂ , R ₇₃ , and R ₇₄ has at least one sulfo group (which may be a free acid group and forms a salt). May be required). W represents -CH = or -N =. Next, specific examples of the compound contained in the general formula (III) used in the present invention will be given. However, the present invention is not limited only to these compounds.

(III-1) 4,4'-bis [4,6-di (benzothiazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (III-2) 4,4'-bis [4,6-di (benzothiazolyl-2-amino) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt (III-3) 4,4'-bis [4 , 6-di (naphthyl-
2-Oxy) pyrimidin-2-ylamino] stilbene-2,2′-disulfonic acid disodium salt (III-4) 4,4′-bis [4,6-di (naphthyl-
2-Oxy) pyrimidin-2-ylamino] bibenzyl-2,2'-disulfonic acid disodium salt (III-5) 4,4'-bis (4,6-dianilinopyrimidin-2-ylamino) stilbene-2, 2'-Disulfonic acid disodium salt (III-6) 4,4'-bis [4-chloro-6- (2-
Naphthyloxy) pyrimidin-2-ylamino] biphenyl-2,2'-disulfonic acid disodium salt

(III-7) 4,4'-bis [4,6-di (1-phenyltetrazolyl-5-thio) pyrimidine-
2-ylamino] stilbene-2,2′-disulfonic acid disodium salt (III-8) 4,4′-bis [4,6-di (benzimidazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2, 2'-Disulfonic acid disodium salt (III-9) 4,4'-bis (4,6-diphenoxypyrimidin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (III-10) 4 , 4'-bis (4,6-diphenylthiopyrimidin-2-ylamino) stilbene-2,2'-
Disulfonic acid disodium salt (III-11) 4,4'-bis (4,6-dimercaptopyrimidin-2-ylamino) biphenyl-2,2'-disulfonic acid disodium salt (III-12) 4,4 ' -Bis (4,6-dianilino-triazin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt (III-13) 4,4'-bis (4-anilino-6-hydroxy-triazine-2 -Ilamino) stilbene-
2,2'-Disulfonic acid disodium salt (III-14) 4,4'-bis (4-naphthylamino-6)
-Anilino-triazin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt Among these specific examples, (III-1) to (III-12) are preferred, and (III-1) to (III-2), (III-3),
(III-4), (III-5) and (III-7) are preferred. The compound of general formula (III) is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion.

The sensitizing dye of the present invention described above and the general formula (II
The ratio (weight ratio) to the compound represented by I) is as follows: sensitizing dye / compound represented by the general formula (III) = 1/1 to 1/10
The range of 0 is preferably used, and the range of 1/2 to 1/50 is particularly preferably used. The compound represented by the general formula (III) used in the present invention can be directly dispersed in an emulsion, or in a suitable solvent (eg, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixed solvent thereof. It is also possible to add it to the emulsion by dissolving it in. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of addition. Further, it can be dispersed and added to the emulsion by the method described in JP-A-50-80119.

In the present invention, a compound capable of undergoing a complex formation reaction with a basic metal compound which is hardly soluble in water used in a light-sensitive material and a metal ion which constitutes the hardly soluble metal compound used in a complexing agent sheet (complex forming compound). Is used as a base precursor. That is, they both release a base as a result of a complexing reaction in the presence of water. Regarding the combination of the sparingly soluble basic metal compound and the complex-forming compound, JP-A-62-129848, European Patent Publication 210,660A2, US Pat.
No. 445, etc. Preferable sparingly soluble basic metal compounds are zinc or aluminum oxides, hydroxides and basic carbonates, particularly preferably zinc oxide, zinc hydroxide and basic zinc carbonate. The sparingly soluble basic metal compound is used by dispersing fine particles in a hydrophilic binder as described in JP-A-59-174830. The average particle size of the fine particles is 0.001 to 5 μm, preferably 0.01 to 2 μm. Content in the light-sensitive material is ^{0.01g / m 2 ~5g / m 2} , preferably 0.
05 to ² g / m ² .

The complex-forming compound used for the sheet containing the complex-forming compound (hereinafter referred to as the complexing agent sheet) is known as a chelating agent in analytical chemistry and a water softening agent in photographic chemistry. The details are described in A. It is also described in "Complexing Reaction" (Sangyo Tosho) translated by Ringbom, Nobuyuki Tanaka, Haruko Sugi. Preferred complex-forming compounds for the present invention are water-soluble compounds, for example, aminopolycarboxylic acids (including salts) such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, aminotris (methylenephosphonic acid), ethylenediamine Examples thereof include aminophosphonic acids (salts) such as tetramethylenephosphonic acid, and pyridinecarboxylic acids (salts) such as 2-picolinic acid, pyridine-2,6-dicarboxylic acid, and 5-ethyl-2-picolinic acid. Among these, pyridinecarboxylic acid (salt) is particularly preferred. In the present invention, the complex-forming compound is preferably used as a salt neutralized with a base. Particularly, salts with organic bases such as guanidines, amidines and tetraalkylammonium hydroxide and salts with alkali metals such as sodium, potassium and lithium are preferred. Specific examples of preferable complex-forming compounds are described in JP-A-62-129848 and European Patent Publication 210,660A.
No. 2 etc. The content of the complex forming compound in the complexing agent sheet is 0.01 to 10 g / m ² , and preferably 0.05 to 5 g / m ² .

In the present invention, the complexing agent sheet contains physical development nuclei. The physical development nuclei reduce the soluble silver salt diffused from the light-sensitive material to convert it into physically developed silver, thereby forming the complexing agent. It is fixed to the seat. Physical development nuclei include zinc, mercury, lead, cadmium, iron, chromium, nickel,
Heavy metals such as tin, cobalt, and copper, or precious metals such as palladium, platinum, silver, and gold, or their sulfur,
All known physical development nuclei such as colloidal particles of chalcogen compounds such as selenium and tellurium can be used.
These physical development nuclei substances are prepared by reducing the corresponding metal ions with a reducing agent such as ascorbic acid or sodium borohydride to form a metal colloidal dispersion, or a soluble sulfide, selenide or telluride solution. It is obtained by mixing to form a colloidal dispersion of water-insoluble metal sulfide, metal selenide or metal telluride. These dispersions are preferably formed in a hydrophilic binder such as gelatin. A method for preparing colloidal silver particles is described in U.S. Pat. No. 2,688,601. If necessary, a desalting method for removing an excessive salt known in the method for preparing a silver halide emulsion may be performed.

These physical development nuclei are formed on the complexing agent sheet,
Usually, 10 ^{-3 to} 100 mg / m ² , preferably 10 ^-2 to 1
It contains 0 mg / m ² . Physical development nuclei can be prepared separately and added to the coating solution, but in a coating solution containing a hydrophilic binder, for example, silver nitrate and sodium sulfide,
Alternatively, it may be prepared by reacting gold chloride with a reducing agent or the like. Silver, silver sulfide, palladium sulfide and the like are preferably used as physical development nuclei. When using physical developed silver transferred to a complexing agent sheet as an image, palladium sulfide,
Silver sulfide and the like are preferably used because they can cut off Dmin. Known silver halide solvents can be used in the complexing agent sheet of the present invention. For example, thiosulfates such as sodium thiosulfate and ammonium thiosulfate,
Sulfites such as sodium sulfite, JP-B-47-113
Organic thioether compounds such as 1,8-dihydroxy-3,6-dithiaoctane, 2,2-thiodiethanol and 6,9-dioxa-3,12-dithiatetradecane-1,14-diol described in No. 86, Japanese Patent Application No. Flat 6-32535
Compounds having a 5- or 6-membered imide ring, such as uracil and hydantoin described in No. 0, Analytica Chemica Acta 248, 604 to 61
A mesoionic thiolate compound such as trimethylthiolate described on page 4 and a compound represented by the following general formula described in JP-A-53-144319 can be used.

N (R ¹ ) (R ² ) —C (═S) —X—R ^{3 In the} formula, X represents a sulfur atom or an oxygen atom. R ¹ and R ² may be the same or different and each represents an aliphatic group, an aryl group, a heterocyclic group or an amino group.
R ³ represents an aliphatic group or an aryl group. R ¹ and R ²
Alternatively, R ² and R ³ may combine with each other to form a 5- or 6-membered heterocycle. In the present invention, among the above compounds, compounds having a 5- or 6-membered imide ring such as uracil and hydantoin are particularly preferable. Particularly, uracil and hydantoin are preferable in that they are added as a potassium salt because the gloss reduction during storage of the complexing agent sheet can be improved. The content of the silver halide solvent in the complexing agent sheet is 0.01-
A 5 g / m ^2, preferably 0.05~2.5g / m ^2. Also, the molar ratio is 1/2 with respect to the coated silver amount of the light-sensitive material.
It is 0 to 20 times, preferably 1/10 to 10 times. The silver halide solvent may be added to the coating solution by dissolving it in a solvent such as water, methanol, ethanol, acetone, DMF, or an alkaline aqueous solution, or may be dispersed in solid fine particles and added to the coating solution. ..

In the present invention, Japanese Patent Application No. 6-32535
By incorporating a polymer having a repeating unit of vinylimidazole and / or vinylpyrrolidone described in No. 0 as a constituent component into the complexing agent sheet, the density of the silver image on the light-sensitive material can be increased. The light-sensitive material used in the present invention basically has a photosensitive silver halide, a hydrophilic binder and a water-insoluble basic metal compound on a support, and further contains a reducing agent, an organic compound, if necessary. A metal salt oxidizing agent, a dye donating compound and the like can be contained. These components are often added to the same layer, but they can also be added in separate layers. The reducing agent is preferably incorporated in the light-sensitive material, but may be supplied from the outside by, for example, a method of diffusing from the complexing agent sheet. The silver halide emulsion light-sensitive layer may be
It may be divided into more layers. The light-sensitive material includes a protective layer between and above the silver halide emulsion layers, and a protective layer at the lowermost layer.
Various non-photosensitive layers such as an undercoat layer, an intermediate layer, a filter layer and an antihalation layer may be provided, and various auxiliary layers such as a back layer may be provided on the opposite side of the support. Specifically, an undercoat layer as described in US Pat. No. 5,051,335, reduction as described in JP-A-1-120,553, 5-34,884, and 2-64,634. Intermediate layer having an agent and a DIR compound, an intermediate layer having an electron transfer agent as described in US Pat. Nos. 5,017,454 and 5,139,919, and JP-A-2-235,044; It is possible to provide a protective layer having a reducing agent as described in JP-A-249,245 or a layer in which these are combined. When the support is polyethylene laminated paper containing a white pigment such as titanium oxide, the back layer has an antistatic function and a surface resistivity of 10%.
It is preferable to design so that it is ¹² Ω · cm or less.

The photosensitive silver halide which can be used in the present invention is silver chloride, silver iodochloride, silver chlorobromide or silver iodochlorobromide.
The silver chloride content is 80 mol% or more. The silver chloride content is preferably 90 mol% or more. The silver iodide content is 2
It is preferably not more than mol%, more preferably not more than 1 mol%, further preferably not more than 0.5 mol%. The silver halide used in the present invention may be either a surface latent image type or an internal latent image type. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging.
Further, a multi-structure particle having a different halogen composition between the inside of the particle and the surface of the particle may be used. Further, silver halide emulsions having different compositions may be joined by epitaxial joining. In particular, in the high silver chloride emulsion used in the present invention, the silver bromide localized phase is, as described above,
A structure having a layered or non-layered silver halide inside and / or on the surface can also be used. The halogen composition of the localized phase preferably has a silver bromide content of at least 20 mol%, more preferably more than 30 mol%. The silver bromide content of the silver bromide localized phase is analyzed by an X-ray diffraction method or the like. For example, CR Berry, SJ Marino's Photographic Science and Technology (Photogra
phic Science and Technology) Vol. 2 pp. 149 (195
5) and Vol. 4, p. 22 (1957), the method of applying the X-ray diffraction method to silver halide is described. The silver bromide localized phase can be present inside the grain, on the edge, corner, or on the surface of the grain, but a preferable example is that which is epitaxially bonded to the corner portion of the grain. The shape of silver halide grains can be a normal crystal without twin planes, a single twin with one twin plane, a parallel multiple twin with two or more parallel twin planes, or a non-parallel twin plane. Any of two or more non-parallel twins, spheres, potatoes, flat plates with a high aspect ratio and composites thereof can be used according to the purpose. The shape of the twin grains is described on page 163, edited by the Photographic Society of Japan, basics of the photo industry-silver salt photography (Corona). In the case of a normal crystal, a cube consisting of (100) faces, an octahedron consisting of (111) faces, or (11
Dodecahedral particles composed of the 0) plane can be used. 1
The dihedral particles are described in JP-B-55-42737 and JP-A-60-222842. Further, it is reported in Journal of Imaging Science, Vol. 30, p. 247 (1986). (H11) plane, (hh
1) plane, (hk0) plane, and (hk1) plane particles can also be used according to the purpose. A tetrahedron having (111) faces and (100) faces and a grain having (111) faces and (110) faces can be used. If necessary, polyhedral particles such as 38-hedron, rhombohedral 24-hedron, 46-hedron, and 68-hedron can also be used.

A flat plate having a high aspect ratio can also be preferably used. Tabular grains of high silver chloride emulsion grains having (111) planes are disclosed in U.S. Pat. Nos. 4,399,215 and 4,400,4.
63, 5,217,858, JP-A-2-32, etc., and tabular grains of high silver chloride emulsion grains having a (100) plane are described in U.S. Pat. No. 4,946,772, 5,275,930, 5,264,337, Japanese Patent Application No. 4-214109, Japanese Patent Application No. 5-96250, and European Patent No. 0534395A1. Such tabular grains having a high aspect ratio have a larger surface area than normal crystals having the same volume, so that the amount of sensitizing dye adsorbed can be increased, which is advantageous in terms of color sensitization sensitivity. Further, since it is advantageous in terms of covering power, a high Dmax can be achieved with a small amount of silver. Since it has a large specific surface area, it has the feature of having high development activity. The average grain size of the silver halide grains is 0.
Any size may be used, from fine particles of not more than 05 μm to large-sized particles having a projected area diameter of more than 10 μm. Preferably 0.1 to 2 μm, especially 0.1 to 0.9 μm
Is preferred. The grain size distribution is, for example, the average grain size ±
A monodisperse emulsion having a grain size distribution such that 80% or more of all grains fall within 30% may be used, or a polydisperse emulsion having a wide grain size distribution may be used. Preferably, monodisperse lactic acid is used.

Further, JP-A-1-167743 and 4-
As described in Japanese Patent No. 223463, two or more kinds of monodispersed silver halide emulsions having substantially the same color sensitivity and different grain sizes may be used in combination for the purpose of adjusting the gradation. Two or more emulsions may be mixed in the same layer or may constitute separate layers. Two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can also be used. In addition, two different heavy metal contents described later are used.
At least one kind of monodispersed silver halide emulsion may be used in combination,
Two or more monodispersed silver halide emulsions having different chemical ripening may be used in combination.

In the process of preparing the silver halide emulsion of the present invention, it is preferable to carry out a desalting step of removing excess salt. A Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (for example, sodium sulfate), an anionic surfactant, an anionic polymer (for example, sodium polystyrene sulfonate), Gelatin derivatives (aliphatic acylated gelatin,
A sedimentation method (flocculation) using aromatic acylated gelatin, aromatic carbamoylated gelatin, or the like may be used. Alternatively, U.S. Patent No. 4,758,505
No., JP-A-62-113137, and JP-B-59-437.
No. 27, U.S. Pat. No. 4,334,012, an ultrafiltration apparatus, a natural sedimentation method, or a centrifugation method may be used. Usually, the sedimentation method is preferably used.

A method for preparing a silver halide emulsion is described in "Graphics and Chemistry of Photography" by Grafkeide, published by Paul Montell (P. G.
lafkides, Chimie et Physique Photographique Paul M
ontel, 1967) "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsio
Chemistry (Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikman et al., VL Zelikman et al. Making and Coating Photogr.
aphic Emulsion. Focal Press, 1964). The preparation method may be any of an acidic method, a neutral method and an ammonia method. As a method of reacting the soluble silver salt and the soluble halogen salt, a one-side mixing method, a simultaneous mixing method, or a combination thereof can be used. A method of forming grains in a state where silver ions are excessive (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid layer in which silver halide is formed,
That is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal system and a nearly uniform grain size is obtained. In the preparation of silver halide emulsion, p during grain formation
It is preferable to adjust Ag and pH. For the adjustment of pAg and pH, please refer to Photographic Science and Engineering.
ineering) Volume 6, 159-165 (1962); Journal of Photographic Science (Jour
nal of Photographic Science), Volume 12, 242-25
1 page (1964), U.S. Pat. No. 3,655,394 and British Patent No. 1,413,748.

By using a silver halide solvent during the formation of silver halide grains, a silver halide emulsion having a higher degree of monodispersion can be produced. Examples of silver halide solvents include thiocyanates (U.S. Pat. No. 2,222,264).
No. 2, ibid. 2,448,534, ibid. 3,320,069
Each specification), thioether compound (US Pat. No. 3,
No. 271,157, No. 3,574,628, No. 3,
704,130, 4,297,439, 4,2
76,347), thione compounds (JP-A Nos. 53-144319, 53-82408 and 55-55).
-77737), imidazole compounds (described in JP-A-54-100717), benzimidazole (JP-B-60-54662), and amine compounds (described in JP-A-54-100717). You can Ammonia can be used in combination with a silver halide solvent within a range that does not cause adverse effects. Nitrogen-containing compounds described in JP-B-46-7781, JP-A-60-222842, JP-A-60-122935 and the like can be added to the silver halide grain formation stage. For details of specific examples of the silver halide solvent, see JP-A-6-61.
2-215272, pages 12-18.

In the process of grain formation or physical ripening of silver halide, a metal salt (including complex salt) may also be present. Examples of metal salts include salts or complex salts of noble metals or heavy metals such as iridium, rhodium, ruthenium, chromium, cadmium, zinc, lead, thallium, platinum, palladium, osmium, rhenium and the like. Among these, salts or complex salts of iridium, rhodium, ruthenium, and chromium are preferable. These compounds may be used alone or in combination of two or more. The addition amount is 10 ^-9 to 10 per mol of silver halide.
^{About -3} mol, particularly preferably 10 ^{-9 to} 5 × 10 ^-6 mol. As a complex ion and a coordination compound, a bromine ion, a chloride ion, a cyanide ion, a nitrosyl ion, a thionitrosyl ion, water, ammonia and the like and a combination thereof are preferably used. For example, yellow blood salt, K
₂ IrCl ₃ , K ₃ IrCl ₅ , (NH ₄ ) ₂ RhCl
₅ (H ₂ O), K ₂ RuCl ₅ (NO), K ₃ Cr (C
N) _{6 and the} like are preferably used. Further, the position to be incorporated into the silver halide grain may be uniform within the grain, or may be a localized position such as the surface or inside of the grain, a silver bromide localized phase, or a high silver chloride grain substrate. The method of adding these compounds is
The metal salt solution is mixed with an aqueous halide solution during grain formation, silver halide emulsion fine grains doped with the metal ions are added, or the metal salt solution is directly added during grain formation and after grain formation. It can be done by doing.
In order to increase the sensitivity and density of high-intensity light exposure, metal complex salts such as iridium and yellow blood salt in which cyanide is used as a ligand, lead chloride, cadmium chloride, and zinc chloride can be preferably used. When spectral sensitization is performed as in the present invention,
It is preferable to use a metal complex salt having a cyanide ion as a ligand such as yellow blood salt, lead chloride, cadmium chloride, or zinc chloride. Iridium salt, rhodium salt,
Ruthenium salts and chromium salts are preferably used.

When silver halide grains are formed, the addition rate, the amount or concentration of the silver salt solution (eg AgNO ₃ aqueous solution) and the halogen compound solution (eg KBr aqueous solution) to be added are increased to accelerate the grain formation rate. Good. As described above, a method for rapidly forming silver halide grains is as follows.
British Patent 1,335,925, US Patent 3,672,
900, 3,650,757, 4,242,4
45, each specification, JP-A-55-142329, 55
-158124, 58-113927, 58-
No. 113928, No. 58-111934, No. 58-1
It is described in each publication of No. 11936. During or after grain formation, the surface of the silver halide grain may be replaced with a halogen that forms a hardly soluble silver halide grain (halogen conversion). This halogen conversion process is described in "Die Grundlagen Die Photography Shen Protese Mitt Gilfer Halogeniden".
der Photographischen Prozesse mit Silverhalogenid
en) pp.662-669 and "The Theory of Photographi"
c Process) Fourth Edition, pages 97 to 98, etc. In this method, the compound may be added in the form of a solution of a soluble halide or in the form of fine grain silver halide.

The silver halide emulsion of the present invention can be used without being chemically sensitized, but it is usually used after being chemically sensitized. The chemical sensitization method used in the present invention includes a sulfur sensitization method,
Chalcogen sensitizing methods such as selenium sensitizing method and tiluru sensitizing method,
A noble metal sensitization method and a reduction sensitization method using gold, platinum, palladium or the like can be used alone or in combination (for example, JP-A-3-110555 and JP-A-5-2412).
No. 67). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9). Further, an antifoggant described below can be added after the completion of chemical sensitization. Specifically, JP-A-5-45
The methods described in JP-A No. 833 and JP-A No. 62-40446 can be used.

An unstable sulfur compound is used as the sulfur sensitizer, and specifically, thiosulfates (eg, hypo), thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.) Well-known sulfur compounds such as allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanines, and mercaptos may be used. The sulfur sensitizer may be added in an amount sufficient to effectively increase the sensitivity of the emulsion.
It varies depending on various conditions such as temperature, balance with other sensitizers, size of silver halide grains, etc., but as a guide, it is used in the range of 10 ^-9 to 10 ^-1 mol per mol of silver halide. Is preferred. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone , Selenamides, aliphatic isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenocarboxylic acids and esters, selenophosphates, diethyl selenides, diethyl diselenides and other selenides it can. The addition amount varies depending on various conditions like the sulfur sensitizer, but as a guide, it is preferably used in the range of 110 ^-10 to 10 ^-1 mol per mol of silver halide.

In the present invention, in addition to the above-mentioned chalcogen sensitization, sensitization with a noble metal can be performed. First, in gold sensitization, the valence of gold may be +1 or +3,
Various gold compounds are used. Representative examples are chloroauric acid, potassium chloroaurate, auric trichloride, potassium aurithiocyanate, potassium iodoaurate, tetraoric acid, ammonium aurothiacyanate, pyridyl trichlorogold, gold sulfide, gold selenide, gold telluride. Etc. The addition amount of the gold sensitizer varies depending on various conditions, but as a guide, it is preferable to use it in the range of 10 ^-10 to 10 ^-1 mol per mol of silver halide. The gold sensitizer may be added at the same time as sulfur sensitization, selenium sensitization, or tellurium sensitization, during or before the sulfur, selenium, or tellurium sensitization step.
Alternatively, it may be performed after completion, or the gold sensitizer may be used alone.

The pAg and pH of the emulsion to be sulfur-sensitized, selenium-sensitized or tellurium-sensitized or gold-sensitized in the present invention are not particularly limited, but the pAg is 5 to 11 and the pH is 3 to 10. Is preferred. More preferably, pAg
Is in the range of 6.8 to 9.0, and pH is in the range of 5.5 to 8.5. In the present invention, noble metals other than gold can be used as the chemical sensitizer. As a noble metal other than gold, for example, a metal salt such as platinum, palladium, iridium and rhodium or a sensitizer based on a complex salt thereof can be used. In the present invention, reduction sensitization can be further performed. As the reduction sensitizer used in the present invention, ascorbic acid, stannous salt, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. In the present invention, one of these known compounds can be selected and used, and two or more compounds can be used in combination. As the reduction sensitizer, silver chloride, thiourea dioxide, dimethylamine borane, L-ascorbic acid, and aminoiminomethanesulfinic acid are preferred compounds. Since the addition amount of the reduction sensitizer depends on the emulsion conditions, it is necessary to select the addition amount, but an appropriate range is 10 ^-9 to 10 ^-2 mol per mol of silver halide.

Besides the above-mentioned method of adding a reduction sensitizer, a method of growing or aging in a low pAg atmosphere of pAg1 to 7 called silver ripening, called high pH ripening.
A method of growing or aging in a high pH atmosphere of pH 8 to 11 or a method of reducing and sensitizing by passing hydrogen gas or by hydrogen at the nascent stage by electrolysis can be selected. Further, two or more methods can be used in combination.
This reduction sensitization can be used alone, but can also be used in combination with the above-described chalcogen sensitization or noble metal sensitization. In the present invention, the amount of the silver halide emulsion used in the light-sensitive material, 0.5 to preferably 2.5 g / m ² as the amount of silver is preferably used in particular 0.8 to 2.0 g / m ^2.

Gelatin is preferably used as the protective colloid used in preparing the emulsion, but other hydrophilic binders can also be used. The hydrophilic binder can be used alone or in combination with gelatin. Examples of the hydrophilic binder include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose and cellulose sulfates,
Sodium alginate, starch derivatives, polysaccharides, carrageenan, polyvinyl alcohol, modified alkyl polyvinyl alcohol, polyvinyl-N-pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Such synthetic hydrophilic polymer, US Pat. No. 3,
The thioether polymer described in 615,624 can also be preferably used. Gelatin is lime-processed gelatin,
Gelatin derivatives such as acid-treated gelatin, demineralized gelatin and phthalated gelatin, and low molecular weight gelatin can also be used.
Gelatin oxidized with an oxidizing agent such as hydrogen peroxide or gelatin treated with oxygen can also be used. A hydrolyzate or an oxygen hydrolyzate of gelatin can also be used.

General formulas (Ia) and (I
In addition to the sensitizing dyes represented by b), (Ic) and (Id), they may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes,
Holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound that does not substantially absorb visible light, or a compound exhibiting supersensitization may be contained in the emulsion.

The dye may be added to the emulsion at any stage of emulsion preparation. Most commonly, it is performed after completion of chemical sensitization but before coating, but is described in U.S. Pat. Nos. 3,628,969 and 4,225,66.
No. 6, adding at the same time as the chemical sensitizer as described in each specification, and performing spectral sensitization simultaneously with chemical sensitization,
JP-A-58-113928 and JP-A-4-63337.
It can also be carried out prior to the chemical sensitization as described in No. It is also possible to start the spectral sensitization by adding the silver halide grains before the completion of precipitation formation. Furthermore, as taught in U.S. Pat. No. 4,225,666, it is possible to add these said compounds separately, i.e. to add some of these compounds prior to the chemical sensitization, the balance being Can be added after chemical sensitization and can be at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756. To enhance the adsorption of the sensitizing dye, a soluble Ca compound, a soluble Br compound, a soluble I compound, a soluble Cl compound, or a soluble SCN compound may be added before, during, and after the addition of the sensitizing dye. These compounds may be used in combination. Preferably CaCl ₂ , K
I, KCl, KBr, KSCN. Further, fine grains of silver bromide, silver chlorobromide, silver iodobromide, silver iodide, and silver rhodane emulsion may be used.

There are no particular restrictions on other additives to the photographic light-sensitive material to which the emulsion of the present invention is applied. For example, Research Disclosure 1
76 volumes, item 17643 (RD-17643), 187 volumes, item 18716 (RD-18716) and 307 volumes, item 307105, etc. can be referred to. RD-17643 and RD-187 are known additives used in such steps and known photographic additives usable in the light-sensitive material and complexing agent sheet of the present invention.
No. 16 and RD-307105, the description places of various additives are listed below.

Additive type RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 page right column 866 page 2 Sensitivity enhancer same as above 3 Spectral sensitizer page 23 to 24 page 648 right column to 866 to 868 supersensitization Agent page 649 Right column 4 Whitening agent page 24 648 Right column to page 868 5 Fog inhibitor page 24 to page 649 Right column to page 868 to 870 and stabilizer 6 Light absorber, page 25 to 26 page 649 Right column to page 873 Filter dye page 650 Left column UV absorber 7 Anti-staining agent page 25 Right column page 650 Left to right column 8 Dye image stabilizer page 25 650 page left column page 872 9 Hardener 26 pages 651 page left Column 874-875 page 10 Binder page 26 same as above 873-874 page 11 plasticizer, lubricant page 27 650 page right column 876 12 coating aid, interface 26-27 page 875-876 same above Activator 13 static 27 Page Same as above Page 876-877 Page 14 Inhibitor 14 Matting agent Page 878-879

Further, the following compounds and the like can also be used. Item This section 1) Silver halide emulsion and JP-A-2-97937, page 20, lower right column, line 12 From its manufacturing method, page 21, lower left column, line 14 and JP-A-2-2236. Page 7, upper right column, line 19 to page 8, lower left column, line 12, JP-A-4-330430 and JP-A-5-11389. 2) Spectral sensitizing dye From JP-A-2-55349, page 7, upper left column, line 8 to page 8, lower right column, line 8 and JP-A 2-39042, page 7, lower right column, line 8 Page 13, lower right column, line 5, Tokukaihei 2-1236, page 8, lower left column, line 13 to same, lower right column, line 4, and No. 2-303536, page 16, lower right column, line 3 To page 17, lower left column, line 20, and spectral sensitizing dyes described in JP-A Nos. 1-112235, 2-1245560, 3-79928, and 5-11389. 3) Surfactant and antistatic From page 7, upper right column, line 7 of JP-A-2-12236 or from the lower right column, line 7 in JP-A-2-18542 and page 13, lower left column, line 13 of JP-A-2-18542. Page 4, lower right column, line 18. 4) Antifoggant / stable JP-A-2-103536, page 17, lower right column, line 19 to line 18, page 18, upper right column, line 4 and lower right column, lines 1 to 5, and Thiosulfinic acid compounds described in JP-A-237538. 5) Polymer latex: JP-A-2-103536, page 18, lower left column, lines 12 to 20. 6) Compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to page 19, upper left column, line 1, and JP-A-2-55349, page 8, lower right column, line 13 From the eye, page 11, line 8 in the upper left column. 7) Polyhydroxyl JP-A-2-55349, page 11, upper left column, line 9, benzenes to lower right column, line 17, same. 8) Matting agent, slipping agent, JP-A-2-103536, page 19, upper left column 15, plasticizer line to page 19, upper right column, line 15 9) Hardener JP-A-2-103536, page 18, upper right column, 5th line to 17th line. 10) Dyes, JP-A-2-103536, page 17, lower right column, line 1 to line 18, and JP-A-2-39042, page 4, upper right column, line 1 to page 6, upper right column, line 5. 11) Binder JP-A-2-18542, page 3, lower right column, line 1 to line 20. 12) Developer and developing method JP-A-2-55349, page 13, lower right column, line 1 to page 16, upper left column, line 10; JP-A-2-103536, page 19, upper right column, line 16 To page 21, upper left column, line 8 of the same. 13) Black spot preventing agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A No. 1-118832. 14) Redox compound A compound represented by the general formula (I) in JP-A No. 2-301743 (particularly compound examples 1 to 50), a general formula (page 3 to page 20 in JP-A No. 3-174143). R-1), (R-2), (R-3), compounds 1 to 75, and compounds described in JP-A-5-257239 and JP-A-4-278939. 15) Monomethine compounds Compounds of the general formula (II) described in JP-A-2-287532 (in particular, compound examples II-1 to I1-26). 16) Hydrazine compounds JP-A-2-12236, page 2, upper right column, line 19 to page 7, upper right column, line 3, line 3-174413, page 20, lower right column, line 1 Page 27, right upper column, line 20, general formula (II) and compound examples II-1 to II-54. 17) Nucleation accelerators JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 General formulas (II-m) to (II-p) and compound example II- 1 to II-22, compounds described in JP-A-1-179939.

Among the above additives, antifoggants and stabilizers are azoles (eg, benzothiazolium salt,
Nitroimidazoles, nitrobenzimidazoles,
Chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles,
Aminotriazoles, etc.); Mercapto compounds (eg, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole and its derivatives), mercapto) Pyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinethione; azaindenes {eg, triazaindenes, tetraazaindenes (especially 4-hydroxy-6-methyl (1,3,3a, 7) Tetraazaindene), pentaazaindenes and the like}, benzenethiosulfones; benzenesulfines; benzenesulfonic acid amide and the like can be preferably used.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the complexing agent sheet. Examples thereof include the above-mentioned Research Disclosure and those described on pages (71) to (75) of JP-A 64-13546. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin or a protein or cellulose derivative such as a gelatin derivative, agar, starch, gum arabic, dextran, pullulan, furceleran, carrageenan described in EP-A-443529, Polysaccharides such as locust bean gum, xanthan gum and pectin, natural compounds such as polysaccharides described in JP-A-1-221736 and polyvinyl alcohol, JP-A-5-
Examples thereof include synthetic polymer compounds such as modified alkyl polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymer described in 339155. U.S. Pat.
960,681, JP-A-62-245260, etc., that is, a superabsorbent polymer such as -COOM or -S
A homopolymer of a vinyl monomer having O ₃ M (M is a hydrogen atom or an alkali metal) or a copolymer of these vinyl monomers or a copolymer with another vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumitomo Chemical Co., Ltd. ) Sumikagel L-5H) manufactured by M.K. These binders can be used in combination of two or more. A combination of gelatin and the above binder is preferable, and gelatin may be selected from lime-processed gelatin, acid-processed gelatin, so-called demineralized gelatin with a reduced content of calcium, etc. according to various purposes. preferable.

When a system in which a small amount of water is supplied for thermal development is adopted, it is possible to quickly absorb water by using the above superabsorbent polymer. When the content of gelatin is low, hydrophilic polymers other than gelatin may be used in accordance with European Patent Publication No. 4435 in terms of settability when applied.
Carrageenan described in No. 29, modified alkyl polyvinyl alcohol described in Japanese Patent Application No. 5-339155, and JP-A-6-6.
The polysaccharide described in No. 7330 is preferably used. The coating amount of all binders of the photosensitive material and the complexing agent sheet is 12 g /
Preferably m ² ~0.5g / m ^2, in particular 5 g / m ² or less,
Further, it is more preferable that the amount is 3 g / m ² or less. As the reducing agent used in the present invention, those known in the field of light-sensitive materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used.

Examples of the reducing agent used in the present invention include:
U.S. Pat. No. 4,500,626, columns 49 to 50, 4,839,272, 4,330,617, 4,590,152, 5,017,454, 5 , 139, 919, JP-A-60-140, 335, pages (17) to (18), 57-40, 245,
56-138,736, 59-178,458.
No. 59-53,831 and 59-182,449.
No. 59-182, 450, 60-119, 55
No. 5, No. 60-128,436, No. 60-128,4
39, 60-198, 540, 60-181.
742, 61-259, 253, and 62-20.
1,434, 62-244,044, 62-1
No. 31,253, No. 62-131, 256, No. 63-
No. 10, 151, No. 64-13, 546 (40)
To (57), JP-A-1-120,553, 2-3.
No. 2,338, No. 2-35, 451 and No. 2-234.
No. 158, No. 3-160,443, European Patent No. 22
There are reducing agents and reducing agent precursors described on pages 78 to 96 of No. 0746. U.S. Pat. No. 3,039,869
Combinations of various reducing agents, such as those disclosed in US Pat.

When a diffusion resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent may be optionally added in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, electron transfer agent precursors can be used in combination. Particularly preferably, said US Patent No. 5,139,
919, European Patent Publication No. 418,743,
Nos. 138,556 and 3-102,345 are used. Further, a method of stably introducing the compound into the layer as described in JP-A-2-230143 or JP-A-2-23504 is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) to be used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the light-sensitive material among the aforementioned reducing agents, and is preferably a hydroquinone, Sulfonamidophenols, sulfonamidonaphthols,
No. 110827, U.S. Pat. Nos. 5,032,487, 5,026,634, and 4,839,272, compounds described as electron donors, and a non-diffusible and reducing dye described later. Donor compounds and the like. Also, an electron donor precursor described in JP-A-3-160,443 is preferably used.

Further, the reducing agent can be used in the intermediate layer and the protective layer for various purposes such as prevention of color mixture, improvement of color reproduction, improvement of white background, and prevention of transfer of silver to dye fixing material. Specifically, European Patent Publication Nos. 524,649 and 357,04
0, JP-A-4-249,245, JP-A-2-64,63
No. 3, No. 2-46,450, JP-A-63-186,2
The reducing agent described in No. 40 is preferably used. In addition, Japanese Examined Patent Publication No. 3-63,733, Japanese Patent Laid-Open Nos. 1-150,135, 2-110,557, 2-64,634, and 3-
43,735 and EP-A-451,833 may also be used.

In the present invention, the total amount of reducing agent added is 1 silver.
0.01 to 20 mol per mol, particularly preferably 0.1 to
10 moles. In the present invention, an organic metal salt may be used as an oxidizing agent together with the light-sensitive silver halide emulsion. Among such organic metal salts, the organic silver salt is
Particularly preferably used. Examples of the organic compound that can be used to form the above organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compounds described in US Pat. No. 4,500,626, columns 52 to 53. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is 0.
01 to 10 mol, preferably 0.01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ^{2 in} terms of silver, preferably
0.4-5 g / m ² is suitable.

Various dyes can be used in the constituent layers of the light-sensitive material of the present invention for the purpose of preventing halation and irradiation. The dye is disclosed in JP-A-3-7931.
It is preferable to disperse the fine particles in a solid state and incorporate them into a light-sensitive material as disclosed in JP-A No. 2-308242. Specifically, the compounds described in the above Research Disclosure and the compounds described in Japanese Patent Application No. 6-259805 can be used. In the light-sensitive material of the present invention, a compound for stabilizing an image simultaneously with activation of development can be used. Specific compounds preferably used are described in US Pat. No. 4,500,626, 51st.
-52 column.

In the present invention, the image forming substance is mainly developed silver in the light-sensitive material. If necessary, a dye (dye donating compound) can be used in the light-sensitive material and the complexing agent sheet. As an example, the PS plate has a spectral sensitivity in the wavelength range of 300 nm to 500 nm so that it can be handled in a bright room of ultraviolet cut, and the image of the photosensitive material for printing plate making becomes an original to be printed on the PS plate. It suffices to have discrimination in the wavelength region, and a dye (dye-donor compound) having an absorption in this wavelength region can be imaged together with a silver image. Further, using at least two kinds of dye-donor compounds that form or release dyes having substantially different color tones, or dye-providing properties to form or release at least two kinds of dyes having substantially different tones from each other. The compounds can also be used to obtain black and white images with dyes along with silver.

As an example of the dye-donating compound that can be used in the present invention, first, a compound (coupler) which forms a dye by an oxidative coupling reaction can be mentioned. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developing agents and couplers include para-phenylenediamine reducing agents and phenolic or active methylene couplers in U.S. Pat. No. 3,531,286, and para-aminophenol reducing agents in U.S. Pat. No. 802519 and Research Disclosure, September 31, 1975, p. 32, a sulfonamide phenol-based reducing agent is disclosed in US Pat.
No. 240, a combination of a sulfonamidephenol-based reducing agent and a 4-equivalent coupler is proposed. Specific examples of other color developing agents and couplers are given in "The Theory of the Photographic Process", 4th edition, 2 by TH James.
91-334 and 354-361.

Another example of the dye-donating compound is a heterocyclic ring containing a nitrogen atom and a sulfur atom or a selenium atom in the presence of a silver ion or a soluble silver complex as described in JP-A-59-180548. The anti-diffusible dye-donating compound (thiazolidine-based compound) having the above-mentioned heterocycle which undergoes a cleavage reaction to release a mobile dye can also be used. As another example of the dye-donating compound, a compound having a function of releasing or diffusing a diffusible dye in an image form can be mentioned. This type of compound can be represented by the following general formula (LI): ((Dye) m-Y) n-Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, and Z represents an image-form. A difference in the diffusivity of the compound represented by ((Dye) m-Y) n-Z corresponding to or opposite to a photosensitive silver salt having a latent image, or (Dye) m
-Y, and released (Dye) m-Y and ((Dy)
e) m-Y) n-Z represents a group having a property of causing a difference in diffusibility, m represents an integer of 1 to 5, n represents 1 or 2, and m and n Either one
When not, a plurality of Dyes may be the same or different. Specific examples of the dye-donating compound represented by the general formula [LI] include those which form a diffusible dye image corresponding to the following developments of silver halide.

US Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, 3,482,972 and Japanese Patent Publication No. 3-68. No. 387, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide. As described in U.S. Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can also be used. An example is U.S. Pat. No. 3,983.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 4,199,
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like. U.S. Pat. No. 4,559,290, European Patent No. 22
0,746A2, U.S. Pat. No. 4,783,396,
Open Technical Report 87-6,199, JP-A-64-13,546
As described in U.S. Pat. No. 4,968,697, a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used.

As an example thereof, US Pat. No. 4,139,
No. 389, No. 4,139,379, JP-A-59-18.
5,333, 57-84,453, etc., which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, US Pat. No. 4,232,10
7, JP-A-59-101,649, 61-88,
257, RD 24,025 (1984) and the like, compounds which release a diffusible dye by an electron transfer reaction in the molecule after reduction, West German Patent 3,008,58.
8A, JP-A-56-142,530, U.S. Pat. Nos. 4,343,893 and 4,619,884, and the like, and after the reduction, the single bond is cleaved to release a diffusible dye. , A nitro compound that releases a diffusible dye after electron acceptance described in US Pat. No. 4,450,223, and a diffusibility after electron acceptance described in US Pat. No. 4,609,810. Examples thereof include compounds that release a dye.

Further, as more preferable ones, European Patent No. 220,748, Open Technical Report 87-6,199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-201,6.
No. 53, No. 63-201, 854, No. 64-13, 5
No. 46, etc., a compound having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, a single molecule described in JP-A 1-26,842 A compound having an SO ₂ —X (X is as defined above) and an electron-withdrawing group, and a PO—X bond (X is as defined above) in one molecule described in JP-A-63-271,344. And a compound having an electron-withdrawing group, JP-A-63-271341
The compound having a C—X ′ bond (X ′ is synonymous with X or represents —SO ₂ —) and an electron-withdrawing group in one molecule described in No. Also, JP-A-1-161,237
And a compound capable of releasing a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group described in JP-A Nos. 1-161 and 342 can be used. Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. When the colored dye-donating compound is present in the lower layer of the light-sensitive silver halide emulsion layer, the reduction in sensitivity can be prevented.

Hydrophobic additives such as dye-donor compounds and diffusion resistant reducing agents can be incorporated into the layers of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat.
470, 4,536,466, 4,536,4
No. 67, No. 4,587, 206, No. 4,555, 47
No. 6,4,599,296, JP-A-63-3064
No. 39, No. 62-8145, No. 62-30247,
A high-boiling organic solvent as described in JP-B-3-62,256 can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C, if necessary. In addition, two or more kinds of these dye donating compounds, diffusion resistant reducing agents, high boiling point organic solvents and the like can be used in combination. The amount of the high boiling point organic solvent is 10 g or less per 1 g of the hydrophobic additive used,
It is preferably 5 g or less, more preferably 1 g to 0.1 g. Also, 1 cc or less for 1 g of binder, and further
0.5 cc or less, particularly 0.3 cc or less is suitable.

Further, a dispersion method using a polymer described in JP-B-51-39,853 and JP-A-51-59,943 and fine particle dispersion described in JP-A-62-30,242. It is also possible to use a method of adding it as a product. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-
157,636, pages (37) to (38), those listed as the surfactants described in the above-mentioned Research Disclosure can be used. In addition, JP-A-7-056
No. 267, Japanese Patent Application No. 6-19247, West German Published Patent No. 1
The phosphate ester type surfactant described in No. 932299A can also be used.

When a dye image is used in combination with the complexing agent sheet, a mordant known in the photographic field can be used,
Specific examples thereof include U.S. Pat. No. 4,500,626, columns 58 to 59, JP-A-61-88,256 (32).
Page (41) and JP-A-1-161,236 (4)
(7) The mordant described on page 7, US Pat.
No. 2, 4,619, 883, 4, 594, 308
And the like. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used. The complexing agent sheet, if necessary, a protective layer, a release layer, an undercoat layer, an intermediate layer,
An auxiliary layer such as a back layer and an anti-curl layer can be provided. In particular, it is useful to provide a protective layer. In the constituent layers of the light-sensitive material and the complexing agent sheet, a high-boiling point organic solvent can be used as a plasticizer, a sliding agent, or an agent for improving the peelability between the light-sensitive material and the complexing agent sheet. Specifically, the research disclosure and JP-A-62-245,
253 and the like.

Further, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oils obtained by introducing various organic groups into dimethylsiloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in “Modified Silicone Oil” technical data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective. Silicone oils described in JP-A Nos. 62-215,953 and 63-46,449 are also effective.

As the hardener used in the constituent layers of the light-sensitive material and the complexing agent sheet, the above-mentioned Research Disclosure,
U.S. Pat. No. 4,678,739, column 41, 4,795;
1,042, JP-A-59-116,655, 62
-245,261 lines, 61-18,942, JP-A-4-218,044 and the like hardeners.
More specifically, aldehyde type hardener (formaldehyde etc.), aziridine type hardener, epoxy type hardener, vinyl sulfone type hardener (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardeners (dimethylol urea, etc.), or polymer hardeners (compounds described in JP-A-62-234,157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of the coated hydrophilic binder. The layer to be added may be any of the layers constituting the photosensitive material or the complexing agent sheet, or may be added in two or more layers.

Various antifoggants or photographic stabilizers and their precursors can be used in the constituent layers of the light-sensitive material and the complexing agent sheet. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A-64-13546 (7). Pages (9), (57) to (71) and (8)
1) to (97), U.S. Pat. No. 4,775,610,
Nos. 4,626,500 and 4,983,494, JP-A-62-174,747 and JP-A-62-239,148.
No. 63-264,747, JP-A-1-150,1.
No. 35, No. 2-110, 557, No. 2-178, 65
No. 0, RD 17, 643 (1978) (24)-(2
5), and the compounds described in Japanese Patent Application No. 6-190529. These compounds are 5 × 10 5 per mole of silver.
^-6 to 1 × 10 ^-1 mol, preferably 1 × 10 ^-5 to 1
× 10 ^-2 mol is preferably used.

Various surfactants can be used in the constituent layers of the light-sensitive material and the complexing agent sheet for the purposes of coating aid, improvement of releasability, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant include Research Disclosure, JP-A Nos. 62-173,463 and 62-18.
3, 457 and the like. The constituent layers of the light-sensitive material and the complexing agent sheet may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. Representative examples of the organic fluoro compound include Japanese Patent Publication No. 57-90.
No. 53, columns 8-17, JP-A-61-20944, 6
Examples include fluorine-based surfactants described in JP-A-2-135826 and hydrophobic fluorine-containing compounds such as oily fluorine-based compounds such as fluorine oil and solid fluorine-containing compounds such as tetrafluoroethylene resin.

For the light-sensitive material and the complexing agent sheet, adhesion prevention,
A matting agent can be used for the purpose of improving slipperiness and making the surface non-glossy. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
-88256 (29), benzoguanamine resin beads, polycarbonate resin beads,
There are compounds such as AS resin beads described in JP-A-63-274944 and JP-A-63-274952. In addition, the compounds described in the above Research Disclosure can be used. These matting agents can be added not only to the uppermost layer (protective layer) but also to the lower layer as needed. In addition, a heat-solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like may be contained in the constituent layers of the photosensitive material and the complexing agent sheet. Specific examples of these additives are disclosed in JP-A-61-88256.
No. (26)-(32), JP-A-3-11,338
And Japanese Patent Publication No. 2-51,496.

In the present invention, an image forming accelerator can be used in the light-sensitive material and / or the complexing agent sheet. From the physicochemical function, the image formation accelerator has an interaction with a base or the aforementioned base precursor, a nucleophilic compound, a high-boiling organic solvent (oil), a thermal solvent, a surfactant, silver or silver ions. Classified as compounds. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40. By adding a high-boiling point organic solvent to the complexing agent sheet, reduction in gloss of the image of the processed light-sensitive material is remarkably improved.

In the present invention, various development terminators can be used in the light-sensitive material and / or the complexing agent sheet for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For more details, see JP-A-62-25
No. 3,159, pages (31) to (32).

In the present invention, as the support for the light-sensitive material and the complexing agent sheet, those which can withstand the processing temperature are used. In general, the Photographic Society of Japan, "Basics of Photographic Engineering-Silver Halide Photography-", published by Corona Co., Ltd. (Showa 54)
Years) Papers described on pages 223 to 240, and photographic supports such as synthetic polymers (films). Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, polyarylate,
Cellulose (for example, triacetylcellulose) or those containing pigments such as titanium oxide in these films, film-processed synthetic paper made from polypropylene, etc., and synthetic resin pulp such as polyethylene and natural pulp mixed with natural pulp. Papermaking, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal,
Cloths, glasses and the like are used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. Titanium oxide, ultramarine,
A pigment or dye such as carbon black may be contained as necessary. In addition, Japanese Patent Application Laid-Open No. 62-25 / 1987
No. 3,159, pages (29) to (31), JP-A-1-16
1,236, pages (14)-(17), JP-A-63-31
6,848, JP-A-2-22,651, and 3-5.
The supports described in US Pat. No. 6,955, US Pat. No. 5,001,033 and the like can be used.

The back surface of these supports may be coated with a hydrophilic binder, an alumina sol, a metal oxide such as tin oxide and antimony oxide, carbon black and other antistatic agents. Specifically, JP-A-63-22024
No. 6, etc. can be used. Surface resistivity is 1
It is desirable to design so as to be 0 ¹² Ω · cm or less.
The surface of the support is preferably subjected to various surface treatments or undercoating for the purpose of improving the adhesion to the hydrophilic binder. The light-sensitive material of the present invention is used in various applications of light-sensitive materials for printing, that is, not only as a film for a scanner, but also as a film for halftone shooting, a film for line drawing, a film for contact (negative-positive type), a film for contact (reversal positive). -Positive type) film or light room film.

The photothermographic material of the present invention is a sheet containing a complex-forming compound for a metal ion constituting the basic metal compound, a physical development nucleus and a silver halide solvent after or at the same time as the imagewise exposure. Then, a silver image can be formed on the light-sensitive material by subjecting it to heat development in the presence of a reducing agent and water. As a method for exposing and recording an image on the photothermographic material of the present invention, for example, a printing original such as a reversal film using a plate making camera,
A method of exposing with a contact screen or a color separation filter, a method of using a plate-making printer, a scanner, an image setter, a facsimile, or the like, and a xenon lamp, a light emitting diode, various lasers (laser diode, Scanning exposure by emitting light such as a gas laser (JP-A-2-129625, JP-A-5-176144, JP-A-5-199372, 6-1)
No. 27021) is known. As a light source for recording an image on the photothermographic material, a xenon lamp, a tungsten lamp, a halogen lamp, a metal halide lamp, a quartz lamp, a light emitting diode, a laser light source, especially an Ar laser can be used. An example of the exposure apparatus in the present invention will be given below. DC of Linotype-Hell, a commercial Ar laser exposure device
Series, Crossfield's Magnscan
A series is mentioned.

The following is an example of a plate-making printer that can be used in the exposure of the present invention. Fuji Photo Film FP
A740, FPA800, FPA800X, FPA80
0Hg, FPA800FX, Dainippon Screen P6
07 series, P617 series, P627 series,
P647 series, P648 series, IPB-1000SH of Eye Graphics, FL2M, F of Ushio
L3M, Kuranami SK-16, Eastman-Kod
AK Versalite ContactPrin
ter840H, Contact2200Printe
r, Contact2200Printer, Agfa
-CDL2002Ri from Gevaert, P-6, P-4, P-2, P-8 from Kitamura, OR from SACK
30, THIEMER VDM5 and CONVAC RD7087D can be used. The following are examples of plate-making cameras that can be used in the exposure of the present invention. Fuji Photo Film's FCS820, FCS820S, FG
C100, FGC200, FGC300, FINE ZOOM880, ZOOMACE8 of Dainippon Screen Co., Ltd.
00, Companica C-680, Companica C-690,
Imagemaker 54 from Aitec Graphics
0, Opti-Cop of Eastman-Kodak
y32, Opti-Copy42, Opti-Copy
23, Image Maker 5060A, Image Maker IM200, Image Maker IM400, Image Maker IM600, Image Maker IM800, Ag
An RPS camera manufactured by fa-Gevaert, a repro master series, a Linears 2000 manufactured by Izumiya, a design scope series, and a repro camera series manufactured by Mitsubishi Paper Mills can be used.

The light-sensitive material and / or complexing agent sheet of the present invention may have a form having a conductive heating element layer as a heating means for heat development and silver salt diffusion transfer.
The heat generating element in this case is disclosed in JP-A-61-145,544.
You can use the ones listed in the issue. In the present invention, U.S. Patent Nos. 4,704,345 and 4,740,445.
It is preferred that heating and development and transfer are carried out simultaneously or continuously in the presence of a small amount of water, as described in JP-A-61-238,056. In this method, the heating temperature is preferably 50 ° C to 100 ° C. As the water used in the present invention, any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the exposure material and the complexing agent sheet of the present invention, water may be used up, or may be circulated for repeated use. In the latter case, water containing components eluted from the material will be used. Also, JP-A-63-144,3
54, 63-144,355, 62-98,4
No. 60, JP-A-3-210,555 and the like may be used with the device and water. Furthermore, a low boiling point solvent that dissolves in water,
It may be contained in a surfactant, an antifoggant, a complex-forming compound with a sparingly soluble metal salt, an antifungal agent, and an antibacterial agent.

These solvents can be applied to the light-sensitive material, the complexing agent sheet, or both, but
It is preferably applied to a sensitive material. The amount used may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film. As a method of applying the water, for example, Japanese Patent Application Laid-Open No. 62-253,
The method described in JP-A No. 63-85,544, page 159 (5) is preferably used. Further, the solvent can be used by being encapsulated in a microcapsule or incorporated in the photosensitive material or the dye-fixing element or both in advance in the form of a hydrate. The temperature of the water to be applied is as described in the above-mentioned JP-A-63-8
The temperature may be 30 ° C. to 60 ° C. as described in US Pat. In particular, it is useful to raise the temperature to 45 ° C. or higher for the purpose of preventing the propagation of various bacteria in water. A hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature can be incorporated in the photosensitive material and / or the complexing agent sheet. The layer to be incorporated may be any of a light-sensitive silver halide emulsion layer, an intermediate layer, a protective layer of the light-sensitive material and a complexing agent sheet. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles.

As a heating method in the developing and / or transferring step, a heated block or plate is brought into contact with a heating plate, a hot presser, a heating roller, a heating drum, a halogen lamp heater, an infrared and far infrared lamp heater. There is a method of contacting with, etc. or passing through in a high temperature atmosphere. The method of superimposing the light-sensitive material and the complexing agent sheet is disclosed in JP-A-62-253,159 and JP-A-6-63.
The method described in pages 1-147, 244 (27) can be applied. Any of a variety of thermal development apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-75,24
No. 7, No. 59-177, 547, No. 59-181, 3
No. 53, No. 60-18, 951, No. 62-25
944, JP-A-6-130, 509 and 6-95,
The devices described in Nos. 338 and 6-95,267 are preferably used. As commercially available devices, there are Pictrostat 100, Pictrostat 200, and Pictrostat 300 manufactured by Fuji Photo Film Co., Ltd.
The same Pictography 3000 and the same Pictography 2000 can be used. The speed (linear speed) at which these heat developing devices convey the film may be slow or fast. If the size of the apparatus is to be reduced, a linear velocity of, for example, 200 mm / min or less may be used. If it is intended to process a large amount of film in a short time, for example, 100
The linear velocity may be 0 mm / min or higher, or even 150
A high linear velocity of 0 mm / min or more may be used. Of course, an intermediate linear velocity may be used depending on the purpose.

The present invention will be described below with reference to examples, but the present invention is not limited to these.

Example 1 A method for preparing a photosensitive silver halide emulsion (I) will be described. Well-stirred pH of the composition shown in Table 1
The gelatin aqueous solution of 3 was prepared at 40 ° C, and then 37 ° C
After the temperature was lowered to, the solution (I) and the solution (II) were simultaneously added over 10 minutes, and 2 minutes after that, the solution (III) and the solution (IV) were simultaneously added over 19 minutes.

[0115]

[Table 1] Table 1 Composition of gelatin aqueous solution pH 3 ────────────────────────────── H ₂ O 650cc lime-processed gelatin 10g NaCl 2.1g Silver halide solvent 0.007g Citric acid 0.45g Sodium benzenethiosulfonate 0.006g Sodium benzenethiosulfinate 0.001g Temperature 40 ° C ───────────── ─────────────────

[0116]

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[0117]

[Table 2] Table 2 ─────────────────────────────────── (I) liquid (II) liquid (III) solution (IV) solution ─────────────────────────────────── AgNO ₃ 37.5g 62. 5g NaCl 12.75g 21.0g KBr 0.45g 0.75g Hekisakuroru 350μg iridium (III) potassium _{(NH 4) 2 RhC1 5 (} H 2 O) 90μg citrate 50 mg 50 mg was added to the total amount H ₂ O H ₂ O Add H ₂ O and add H ₂ O 120cc 120cc 200cc 200cc ───────────────────────────────── ────

After washing with water and desalting (using a precipitating agent and adjusting the pH to 3 with sulfuric acid) by a conventional method, 22 g of lime-processed gelatin was added to adjust the pH to 5.7 and pAg 7.8, and then 60 ° C.
With chemical sensitization. The compounds used for chemical sensitization were added sequentially as shown in Table 3. After gelatin dispersion, preservative, potassium bromide, sodium chloride, and ribonucleic acid degradation product were added at the same time, 2 minutes later, thiosulfonate and sulfinate were added, and 2 minutes later, sodium thiosulfate was added. 3 minutes later, chloroauric acid was added, the mixture was aged for 64 minutes, tetraazaindene was added to stop the chemical sensitization, and 2 minutes later, the temperature was lowered and set. Silver bromide content
It was a 1.7 mol% silver chlorobromide emulsion. The shape of the particles is cubic, the side length is 0.21 μm on average and the standard deviation is 0.019.
μm. The yield of this emulsion is 630 g.

[0119]

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[0120]

[Table 3] Table 3 pH 5.7 pAg 7.4 ───────────────────────────────── Chemicals used for chemical sensitization Additives ──────────────────────────────── Preservative 50 mg Sodium chloride 0.25 g Potassium bromide 0.1 g Degradation product of ribonucleic acid 0.068 g Sodium benzenethiosulfinate 71 mg Sodium benzenethiosulfonate 18 mg Sodium thiosulfate pentahydrate 1.5 mg Chloroauric acid 6.1 mg 4-Hydroxy-6-methyl-1,3,3a , 7-20mg Tetraazaindene ────────────────────────────────

To 100 g of the light-sensitive silver halide emulsion (I), the amount of the sensitizing dye, the compound of the general formula II, the compound of the general formula III and the surfactant were added in an amount of 160 m.
g and 150 mg of a water-soluble polymer, respectively, to prepare a coating solution for a photosensitive silver halide emulsion layer.
The coating was carried out so as to be g / m ² .

[0122]

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[0123]

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Next, a method for preparing a dispersion of the reducing agent 1,5-diphenyl-3-pyrazolidone will be described. 1,5-Diphenyl-3-pyrazolidone 10g, Kao Demol 0.2g
Was added to 90 cc of 5.7% lime-processed gelatin to give an average particle size of 0.
Disperse in a mill for 30 minutes using 75 mm glass beads. The glass beads were separated to obtain a gelatin dispersion of a reducing agent. Next, a solid-state dispersion of an antihalation dye was also prepared according to the above method to obtain a gelatin dispersion.

[0125]

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Next, a method for preparing a zinc hydroxide dispersion will be described. Zinc hydroxide with an average particle size of 0.2 μm 12.
5 g, 1 g of carboxymethyl cellulose as a dispersant,
0.1 g of sodium polyacrylate 4% gelatin aqueous solution 10
In addition to 0 cc, it was dispersed in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide. Photosensitive materials 1-1 to 7-5 shown in Table 4 were prepared using the above materials.
The polymer is methylmethacrylate-styrene-2-
It is a copolymer of ethylhexyl acrylate-methacrylic acid.

[0127]

[Table 4] Table 4 Composition of photosensitive materials ──────────────────────────────────── Layer name addition Material Coating amount (mg / m ² ) ──────────────────────────────────── 4th layer Acid-treated gelatin 172 (Protective layer) PMMA latex (diameter 3 μm) 12 Sumikagel L5-H (Sumitomo Chemical Co., Ltd.) 64 Calcium nitrate 3 Surfactant 1 Surfactant 5 ─────────────────── ────────────────── Third layer (described in the text) (Emulsion layer) ─────────────────── ──────────────── Second layer 1,5-diphenyl-3-pyrazolidone 1657 (Intermediate layer) Lime-treated gelatin 828 Dextran 62 Hardener 35 Surfactant 7 Water-soluble polymer 10 ────────────────────────────────── 1st layer lime-processed gelatin 660 (anti-halation antihalation dye 150 sion layer) Zinc hydroxide 900 Zinc thiosalicylate 36 Surfactant 22 Water-soluble polymer 35 ─────────────────────────────────── ─ Support: Polyethylene terephthalate (undercoating with gelatin, 100 μm) ──────────────────────────────────── Backcoat Lime-treated gelatin 60 1st layer SN-38 180 (conductive layer) (manufactured by Ishihara Sangyo) ─────────────────────────────── ───── Back coat Lime treated gelatin 2000 Second layer Surfactant 7 (Gelatin layer) Hardener 30 PMMA latex (diameter 6 μm) 49 ──────────────────────────────────── Backcoat polymer 1000 Third layer (Polymer layer) ────────────────────────――

[0128]

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Next, a complexing agent sheet R1 as shown in Table 5
It was created. A gelatin dispersion of a high boiling organic solvent is used.

[Table 5] Table 5 Composition of complexing agent sheet R1 ─────────────────────────────────── Layer Name additive Application amount (mg / m ² ) ─────────────────────────────────── 4th layer κ Carrageenan 58 (Protective layer) Sumikagel L5-H (Sumitomo Chemical Co., Ltd.) 164 Lime-treated gelatin 32 Surfactant 8 Surfactant 7 Surfactant 61 Colloidal silver (0.04 μm) 12 Potassium nitrate 82 3.6 μm Silica 9 ── ───────────────────────────────── 3rd layer lime-processed gelatin 245 (intermediate layer) Sumika gel L5-H (Sumitomo 26) Surfactant 9 Hardener 182 ─────────────────────────────────── 2nd layer Lime-processed gelatin 2 422 (Complexing agent layer) High boiling point organic solvent 2000 Dextran 620 Polymer 2280 Guanidine picolinate 2700 Quinophosphate (molar ratio of potassium / nato 270 1: 1) Hydantoin potassium 762 Surfactant 22 ─────── ───────────────────────────── 1st layer lime-processed gelatin 185 (intermediate layer) Sumikagel L5-H (Sumitomo Chemical) 8 interfaces Activator 9 Hardener 182 ─────────────────────────────────── Support: Polyethylene terephthalate (gelatin undercoat) (60 μm) ───────────────────────────────────

[0130]

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Photosensitive materials 1-1 to 7 obtained as described above
-5 with an Ar ion laser having a peak at 488 nm
Each pixel (100 μm ² ) was exposed by changing the amount of light in 1 / 10,000,000 seconds. The exposed light-sensitive material was immersed in water kept at 40 ° C. for 2.5 seconds, squeezed with a roller, and immediately superposed so that the complexing agent sheet and the film surface were in contact with each other. Then, the complexing agent sheet R1 is heated for 15 seconds by using a heat drum whose temperature is adjusted so that the temperature of the water-absorbed film surface becomes 80 ° C.
When peeled off, a black and white silver image was obtained on the light-sensitive material. Using an automatic densitometer, a characteristic curve, which is the relationship between the blue density of the transmitted image and the exposure amount, was obtained. From this characteristic curve, the maximum density Dmax and the minimum density Dmin were measured. The sensitivity was evaluated by the reciprocal of the concentration giving 1.5. The halftone dot breakage is shown in four stages: A = very good, B = good, C = normal, D = somewhat bad for practical use. The above results are shown in Tables 6 to 12.

[0132]

[Table 6] Table 6 ─────────────────────────────────── Sensitizing dye General formula (II) General formula (III) Compound of sample No. Compound sensitivity D _max D _min Halftone dot No. Addition amount No. Addition amount No. Addition amount Cut off (mg) (mg) (mg) 1-1 I-2 40 II -6 70 III-3 14 100 3.42 0.22 B (standard) 1-2 I-3 40 〃 〃 〃 123 3.40 0.23 B 1-3 I-4 40 〃 〃 〃 〃 135 3.44 0.23 B 1-4 -6 40 〃 〃 〃 170 3.42 0.24 A 1-5 I-8 40 〃 〃 〃 〃 89 3.39 0.25 B 1-6 I-11 40 〃 〃 〃 〃 105 3.45 0.21 B 1-7 I-12 40 〃 〃 〃 148 3.44 0.20 A 1-8 I-14 40 〃 〃 〃 〃 151 3.46 0.21 A 1-9 I-15 40 〃 〃 〃 〃 186 3.44 0.20 A 1-10 I-16 40 〃 〃 〃 〃 162 3.41 0.22 B −11 I-22 40 〃 〃 〃 〃 155 3.43 0.21 B 1-12 − − 〃 〃 〃 〃 − − 0.23 − ─────────────────────── ────────────

[0133]

[Table 7] Table 7 ─────────────────────────────────── Sensitizing dye General formula (II) General formula (III) Compound of sample No. Compound sensitivity D _max D _min Halftone dot No. Addition amount No. Addition amount No. Addition amount Cut off (mg) (mg) (mg) 2-1 I-25 17 II -6 65 III-3 35 100 3.43 0.21 B (standard) 2-2 I-27 17 〃 〃 〃 107 3.44 0.21 B 2-3 I-28 17 〃 〃 〃 〃 141 3.42 0.20 A 2-4 I-31 17 〃 〃 〃 〃 129 3.45 0.23 A 2-5 I-34 17 〃 〃 〃 〃 138 3.41 0.20 B 2-6 I-36 17 〃 〃 〃 〃 129 3.42 0.24 B 2-7 I 〃 〃 ッ 17 〃 120 3.44 0.20 A 2-8 I-27 10 〃 〃 〃 〃 132 3.44 0.21 A I-92 7 2-9 I-28 10 〃 〃 〃 〃 151 3.43 0.20 A I-92 7 ───────── ──────────────────────────

[0134]

[Table 8] Table 8 ─────────────────────────────────── Sensitizing dye General formula (II) General formula (III) Compound of sample No. Compound sensitivity D _max D _min Halftone dot No. Addition amount No. Addition amount No. Addition amount Cut off (mg) (mg) (mg) 3-1 I-43 18 II -3 55 III-5 30 100 3.42 0.23 B (standard) 3-2 I-44 18 〃 〃 〃 〃 115 3.41 0.24 B 3-3 I-46 18 〃 〃 120 3.40 0.23 B 3-4 I-49 18 〃 〃 〃 〃 107 3.44 0.22 A 3-5 I-50 18 〃 〃 〃 〃 126 3.43 0.22 A 3-6 I-57 18 〃 〃 〃 〃 85 3.45 0.21 B ─────────── ────────────────────────

[0135]

[Table 9] Table 9 ─────────────────────────────────── Sensitizing dye General formula (II) General formula (III) Compound of sample No. Compound sensitivity D _max D _min Halftone dot No. Addition amount No. Addition amount No. Addition amount Cut off (mg) (mg) (mg) 4-1 I-58 16 II -20 60 III-12 30 100 3.41 0.21 A (Standard) 4-2 I-59 16 〃 〃 〃 〃 117 3.42 0.20 A 4-3 I-61 16 〃 〃 〃 〃 93 3.44 0.19 A 4-4 I-63 16 〃 〃 〃 〃 102 3.45 0.19 B ────────────────────────────────────

[0136]

[Table 10] Table 10 ─────────────────────────────────── Sensitizing dye General formula (II) General formula (III) Compound of sample No. Compound Sensitivity D _max D _min Halftone dot No. Addition amount No. Addition amount No. Addition amount Cut off (mg) (mg) (mg) 5-1 I-64 18 II -6 70 III-12 35 100 3.42 0.21 A (standard) 5-2 I-65 18 〃 〃 〃 〃 129 3.43 0.19 A 5-3 I-66 18 〃 〃 〃 〃 105 3.41 0.21 B 5-4 I-69 18 〃 〃 〃 〃 107 3.40 0.22 B 5-5 I-72 18 〃 〃 〃 〃 123 3.42 0.20 A ────────────────────────── ─────────

[0137]

Table 11 Table 11 ─────────────────────────────────── Sensitizing dyes General formula (II) General formula (III) Compound of sample No. Compound Sensitivity D _max D _min Halftone dot No. Addition amount No. Addition amount No. Addition amount Cut off (mg) (mg) (mg) 6-1 I-77 17 II -3 60 III-12 35 100 3.45 0.20 A (standard) 6-2 I-79 17 〃 〃 〃 〃 110 3.43 0.21 B 6-3 I-83 17 〃 〃 〃 〃 102 3.42 0.21 B 6-4 I-84 17 〃 〃 〃 〃 107 3.41 0.21 A 6-5 I-90 17 〃 〃 〃 〃 135 3.45 0.20 A 6-6 I-77 10 〃 〃 〃 〃 145 3.46 0.20 A I-28 7 6-7 I-90 〃 〃 〃 〃 158 3.45 0.19 AI-28 7 ────────────────────────────────────

[0138]

[Table 12] Table 12 ─────────────────────────────────── Sensitizing dye General formula (II) General formula (III) Compound of sample No. Compound sensitivity D _max D _min Halftone dot No. Addition amount No. Addition amount No. Addition amount Cut off (mg) (mg) (mg) 7-1 I-94 44 II -6 70 III-5 12 100 3.43 0.25 B (standard) 7-2 I-95 44 〃 〃 〃 〃 93 3.45 0.22 A 7-3 I-96 44 〃 〃 126 3.43 0.24 A 7-4 I-97 44 〃 〃 〃 〃 120 3.42 0.23 A 7-5 I-99 44 〃 〃 〃 〃 105 3.44 0.27 B ─────────────────────────── All of the sensitizing dyes of the present invention give good sensitivity to Ar ion lasers, have low Dmin and high Dmax, and can obtain good halftone dots. It was

[0139]

Example 2 A method for preparing the photosensitive silver halide emulsion (II) will be described. Of the composition shown in Table 13 with good stirring
Solution (I) and solution (II) shown in Table 14 were simultaneously added to a pH 6 gelatin aqueous solution over 3 minutes, and after 5 minutes, (I)
Solution II and solution (IV) were added simultaneously over 15 minutes.

[0140]

[Table 13] Table 13 Composition of aqueous gelatin solution ─────────────────────────────── H ₂ O 650cc Lime-treated gelatin 20 g NaCl 3 g Silver halide solvent 0.015 g Temperature 40 ℃ ───────────────────────

[0141]

[Table 14] Table 14 ────────────────────────────────── (I) Liquid (II) Liquid ( III) Liquid (IV) Liquid ────────────────────────────────── AgNO ₃ 25g 75g NaCl 8.7g 25 0.8 g Yellow blood salt 0.023 g (NH ₄ ) ₂ Rh 15 μg Cl ₅ (H ₂ O) Total amount H ₂ O is added, H ₂ O is added, H ₂ O is added, H ₂ O is added 122cc 122cc 225cc 225cc ──────────────────────────────────

After washing with water and desalting (adjusted to pH 4.1 with sulfuric acid using a precipitating agent) by a conventional method, 22 g of lime-processed gelatin was added to adjust the pH to 6.1 and pAg 7.1, and then 5
Chemical sensitization at 0 ° C. The compounds used for chemical sensitization are the first
Sequentially added as shown in Table 5. Five minutes after the addition of the preservative and gentamicin, the temperature was lowered to stop the chemical sensitization. Particle size is 0.22 μm on average side length, standard deviation
It was a 0.019 μm silver chloride cubic emulsion. The yield of this emulsion is 630 g. The silver bromide fine grain emulsion (A) used for chemical sensitization had a grain size of 0.05 μm and a silver amount of 5.5.
%Met. The preservative is phenoxyethanol.

[0143]

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[0144]

[Table 15] Table 15 pH 6.1 pAg 7.1 ──────────────────────────────── Chemicals used for chemical sensitization Additive amount ──────────────────────────────── Silver bromide fine grain emulsion (A) 18.9 g Sodium chloride 1 .38 g triethylthiourea 76 mg ribonucleic acid degradation product 252 mg preservative 70 mg preservative 3.78 g gentamicin 8.7 mg ─────────────────────────── ──────

Next, a method for preparing the silver bromide fine grain emulsion (A) will be described. The well-stirred aqueous gelatin solution having the composition shown in Table 16 was cooled to 30 ° C., and the solutions (I) and (II) shown in Table 17 were simultaneously added over 3 minutes and 40 seconds, and then 5 minutes After that, the solution (III) and the solution (IV) were added over 13 minutes while controlling the flow rate of the solution (IV) so that the silver potential was 50 mV simultaneously.

[0146]

[Table 16] ────────────────────────── H ₂ O The composition of Table 16 aqueous gelatin solution 1120cc lime-processed gelatin 40 g KBr 3 g acetic acid (100 %) 3.5cc temperature 40 ℃ ──────────────────────────

[0147]

[Table 17] Table 17 30 ° C ────────────────────────────────── (I) Liquid (II) Liquid (III) Liquid (IV) Liquid ────────────────────────────────── AgNO ₃ 35g 65g KBr 24. 6g 49.4g Hexachlor 11 mg Potassium iridium (IV) ate Total H ₂ O and H ₂ O and H ₂ O and H ₂ O 175cc 183cc 325cc 350cc ───────── ──────────────────────────

After washing with water and desalting (adjusted to pH 4.1 with phosphoric acid using a precipitating agent) by a conventional method, 22 g of lime-processed gelatin was added to adjust pH 6.1 and pAg 7.8 (by KBr). did. A preservative was used as a preservative. Particle size 0.
It was a 05 μm silver bromide cubic emulsion. The yield of this emulsion is 630 g. 16 to 100 g of this emulsion (II)
% Lime-processed gelatin aqueous solution 15 cc, the amount of the sensitizing dye shown in Table 18, the compound of the general formula II, the compound of the general formula III and 160 mg of the surfactant, and the water-soluble polymer of 15
0 mg each was added to prepare a coating solution for the photosensitive silver halide emulsion layer, and the photosensitive material was prepared in the same manner as in the photosensitive material 1-1 except that the silver amount was adjusted to 1.35 g / m ^2. 1-8
-12 was created. Light-sensitive material 8 obtained as described above
Processing and density measurement were performed in the same manner as in Example 1 except that 1 to 8-12 were exposed by the plate camera through the optical wedge. The above results are shown in Table 18.

[Table 18] Table 18 ─────────────────────────────────── Sensitizing dye General formula (II) General formula (III) Compound of sample No. Compound sensitivity D _max D _min Halftone dot No. Addition amount No. Addition amount No. Addition amount Cut off (mg) (mg) (mg) 8-1 I-26 18 II -6 65 III-3 35 100 3.45 0.19 B (standard) 8-2 I-28 〃 〃 〃 〃 148 3.51 0.17 A 8-3 I-34 〃 〃 〃 〃 〃 129 3.48 0.18 B 8-4 I-44 〃 〃 〃 〃 〃 123 3.47 0.21 A 8-5 I-51 〃 〃 〃 〃 〃 126 3.45 0.23 A 8-6 I-65 〃 〃 〃 〃 〃 〃 〃 〃 8 〃 8 〃 117 3.52 0.19 A 8-8 I-84 〃 〃 〃 〃 〃 91 3.49 0.24 A 8-9 I-94 50 〃 〃 III-3 10 129 3.53 0.27 A 8-10 I-96 〃 3.5 〃 〃 3.5 6 〃 〃 A 8-11 I-100 〃 〃 〃 〃 〃 135 3.51 0.28 B 8-12 I-95 〃 〃 〃 〃 〃 115 3.52 0.20 B ─────────────── All of the sensitizing dyes of the present invention give good sensitivity to a plate-making camera, have a low Dmin, and have a high Dmax. ─────────────────── ,
Moreover, good halftone dots can be obtained.

[0149]

Example 3 A method for preparing a photosensitive silver halide emulsion (III) will be described. A silver halide emulsion (III) was prepared in the same manner as the silver halide emulsion (II) except that the chemical sensitization method was changed from those shown in Table 14 to Table 19 in the silver halide emulsion (II). did.

[0150]

[Table 19] Table 19 ────────────────────────────────── (I) Liquid (II) Liquid ( III) Liquid (IV) Liquid ────────────────────────────────── AgNO ₃ 25g 75g NaCl 8.7g 25 0.8 g Yellow blood salt 0.023 g 6 Cyanochromate 60 μg Potassium Total amount H ₂ O is added, H ₂ O is added, H ₂ O is added, H ₂ O is added, 122 cc 122 cc 225 cc 225 cc ───────── ──────────────────────────

The method for preparing the photosensitive silver halide emulsion (IV) will be described. The composition shown in Table 20 is well stirred.
Solution (I) and solution (II) shown in Table 21 were simultaneously added to a pH 3 gelatin aqueous solution over 4 minutes, and after 5 minutes,
Solution (III) and solution (IV) were added simultaneously over 15 minutes. The liquid (V) shown in Table 22 was added after the addition of the liquids (I) and (II) was completed. Concentration of gelatin dispersion of sensitizing dye is 1
%.

[0152]

[Table 20] Composition of Table 20 aqueous gelatin solution pH3.6 ─────────────────────────── H ₂ O 400cc Lime-processed gelatin 10 g NaCl 3g Silver halide solvent 0.010g Citric acid 0.45g Temperature 40 ℃ ────────────────────────────

[Table 21] Table 21 ────────────────────────────────── (I) Liquid (II) Liquid ( III) Liquid (IV) Liquid ────────────────────────────────── AgNO ₃ 50g 50g NaCl 16.5g 16 0.5g KBr 1.40g 1.4g Hexachlor 175μg Potassium iridium (III) (NH ₄ ) ₂ Rh 210μg Cl ₅ (H ₂ O) ──────────────────── ─────────────── Total H ₂ O, H ₂ O, H ₂ O, H ₂ O, 244cc 244cc 150cc 150cc ────── ────────────────────────────

[0153]

[Table 22] Table 22 ─────────────────────────── (V) Liquid ────────────── ───────────── 1-95 gelatin dispersion 30g Total H ₂ O 75cc ───────────────────── ─────

After washing with water and desalting (using a precipitating agent and adjusting the pH to 4 with sulfuric acid) by a conventional method, 32 g of lime-processed gelatin was added to adjust the pH to 6.1 and pAg7.4, and then 60 ° C.
With chemical sensitization. The compounds used for chemical sensitization were sequentially added as shown in Table 23. The yield of this emulsion is 630
g. The silver chlorobromide cubic grains had a grain size of 0.21 μm and a silver bromide content of 4 mol%.

[0155]

[Table 23] Table 23 pH 6.1 pAg 7.8 ────────────────────────────────── Used for chemical sensitization Chemicals Additives ───────────────────────────────── Preservatives 50 mg Sodium chloride 0.25 g Potassium bromide 0. 1 g Sodium benzenethiosulfinate 7.1 mg Sodium benzenethiosulfonate 1.1 mg Sodium thiosulfate pentahydrate 2.1 mg Chloroauric acid 4.8 mg 4-Hydroxy-6-methyl-1,3,3a, 768 mg- Tetraazaindene preservative 3.2g ──────────────────────────────────

Photosensitive silver halide emulsion 1 shown in Table 24
In 100 g of sensitizing dye, the compound of the general formula II, the compound of the general formula III and the surfactant in the amount shown in Table 24 are added in an amount of 160 m.
g and 150 mg of a water-soluble polymer, respectively, to prepare a coating solution for a photosensitive silver halide emulsion layer.
Photosensitive materials 9-1 to 9-6 were prepared in the same manner as the photosensitive material 1-1 except that it was changed to g / m ² . In the light-sensitive material 9-7, the emulsion (IV) containing the sensitizing dye I-95 was used to prepare the sensitizing dye in the same amount as the light-sensitive material 9-6. No. of No. and the addition amount are put in parentheses. Light-sensitive materials 9-1 to 9-1 obtained as described above
The same exposure, processing and density measurement as in Example 1 were carried out except that 9-7 was carried out at a developing temperature of 75 ° C. for 25 seconds. The above results are shown in Table 24.

[0157]

[Table 24] Table 24 ──────────────────────────────────── Sensitizing dye General formula (II) General Formula (III) Sample Emulsion Compound Compound Sensitivity D _max D _min Halftone dot No. No. Addition amount No. Addition amount No. Addition amount Cut off (mg) (mg) (mg) 9-1 (I) I -28 20 II-6 65 III-3 35 79.4 3.42 0.21 A 9-2 (II) 〃 − − 〃 〃 100 3.52 0.18 A (reference) 9-3 (III) 〃 〃 − − 〃 〃 107 3.49 0.19 A 9-4 (I) I-95 50 II-6 65 〃 10 85 3.45 0.22 A 9-5 (II) 〃 〃 − − 〃 〃 115 3.53 0.21 A 9-6 (III) 〃 〃 − − 〃 〃 123 3.52 0.21 A 9-7 (IV) (I-95) (50) II-6 65 〃 〃 126 3.54 0.19 A ──────────────────────── ─────────────

Each of the sensitizing dyes of the present invention gives good sensitivity to an Ar ion laser, has a low Dmin and a Dma.
It can be seen that x is high and good halftone dots are obtained.

[Procedure amendment]

[Submission date] November 5, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image In the formula, Z ₁₁ and Z ₁₂ represent a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₁₁ and R ₁₂ each represent an alkyl group, a substituted alkyl group, or an aryl group. n ₁₁ and n ₁₂ each represent 0 or 1. X ₁ represents an anion. m represents 0 or 1, and m = 0 when forming an intramolecular salt.

Embedded image In the formula, Z ₂₁ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. Q ₂₁ represents a non-metallic atomic group necessary for completing a 4-thiazolidinone, a 5-thiazolidinone, or a 4-imidazolidinone nucleus.
R ₂₁ and R ₂₂ each represent an alkyl group, a substituted alkyl group, or an aryl group. n ₂₁ represents 0 or 1.

Embedded image In the formula, Z ₃₁ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₃₁ and R ₃₂ each represent an alkyl group, a substituted alkyl group, or an aryl group. Q ₃₁ represents a non-metallic atomic group necessary for completing a 4-thiazolidinone, a 5-thiazolidinone, or a 4-imidazolidinone nucleus. n ₃₁ represents 0 or 1.

Embedded image In the formula, Z ₄₁ and Z ₄₂ represent a nonmetallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₄₁ and R ₄₂ each represent an alkyl group, a substituted alkyl group, or an aryl group. L ₄₁ represents a methine group or a substituted methine group. X ₄ represents an anion. m represents 0 or 1,
When forming an intramolecular salt, m = 0.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction contents]

[0007]

Embedded image

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

[0013]

Embedded image

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0065

[Correction method] Change

[Correction contents]

A flat plate having a high aspect ratio can also be preferably used. Tabular grains of high silver chloride emulsion grains having (111) planes are disclosed in U.S. Pat. Nos. 4,399,215 and 4,400,4.
63, 5,217,858, JP-A-2-32, etc., and tabular grains of high silver chloride emulsion grains having a (100) plane are described in U.S. Pat. No. 4,946,772, 5,275,930, 5,264,337, Japanese Patent Application No. 4-214109, Japanese Patent Application No. 5-96250, and European Patent No. 0534395A1. Such tabular grains having a high aspect ratio have a larger surface area than normal crystals having the same volume, so that the amount of sensitizing dye adsorbed can be increased, which is advantageous in terms of color sensitization sensitivity. Further, since it is advantageous in terms of covering power, a high Dmax can be achieved with a small amount of silver. Since it has a large specific surface area, it has the feature of having high development activity. The average grain size of the silver halide grains is 0.
Any size may be used, from fine particles of not more than 05 μm to large-sized particles having a projected area diameter of more than 10 μm. Preferably 0.1 to 2 μm, especially 0.1 to 0.9 μm
Is preferred. The grain size distribution is, for example, the average grain size ±
A monodisperse emulsion having a grain size distribution such that 80% or more of all grains fall within 30% may be used, or a polydisperse emulsion having a wide grain size distribution may be used. A monodisperse emulsion is preferably used.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0072

[Correction method] Change

[Correction contents]

The silver halide emulsion of the present invention can be used without being chemically sensitized, but it is usually used after being chemically sensitized. The chemical sensitization method used in the present invention includes a sulfur sensitization method,
Chalcogen sensitization methods such as selenium sensitization and tellurium sensitization,
A noble metal sensitization method and a reduction sensitization method using gold, platinum, palladium or the like can be used alone or in combination (for example, JP-A-3-110555 and JP-A-5-2412).
No. 67). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9). Further, an antifoggant described below can be added after the completion of chemical sensitization. Specifically, JP-A-5-45
The methods described in JP-A No. 833 and JP-A No. 62-40446 can be used.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0077

[Correction method] Change

[Correction contents]

Gelatin is preferably used as the protective colloid used in preparing the emulsion, but other hydrophilic binders can also be used. The hydrophilic binder can be used alone or in combination with gelatin. Examples of the hydrophilic binder include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose and cellulose sulfates,
Sodium alginate, starch derivatives, polysaccharides, carrageenan, polyvinyl alcohol, modified alkyl polyvinyl alcohol, polyvinyl-N-pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, etc. Such synthetic hydrophilic polymer, US Pat. No. 3,
The thioether polymer described in 615,624 can also be preferably used. Gelatin is lime-processed gelatin,
Gelatin derivatives such as acid-treated gelatin, demineralized gelatin and phthalated gelatin, and low molecular weight gelatin can also be used.
Gelatin oxidized with an oxidizing agent such as hydrogen peroxide or gelatin treated with an enzyme can also be used. A hydrolyzate or an enzymatic hydrolyzate of gelatin can also be used.

Claims (1)

[Claims] 1. A support having a silver chloride content of at least 8
In a silver halide light-sensitive material containing 0 mol% or more of a light-sensitive silver halide emulsion, a hydrophilic binder, and a water-insoluble basic metal compound, the following general formula (Ia):
General formula (Ib), general formula (Ic) and general formula (Id)
A silver halide photographic light-sensitive material containing at least one sensitizing dye represented by Embedded image In the formula, Z ₁₁ and Z ₁₂ represent a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₁₁ and R ₁₂ each represent an alkyl group, a substituted alkyl group, or an aryl group. n ₁₁ and n ₁₂ each represent 0 or 1. X ₁ represents an anion. m represents 0 or 1, and m = 0 when forming an intramolecular salt. Embedded image In the formula, Z ₂₁ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. Q ₂₁ represents a non-metal atom group necessary for completing a 4-thiazolidinone, a 5-thiazolidinone, or a 4-imidazolidinone nucleus.
R ₂₁ and R ₂₂ each represent an alkyl group, a substituted alkyl group, or an aryl group. n ₂₁ represents 0 or 1. Embedded image In the formula, Z ₃₁ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₃₁ and R ₃₂ each represent an alkyl group, a substituted alkyl group, or an aryl group. Q ₃₁ represents a non-metallic atomic group necessary for completing a 4-thiazolidinone, a 5-thiazolidinone, or a 4-imidazolidinone nucleus. n ₃₁ represents 0 or 1. Embedded image In the formula, Z ₄₁ and Z ₄₂ represent a nonmetallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₄₁ and R ₄₂ each represent an alkyl group, a substituted alkyl group, or an aryl group. L ₄₁ represents a methine group or a substituted methine group. X ₄ represents an anion. m represents 0 or 1,
When forming an intramolecular salt, m = 0.