JPH10301226A - Silver halide photographic sensitive material and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material prevented from rise of fog and drop of sensitivity during storage and small in dependency on temperature at the time of exposure and high in sensitivity and using laser beams by incorporating 2 kinds of specified compounds and silver halide emulsion grains having a spectral sensitivity maximum having a specified value or more and to provide its manufacturing method. SOLUTION: This silver halide photographic sensitive material contains the silver halide emulsion grains having the spectral maximum sensitivity in the wavelength region of >=700 nm and the compound represented by formula I and the compound represented by formula II and in formulae I and II, Z is a nonmetallic atomic group necessary to form a 5- or 6-membered hetero ring optionally having a benzene ring condensed with it; Z1 is an atomic group necessary to form a hetero ring having at least one N atom; and X is an N atom or a methine group. The silver halide emulsion grains are sensitized with a selenium or tellurium compound, and it is preferred that these emulsion grains principal (100) faces in an amount of >=80%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material and a method for producing the same, and more particularly, to a high-sensitivity laser light source which has no increase in fog and no decrease in sensitivity during storage and has a small temperature dependency during exposure. The present invention relates to a silver halide photographic material and a method for producing the same.

[0002]

2. Description of the Related Art In the field of medical diagnosis, MR, CT, R
The importance of diagnostic imaging using diagnostic equipment such as I is increasing. A laser imager which modulates the intensity of a laser beam with an image signal as an output of these diagnostic devices and draws it on a silver halide photographic light-sensitive material is highly evaluated for its usefulness because of its high image quality, and is becoming popular.

[0003] These scanning laser exposure apparatuses use argon, helium-neon, semiconductors, or the like as a laser light source. Among them, a semiconductor laser has advantages such as being inexpensive, having a long life, being small, and capable of direct modulation. In particular, 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 a recording material with high sensitivity in order to extend the life of the apparatus as much as possible.

As means for spectrally sensitizing silver halide to near infrared, for example, the theory of the photographic process (The Theory of Theory)
the Photographic Process)
As described in the third 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 rays have poor storage stability, and storage conditions such as storage in a refrigerator are strongly restricted for long-term storage.
In addition, the sensitivity fluctuates greatly depending on the exposure temperature, and the apparatus is easily affected by the installation environment of the apparatus and the seasonal temperature.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material for a high-sensitivity laser light source, which has no increase in fog and a decrease in sensitivity during storage and has a small temperature dependency during exposure. It is to provide a manufacturing method.

[0006]

The above objects of the present invention are as follows. A silver halide photographic material comprising a compound represented by the general formula (1), a compound represented by the general formula (2), and silver halide emulsion grains having a spectral maximum sensitivity at 700 nm or more. ,

[0007]

Embedded image In the formula, Z represents a group of nonmetal atoms necessary to form a 5- or 6-membered heterocyclic ring, and the heterocyclic ring may have a condensed ring such as a benzene ring.

[0008]

Embedded image In the formula, Z ₁ represents an atomic group necessary for forming a heterocyclic ring containing at least one nitrogen atom, and X represents a nitrogen atom or a methine group.

[0009] 2. 2. The silver halide photographic material according to the above 1, wherein the silver halide emulsion grains are selenium or tellurium-sensitized.

[0010] 3. When the silver halide emulsion grains are (10
0) The silver halide photographic material as described in 1 or 2, wherein the material has 80% or more of a plane.

4. Average AgCl of the silver halide emulsion
4. The silver halide photographic light-sensitive material according to the above 1, 2, or 3, wherein the content is less than 30 mol%.

5. 5. The method for producing a silver halide photographic light-sensitive material according to any one of the above 1 to 4, wherein at least 60 seconds before the addition of a sensitizing dye that gives a spectral maximum sensitivity to 700 nm or more to the silver halide emulsion, A method for producing a silver halide photographic light-sensitive material, characterized by adding a compound represented by (1);

6. 6. The method for producing a silver halide photographic material as described in 5 above, wherein selenium or tellurium is sensitized in the presence of the compound represented by the general formula (1).

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below. The silver halide photographic light-sensitive material according to the present invention (hereinafter, referred to as
It may simply be a photosensitive material. ) Contains a compound represented by the following general formula (1), a compound represented by the following general formula (2), and silver halide emulsion grains having a spectral sensitivity of 700 nm or more.

First, the compound represented by the following general formula (1) will be described.

[0016]

Embedded image In the formula, Z represents a group of nonmetal atoms necessary to form a 5- or 6-membered heterocyclic ring, and the heterocyclic ring may have a condensed ring such as a benzene ring.

Specific examples of the compound represented by formula (1) are shown below, but the present invention is not limited thereto.

[0018]

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[0019]

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[0020]

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These compounds may be incorporated into a silver halide photographic material by adding them to an emulsion coating solution. The timing of addition may be any time after the formation of the emulsion grains until coating, but is preferably at least 60 seconds before the addition of a sensitizing dye which gives a spectral maximum sensitivity to 700 nm or more to the silver halide emulsion. More preferably, at least 180 seconds ago.

The chemical sensitization in the presence of these compounds is a preferable method, and the use of a selenium or tellurium compound as the chemical sensitizer is a more preferable method.

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

Next, the compound represented by the following formula (2) will be described.

[0025]

Embedded image In the formula, Z ₁ represents an atomic group necessary for forming a heterocyclic ring containing at least one nitrogen atom, and X represents a nitrogen atom or a methine group.

[0026] As nitrogen-containing heterocyclic ring formed by Z ₁ may be selected various ones. For example, a pyrrole ring, a pyrazole ring, an imidazole ring, a triazole ring,
Oxazole ring, thiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, oxazine ring, thiazine ring, triazine ring, indole ring, indazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, purine ring, quinoline ring Quinazoline ring, quinoxaline ring, cinnoline ring, phthalazine ring, naphthyridine ring, pteridine ring and the like. In particular, a compound having a triazine ring, a pyrimidine ring, or a pyrimidine ring having a fused ring is preferable.

As a method for incorporating these compounds into a silver halide photographic material, an emulsion coating solution or a hydrophilic colloid layer on the side where an emulsion layer is present may be added, but the emulsion layer is preferred. The timing of addition may be any time from emulsion grain formation to coating. The addition amount is from 5 × 10 ⁻⁵ mol to 1 × 10 per mol of silver halide.
^-1 mol, preferably 1 × 10 ⁻⁴ mol to 1 × 1
0 ^-2 mol.

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

[0029]

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[0030]

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[0031]

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The synthesis of these compounds is described in Journal
of the American Chemical S
ociety, 73, 2981 and Journa
lof the Organic Chemistry,
27, p. 4054.

The sensitizing dye having a spectral maximum sensitivity of 700 nm or more in the present invention is a sensitizing dye which is adsorbed on silver halide emulsion grains and spectrally sensitized, particularly a light having a wavelength of 700 nm or more. Refers to something that gives sensitivity,
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]. It is an effective method to use two or more sensitizing dyes having different spectral maximum sensitivities in order to obtain a stable photographic density even when the wavelength of the light source fluctuates.

These compounds can be added by dissolving them 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.

The amount of addition may be optimal depending on the compound, but is generally 1 mg / molAgX to 100 mg / molA.
gX, and the amount that gives the highest sensitivity can be selected.

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 termination of selenium or tellurium sensitization, but preferably at the time 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 here is a known chemical sensitizer, for example, a chalcogen sensitizer such as sodium thiosulfate, potassium thiosulfate, and triphenylphosphine selenide, chloroauric acid, and sodium chloroaurate. And reduction sensitizers such as stannous chloride, sodium borohydride and ascorbic acid. Preferably, the sensitizing dye in the present invention is added before the chalcogen sensitizer. When the noble metal sensitizer is added after the addition, it is preferable to add the noble metal sensitizer at least 10 minutes after the end of the addition. Further, as described above, at least 6 sensitizing dyes of the present invention are added.
It is preferable that the compound represented by the general formula (1) is added 0 seconds before, preferably 180 seconds before.

The light-sensitive silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention containing silver halide emulsion grains having a spectral sensitivity of not less than 700 nm is represented by the following formula [D-1] or [D-1]. It is preferable that the dye is spectrally sensitized to 700 nm or more and 1500 nm or less by the dye represented by D-2].

Next, the general formula [D-1] and the general formula [D-
The compound represented by 2] will be described.

[0039]

Embedded image In the formula, Z ¹ and Z ³ represent a benzothiazole, a naphthothiazole, a benzoxazole, and 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 ^- represents a counter ion, n represents 1 or 2. The benzothiazole ring, naphthothiazole ring, benzoxazole ring and naphthoxazole ring represented by Z ¹ and Z ^{3 in the} formula may each have a substituent, for example, an alkyl group having 1 to 4 carbon atoms, The alkoxyl group, phenyl group, halogen atom (for example, chlor atom, bromo atom), etc. may be substituted. R ¹ and R ² are an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, hydroxyethyl, 2-methoxyethyl, 2-acetoxyethyl, carboxymethyl, 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.

Z in the general formula [D-1]
A preferred compound when ² is a 5-membered carbon atom ring can be represented by the following general formula [D-1-a].

[0041]

Embedded image R ¹³ and R ¹⁴ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom (for example, a chlor atom or a bromo atom);
¹⁵ and R ¹⁶ each represent an alkyl group having 1 to 12 carbon atoms;
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, a p-substituted alkoxy group having 1 to 4 carbon atoms, for example,
-Methoxyphenyl group) and an alkoxycarbonylalkyl group having 1 to 4 carbon atoms (for example, 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 the general formula [D-1].

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

[0044]

Embedded image In the formula, R ¹⁸ and R ¹⁹ each represent a hydrogen atom and a carbon number of 1 to 1.
4 represents an alkyl group or a phenyl group. Z ¹ , Z ³ , R
¹ , R ^2, X ₁ ⁻ and n have the same meaning as in the general formula [D-1].

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

[0046]

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[0047]

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[0048]

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[0049]

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Next, the compound represented by formula [D-2] will be described in detail.

[0051]

Embedded image 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 (preferably having 7 or less carbon atoms), 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,
Examples include 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 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkoxy group, or a halogen atom (for example, a chlorine atom, a bromine atom, and a fluorine atom).

[0053] The 5- or 6-membered nitrogen-containing heterocycle represented by ^{Z 4,} for example a thiazole ring include selenazole ring, an oxazole ring, 3,3-dialkylindolenine ring, and 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.
X ₁ ^- represents a counter ion, m, n and p is 1 or 2.

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

[0055]

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[0056]

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In the present invention, it is preferable to use a selenium compound or tellurium compound for chemical sensitization. Specific compounds are shown below.

As the selenium sensitizer used in the present invention, various selenium compounds including conventionally known ones can be used. Usually, an unstable selenium compound and / or a non-unstable selenium compound is added,
The emulsion is stirred for a certain period of time at 0 ° C or higher.

As the unstable selenium compound, preferred are JP-B-41-15748 and JP-B-43-13489,
The compounds described in Japanese Patent Application Nos. 2-130976 and 2-229300 are used. Specific compounds include isoselenocyanates (such as aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, and selenocarboxylic acids (such as 2-selenium butyric acid). , Selenoesters, diacyl selenides {bis (3-chloro-2,6-dimethoxybenzoyl) selenide, etc.}, selenophosphates, phosphine selenides, colloidal metal selenium, and the like.

Examples of non-labile selenium compounds include 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 are compounds represented by the following general formulas (3) and (4).

[0062]

Embedded image In the formula, R ₁ and R ₂ may be the same or different from each other, and include an alkyl group (eg, methyl, ethyl, t-butyl, adamantyl, t-octyl), an alkenyl group (eg, vinyl, propenyl), and an aralkyl group (eg, benzyl group). , Phenethyl, etc.), aryl groups (phenyl, pentafluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 4-octylsulfamoylphenyl, α-naphthyl, etc.), heterocyclic groups (pyridyl, thienyl, furyl, imidazolyl, etc.) , -NR ₁₁ (R ₁₂ ), -OR ₁₃ or -SR
₁₄ is represented. R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ may be the same or different, and include an alkyl group, an aralkyl group,
Represents an aryl group or a heterocyclic group. The alkyl group, an aralkyl group, the aryl group and heterocyclic group include the same groups as R _1. However, R ₁₁ and R ₁₂ represent a hydrogen atom or an acyl group (acetyl, propanoyl, benzoyl, heptafluorobutanoyl, difluoroacetyl,
4-nitrobenzoyl, a-naphthoyl, 4-trifluoromethylbenzoyl, etc.).

In the general formula (3), preferably, R ₁ represents an alkyl group, an aryl group or —NR ₁₁ (R ₁₂ );
R ₂ represents —NR ₁₅ (R ₁₆ ). R ₁₁ , R ₁₂ ,
R ₁₅ and R ₁₆ may be the same or different and represent a hydrogen atom, an alkyl group, an anneal group or an acyl group.

In the general formula (3), more preferably, N, N
-Dialkylselenourea, N, N, N'-trialkyl-N'-acylselenourea, tetraalkylselenourea, N, N-dialkyl-arylselenoamide, N-
Represents alkyl-N-aryl-arylselenoamide.

[0065]

Embedded image In the formula, R ₃ , R ₄ and R ₅ may be the same or different, and each represents an aliphatic group, an aromatic group, a heterocyclic group, —OR ₂₁ , or —O 2.
R ₂₂ (R ₂₃ ), —SR ₂₄ , —SeR ₂₅ , a halogen atom or a hydrogen atom. R ₂₁ , R ₂₄ and R ₂₅
Represents 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
Aliphatic groups represented by ₂₃ , R ₂₄ and R ₂₅ are a linear, branched or cyclic alkyl group, alkenyl group, alkynyl group, aralkyl group (methyl, ethyl, propyl, i-propyl, t-butyl, butyl, Octyl, decyl, hexadecyl, cyclopentyl, cyclohexyl, allyl,
2-butenyl, 3-pentenyl, propargyl, 3-pentynyl group, allyl group, 2-butenyl group, benzyl group, phenethyl, etc.).

R ₃ , R ₄ , R ₅ , R ₂₁ , R ₂₂ , R
_23, the aromatic group represented by _{R 24} and _{R 25,} a monocyclic or condensed aryl group (phenyl, pentafluorophenyl, 4-chlorophenyl, 3-sulfophenyl, alpha-
Naphthyl, 4-methylphenyl, etc.).

R ₃ , R ₄ , R ₅ , R ₂₁ , R ₂₂ , R
_The heterocyclic group represented by R ₂₃ , R ₂₄ and R ₂₅ includes 3 to 3 containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom.
10-membered saturated or unsaturated groups (pyridyl, thienyl,
Furyl, thiazolyl, imidazolyl, benzimidazolyl, etc.).

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

In the general formula (4), preferably, R ₃ and 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 trialkylphosphine selenide, triarylphosphine selenide, trialkylselenophosphate or triarylselenophosphate.

Specific examples of the compound represented by formula (3) or (4) are shown below, but the present invention is not limited thereto.

[0072]

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[0073]

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Examples of tellurium sensitizers used in the present invention include US Pat. Nos. 1,623,499 and 3,320,0.
Nos. 69 and 3,772,031, British Patent 235,2
No. 11, 1,121,496, 1,295,46
No. 2, No. 1,396,696, Canadian Patent 800,9
No. 58, Journal of Chemical Society
Chemical Communication (J. Chem. So
c. Chem. Commun. ) 635 (1980),
1102 (1979), 645 (1979), Journal of Chemical Society Parkin Transaction (J. Chem. Soc. Perkin)
Trans. ) And compounds described in 1,191 (198).

Specific tellurium sensitizers include colloidal tellurium, telluroureas (allyl tellurourea) N, N-
Dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N,
N'-dimethylethylene tellurourea, N, N'-diphenylethylene tellurourea), isotellurocyanates (allyl isotellurocyanate, etc.), telluroketones (telluroacetone, telluroacetophenone, etc.), telluramides (telluroacetamide, N , N-dimethyltellurobenzamide, etc.), tellurohydrazides (N, N'-
Trimethyl tellrobenz hydrazide), telluro esters (t-butyl-t-hexyl telluride, etc.), phosphine tellurides (tributyl phosphine telluride,
Tricyclohexylphosphine telluride, tri-i-propylphosphine telluride, butyl-di-i-propylphosphine telluride, dibutylphenylphosphine telluride, etc., and other tellurium compounds (for example, British Patents 1, 2
No. 95,462, gelatin containing negatively charged telluride ions, potassium telluride, potassium tellurocyanate, sodium telluropentathionate, allyl tellurocyanate, etc.).

Of these tellurium compounds, compounds preferably represented by the following formulas (5) and (6) are preferably used.

[0077]

Embedded image Wherein R ₆ , R ₇ and R ₈ are each an aliphatic group, an aromatic group,
Heterocyclic group, -OR ₃₁ , -NR ₃₂ (R ₃₃ ), -SR
_{34, -OSiR 35 (R 36)} (R 37), 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; R ₃₂ and R ₃₃ each represent an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, R ₃₅ , R ₃₆ and R ₃₇ each represent an aliphatic group.

In the general formula (5), R _{6 to} R ₈ and R
₃₁ aliphatic group represented by to R _37, are preferably of 1 to 30 carbon atoms, especially straight-chain having 1 to 20 carbon atoms, branched or cyclic alkyl group, an alkenyl group, an alkynyl group, an aralkyl group . Specific examples include methyl, ethyl, propyl, 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 monocyclic or condensed ring aryl groups having 6 to 20 carbon atoms. For example, phenyl, naphthyl and the like can be mentioned.

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 benzimidazolyl.

The cation represented by R ₃₁ and R ₃₄ is
For example, it represents 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 and 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 group. Good.

In the general formula (5), 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.

[0085]

Embedded image 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 —NR
_{43 (R 44), - N} (R 45) N (R 46) represents an _{R 47} or _{-OR 48.} R _{41 to} R ₄₈ each represent a hydrogen atom,
Represents an aliphatic group, an aromatic group, a heterocyclic group or an acyl group.
Also, 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 or form a ring.

In the general formula (6), R ₉ and R ₄₁ to
The aliphatic group represented by R ₄₈ preferably has 1 to 3 carbon atoms.
0, and 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, i-propyl, t-butyl, octyl, decyl,
Hexadecyl, cyclopentyl, cyclohexyl, allyl, 2-butenyl, 3-pentenyl, propargyl, 3-
Pentynyl, benzyl, phenethyl and the like.

The aromatic group represented by R ₉ and R _{41 to} R ₄₈ preferably has 6 to 30 carbon atoms, particularly preferably 6 to 30 carbon atoms.
To 20 monocyclic or condensed ring aryl groups such as 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 group represented by R ₈ , R ₉ and R _{41 to} R ₄₈ is preferably a linear or branched acyl group having 1 to 30 carbon atoms, particularly 1 to 20 carbon atoms. Acetyl, benzoyl, formyl, pivaloyl, decanoyl and the like can be mentioned.

Also, R₉And R₄₃, R₉And R₄₅, R₉When
R₄₆, R₉And R₄₈, R₄₁And R ₄₃, R₄₁And R
₄₅, R₄₁And R₄₆And R₄₁And R₄₈Are combined to form
The ring which may be formed includes an alkylene group, an arylene
Groups, aralkylene groups or alkenylene groups.

These aliphatic groups, aromatic groups and heterocyclic groups may be substituted with the substituents mentioned in the formula (5).

In the general formula (6), R ₉ preferably represents an aliphatic group, an aromatic group or —NR ₄₁ (R ₄₂ ), and R ₁₀
Represents -NR ₄₃ (R ₄₄ ). R ₄₁ , R ₄₂ , R
₄₃ and R ₄₄ each represent an aliphatic group or an aromatic group. More preferably, R ₉ is an aromatic group or —NR ₄₁ (R ₄₂ )
And R _{41 to} R ₄₄ represent an alkyl group or an aromatic group. Here, it is more preferable that R 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 following are typical examples of the compounds represented by formulas (5) and (6), but the present invention is not limited thereto.

[0094]

Embedded image

[0095]

Embedded image

The compounds represented by formulas (5) and (6) can be synthesized according to a known method. For example, Journal of Chemical Society (J. Chem. Soc. (A)) 1969, 2
927, Journal of Organometallic Chemistry (J. Organome. Chem.) 4, 3
20 (1965), 1,200 (1963), 11
3, C35 (1976), Phosphorus Sulfur 15,155.
(1983), Hemissie Berichte (Chem. Be)
r. 109, 2996 (1976), Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commu).
n. ) 635 (1980), 1102 (1976),
645 (1979), 820 (1987), Journal of Chemical Society Parkin Transaction (J. Chem. Soc. Perkin.
Trans. ) 1,191 (1980), The Chemistry of Organo Selenium and Tellurium Compounds (The Chemistry o)
f Organosellenium and Tell
urium Compounds) Volume 2, 216-26
7 (1987).

These compounds may be added by dissolving them in a suitable organic solvent such as ethyl acetate, or may be added in the form of a solid dispersed in water. A method with a small amount is more preferable.

Selenium sensitization or tellurium sensitization is preferably used in combination with gold sensitization or in combination with gold sensitization and sulfur sensitization.

The silver halide emulsion in the present invention may have any composition of silver bromide, silver chlorobromide, silver iodobromide and silver chloroiodobromide, but preferably has an average AgCl content. Less than 30 mol% of silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide. The particle size distribution of the silver halide emulsion may be monodisperse or polydisperse, but more preferably monodisperse. When the monodispersity is expressed as a coefficient of variation of the particle size, 20
% Or less, more preferably 15% or less.

The average grain size of the silver halide grains is 0.1.
1 μm to 2.0 μm is preferred, and particularly 0.15 μm to
0.6 μm is preferred.

The shape of the silver halide grains may be octahedral, cubic, tetradecahedral, dodecahedral, tabular or spherical, but is preferably a grain having at least 80% of the (100) plane. The particles preferably have 90% or more of the (100) plane.

Core / shell type grains having a multiple structure in which the inside and the surface of the grains have different halogen compositions are 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 of growing by supplying fine silver halide particles is also preferable.

As methods for producing silver halide grains, JP-A-59-177535 and JP-A-59-178647,
Nos. 60-35726 and 60-147727 can be referred to. The photosensitive material according to the present invention is most suitable for laser light source exposure, and a semiconductor laser having an oscillation wavelength of 700 nm or more can be used as a laser light source.

[0105]

【Example】

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 were added while controlling so that pAg = 7.3. Monodisperse cubic emulsion having a particle size of 0.25 μm # 10
As a result of measuring 00 particles, the (100) plane was 98%, and the variation coefficient of the particle diameter was 10%. I got｝. While maintaining the emulsion at 40 ° C., a formaldehyde condensate of sodium naphthalenesulfonate and magnesium sulfate were added, and the mixture was stirred and allowed to stand. After that, excess salts were removed by decantation. Next, the resulting mixture was redispersed in an appropriate amount of an aqueous gelatin solution to prepare emulsion A.
I got

(Chemical Sensitization and Spectral Sensitization) While stirring Emulsion A while keeping it at 50 ° C., the exemplified compound of the general formula (1) was added as shown in Table 1, and after 5 minutes, the exemplified sensitization was carried out. 17 ml of a 0.2% methanol solution of the dye was added per mole of silver. After another 10 minutes, 5 ml of 1% ammonium thiocyanate and 1.2 ml of 0.2% chloroauric acid per mole of silver
1, 7 ml of 0.25% sodium thiosulfate and 3 ml of a 0.4% ethyl acetate solution of the exemplified Se / Te compound as shown in Table 1 were added, and subjected to chemical sensitization for an optimum time to obtain the highest sensitivity. Thereafter, 4-hydroxy-6-methyl-
6% 1% aqueous solution of 1,3,3a, 7-tetrazaindene
0 ml was added.

(Preparation of Coating Sample) 1) Preparation of Emulsion Coating Solution The following compounds were added per mole of silver to the above emulsion which had been subjected to chemical sensitization and spectral sensitization to prepare an emulsion coating solution.

Ossein gelatin 75.5 g / molAg 1-phenyl-5-mercaptotetrazole 10 mg / molAg trimethylolpropane 12 g / molAg t-butylcatechol 70 mg / molAg nitrophenyl-triphenylphosphonium chloride 30 mg / molAg 1,3-dihydroxy Ammonium benzene-4-sulfonate 1.5 g / molAg 1,1-Dimethylol-1-bromo-1-nitromethane 6 mg / molAg Sodium polystyrenesulfonate 2 g / molAg Polyethyl acrylate latex 20 g / molAg Compound of general formula (2) Table As described in 1

2) Preparation of protective layer solution (per liter) Ossein gelatin 40 g / l Polymethyl methacrylate particles having an average particle size of 3 μm 2.5 g / l Sodium dodecylbenzenesulfonate 0.4 g / l C ₈ F ₁₇ SO ₃ K 100mg / l

[0110]

Embedded image (C ₉ H ₁₉ ) ₂ C ₆ H ₃ O (CH ₂ CH ₂ O) ₁₂ H 80 mg / l 35% formaldehyde aqueous solution 2 ml / l as a hardener 40% glyoxal aqueous solution 2 ml / l

3) Preparation of backing layer solution (per liter) 3-1) Backing layer solution Ossein gelatin 40 g / l Sodium dodecylbenzenesulfonate 0.2 g / l Antihalation dye 4 g / l

[0112]

Embedded image 3-2) Backing protective layer liquid Ossein gelatin 40 g / l Polymethyl methacrylate having an average particle size of 6 μm 2 g / l Sodium dodecylbenzenesulfonate 0.6 g / l C ₈ F ₁₇ SO ₃ K 25 mg / l

[0113]

Embedded image (C ₉ H ₁₉ ) ₂ C ₆ H ₃ O (CH ₂ CH ₂ O) ₁₂ H 80 mg / l 35% formaldehyde aqueous solution 2 ml / l as a hardener 40% glyoxal aqueous solution 2 ml / l

4) Preparation of Coated Sample A backing layer solution and a backing protective layer solution were simultaneously coated on one side of a 175 μm-thick polyethylene terephthalate support, both sides of which had been subbed, followed by emulsion coating on the other side. The solution and the emulsion protective layer solution were simultaneously coated in multiple layers and dried.

The emulsion coating amount of the emulsion layer was 2.2 in terms of silver.
g / m ² , the amount of gelatin was 2.0 g / m ² , and the amount of gelatin in the emulsion protective layer was 1.0 g / m ² . The amount of gelatin in the backing layer was 2.5 g / m ² , and the amount of gelatin in the backing protective layer was 1.0 g / m ² .

<Evaluation method> (Evaluation of storage stability) The obtained sample was subjected to a temperature of 23 ° C and a relative humidity of 47 ° C.
% For 2 hours, sealed in a light-shielding moisture-proof bag, and subjected to a storage stability test.

Test conditions 1. Natural leave: 3 days 2. Natural leave: 6 months High-humidity storage test: 3 days at 40 ° C. and 80% relative humidity without placing in a light-shielding moisture-proof bag The sample thus obtained was printed with a step image using a semiconductor laser scanner having a wavelength of 820 nm. Exposure was performed at an exposure unit temperature of 25 ° C. in the apparatus.

The developing process includes the developing solution XD-SR and the fixing solution X.
Automatic developing machine SRX-5 using F-SR (manufactured by Konica)
02 (manufactured by Konica) for 45 seconds.

(Evaluation of Dependence on Exposure Temperature) The sample was exposed to the laser at 25 ° C. and 35 ° C. in the in-machine exposure section, and subjected to the same development processing as described above.

[0120]

[Table 1]

[0121]

According to the present invention, there is provided a silver halide photographic light-sensitive material for a laser light source having a high sensitivity which is free from increase in fog and a decrease in sensitivity during storage and which has a small temperature dependency during exposure, and a method for producing the same. be able to.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification code FI G03C 1/20 G03C 1/20

Claims (6)

[Claims] 1. A halogen containing a compound represented by the general formula (1), a compound represented by the general formula (2), and silver halide emulsion grains having a spectral maximum sensitivity at 700 nm or more. Silver halide photographic material. Embedded image In the formula, Z represents a group of nonmetal atoms necessary to form a 5- or 6-membered heterocyclic ring, and the heterocyclic ring may have a condensed ring such as a benzene ring. Embedded image In the formula, Z ₁ represents an atomic group necessary for forming a heterocyclic ring containing at least one nitrogen atom, and X represents a nitrogen atom or a methine group. 2. A silver halide photographic material according to claim 1, wherein said silver halide emulsion grains are sensitized with selenium or tellurium. 3. A silver halide photographic light-sensitive material according to claim 1, wherein said silver halide emulsion grains have a (100) plane of 80% or more. 4. The silver halide emulsion according to claim 1, wherein the silver halide emulsion has an average AgCl content of less than 30 mol%.
4. The silver halide photographic light-sensitive material according to 2 or 3. 5. The method for producing a silver halide photographic light-sensitive material according to claim 1, wherein a sensitizing dye which gives a spectral maximum sensitivity to 700 nm or more is added to the silver halide emulsion. Seconds before the general formula (1)
A method for producing a silver halide photographic light-sensitive material, characterized by adding a compound represented by the formula: 6. A method for producing a silver halide photographic material according to claim 5, wherein selenium or tellurium is sensitized in the presence of the compound represented by the general formula (1).