JP2000206639A - Silver halide photographic sensitive material and manufacture of same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide high sensitivity without the increase of fog and the lowering of sensitivity during aged preservation and without the dependency of temperature during exposure by including a specific compound in a silver halide emulsion larger or a hydrophilic colloidal layer adjacent thereto. SOLUTION: The sensitive material is provided on a support with at least one silver halide emulsion layer containing silver halide grains having a spectral sensitive region of 700-1500 nm, and this layer or its adjacent hydrophilic colloidal layer contains one of the compounds represented mainly by the formula in which R is an optionally substituted aryl group; and each of R1-R5 is, independently, an H atom or an optionally substituted alkyl or optionally substituted aralkyl or optionally substituted aryl group. The silver halide emulsion grains are sensitized with a selenium or tellurium compound and it is preferred that the >=80% of the grains have (100) principal faces and a 0-30 mol % average silver chloride content.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material for laser exposure and a method for producing the silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, MR, C
The importance of image diagnosis using diagnostic devices such as T and RI has been increasing.

A laser imager which modulates the intensity of a laser beam with an image signal as an output of these diagnostic devices and renders the image on a silver halide photographic material is highly evaluated for its usefulness because of its high image quality. It is becoming.

In these scanning laser exposure apparatuses, argon, helium-neon, semiconductor lasers and the like are used as laser light sources. Among these, the semiconductor laser has advantages such as being inexpensive, having a long life, being compact, and capable of direct modulation.

[0005] The emission wavelength of a semiconductor laser is in the red to infrared region, and a laser having a near-infrared emission wavelength is particularly important in terms of cost and stability. Since the life of a semiconductor laser is said to be inversely proportional to the fourth power of its output,
There is a strong demand for high-sensitivity recording materials in order to extend the life of the apparatus as much as possible.

Means for spectrally sensitizing silver halide grains to the near infrared include, for example, The Theory of
As described in the Photographic Process, 3rd edition, pages 198 to 201 (Macmillan, 1966), a method using a long-chain cyanine dye is well known. However, silver halide photographic materials sensitized to near-infrared light are not excellent in preservability, and storage conditions such as storage in a refrigerator are strongly restricted for long-term storage.

Further, the sensitivity greatly varies depending on the exposure temperature, and the apparatus is easily affected by the installation environment of the apparatus and the seasonal temperature.

The inventor of the present application has solved the problems described in JP-A-9-90541, JP-A-9-230527 and JP-A-9-230527.
No. 230528, No. 10-55040, No. 10-69
No. 021, No. 10-254086, No. 10-2540
No. 87 discloses a solution. However, it cannot be said that it is still sufficient, and further technical progress is desired.

Further, when a silver halide photographic light-sensitive material is produced, a coating solution containing an emulsion sensitized to near infrared rays is kept for a long time (so-called stagnation of the coating solution) to reduce fog and desensitization. There were drawbacks that occurred. By improving the stagnation of the coating liquid, long continuous coating becomes possible.
It is expected that the loss of the support and the waste of the process time due to the switching of the coating solution are eliminated, leading to cost reduction.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a high-sensitivity silver halide photographic material for laser exposure which has no increase in fog and no decrease in sensitivity during storage over time and has no temperature dependence upon exposure. And a method for producing the silver halide photographic light-sensitive material.

Another object of the present invention is to provide a silver halide photographic light-sensitive material which does not cause an increase in fog even when the coating solution is stagnated for a long time and does not cause desensitization, and a method for producing the same.

[0012]

The object of the present invention has been attained by the following.

(1) In a silver halide photographic material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer contains 700 silver halide grains.
Each of the compounds represented by the following general formulas (1) and (2) in the silver halide emulsion layer or in at least one of the hydrophilic colloid layers adjacent to the silver halide emulsion layer or at least one hydrophilic colloid layer. A silver halide photographic material comprising at least one kind.

[0014]

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(In the formula, R represents a substituted or unsubstituted aryl group. R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different and each represents a hydrogen atom, a substituted or Represents an unsubstituted alkyl group, a substituted or unsubstituted aralkyl group or a substituted or unsubstituted aryl group.

[0016]

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(In the formula, R ₆ represents a hydrogen atom or a hydroxy group, and R ₇ represents a hydrogen atom or a group represented by the following general formula (3). N represents 1 to _6. )

[0018]

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(Wherein R ₈ represents a hydrogen atom or a hydroxy group). (2) In a silver halide photographic material having at least one silver halide emulsion layer on a support, said silver halide emulsion Silver halide grains of the layer are 700 to 1500 n
m has a spectral maximum sensitivity and is represented by the general formula (2) and the following general formula (4) in at least one of the silver halide emulsion layer and the hydrophilic colloid layer adjacent thereto. A silver halide photographic material comprising at least one compound.

[0020]

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(Wherein R ₉ and R ₁₀ are each independently a hydroxy group, a mercapto group, a substituted or unsubstituted amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group or an alkylthio group Z represents an atomic group necessary for forming a substituted or unsubstituted 5- or 6-membered ring.) (3) The silver halide emulsion grains are sensitized with selenium or tellurium. Yes (1) or (2)
The silver halide photographic light-sensitive material as described above.

(4) The above silver halide emulsion grains are
The silver halide photographic light-sensitive material according to any one of (1) to (3), wherein the silver halide photographic material is a grain having a (100) plane of 80% or more.

(5) The halogenation according to any one of (1) to (4), wherein the silver halide emulsion grains have an average silver chloride content of 0 to 30 mol%. Silver photographic photosensitive material.

(6) The above (1), (3), (4),
(5) The silver halide photographic material as described in any one of (5) above, wherein the silver halide emulsion grains have a particle size of 700 to 150.
Halogenation characterized by adding at least one of the compounds represented by the general formulas (1) and (2) at least 30 seconds before adding a sensitizing dye which gives a spectral maximum sensitivity to 0 nm. Method for producing silver photographic light-sensitive material

(7) The above (2), (3), (4),
(5) The silver halide true-sensitive material according to any one of (1) to (5), wherein the silver halide emulsion grains have a particle size of 700 to 1500.
a halogenating method characterized by adding at least one of the compounds represented by the general formulas (2) and (4) at least 30 seconds before adding a sensitizing dye that gives spectral sensitivity to nm. A method for producing a silver photographic light-sensitive material.

Hereinafter, the present invention will be described in detail.

The compound represented by the general formula (1) used in the silver halide photographic light-sensitive material of the present invention is a pyrazolidone compound, and specific compounds are listed below, but the present invention is not limited thereto. It is not something to be done.

1-1: 1-phenyl-3-pyrazolidone 1-2: 2-phenyl-4,4-dihydroxymethyl-
3-pyrazolidone 1-3: 1-phenyl-4,4-dimethyl-3-pyrazolidone 1-4: 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 1-5: 1- (p-tolyl ) -4,4-Dihydroxymethyl-3-pyrazolidone 1-6: 1-phenyl-2-hydroxymethyl-4,4
-Dimethyl-3-pyrazolidone 1-7: 1-phenyl-2-morpholinomethyl-4,4
-Dimethyl-3-pyrazolidone 1-8: 1-phenyl-2-morpholinomethyl-4-methyl-3-pyrazolidone 1-9: 1-phenyl-2-hydroxymethyl-4-methyl-3-pyrazolidone 1-10: 1-phenyl-5,5-dimethyl-3-pyrazolidone 1-11: 1-phenyl-5-methyl-3-pyrazolidone 1-12: 1- (p-tolyl) -4-hydroxymethyl-4-methyl-3 -Pyrazolidone 1-13: 1- (p-hydroxyphenyl) -4,4-
Dimethyl-3-pyrazolidone 1-14: 1- (o-tolyl-4-hydroxymethyl)
-4-Methyl-3-pyrazolidone 1-15: 1- (p-methoxyphenyl) -4-hydroxymethyl-4-methyl-3-pyrazolidone 1-16: 1- (3,5-dimethylphenyl) -4- Hydroxymethyl-4-methyl-3-pyrazolidone In the present invention, these compounds may be added to a silver halide photographic light-sensitive material by adding them to an emulsion coating solution.

The timing of addition may be any time after the formation of emulsion grains until coating, but preferably at least 30 seconds before the addition of a sensitizing dye which gives a spectral maximum sensitivity to 700 to 1500 nm to a silver halide emulsion. is there. More preferably, at least 120 seconds before the addition of the sensitizing dye.

The addition amount is 1 × 1 per mol of silver halide.
0 ⁻⁵ mol to 5 × 10 ⁻² mol, preferably 5 × 10 ² mol
^-5 mol to 1 × 10 ^-2 mol.

Next, specific examples of the compound represented by the general formula (2) of the present invention are shown, but the present invention is not limited thereto.

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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In the present invention, in order to incorporate these compounds into a silver halide photographic light-sensitive material, a light-sensitive silver halide emulsion layer and / or a hydrophilic colloid layer adjacent thereto are preferably used. This is a coating solution for an emulsion layer.

The compound may be added at any time from the formation of the silver halide emulsion grains to the coating, but preferably from 700 to 150
It is at least 30 seconds before the addition of the sensitizing dye that gives the spectral maximum sensitivity to 0 nm, more preferably 120 seconds.

The addition amount is 1 × 1 per mol of silver halide.
0 ⁻⁵ mol to 5 × 10 ⁻² mol, preferably 5 × 10 ² mol
^-5 mol to 1 × 10 ^-2 mol.

In the present invention, at least one of the above-mentioned compound of the general formula (1) and the compound of the general formula (2) is contained, and the order of adding each compound is as follows. May be. Preferably, the compound of general formula (2) is added at least 30 seconds before the addition of the compound of general formula (1). Further, the compounds of the general formulas (1) and (2) are both 700 to 1
It is preferably added at least 30 seconds before the addition of the sensitizing dye giving the spectral sensitivity at 500 nm, more preferably 120 seconds before.

Next, the compound represented by formula (4) used in combination with the compound represented by formula (2) will be described.

In the general formula (4), R ₈ and R ₉ are each independently a hydroxy group, a mercapto group or an amino group (the amino group is an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, n-butyl, hydroxy An acylamino group (eg, acetylamino, benzoylamino group, etc.), an alkylsulfonylamino group (eg, methanesulfonylamino group, etc.), an arylsulfonylamino group (eg, benzenesulfonylamino group, a p-toluenesulfonylamino group, an alkoxycarbonylamino group (eg, a methoxycarbonylamino group), and an alkylthio group (eg, a methylthio, ethylthio group, etc.).

Preferred examples of R ₈ and R ₉ include a hydroxy group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group. Z is preferably composed of a carbon atom, an oxygen atom or a nitrogen atom, and forms a 5- to 6-membered ring together with the two vinyl carbons and the carbonyl carbon substituted by R ₈ and R ₉ ; preferable.

Specific examples of Z include -O-, -C
_{(R 10) (R 11)} -, - C (R 12), - C (= O) -,
-N (R ₁₃₎ -, - formed by combining the N =. However, R ₁₀ , R ₁₁ , R ₁₂ , and R ₁₃ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group, or a sulfo group can be given as a substituent) Represents an aryl group having 6 to 15 carbon atoms which may be substituted (an alkyl group, a halogen atom, a hydroxy group, a carboxy group or a sulfo group can be mentioned as a substituent), a hydroxy group or a carboxy group. This 5
A saturated or unsaturated condensed ring may be formed in the 6-membered ring. Examples of the 5- to 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. Preferred examples of the 5- or 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring and a uracil ring.

Hereinafter, specific examples of the compound represented by formula (4) of the present invention are shown, but the present invention is not limited to these.

[0047]

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[0048]

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[0049]

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The light-sensitive material of the present invention has a viscosity of 700 to 1500 n.
m has a spectral maximum sensitivity. 700 used in the present invention
Sensitizing dyes having a spectral maximum sensitivity in the range of 700 nm to 1500 nm when adsorbed on silver halide grains.
Which gives the spectral maximum sensitivity to light of the wavelength
In particular, it is preferably at least one arbitrarily selected from the group consisting of compounds represented by the following general formulas [D-1] and [D-2].

The silver halide grains of the silver halide photographic light-sensitive material of the present invention preferably have a spectral maximum sensitivity in the range of 700 to 1500 nm, and more preferably have a spectral sensitivity maximum in the range of 750 to 1000 nm. In the present invention, any spectral sensitizing dye can be used as long as it gives the above-mentioned spectral maximum sensitivity, but preferably a sensitizing dye represented by the following general formula [D-1] or [D-2] Is preferably at least one arbitrarily selected from the group consisting of The reason is that a stable photographic density can be obtained with respect to fluctuations in the wavelength of the light source. It is effective to use two or more sensitizing dyes having different spectral maximum sensitivities in the present invention.

The sensitizing dyes represented by formulas [D-1] and [D-2] preferably used in the present invention will be described below.

[0053]

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In the formula, Z ¹ and Z ³ represent a benzothiazole, a naphthothiazole, a benzoxazole or a nonmetal atom group necessary for forming a naphthoxazole ring which may have a substituent. Z ² represents a 5- or 6-membered carbon atom ring which may have a substituent, and R ¹ and R ² each represent an alkyl group or a substituted alkyl group. X ₁ ^- it is n represents a counter ion is 1 or 2. The benzothiazole ring, naphthothiazole ring, benzoxazole ring, and naphthoxazole ring represented by Z ¹ and Z ³ may have a substituent, for example, an alkyl group having 1 to 4 carbon atoms,
And 4 to 4 alkoxy groups, phenyl groups, halogen atoms (eg, chlor atom, bromo atom) and the like may be substituted. R ¹ and R ² are an alkyl group having 1 to 4 carbon atoms,
Examples of the substituted alkyl group having 1 to 4 carbon atoms include methyl, ethyl, hydroxyethyl, 2-methoxyethyl, 2-acetoxyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl,
Examples thereof include 2-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, vinylmethyl, benzyl, phenethyl, p-sulfophenethyl, n-propyl, isopropyl, and n-butyl groups.

A preferred compound of the present invention wherein Z ^{2 of the} formula [D-1] is a 5-membered carbon atom ring is represented by the following formula [D-1a]. it can.

[0056]

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[0057] In the formula, R ^13, R ¹⁴ are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (e.g. chlorine atom, etc. bromine atom), R ¹⁵ , R ¹⁶ each represents an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent (for example, a phenyl group, an m-tolyl group, a p-tolyl group, an m-chlorophenyl group, Examples thereof include an alkoxy group-substituted p-methoxyphenyl group and the like, and an alkoxycarbonylalkyl group having 1 to 4 carbon atoms (such as an ethoxycarbonylmethyl group).

R ¹⁷ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms or a phenyl group. Z ¹ , Z ³ , R ¹ ,
R ^2, X ₁ ⁻ and n have the same meanings as in formula [D-1].

A preferred compound of the present invention wherein Z ² is a 6-membered carbon atom ring in the above general formula [D-1] can be represented by the following general formula [D-1b].

[0060]

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In the formula, R ¹⁸ and R ¹⁹ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or phenyl. Z ¹ ,
Z ³ , R ¹ , R ² and X ₁ ⁻ , n have the same meanings as in the general formula [D-1].

Hereinafter, specific examples of the compound represented by formula [D-1] of the present invention will be shown, but the present invention is not limited thereto.

[0063]

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[0064]

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[0065]

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[0066]

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Next, the compound of the formula [D-2] of the present invention will be described.

[0068]

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In the formula, R ⁴ and R ⁵ represent an alkyl group or a substituted alkyl group, preferably an alkyl group having 1 to 8 carbon atoms. Examples of the group substituted with the alkyl group include a carboxyl group, a sulfone group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, and a fluorine atom), a hydroxyl group, an alkoxycarbonyl group (preferably having 8 or less carbon atoms), an alkoxy group, Group (preferably having 7 or less carbon atoms),
Examples thereof include an aryloxy group, an acyloxy group (preferably having 3 or less carbon atoms), an acyl group (preferably having 8 or less carbon atoms), a carbamoyl group, a sulfamoyl group, and an aryl group.

R ⁶ is a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a benzyl group, preferably an alkyl group having 1 to 4 carbon atoms or a benzyl group. Y is a hydrogen atom, a substituted or unsubstituted carbon number 1 to
8 represents an alkyl group, an alkoxy group or a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom).

Examples of the 5- to 6-membered nitrogen-containing heterocyclic ring represented by Z ⁴ include a thiazole ring, a selenazole ring, an oxazole ring, a 3,3-dialkylindolenin ring and an imidazole ring. Of these, preferred are a thiazole ring and an oxazole ring, and more preferred are a benzothiazole ring, a naphthothiazole ring, a benzoxazole ring and a naphthoxazole ring.

[0072] X ₁ ^- represents a counter ion, m, n and p 1
Or 2 is represented.

Hereinafter, specific examples of the compound represented by formula [D-2] of the present invention will be shown, but the present invention is not limited thereto.

[0074]

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[0075]

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In the present invention, it is effective to use two or more sensitizing dyes having different spectral maximum sensitivities in order to obtain a stable photographic density with respect to the wavelength fluctuation of the light source.

Although the optimum amount of the spectral sensitizing dye varies depending on the compound, it is generally 1 to 1 per mol of silver halide.
The amount can be selected from the range that gives the highest sensitivity within the above wavelength.

In the present invention, the above compounds can be added by dissolving them in a suitable organic solvent, for example, a solvent such as alcohols, glycols, ketones, esters and amides. Preferably, it is added using an activator without using a solvent or in a state of being solid-dispersed in water without using an activator.

These compounds are preferably added so as to be present at the time of selenium or tellurium sensitization, and may be added at any time before the completion of selenium or tellurium sensitization. Before at least one of the sensitizers is added. More preferably, before all the chemical sensitizers have been added.

The chemical sensitizer mentioned here is a known chemical sensitizer, for example, a chalcogen sensitizer such as sodium thiosulfate, potassium thiosulfate, and triphenylphosphine selenide, chloroauric acid, chloroauric acid, and the like. Noble metal sensitizers such as sodium and reduction sensitizers such as stannous chloride, sodium borohydride and ascorbic acid.

The spectral sensitizing dye in the present invention is preferably added before the chalcogen sensitizer. Also, in the case of adding after the noble metal sensitizer, it is preferable to add the noble metal sensitizer at least 10 minutes after the end of addition. Further, as described above, it is preferable that the compounds represented by the general formulas (1) and (2) are added at least 30 seconds, preferably 120 seconds before the addition of the spectral sensitizing dye in the present invention.

In the present invention, it is preferable to use a selenium compound or tellurium compound for chemical sensitization.

The spectral sensitizing dye of the present invention has the general formula [D
-1] and [D-2] may be used alone or in combination. In the case of a single dye, a dye selected from the general formula [D-1] is particularly preferably used. The addition amount of the sensitizing dye is 1 to 100 per mol of silver halide.
mg, more preferably 2 to 40 mg.

In the present invention, the above-mentioned spectral sensitizing dye can be added by dissolving it in a suitable organic solvent, for example, a solvent such as alcohols, glycols, ketones, esters and amides. It is preferably added in the form of a solid dispersion in water using an activator without a solvent or without an activator.

These spectral sensitizing dyes are preferably added so as to be present at the time of selenium or tellurium sensitization described later. The timing of addition may be any time before the end of selenium or tellurium sensitization. Preferably before the addition of at least one of the selenium or tellurium sensitizers, more preferably before the addition of all the chemical sensitizers. Here, the chemical sensitizer is as described above.

The spectral sensitizing dye in the present invention is preferably added before the chalcogen sensitizer. When the noble metal sensitizer is added after the noble metal sensitizer, it is preferable to add the noble metal sensitizer at least 10 minutes after the end of the addition.

Next, the selenium compound or tellurium compound preferably used in the present invention will be described in detail. As the selenium sensitizer that can be used in the present invention, various selenium compounds including conventionally known selenium sensitizers can be used.
Usually, an unstable selenium compound and / or a non-unstable selenium compound is added, and the emulsion is stirred at a high temperature, preferably at 40 ° C. or higher for a certain time.

As the unstable selenium compound, compounds described in JP-B-41-15748 and JP-B-43-13489 are preferably used. Specific compounds include
Isoselenocyanates (aliphatic isoselenocyanates such as allyl isoselenocyanate, etc.), selenoureas, selenoketones, selenoamides, selenocarboxylic acids (2-seleniumbutyric acid, etc.), selenoesters, diacylselenides (Such as bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, and colloidal metal selenium.

The non-labile selenium compounds are described in JP-B-46-4553, JP-B-52-34492 and JP-B-52-34492.
No. 34491 can be used. Specific compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenide, diaryl diselenide, dialkyl selenide, dialkyl diselenide, 2-selenazolidinedione, -Selenooxazolidinethione and derivatives thereof.

Among these selenium compounds, preferred compounds include those represented by the following general formulas [I] and [II].

[0091]

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In the formula, R ₁ and R ₂ may be the same or different and each represents an alkyl group (methyl, ethyl, t-butyl,
Adamantyl, t-octyl, etc.), alkenyl group (vinyl, propenyl, etc.), aralkyl group (benzyl, phenethyl, etc.), aryl group (phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-nitrophenyl)
Octylsulfamoylphenyl, α-naphthyl, etc.),
Hajime Tamaki (pyridyl, thienyl, furyl, imidazolyl, _{etc.), - NR 11 (R 12} ), - represents a OR ₁₃ or -SR _14. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ may be the same or different and each represents an alkyl group, an aralkyl group, an aryl group or a heterocyclic group. Examples of the alkyl group, aralkyl group, aryl group and heterocyclic group include the same groups as for R ₁ . However, R ₁₁ and R ₁₂ may be a hydrogen atom or an acyl group (acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl, 4-nitrobenzoyl, a-naphthoyl, 4-trifluoromethylbenzoyl, etc.). .

[0093] In the general formula (I), preferably, R ₁ represents an alkyl group, an aryl group or _{-NR 11 (R 1 2),} R 2
Represents —NR ₁₅ (R ₁₆ ). R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆
May be the same or different and each represents a hydrogen atom, an alkyl group, an anneal group or an acyl group.

In the general formula [I], more preferably, N, N
-Dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N-
Represents an alkyl-N-aryl-arylselenoamide.

[0095]

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In the formula, R ₃ , R ₄ and R ₅ may be the same or different, and may be an aliphatic group, an aromatic group, a heterocyclic group, —O
R ₂₁ , —OR ₂₂ (R ₂₃ ), —SR ₂₄ , —SeR ₂₅ , a halogen atom or a hydrogen atom. R ₂₁ , R ₂₄ and R ₂₅ represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₂₂ and R ₂₃ represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom .

R ₃ , R ₄ , R ₅ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄
And an aliphatic group represented by R ₂₅ represents a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, or aralkyl group, for example, methyl, ethyl, propyl, i-propyl, t-butyl, n-butyl , Octyl, decyl, hexadecyl, cyclopentyl, cyclohexyl, allyl,
Represents 2-butenyl, 3-pentenyl, 3-pentynyl, propargyl, benzyl group, phenethyl group and the like.

R ₃ , R ₄ , R ₅ , R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄
And an aromatic group represented by R ₂₅ are a monocyclic or condensed-ring aryl group (phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, α-naphthyl,
A methylphenyl group). R ₃ , R ₄ , R ₅ , R ₂₁ ,
The heterocyclic group represented by R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ is a group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom.
Represents a 10-membered saturated or unsaturated group (pyridyl, thienyl, furyl, thiazolyl, imidazolyl, benzimidazolyl group, etc.).

The cation represented by R ₂₁ , R ₂₄ and R ₂₅ represents an alkali metal atom or an ammonium group, and the halogen atom represents a fluorine, chlorine, bromine or iodine atom.

[0100] In formula (II), preferably, R _3, R ₄ or R ₅ represents an aliphatic group, an aromatic group, or -OR _26, R ₂₆
Represents an aliphatic group or an aromatic group. More preferably, it represents a trialkylphosphine selenide, a triarylphosphine selenide, a trialkylselenophosphate or a triarylselenophosphate.

Specific examples of the compound represented by formula (I) or (II) are shown below.

[0102]

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[0103]

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Next, specific examples of tellurium sensitizers that can be used in the present invention include colloidal tellurium, telluroureas (allyl tellurourea, N, N-dimethyltellurourea,
Tetramethyltellurourea, N-carboxyethyl-N '
N'-dimethyltellurourea, N, N'-dimethylethylenetellurourea, N, N'-diphenylethylenetellurourea, etc., isotellurocyanates (allyl isotellurocyanate, etc.), telluroketones (telluroacetone, telluroacetophenone, etc.) ), Telluroamides (telluroacetamide, N, N-dimethyltellurobenzamide, etc.), tellurohydrazides (N, N'-trimethyltellurobenzhydrazide), telluroesters (t-butyl-t-hexyltelluroester, etc.), phosphine Tellurides (tributylphosphine telluride, tricyclohexylphosphine telluride, tri-i-propylphosphine telluride, butyl-di-i-propylphosphine telluride, dibutylphenylphosphine telluride, etc.) and other tellurium compounds (for example, UK Negatively charged telluride ion-containing gelatin described in JP Patent 1,295,462, Potassium nitrosium telluride, Potassium nitrosium tellurocyanate diisocyanate, tellurocarbonyl penta isethionate, sodium salt, allyl tellurocyanate diisocyanate and the like).

Of these tellurium compounds, compounds preferably represented by the following general formula [III] or [IV] are preferably used.

[0106]

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In the formula, R ₆ , R ₇ and R ₈ are each an aliphatic group, an aromatic group, a heterocyclic group, —OR ₃₁ , —N (R ₃₂ ) (R
_{33), - SR 34, -OSi} (R 35) (R 36) (R 37),
Represents a halogen atom or a hydrogen atom. R ₃₁ and R ₃₄ each represent an aliphatic group, an aromatic group, a heterocyclic group, a hydrogen atom or a cation, and R ₃₂ and R ₃₃ each represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom. Represents R ₃₅ , R ₃₆ and R ₃₇
Each represents an aliphatic group.

In the general formula [III], R _{6 to} R ₈ and R
₃₁ aliphatic group represented by to R ₃₇ is preferably 1 to carbon atoms
And those having 30 carbon atoms, particularly a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group or aralkyl group having 1 to 20 carbon atoms. Specifically, methyl, ethyl, propyl,
Examples include i-propyl, t-butyl, octyl, decyl, hexadecyl, cyclopentyl, cyclohexyl, allyl, butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl and the like.

The aromatic groups represented by R _{6 to} R ₈ and R _{31 to} R ₃₇ are preferably those having 6 to 30 carbon atoms, particularly those having 6 to 30 carbon atoms.
To 20 monocyclic or condensed ring aryl groups such as phenyl and naphthyl.

The heterocyclic group represented by R _{6 to} R ₈ and R _{31 to} R ₃₇ is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. And these may be monocyclic or may form a condensed ring with another aromatic or heterocyclic ring. It is preferably a 5- or 6-membered aromatic heterocyclic group, and examples thereof include pyridyl, furyl, thienyl, thiazolyl, imidazolyl, and penzoimidazolyl.

The cation represented by R ₃₁ and R ₃₄ represents, for example, an alkali metal atom or an ammonium group. A halogen atom represents a fluorine, chlorine, bromine or iodine atom.

The above-mentioned aliphatic group, aromatic group and heterocyclic group may be substituted. Examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, Amino group,
Acylamino group, ureido group, urethane group, sulfonylamino group, sulfamoyl group, carbamoyl group, sulfonyl group, sulfinyl group, alkyloxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, phosphoramide group, diacylamino group, imide Group,
Examples include an alkylthio group, an arylthio group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a hydroxyl group, a phosphono group, a nitro group, and a heterocyclic group.

These groups may be further substituted,
When there are two or more substituents, they may be the same or different.

R ₆ , R ₇ and R ₈ may be bonded to each other to form a ring together with a phosphorus atom, or R ₃₂ and R ₃₃ may be bonded to form a nitrogen-containing heterocyclic ring. .

In formula [III], R ₆ , R ₇ and R ₈ preferably represent an aliphatic group or an aromatic group, more preferably an alkyl group or an aromatic group.

[0116]

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In the formula, R ₉ represents an aliphatic group, an aromatic group, a heterocyclic group or —N (R ₄₁ ) (R ₄₂ ), and R ₁₀ represents —N (R
_{43) (R 44), -} N (R 45), represents a _{N (R 46) (R 47} ) or -OR _48. R _{41 to} R ₄₈ each represent a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an acyl group.

R ₉ and R ₄₃ , R ₉ and R ₄₅ , R ₉ and R ₄₆ ,
R ₉ and R ₄₈ , R ₄₁ and R ₄₃ , R ₄₁ and R ₄₅ , R ₄₁ and R _46, and R ₄₁ and R ₄₈ may combine with each other to form a ring.

In the general formula [IV], R ₉ and R _{41 to} R
_The aliphatic group represented by ₄₈ preferably has 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, or aralkyl group having 1 to 20 carbon atoms. Specifically, methyl, ethyl, propyl, i
-Propyl, t-butyl, octyl, decyl, hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-
Butenyl, 3-pentenyl, propargyl, 3-pentynyl, benzyl, phenethyl and the like.

The aromatic groups represented by R ₉ and R _{41 to} R ₄₈ are preferably those having 6 to 30 carbon atoms, particularly those having 6 to 30 carbon atoms.
20 monocyclic or condensed-ring aryl groups, for example, phenyl and naphthyl groups.

The heterocyclic group represented by R ₉ and R _{41 to} R ₄₈ is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom.
These may be a single ring, or may form a condensed ring with another aromatic or heterocyclic ring.

The heterocyclic group is preferably a 5- or 6-membered aromatic heterocyclic group, and examples thereof include pyridyl, furyl, thienyl, thiazolyl, imidazolyl and benzimidazolyl.

The acyl groups represented by R ₈ , R ₉ and R _{41 to} R ₄₈ are preferably those having 1 to 30 carbon atoms, especially those having 1 carbon atom.
To 20 linear or branched acyl groups such as acetyl, benzoyl, formyl, pivaloyl, and decanoyl.

R ₉ and R ₄₃ , R ₉ and R ₄₅ , R ₉ and R ₄₆ ,
R ₉ and R _48, R ₄₁ and R _43, R ₄₁ and R _45, R ₄₁ and R _46, R
₄₁ and R ₄₈ are as good ring be formed by another bond, an alkylene group, an arylene group, and aralkylene group or alkenylene group.

These aliphatic groups, aromatic groups and heterocyclic groups may be substituted with the substituents mentioned in the formula (III).

In the general formula [IV], preferably, R ₉ represents an aliphatic group, an aromatic group or —N (R ₄₁ ) (R ₄₂ ), and R ₁₀ represents —N (R ₄₃ ) (R ₄₄ ). Represent. R ₄₁ , R ₄₂ , R ₄₃ and R
₄₄ represents an aliphatic group or an aromatic group, respectively. More preferably, R ₉ represents an aromatic group or —N (R ₄₁ ) (R ₄₂ );
₄₁ to R ₄₄ represents an alkyl group or an aromatic group. Where R
It is more preferred that ₉ and R ₄₃ and R ₄₁ and R ₄₃ form a ring via an alkylene group, an arylene group, an aralkylene group or an alkenylene group.

The specific examples of the compounds represented by the general formulas [III] and [IV] are shown below, but the present invention is not limited thereto.

[0128]

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[0129]

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The compound represented by the general formula [III] or [IV] can be synthesized according to a known method. For example, (J. Chem. Soc. (A))
969, 2927, etc., and can be synthesized.

These compounds are added by dissolving in a suitable organic solvent such as ethyl acetate or in the form of a solid dispersed in water. A method with a small amount is more preferable.
Selenium sensitization or tellurium sensitization is combined with gold sensitization,
Alternatively, it is preferable to use a combination of gold sensitization and sulfur sensitization.

The silver halide emulsion used in the present invention may have any composition of silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide. Silver chlorobromide and silver chloroiodobromide having a content of 0 to 30 mol%. More preferred are silver chlorobromide and silver chloroiodobromide having an average silver chloride content of 0 to 10 mol%.

The particle size distribution of the silver halide emulsion may be monodisperse or polydisperse, but a monodisperse one is more preferable.
When the monodispersity is expressed as a coefficient of variation of the particle size, it is preferably at most 20%, more preferably at most 15%.

The average grain size of the silver halide grains is 0.1.
1 to 2.0 μm is preferred, and particularly 0.15 to 0.6 μm
Is preferred. The shape of the silver halide grains may be any shape such as an octahedron, a cube, a tetrahedron, a dodecahedron, a tabular shape, and a spherical shape, but is preferably a grain having a (100) plane of 80% or more, more preferably ( 100) 9 faces
The particles have 0% or more.

In the present invention, a core / shell type grain having a multiple structure in which the inside and the surface of the silver halide grain have different halogen compositions is also preferably used.

For the grain growth, a so-called controlled double jet method in which an aqueous solution of a silver salt and an aqueous solution of a halide are added in accordance with the growth rate of the grains is preferably used, but a method in which silver halide fine grains are supplied to grow the grains is also preferable.

The method for producing silver halide grains is described in JP-A-59-177535 and JP-A-59-178449.
Nos. 60-35726 and 60-147727 can be referred to.

[0138]

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

Example 1 Preparation of Emulsion While controlling to 60 ° C., pAg = 8.0 and pH = 2.0,
An aqueous solution of potassium bromide and an aqueous solution of silver nitrate are added to a 0.5% aqueous gelatin solution by a double jet method, and the average particle size is 0.1 μm.
m monodispersed cubic emulsion was obtained. Using this silver bromide emulsion as a core, an aqueous solution of potassium bromide containing 1 × 10 ⁻⁶ mol of potassium hexachloridate per mol of silver and an aqueous solution of silver nitrate are added while controlling so that pAg = 7.3, Monodisperse cubic emulsion having an average particle size of 0.25 μm (10
As a result of measuring 00 particles, 98% of the (100) plane was obtained, and the variation coefficient of the particle diameter was 10%. While maintaining the emulsion at 40 ° C., a formaldehyde condensate of sodium naphthalene sulfonate and magnesium sulfate were added thereto, and the mixture was stirred and allowed to stand. Then, excess salts were removed by decantation. Next, it was redispersed in an appropriate amount of an aqueous gelatin solution to obtain Emulsion A.

(Chemical Sensitization and Spectral Sensitization) While stirring the emulsion A at 50 ° C., the exemplary compound of the general formula (2) was added as shown in Table 1, and after 3 minutes, the compound of the general formula (1) was added. ) Or the compound of the formula (4), and 2 minutes later, 17 ml of a 0.2% methanol solution of the exemplified sensitizing dye was added per 1 mol of silver. After another 10 minutes, 5 ml of 1% ammonium thiocyanate, 1.2 ml of 0.2% chloroauric acid, 7 ml of 0.25% sodium thiosulfate per mole of silver
And 3 ml of a 0.4% ethyl acetate solution of the exemplified Se / Te sensitizer shown in Table 1 were added thereto, and subjected to chemical sensitization for an optimum time to obtain the highest sensitivity.

Thereafter, 4-hydroxy-6-methyl-
60 ml of a 1% aqueous solution of 1,3,3a, 7-tetrazaindene was added per mole of silver. General formula (1),
Comparative examples without addition of the compounds represented by (2) and (4) were prepared in the same manner.

(Preparation of Photosensitive Material) Preparation of Emulsion Layer Coating Solution The following compounds were added to the above-mentioned emulsion subjected to chemical sensitization and spectral sensitization to prepare an emulsion layer coating solution. (Amount added per mole of silver) Ossein gelatin 75.5 g 1-phenyl-5-mercaptotetrazole 10 mg trimethylolpropane 12 g t-butylcatechol 70 mg nitrophenyl-triphenylphosphonium chloride 30 mg 1,3-dihydroxybenzene-4- Ammonium sulfonate 1.5 g 1,1-Dimethylol-1-bromo-1-nitromethane 6 mg Sodium polystyrene sulfonate 2 g Polyethyl acrylate latex 20 g Compounds of general formulas (1), (2) and (4) sodium polymethylmethacrylate particles 2.5g dodecylbenzenesulfonate preparation street protective layer coating solution (addition amount of coating per liter) ossein gelatin 40g average particle size _{3μm 0.4g C 8 F 17 SO 3} K _{5mg C 8 F 17 SO 2 N} (C 3 H 7) (CH 2 CH 2 O) 8 H 100mg (C 9 H 19) 2 C 6 H 3 O (CH 2 CH 2 O) 12 H 80mg 35% formaldehyde Aqueous solution 2 ml 40% glyoxal aqueous solution 2 ml Preparation of coating solution for backing layer (addition amount per liter of coating solution) Ossein gelatin 40 g Sodium dodecylbenzenesulfonate 0.2 g Antihalation dye (described below) 4 g

[0143]

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Preparation of Backing Protective Layer Coating Solution (Amount Added per L of Coating Solution) Ossein Gelatin 40 g Polymethyl methacrylate having an average particle size of 6 μm 2 g Sodium dodecylbenzenesulfonate 0.6 g C ₈ H ₁₇ SO ₃ K 25 mg C _{8 F 17 SO 2 N (C} 3 H 7) (CH 2 CH 2 O) 8 H 100mg (C 9 H 19) 2 C 6 H 3 O (CH 2 CH 2 O) 12 H 80mg 35% formaldehyde aqueous solution 2ml 2 ml of 40% aqueous glyoxal solution Next, a backing layer coating solution and a backing protective layer coating solution are simultaneously coated on one side of a polyethylene terephthalate support having a thickness of 175 μm which has been coated on both sides, and then an emulsion layer is coated on the other side. The solution and the coating solution for the protective layer were coated simultaneously and dried.

The coating amount was 2.2 g in terms of silver, the amount of gelatin was 2.0 g per m ² , and the amount of gelatin in the emulsion protective layer was 1.0 g. The amount of gelatin in the backing layer was 2.5 g, and the amount of gelatin in the backing protective layer was 1.0 g. The following evaluation was performed about the obtained sample.

(Evaluation of storage stability with time) The obtained coated sample was conditioned at 23 ° C. and a relative humidity of 47% for 2 hours, then sealed in a light-shielding moisture-proof bag, and subjected to the following storage stability test.

Test conditions 1. Natural leave: 3 days and 6 months High-temperature, high-humidity storage test: The film sample was left in a light-shielding moisture-proof bag at 40 ° C. and a relative humidity of 80% for 3 days without the film sample.

The sample thus obtained was set to 820 nm
The step image was printed using a semiconductor laser scanner having a wavelength of. Exposure was performed at an exposure unit temperature of 25 ° C. in the apparatus.

The developing process is performed with the developing solution XD-SR and the fixing solution X
Using F-SR, processing was performed for 45 seconds with an automatic developing machine SRX-502 (both manufactured by Konica Corporation).

(Evaluation of Dependence on Exposure Temperature) The laser exposure was performed on the sample which had been allowed to stand for 3 days at 25 ° C. and 35 ° C. in the in-machine exposure section, and the same development processing as described above was performed.

The results obtained are shown in the table below.

[0152]

[Table 1]

[0153]

[Table 2]

From the results shown in Table 2, it can be seen that the sample according to the present invention has excellent storage stability over time, has no fog increase even when stored under high humidity, and has little desensitization. It can be seen that there is little temperature dependency at the time of exposure and that the film has stable sensitivity.

(Evaluation of coating solution stagnation) The emulsion coating solution prepared as described above was kept at 37 ° C while stirring, and
After hours, 12 hours and 18 hours, coated samples were prepared in the same manner as described above. Also, the coating solution stagnation time is 0
A timed one was similarly made. The obtained sample was treated in the same manner as above, and the fog and sensitivity were measured. The results are shown in Table 3 below. Note that the sensitivities in the table indicate the sample numbers. The reciprocal of the exposure amount that gives an optical density of 1 (fog density of 1.0 h) and an optical density of 1.0 is shown as a relative value when 100 is used.

[0156]

[Table 3]

As is evident from the results in Table 3, the sample according to the present invention has no fog increase and little desensitization even when the coating solution stagnation time is extended.

[0158]

As shown in the Examples, according to the present invention, a silver halide photographic light-sensitive material for laser exposure, which is excellent in storage stability over time and stagnation resistance of a coating solution, and has little temperature dependency upon exposure. A method for producing the silver halide photographic light-sensitive material is obtained.

Claims (7)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
When the silver halide grains in the silver halide emulsion layer are 700 to 1
At least one of the compounds represented by the following general formulas (1) and (2) in the silver halide emulsion layer or in at least one of the hydrophilic colloid layers adjacent thereto having a spectral maximum sensitivity at 500 nm: A silver halide photographic light-sensitive material characterized by containing one kind. Embedded image (In the formula, R represents a substituted or unsubstituted aryl group.
R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted group. Represents an aryl group. ) (Wherein, R ₆ represents a hydrogen atom or a hydroxy group, R ₇
Is a hydrogen atom or a group represented by the following general formula (3). n represents 1 to 6. ) (In the formula, R ₈ represents a hydrogen atom or a hydroxy group.) 2. A silver halide photographic material having at least one silver halide emulsion layer on a support,
When the silver halide grains in the silver halide emulsion layer are 700 to 1
The compound having the spectral maximum sensitivity at 500 nm and having at least one of the silver halide emulsion layer and the hydrophilic colloid layer adjacent thereto in the general formula (2) and the general formula (4) A silver halide photographic material comprising at least one of the above. Embedded image (In the formula, R ₉ and R ₁₀ each independently represent a hydroxy group, a mercapto group, a substituted or unsubstituted amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group or an alkylthio group. Z represents an atomic group necessary to form a substituted or unsubstituted 5- or 6-membered ring.) 3. A silver halide photographic material according to claim 1, wherein said silver halide emulsion grains are sensitized with selenium or tellurium. 4. The method according to claim 1, wherein the silver halide emulsion grains are (10)
The silver halide photographic light-sensitive material according to any one of claims 1 to 3, wherein the silver halide photographic material is a grain having 80% or more of a 0) plane. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide emulsion grains have an average silver chloride content of 0 to 30 mol%. material. 6. A silver halide photographic material according to claim 1, wherein said silver halide emulsion grains are provided with spectral maximum sensitivity at 700 to 1500 nm. At least 30 seconds before the addition of the dye, at least one of the compounds represented by the general formulas (1) and (2) is added. 7. The silver halide photographic material according to claim 2, wherein the silver halide emulsion grains are provided with spectral maximum sensitivity at 700 to 1500 nm. A method for producing a silver halide photographic light-sensitive material, wherein at least one of the compounds represented by formulas (2) and (4) is added at least 30 seconds before the dye is added.