JPH10142727A - Heart developable photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photographic sensitive material having high Dmax, ultrahigh contrast and satisfactory image quality by incorporating an org. silver salt, silver halide, a reducing agent, a specified hydrazine compd. and other specified compd. SOLUTION: This heat developable photographic sensitive material contains an org. silver salt, sliver halide, a reducing agent, a hydrazine compd. represented by formula I and a sensitizing dye such as a compd. represented by formula II. In the formula I, R<1> is an aliphatic or arom, group, etc., R<2> is H, alkyl, etc., G<1> is -CO-, -SO2 -, etc., and A<1> and A<2> are H or one of them is H and the other is optionally substd. alkylsulfonyl, etc. In the formula II, each of R31 and R32 is alkyl, R33 is H, lower alkyl, etc., V is H, lower alkyl, etc., Z<1> is a group of nonmetallic atoms required to complete a 5- or 6-membered N-contg. hetero ring, X1 is an acid anion, each of (p) and (q) is 1 or 2, and when the dye forms an inner salt, (q) is 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photothermographic material.

[0002]

2. Description of the Related Art In recent years, there has been a strong demand in the printing field to reduce the amount of waste liquid from the viewpoint of environmental protection and space saving. Therefore, there is a need for a technique relating to a photothermographic material for printing, which can be efficiently exposed by a laser imagesetter and can form a sharp black image having high resolution and sharpness. I have. These photothermographic materials can eliminate the use of solution processing chemicals and provide a simpler and more environmentally friendly thermal development system to customers.

A heat-developable photographic material for forming a photographic image by using a heat-development processing method is disclosed in, for example, US Pat. No. 3,152,904.
3457075 and "Thermally Processed Silver Systems" by D. Morgan and B. Shely, Imaging Processes and Materials (Imagin)
gProcesses and Materials) Neblette 8th Edition, Sturge, V. Walworth, A. Shepp Edited, Section 2, 1969.

Such a photothermographic material usually contains a reducible silver source (eg, an organic silver salt), a catalytically active amount of a photocatalyst (eg, silver halide), a color tone controlling agent for controlling the color tone of silver, and a developer. It is contained in a dispersed state in the binder matrix. Photothermographic materials are stable at room temperature, but can be reduced when heated to a high temperature (for example, 80 ° C or higher) after exposure through a redox reaction between a silver source (which functions as an oxidizing agent) and the developer. Forms silver. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image.

[0005] However, at present, such heat-developable photographic light-sensitive materials are often used as micro light-sensitive materials or medical light-sensitive materials, and are used only in a very small part as print light-sensitive materials. This is because the obtained image has a low Dmax and soft gradation, so that the image quality of the printing photosensitive material is extremely poor.

A method for obtaining a heat-developable photographic material having a high Dmax and a high gradation is described in Japanese Patent Application No. 7-228627.
There is a method of adding a hydrazine derivative described in No. 3 to a light-sensitive material. As a result, a high Dmax, ultra-high contrast photothermographic material can be obtained, but the image quality of the dot edge portion may be degraded when performing high-definition exposure made possible by recent advances in laser technology. It is a problem.

[0007]

An object of the present invention is to provide a high Dm
Provide heat-developable photographic light-sensitive materials with ax, ultra-high contrast and good image quality. Another object of the present invention is to provide a heat-developable photographic light-sensitive material having good storage stability.

[0008]

The above objects have been achieved by the following inventions. (1) In a photothermographic material having at least one photosensitive layer, an organic silver salt, a silver halide, a reducing agent, a hydrazine compound represented by the general formula (H), and a compound represented by the general formula (D-
A photothermographic material comprising a compound represented by formula (I) or (D-II). General formula (H)

[0009]

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[Wherein, R ¹ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ² represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group,
Represents an amino group or a hydrazino group, G ¹ is a —CO— group, —SO ₂
- group, -SO- group, -P (= O) (- R 3) - represents group, -CO-CO- group, a thiocarbonyl group or an iminomethylene group,, A ¹ and A ²
Each represents a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ³ is selected from the same range as the groups defined in R ^2, may be different from R ^2. General formula (DI)

[0011]

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[In the formula, R ₃₁ and R ₃₂ may be the same or different, and each represents an alkyl group. R ₃₃ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. V represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group. Z ₁ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring. X ₁
Represents an acid anion. p and q each independently represent 1 or 2. However, q is 1 when the dye forms an inner salt. General formula (D-II)

[0013]

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In the formula, R ₃₁ ′ and R ₃₂ ′ may be the same or different and each represents an alkyl group. R
₃₃ ′ and R ₃₄ ′ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. R ₃₅ ′ and R ₃₆ ′ each represent a hydrogen atom, or R ₃₅ ′ and R ₃₆ ′ are linked to form a divalent alkylene group. R ₃₇ ′ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group, or —NW ₁ ′ (W ₂ ′). Here, W ₁ ′ and W ₂ ′ each independently represent an alkyl group or an aryl group, and W ₁ ′ and W ₂ ′ may be linked to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. it can. Also R _{3 3} '
R ₃₇ ′ or R ₃₄ ′ and R ₃₇ ′ may be linked to form a divalent alkylene group. Z ′ and Z ₁ ′ each independently represent a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring. X ₁ represents an acid anion, and m ′ represents 1 or 2. However, m 'is 1 when the dye forms an inner salt. (2) In a photothermographic material having at least one photosensitive layer, an organic silver salt, a silver halide, a reducing agent, a hydrazine compound represented by the formula (H), and a compound represented by the formula (D-
A photothermographic material comprising a compound represented by the formula (III): General formula (D-III)

[0015]

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Wherein R ₄₁ represents an alkyl group. Z ₂ is 5
A group of atoms necessary to form a 6-membered or 6-membered nitrogen-containing heterocyclic ring. D and Da represent an atomic group necessary for forming an acyclic or cyclic acidic nucleus. L ₄₁ , L ₄₂ , L ₄₃ , L
₄₄ , L ₄₅ and L ₄₆ represent a methine group. M ₁ represents a charge neutralizing counter ion, and m ₁ is a number of 0 or more necessary to neutralize the charge in the molecule. i represents 0 or 1. (3) In a photothermographic material having at least one photosensitive layer, an organic silver salt, a silver halide, a reducing agent, a hydrazine compound represented by the general formula (H), and a compound represented by the general formula (D-
A photothermographic material comprising a compound represented by the formula (IV). General formula (D-IV)

[0017]

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Wherein Z ₃ and Z ₄ are each a 5-member or 6-member
Represents a group of non-metallic atoms necessary for completing a membered nitrogen-containing heterocyclic nucleus. R ₅₀ and R ₅₁ each represent an alkyl group, a substituted alkyl group, or an aryl group. Q and Q ₁ together represent the non-metallic atoms required to complete a 4-thiazolidinone, 5-thiazolidinone or 4-imidazolidinone nucleus. L ₅₀ , L ₅₁ , L ₅₂ , L ₅₃ and L ₅₄ each represent a methine group or a substituted methine group. L ₅₀ and L ₅₂ or L ₅₁ and L ₅₃ are 5
It may form a six-membered or six-membered ring. n ₁ and n ₂ each represent 0 or 1. x represents an anion. r represents 0 or 1, and r = 0 when forming an inner salt. (4) In a photothermographic material having at least one photosensitive layer, an organic silver salt, a silver halide, a reducing agent, a hydrazine compound represented by the formula (H), and a compound represented by the formula (D-
A photothermographic material comprising a compound represented by formula (V). General formula (D-V)

[0019]

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[Wherein Y ₁ and Y ₂ each independently represent a group of nonmetallic atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, and these heterocyclic rings have a substituent. You may.
R ₆₁ and R ₆₂ may be the same or different and each represents a substituted or unsubstituted lower alkyl group. R ₆₃ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. X ₁ represents an acid anion. n ₁ and n ₂ independently represent 0 or 1. s represents 0 or 1, and in the case of an inner salt, s = 0. (5) In a photothermographic material having at least one photosensitive layer, an organic silver salt, a silver halide, a reducing agent, a hydrazine compound represented by the general formula (H), and a compound represented by the general formula (D-
A photothermographic material comprising a compound represented by the formula (VI). General formula (D-VI)

[0021]

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Wherein Y ¹ , Y ² and Y ³ are each independently -N-
(R ¹⁰ )-represents a group, an oxygen atom, a sulfur atom or a selenium atom. R ¹⁰ , R ¹¹ , R ¹² and R ¹³ each represent an aliphatic group, an aryl group, or a heterocyclic group. V ¹ and V ² each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a group which forms a condensed ring together with an azole ring by bonding to V ¹ and V ² ;
L ¹ , L ² , L ³ and L ⁴ each independently represent a substituted or unsubstituted methine carbon. n3 represents 1 or 2, and m3 is 0
Or represents 1. M ¹ represents an ion necessary to offset the total charge of the molecule, and n4 represents a number required to neutralize the charge of the molecule. (6) The photothermographic material according to (1), wherein the compound represented by formula (D-1) is used. (7) In the above (2), G ¹ in the general formula (H) is-
When CO—, R ² represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and G ¹ represents a —SO ₂ — group, —SO—
R ² represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryl group when the group is a group, —P (＝ O) (R ³ ) — group, —COCO— group, thiocarbonyl group or iminomethylene group; A photothermographic material comprising an oxy group, an amino group or a hydrazino group. (8) In the above (6), G ¹ in the general formula (H) is-
When CO—, R ² represents an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, and G ¹ represents a —SO ₂ — group, —SO—
R ² when it is a group, —P (＝ O) (— R ³ ) —, —COCO—, thiocarbonyl or iminomethylene;
Is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group. (9) In the above (7), G ¹ in the general formula (H) is-
CO—, R ² represents an alkyl group, A ¹ and A ²
Are both hydrogen atoms. (10) In the above (8), G ¹ in the general formula (H) is-
CO—, R ² represents an alkyl group, A ¹ and A ²
Are both hydrogen atoms.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a compound represented by the general formula (D-
Sensitizing dyes represented by I) or (D-II), sensitizing dyes represented by general formula (D-III), sensitizing dyes represented by general formula (D-IV), A sensitizing dye represented by -V) or a sensitizing dye represented by the general formula (D-VI) is used. The hydrazine compound represented by the general formula (H) used in the present invention will be described. General formula (H)

[0024]

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In the formula, R ¹ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ² represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, Represents a hydrazino group, G ¹ is a -CO- group, -SO _2-
Group, -SO- group, -P (= O) (- R 3) - group, -CO-CO- group, thiocarbonyl group or an iminomethylene group,, A ^1, A ² are both hydrogen atoms or, One represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group. R ³ is selected from the same range as the groups defined in R ^2, may be different from R _2.

In the general formula (H), the aliphatic group represented by R ¹ is preferably a substituted or unsubstituted linear or branched or cyclic alkyl, alkenyl or alkynyl group having 1 to 30 carbon atoms. is there.

In the general formula (H), the aromatic group represented by R ¹ is a monocyclic or bicyclic aryl group such as a benzene ring and a naphthalene ring. The heterocyclic group represented by R ¹ is a monocyclic or bicyclic aromatic or non-aromatic heterocyclic ring, which may be condensed with an aryl group to form a heteroaryl group. Examples include a pyridine ring, a pyrimidine ring, an imidazole ring, a pyrazole ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a thiazole ring, a benzothiazole ring and the like.

Preferred as R ¹ is an aryl group. R ¹ may be substituted. Representative examples of the substituent include an alkyl group (including an active methine group), a nitro group, an alkenyl group, an alkynyl group, an aryl group, a group including a heterocyclic group, and a quaternized group. Group containing a heterocyclic ring containing a nitrogen atom (for example, a pyridinio group), a hydroxy group, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group Group, aryloxycarbonyl group, carbamoyl group, urethane group,
Carboxyl group, imide group, amino group, carboxamide group, sulfonamide group, ureido group, thioureido group,
A group containing a sulfamoylamino group, a semicarbazide group, a thiosemicarbazide group, a hydrazino group, a group containing a quaternary ammonium group, a mercapto group, (alkyl, aryl,
Or heterocycle) thio group, (alkyl or aryl)
Sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group, sulfamoyl group, acylsulfamoyl group, (alkyl or aryl) sulfonyluureido group, (alkyl or aryl) sulfonylcarbamoyl group, halogen atom, cyano group, phosphoric amide Groups, a group having a phosphate ester structure, a group having an acylurea structure, a group having a selenium atom or a tellurium atom, and a group having a tertiary sulfonium structure or a quaternary sulfonium structure.

Preferred substituents are linear, branched or cyclic alkyl groups (preferably having 1 to 20 carbon atoms),
Nitro group, aralkyl group (preferably having 1 to 20 carbon atoms), alkoxy group (preferably having 1 to 20 carbon atoms), substituted amino group (preferably substituted amino group having 1 to 20 carbon atoms), acylamino Group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 30 carbon atoms)
A ureido group (preferably having 1 to 30 carbon atoms)
), A carbamoyl group (preferably having 1 to carbon atoms)
30), a phosphoric amide group (preferably having 1 to 30 carbon atoms)
).

In the formula (H), the alkyl group represented by R ² is preferably an alkyl group having 1 to 10 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group. It contains a ring.

The heterocyclic group is a 5- to 6-membered ring compound containing at least one nitrogen, oxygen and sulfur atom, such as an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, a pyridyl group, a pyridinio group and a quinolinio group. And a quinolinyl group. Pyridyl or pyridinio groups are particularly preferred.

The alkoxy group is preferably an alkoxy group having 1 to 8 carbon atoms, the aryloxy group is preferably a monocyclic one, and the amino group is an unsubstituted amino group or an alkylamino having 1 to 10 carbon atoms. Groups, arylamino groups and heterocyclic amino groups are preferred.

R ² may be substituted, and preferred substituents include those exemplified as the substituent of R ¹ .

G ¹ is -CO-, -SO _2- , -SO-, -P (= O) (-R ³ )-,
-CO-CO-, thiocarbonyl, iminomethylene,
In particular, -CO-, -SO ₂ -and -CO-CO- are preferable.

Preferred among the groups represented by R ² are G ¹
Is a -CO- group, a hydrogen atom, an alkyl group (for example,
Methyl group, trifluoromethyl group, difluoromethyl group, 2-carboxytetrafluoroethyl group, pyridiniomethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, phenylsulfonylmethyl group, etc., aralkyl group (for example, o -Hydroxybenzyl group, etc., aryl group (for example, phenyl group, 4-nitrophenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidophenyl group, o-carbamoylphenyl group,
4-cyanophenyl group, 2-hydroxymethylphenyl group, etc.), and particularly preferably a hydrogen atom, an alkyl group, or an aryl group.

When G ¹ is a —SO ₂ — group, R ² is an alkyl group (eg, a methyl group), an aralkyl group (eg, an o-hydroxybenzyl group), an aryl group (eg, a phenyl group). Group) or a substituted amino group (eg,
And a dimethylamino group.

When G ¹ is a —CO—CO— group, an alkoxy group;
An aryloxy group and an amino group are preferred, and particularly a substituted amino group (for example, 2,2,6,6-tetramethylpiperidine
-4-ylamino group, propylamino group, anilino group, o-
Hydroxyanilino group, 5-benzotriazolylamino group, N-benzyl-3-pyridinioamino group, etc.) are preferable.

R ² is such as to cause a cyclization reaction that cleaves the G ¹ -R ² moiety from the residual molecule to form a cyclic structure containing atoms of the -G ¹ -R ² moiety. Examples thereof include those described in JP-A-63-29751.

A ¹ and A ² are a hydrogen atom, an alkyl or arylsulfonyl group having 20 or less carbon atoms (preferably a phenylsulfonyl group, or a phenylsulfonyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more) Group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is -0.5 or more, or a straight-chain, branched, or cyclic unsubstituted group And substituted aliphatic acyl groups (substituents include, for example, halogen atoms, ether groups, sulfonamide groups, carbonamide groups, hydroxyl groups, carboxy groups, and sulfonic acid groups).

A ¹ and A ² are most preferably hydrogen atoms.

The substituents of R ¹ and R ^{2 in} the general formula (H) may be further substituted, and preferred examples include those exemplified as the substituent of R ₁ . Furthermore, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent, etc. may be substituted multiple times, and preferred examples are also those exemplified as the substituent of R ^1. Applicable.

R ¹ or R ^{2 in} the general formula (H) may have a ballast group or polymer commonly used in immobile photographic additives such as couplers incorporated therein. The ballast group is a group having a carbon number of 8 or more and relatively inactive to photographic properties, such as an alkyl group, an aralkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, and an alkylphenoxy group. You can choose from. Examples of the polymer include those described in JP-A-1-100530.

R ¹ or R ^{2 in} the general formula (H) may have a built-in adsorptive group that adsorbs to silver halide. Examples of such adsorptive groups include alkylthio, arylthio, thiourea, thioamide, mercapto heterocyclic, and triazole groups.
No. 5,108, 4,459,347, JP-A-59-195233, 59
-200231, 59-201045, 59-201046, 59-2
01047, 59-201048, 59-201049, JP-A-61
-170733, 61-270744, 62-948, 63-23424
And the groups described in Nos. 4, 63-234245, and 63-234246. The adsorbing groups to these silver halides are
It may be a precursor. Examples of such a precursor include groups described in JP-A-2-285344.

R ¹ or R ² in the general formula (H) may contain a plurality of hydrazino groups as substituents. At this time, the compound represented by the general formula (H) is a polymer having a hydrazino group. Specific examples include the compounds described in JP-A-64-86134, JP-A-4-16938, and JP-A-5-97091.

Specific examples of the compound represented by the formula (H) are shown below. However, the present invention is not limited to the following compounds.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

[Table 6]

[0052]

[Table 7]

[0053]

[Table 8]

[0054]

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[0055]

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[0056]

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The nucleating agent of the present invention may be used in combination with another nucleating agent.

The hydrazine-based nucleating agent of the present invention includes a suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, It can be used by dissolving it in methylcellosolve or the like.

Also, by a well-known emulsification and dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, or an auxiliary solvent such as ethyl acetate or cyclohexanone is used to dissolve the compound. An emulsified dispersion can be prepared and used. Alternatively, a powder of a hydrazine derivative can be dispersed in water by a ball mill, a colloid mill, or an ultrasonic wave by a method known as a solid dispersion method and used.

The hydrazine compound of the present invention may be added to the photosensitive layer or any other non-photosensitive layer on the photosensitive layer side with respect to the support, but may be added to the photosensitive layer or a non-photosensitive layer adjacent thereto. It is preferred to add.

The addition amount of the nucleating agent of the present invention is preferably 1 μm to 10 mmol, more preferably 10 μm to 5 mmol, and most preferably 20 μm to 5 mmol per 1 mol of silver.

In the present invention, a nucleation accelerator may be contained. As nucleation accelerators, amine derivatives, onium salts,
Examples thereof include a disulfide derivative and a hydroxymethyl derivative. Examples are listed below. JP 7-7778
No. 3 gazette, page 48, lines 2 to 37, specifically
Compounds A-1) to A-73) described on pages 49 to 58). JP-A-7-
Compounds represented by (Chemical Formula 21), (Chemical Formula 22) and (Chemical Formula 23) described in No. 84331, specifically, the compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426, specifically, compounds of Na-1 to Na-22 described on pages 16 to 20 of the same publication And Nb-1 to Nb-12. The general formula (1), the general formula (2), the general formula (3), the general formula (4), the general formula (5), the general formula (6) and the general formula (7) described in Japanese Patent Application No. 7-37817. ), Specifically, the compounds of 1-1 to 1-19, the compounds of 2-1 to 2-22, and the compounds of 3-1 to 3- described in the same specification.
36 compounds, 4-1 to 4-5 compounds, 5-1 to 5-41 compounds, 6-1 to 6-58 compounds and 7-1 to 7-38 compounds.

The nucleation accelerator of the present invention comprises a suitable organic solvent,
For example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone,
Methyl ethyl ketone), dimethylformamide, dimethylsulfoxide, methylcellosolve and the like can be used.

Further, by a well-known emulsification and dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate or an auxiliary solvent such as ethyl acetate or cyclohexanone is used for dissolution, An emulsified dispersion can be prepared and used. Alternatively, a powder of a nucleation accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method, and used.

The nucleation accelerator of the present invention may be added to the photosensitive layer or any other non-photosensitive layer on the photosensitive layer side with respect to the support. Preferably, it is added to the layer.

The addition amount of the nucleation accelerator of the present invention is preferably 1 × 10 ^-6 to 2 × 10 ^-2 mol, and more preferably 1 × 10 ^-5 to 2 ×, per mol of silver.
10 ^-2 mol is more preferred, and 2 × 10 ^-5 to 1 × 10 ^-2 mol is most preferred.

Hereinafter, the general formula (DI) will be described in detail. General formula (DI)

[0068]

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In the formula, R ₃₁ and R ₃₂ may be the same or different and each represents an alkyl group (including a substituted alkyl group). Preferably it has 1 to 8 carbon atoms. Examples are a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a heptyl group and an octyl group.

Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom,
A chlorine atom, a bromine atom), a hydroxyl group, an alkoxycarbonyl group (preferably having 8 or less carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, and benzyloxycarbonyl), and an alkoxy group (preferably having 7 or less carbon atoms, such as methoxy, Ethoxy, propoxy,
Butoxy, benzyloxy), aryloxy group (eg, phenoxy, p-tolyloxy, naphthyloxy), acyloxy group (preferably having 3 or less carbon atoms, eg, acetyloxy, propionyloxy), acyl group (preferably having 8 carbon atoms) Hereinafter, for example, acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), a sulfamoyl group (eg, sulfamoyl, N,
N-dimethylsulfamoyl, morpholinosulfonyl), an alkyl group substituted with an aryl group (eg, phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl) (preferably a carbon atom in the alkyl moiety) 6 atoms or less). However, two or more of these substituents may be substituted with an alkyl group.

R ₃₃ is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, butyl), a lower alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, Propoxy, butoxy), a phenyl group, a benzyl group or a phenethyl group. Particularly, a lower alkyl group and a benzyl group are advantageously used.

V is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl), an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, butoxy), halogen, Atom (for example, fluorine atom, chlorine atom), substituted alkyl group (preferably having 1 to 4 carbon atoms, for example, trifluoromethyl,
Carboxymethyl).

Z ₁ represents a group of non-metallic atoms necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring, for example, a thiazole nucleus [for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6 -Chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenyl Benzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole,
5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-
Fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho [2,1-d] thiazole, Naphtho [1,2-d] thiazole,
Naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-
d) thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole], selenazole nucleus (for example, benzoselena Zole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole] , An oxazole nucleus (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-
Bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole,
5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole,
6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [ 2,3-
d) oxazole], a quinoline nucleus (eg, 2-quinoline,
3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 8-fluoro-2-quinoline, 6-methoxy
2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2
-Quinoline, 8-fluoro-4-quinoline], 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus (for example, 1-methylbenzimidazole, 1 -Ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-
Ethyl-5-chlorobenzimidazole, 1-methyl-5,6-
Dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-methoxybenzimidazole, 1-methyl-5-cyanobenzimidazole, 1-
Ethyl-5-cyanobenzimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-di Chlorbenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoro Examples thereof include methylbenzimidazole, 1-ethylnaphtho [1,2-d] imidazole) and pyridine nuclei (for example, pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine).
Of these, thiazole nuclei and oxazole nuclei are preferably used advantageously. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used. m, p and q each independently represent 1 or 2.

However, when the dye forms an inner salt, q is 1.

X ₁ is an acid anion (eg, chloride, bromide, iodide, tetrafluoroborate, hexafluorophosphate, methyl sulfate, ethyl sulfate, benzenesulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfonate, 4-nitrobenzenesulfonate, trifluoromethanesulfonate,
Perchlorate).

Next, the formula (D-II) will be described in detail. General formula (D-II)

[0077]

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In the formula, R ₃₁ ′ and R ₃₂ ′ may be the same or different and each represents an alkyl group (including a substituted alkyl group). Preferably it has 1 to 8 carbon atoms. For example, methyl, ethyl, propyl, butyl, pentyl, heptyl and octyl.

Examples of the substituent include a carboxyl group, a sulfo group, a cyano group and a halogen atom (for example, a fluorine atom,
A chlorine atom, a bromine atom), a hydroxyl group, an alkoxycarbonyl group (preferably having 8 or less carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, and benzyloxycarbonyl), and an alkoxy group (preferably having 7 or less carbon atoms, such as methoxy, Ethoxy, propoxy,
Butoxy, benzyloxy), aryloxy group (eg, phenoxy, p-tolyloxy), acyloxy group (preferably having 3 or less carbon atoms, for example, acetyloxy, propionyloxy), acyl group (preferably having 8 or less carbon atoms, for example, acetyl , Propionyl, benzoyl, mesyl), carbamoyl groups (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl groups (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl), aryl And an alkyl group (preferably having 6 or less carbon atoms in the alkyl portion) substituted with a group (eg, phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl) and the like. However, two or more of these substituents may be substituted with an alkyl group.

R ₃₃ ′ and R ₃₄ ′ are a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, butyl) and a lower alkoxy group (preferably having 1 to 4 carbon atoms, For example, methoxy, ethoxy, propoxy, butoxy), phenyl, benzyl or phenethyl. Particularly, a lower alkyl group and a benzyl group are advantageously used.

R ₃₅ ′ and R ₃₆ ′ each represent a hydrogen atom, or R ₃₅ ′ and R ₃₆ ′ are linked to form a divalent alkylene group (for example, ethylene or trimethylene). The alkylene group may be one, two or more suitable groups, such as an alkyl group (preferably having 1 to
4, for example, methyl, ethyl, propyl, isopropyl,
Butyl), a halogen atom (eg, a chlorine atom or a bromine atom), or an alkoxy group (preferably having 1 carbon atom).
-4, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy) and the like.

R ₃₇ ′ is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, etc.) and a lower alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, Propoxy, butoxy, etc.), phenyl, benzyl, or -N (W
₁ ') (W _2' represents a). Here, W ₁ ′ and W ₂ ′ are each independently an alkyl group (including a substituted alkyl group. Preferably, the alkyl moiety has 1 to 18 carbon atoms, more preferably 1 to 18 carbon atoms.
4, eg, methyl, ethyl, propyl, butyl, benzyl, phenylethyl), or aryl groups (including substituted phenyl groups, eg, phenyl, naphthyl, tolyl, p-
Chlorophenyl), and W ₁ ′ and W ₂ ′ can be linked to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. Provided that R ₃₃ ′ and R ₃₇ ′ or R ₃₄ ′ and R ₃₇ ′ are linked to form a divalent alkylene group (synonymous with the divalent alkylene group formed by linking R ₃₅ ′ and R ₃₆ ′) ) Can also be formed.

Z ′ and Z ₁ ′ represent a group of nonmetal atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic ring, such as a thiazole nucleus (eg, benzothiazole, 4-chlorobenzothiazole, 5-chloro) Benzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-
Bromobenzothiazole, 5-iodobenzothiazole,
5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5 -Trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho [2,1-d] thiazole, naphtho [1,2 -d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-
d) thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] thiazole], selenazole nucleus (e.g. benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzo) Selenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [2,1-d] selenazole, naphtho [1,2-d]
Selenazole), oxazole nucleus (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-
Methoxybenzoxazole, 5-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6 -Dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho [2,1-
d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole], quinoline nucleus [for example, 2-
Quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 8-fluoro-2-quinoline,
6-methoxy-2-quinoline, 6-hydroxy-2-quinoline,
8-chloro-2-quinoline, 8-fluoro-4-quinoline), 3,
3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl
-5-cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine,
3-dimethyl-5-chloroindolenine), imidazole nucleus (for example, 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1- Methyl
-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-methoxybenzimidazole, 1-methyl-5-cyanobenzimidazole, 1-ethyl-5-cyano Benzimidazole, 1-methyl
-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chloro Benzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho [1,2 -d] imidazole) and a pyridine nucleus (eg, pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine).
Of these, thiazole nuclei and oxazole nuclei are preferably used advantageously. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used.

X ₁ ′ is an acid anion (eg, chloride, bromide, iodide, tetrafluoroborate, hexafluorophosphate, methyl sulfate, ethyl sulfate, benzenesulfonate, 4-methylbenzenesulfonate, 4-chlorobenzenesulfonate) , 4-nitrobenzenesulfonate, trifluoromethanesulfonate, perchlorate).

M ′ represents 0 or 1, and is 1 when the dye forms an internal salt.

Specific examples of the compounds are shown below. However, the present invention is not limited only to these.

[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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The amount of the sensitizing dye of the present invention varies depending on the shape, size, halogen composition, method and degree of chemical sensitization, type of antifoggant, etc. of silver halide grains. 4 × 10 ^-6 to 8 × 10 ^-3 mol. For example, when the silver halide grain size is 0.2
１1.3 μm, the surface area of the silver halide grains is 1
The addition amount of 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per m ² is preferable, and the addition amount of 6.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

Among the sensitizing dyes represented by formulas (DI) and (D-II), it is preferable to use the sensitizing dye represented by formula (I).

In the combination with the sensitizing dye represented by the general formula (DI), a preferable hydrazine derivative represented by the general formula (H) is that when G ¹ is —CO—, R ² is alkyl. A group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, wherein G ¹ is a —SO ₂ — group, a —SO— group, a —P (＝ O)
When (—R ³ ) —, —COCO—, thiocarbonyl or iminomethylene, R ² represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group; Is the base. Particularly preferred are those in which G ¹ is —CO—, R ² is an alkyl group, and A ¹ and A ² are both hydrogen atoms. By using such a hydrazine derivative in combination with the compound represented by formula (DI), the storage stability is particularly improved.

Next, the formula (D-III) will be described in detail. General formula (D-III)

[0100]

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R ₄₁ is preferably an alkyl group having 8 or less carbon atoms or a substituted alkyl group (for example, a carboxy group, a sulfo group, a cyano group, or a halogen atom), a hydroxy group, an alkoxycarbonyl group, an alkane sulfonylamino A carbonyl group, an alkoxy group, an alkylthio group, an arylthio group, an aryloxy group, an acyloxy group, an acylthio group, an acyl group, a carbamoyl group, a sulfamoyl group, an aryl group, and more preferably an unsubstituted alkyl group or a carboxyalkyl group. , A sulfoalkyl group and a methanesulfonylcarbamoylmethyl group.

The nucleus formed by Z ₂ includes a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a thiazoline nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, an oxazoline nucleus, a selenazole nucleus,
Benzoselenazole nucleus, naphthoselenazole nucleus, tellurazole nucleus, benzotellurazole nucleus, naphthotellurazole nucleus, tellurazoline nucleus, 3,3-dialkylindolenine nucleus,
Imidazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, pyridine nucleus, quinoline nucleus, isoquinoline nucleus,
Imidazo [4,5-b] quinoxalin nucleus, oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus, preferably, benzothiazole nucleus, naphthothiazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, 2-quinoline Nuclear, 4-quinoline nucleus.

D and Da represent a group of atoms necessary for forming an acidic nucleus, and can take the form of an acidic nucleus of any general merocyanine dye. The acidic nucleus mentioned here is
For example, James (ed.), The Theory of
The Theory of t
he Photographic Process) 4th edition, Macmillan publisher,
Defined by p. 198, 1977. In a preferred form, substituents involved in the resonance of D are, for example, carbonyl, cyano, sulfonyl, and sulfphenyl. D ′ represents the remaining group of atoms required to form an acidic nucleus. Specifically, US Pat. Nos. 3,567,719 and 3,
No. 575,869, No. 3,804,634, No. 3,837,862, No. 4,00
Nos. 2,480, 4,925,777, and JP-A-3-167546.

Preferred are 2-thiohydantoin, 2-oxazolin-5-one and rhodanine nucleus.

L ₄₁ , L ₄₂ , L ₄₃ , L ₄₄ , L ₄₅ and L _{46 each} represent a methine group or a substituted methine group (for example, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a heterocyclic group, Substituted with a halogen atom, an alkoxy group, an amino group, an alkylthio group, etc.), may form a ring with another methine group, or may form a ring with an auxochrome. .

M ₁ m ₁ is included in the formula to indicate the presence or absence of a cation or anion when necessary to neutralize the ionic charge of the dye.

More preferably, the compound of formula (D-III) is a compound selected from formula (D-III-a). General formula (D-III-a)

[0108]

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In the formula, R ₄₂ and R ₄₃ represent an alkyl group having a group that imparts water solubility to the compound.

V ₁ , V ₂ , V ₃ and V _{4 each} represent a hydrogen atom or 1
Represents a valent substituent. Provided that the substituents (V ₁ , V ₂ , V ₃ ,
V ₄ ) do not form a ring with each other, and the total molecular weight of the substituents is 100 or less.

L ₇ , L ₈ , L ₉ and L ₁₀ represent a methine group.

M ₂ represents a charge neutralizing counter ion, and m ₂ is a number of 0 or more necessary to neutralize the charge in the molecule.

Hereinafter, typical examples of the compound represented by formula (D-III) or (D-III-a) of the present invention are shown.
It is not limited to this.

[0114]

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[0115]

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[0116]

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[0117]

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The compound represented by formula (D-III) of the present invention is preferably used in a silver halide emulsion layer.
It is particularly preferably used as a silver halide sensitizing dye.

The amount of addition is not particularly limited, but is from 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁵ per mol of silver halide.
〜1 × 10 ^-3 mol is preferred.

In the combination with the sensitizing dye represented by the general formula (D-III), a preferable hydrazine derivative represented by the general formula (H) is that when G ¹ is —CO—, R ² is alkyl. Group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, wherein G ¹ is a —SO ₂ — group, a —SO— group, a —P (=
O) (- R ³⁾ - group, -COCO- group, if a thiocarbonyl group or an iminomethylene group R ² is a hydrogen atom,
Alkyl group, aryl group, heterocyclic group, alkoxy group,
It is an aryloxy group, an amino group or a hydrazino group. Particularly preferred are those wherein G ¹ is -CO-
Wherein R ² is an alkyl group and A ¹ and A ² are both hydrogen atoms. When used in combination with such a particularly preferred hydrazine derivative, the storage stability is improved.

The general formula (D-IV) will be described in detail. General formula (D-IV)

[0122]

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In the above formula (D-IV) of the sensitizing dye used in the present invention, the following nitrogen-containing heterocyclic nuclei completed by Z ₃ or Z ₄ can be used.

Thiazole nucleus {eg, thiazole, 4-methylthiazole, 4-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, etc.), benzothiazole nucleus {eg, benzothiazole, 5-chlorobenzothiazole , 6-chlorobenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 5-phenylbenzothiazole, 5 -Methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-
Hydroxybenzothiazole, 5-carboxybenzothiazole, 5-fluorobenzothiazole, 5-dimethylaminobenzothiazole, 5-acetylaminobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy- 6-methylbenzothiazole, 5-ethoxy-6-methylbenzothiazole, tetrahydrobenzothiazole, etc., a naphthothiazole nucleus such as naphtho [2,1-d] thiazole, naphtho [1,2-
d) thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d Thiazole, 5-methoxynaphtho [2,3-d] thiazole and the like, selenazole nucleus such as 4-methylselenazole,
4-phenyl selenazole, etc., benzo selenazole nucleus such as benzo selenazole, 5-chlorobenzo selenazole, 5-phenyl benzo selenazole, 5-methoxy benzo selenazole, 5-methyl benzo selenazole, 5-hydroxybenzo Selenazole and the like, naphtho selenazoles such as naphtho [2,1-d] selenazole, naphtho [1,
2-d] selenazole, etc., oxazole nucleus such as oxazole, 4-methyloxazole, 5-methyloxazole, 4,5-dimethyloxazole, etc., benzoxazole nucleus such as benzoxazole, 5-fluorobenzoxazole, 5-chloro Benzoxazole, 5-bromobenzoxazole, 5-trifluoromethylbenzoxazole, 5-methylbenzoxazole, 5-methyl-6
-Phenylbenzoxazole, 5,6-dimethylbenzoxazole, 5-methoxybenzoxazole, 5,6-dimethoxybenzoxazole, 5-phenylbenzoxazole, 5-carboxybenzoxazole, 5-methoxycarbonylbenzoxazole, 5-acetylbenzoz Oxazole, 5-hydroxybenzoxazole, etc.｝, naphthooxazole nucleus ｛for example, naphtho [2,1-d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d]
Oxazole, etc., 2-quinoline nucleus, imidazole nucleus,
A benzimidazole nucleus, a 3,3′-dialkylindolenin nucleus, a 2-pyridine nucleus, a thiazoline nucleus, and the like can be used. Particularly preferably, at least one of Z ₃ and Z ₄ is a thiazole nucleus, a thiazoline nucleus, an oxazole nucleus, or a benzoxazole nucleus.

The alkyl group represented by R ₅₀ in the above general formula includes an alkyl group having 5 or less carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc.), a substituted alkyl group As a substituted alkyl group having 5 or less carbon atoms in an alkyl radical such as a hydroxyalkyl group (eg, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, etc.), a carboxyalkyl group (eg, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2- (2-carboxyethoxy) ethyl group, etc.), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 3 -Sulfobutyl group, 4-sulfobutyl group, 2-
Hydroxy-3-sulfopropyl group, 2- (3-sulfopropoxy) ethyl group, 2-acetoxy-3-sulfopropyl group,
3-methoxy-2- (3-sulfopropoxy) propyl group, 2-
[3-sulfopropoxy) ethoxy] ethyl group, 2-hydroxy-3- (3'-sulfopropoxy) propyl group, etc., aralkyl group (alkyl radical has 1 to 1 carbon atoms)
5 is preferred, and the aryl group is preferably a phenyl group, for example, benzyl, phenethyl, phenylpropyl, phenylbutyl, p-tolylpropyl, p-tolyl
Methoxyphenethyl group, p-chlorophenethyl group, p-
Carboxybenzyl group, p-sulfophenethyl group, p-
A sulfoxybenzyl group), an aryloxyalkyl group (the alkyl radical preferably has 1 to 5 carbon atoms, and the aryl group of the aryloxy group is preferably a phenyl group; for example, phenoxyethyl, phenoxypropyl, phenoxybutyl, p -Methylphenoxyethyl group, p-
Aryl groups such as｝, such as methoxyphenoxypropyl group), vinylmethyl group, etc., represent phenyl groups.

L ₅₀ , L ₅₁ , L ₅₂ , L ₅₃ and L ₅₄ represent a methine group or a substituted methine group = C (R ′) −. R ′ is an alkyl group (eg, methyl group, ethyl group, etc.), a substituted alkyl group (eg, alkoxyalkyl group (eg, 2-ethoxyethyl group, etc.), a carboxyalkyl group (eg, 2-carboxyethyl group, etc.), an alkoxycarbonylalkyl group (Eg, 2-methoxycarbonylethyl group), aralkyl group (eg, benzyl group, phenethyl group, etc.), and aryl group (eg, phenyl group, p-methoxyphenyl group, p-chlorophenyl group, o-carboxyphenyl group) L ₅₀ and R ₅₀ , and L ₅₁ and R ₅₁ may be each bonded by a methine chain to form a nitrogen-containing heterocyclic ring.

The substituent attached to the nitrogen atom at the 3-position of the thiazolinone nucleus or imidazolinone nucleus formed by Q and Q ₁ is, for example, an alkyl group (having preferably 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, Propyl group, etc.), allyl group, aralkyl group (alkyl group, radical preferably has 1 to 5 carbon atoms, such as benzyl group, p-carboxyphenylmethyl group, etc.), and aryl group (total carbon number is 6).
To 9, preferably a phenyl group, a p-carboxyphenyl group, etc., a hydroxyalkyl group (the alkyl radical preferably has 1 to 5 carbon atoms, for example, a 2-hydroxyethyl group), a carboxyalkyl group (carbon atom of the alkyl radical). The number is preferably 1 to 5; for example, a carboxymethyl group or the like; an alkoxycarbonylalkyl group (the alkyl radical in the alkoxy moiety preferably has 1 to 3 carbon atoms; the alkyl moiety preferably has 1 to 5 carbon atoms; for example, methoxycarbonyl Ethyl group) and the like.

Examples of anions represented by X include halogen ions (iodine ions, bromine ions, chloride ions, etc.), perchlorate ions, thiocyanate ions, benzenesulfonate ions, p-toluenesulfonate ions, Methyl sulfate ion, ethyl sulfate ion and the like can be mentioned. r
Is 0 or 1.

The specific examples of the compounds represented by formula (D-IV) are shown below, but the invention is not limited thereto.

[0130]

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[0131]

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[0132]

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[0133]

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The amount of the sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, and the like. 4 × 10 ^-6 to 8 × 10 ^-3 mol. For example, when the silver halide grain size is 0.2 to
In the case of 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains,
An addition amount of 6.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

The compound represented by formula (DV) will be described in detail. General formula (D-V)

[0136]

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In the formula, R ₆₁ and R ₆₂ may be the same or different and each represents an alkyl group (including a substituted alkyl group). Preferably it has 1 to 8 carbon atoms. Examples are a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a heptyl group and an octyl group.

Examples of the substituent include a carboxyl group, a sulfo group, a cyano group, a halogen atom (for example, a fluorine atom,
A chlorine atom, a bromine atom), a hydroxyl group, an alkoxycarbonyl group (preferably having 8 or less carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, and benzyloxycarbonyl), and an alkoxy group (preferably having 7 or less carbon atoms, such as methoxy, Ethoxy, propoxy,
Butoxy, benzyloxy), aryloxy group (eg, phenoxy, p-tolyloxy), acyloxy group (preferably having 3 or less carbon atoms, for example, acetyloxy, propionyloxy), acyl group (preferably having 8 or less carbon atoms, for example, acetyl , Propionyl, benzoyl, mesyl), carbamoyl groups (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbamoyl, piperidinocarbamoyl), sulfamoyl groups (eg, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl), aryl And an alkyl group (preferably having 6 or less carbon atoms in the alkyl portion) substituted with a group (eg, phenyl, p-hydroxyphenyl, p-carboxyphenyl, p-sulfophenyl, α-naphthyl) and the like. However, two or more of these substituents may be substituted with an alkyl group.

R ₆₃ is a hydrogen atom, a lower alkyl group (preferably having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, butyl), a lower alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, Propoxy, butoxy), a phenyl group, a benzyl group or a phenethyl group. Particularly, a lower alkyl group and a benzyl group are advantageously used. Y ₁ and Y ₂ represent a group of nonmetal atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic ring, such as a thiazole nucleus (eg, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6 -Chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenyl Benzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoro Methylbenzothiazole, 5,6-dimethylbenzothia Lumpur,
5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-
Methoxynaphtho [2,3-d] thiazole], selenazole nucleus (for example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [ 2,1-d] selenazole, naphtho [1,2-d] selenazole], oxazole nucleus (benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5 -Phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-
Chlorobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole, naphtho [2,1-d]
Oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole], quinoline nucleus (for example, 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline,
6-methyl-2-quinoline, 8-fluoro-2-quinoline, 6-
Methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-
Chloro-2-quinoline, 8-fluoro-4-quinoline), 3,3-
Dialkylindolenine nucleus (for example, 3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5
-Cyanoindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-
Dimethyl-5-chloroindolenine), imidazole nucleus (eg, 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-methyl
-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-ethyl-5-methoxybenzimidazole, 1-methyl-5-cyanobenzimidazole, 1-ethyl-5-cyano Benzimidazole, 1-methyl
-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chloro Benzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho [1,2 -d] imidazole) and pyridine nucleus (for example, pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine).
Of these, thiazole nuclei and oxazole nuclei are preferably used advantageously. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used. s, n ₁ and
n ₂ each independently represents 0 or 1.

However, when the dye forms an inner salt, s is 0.

Specific examples of the compound represented by the general formula (DV) are shown below, but the present invention is not limited to the following compounds.

[0142]

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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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The amount of the sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, and the like. 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol. For example, when the silver halide grain size is 0.2 to
In the case of 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains,
An addition amount of 6.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

The compound represented by formula (D-VI) will be described in detail. General formula (D-VI)

[0154]

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In the formula, Y ¹ , Y ² and Y ³ are each independently -N- (R
¹⁰ )-represents a group, an oxygen atom, a sulfur atom or a selenium atom.

As the aliphatic group represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ , for example, a branched or linear alkyl group having 1 to 10 carbon atoms (eg, methyl, ethyl, n-propyl,
groups such as n-pentyl and isobutyl), 3 to 10 atoms
(E.g., 3-butenyl, 2-propenyl, etc.) or an aralkyl group having 3 to 10 carbon atoms (e.g., benzyl, phenethyl, etc.).

The aryl group represented by R ¹⁰ , R ¹¹ , R ¹² and R ¹³ includes, for example, a phenyl group, and the heterocyclic group includes, for example, a pyridyl group (2-, 4-) and a furyl group (2 -), Thienyl group (2-), sulfolanyl group, tetrahydrofuryl group, piperidinyl group and the like.

Each of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.),
Alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), cyano group, carbamoyl group (eg, carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl) Group), sulfamoyl group (eg, sulfamoyl group, N, N-3-oxapentamethyleneaminosulfonyl group, etc.), methanesulfonyl group, alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.), aryl group (eg, phenyl group) Group, carboxyphenyl group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.) even if substituted with a substituent such as sulfo group, carboxy group, phosphono group, sulfate group, sulfino group, sulfonamide group, sulfamoyl group, etc. good.

As the alkyl group represented by V ¹ and V ² , a linear or branched group (eg, methyl, ethyl, is
o-propyl, t-butyl, iso-butyl, t-pentyl, hexyl, etc.). V ¹ and V
^{As the} alkoxy group represented by ² , for example, methoxy,
Each group such as ethoxy and propoxy is exemplified.

The aryl group represented by V ¹ and V ² may have a substituent at any position, for example, phenyl, p-tolyl, p-hydroxyphenyl and p-hydroxyphenyl.
Each group such as methoxyphenyl is exemplified. Examples of the condensed ring formed by V ¹ and V ² together with the azole ring by bonding to each other include benzoxazole, 4,5,6,7
Tetrahydrobenzoxazole, naphtho [1,2-
d] oxazole, naphtho [2,3-d] oxazole, benzothiazole, 4,5,6,7-tetrahydrobenzothiazole, naphtho [1,2-d] thiazole,
Condensed rings such as naphtho [2,3-d] thiazole, benzoselenazole, naphtho [1,2-d] selenazole and the like can be mentioned.

Specific examples of the alkoxy groups represented by V ¹ and V ² include, for example, unsubstituted alkyl groups such as methoxy group, ethoxy group and butoxy group, and alkoxy groups such as 2-methoxyethoxy group and benzyloxy group. Is mentioned.

The above-mentioned substituents represented by V ¹ and V ² , and the formed condensed ring may have a substituent at any position, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom) Atom, iodine atom), trifluoromethyl group, alkoxy group (for example, unsubstituted alkyl groups such as methoxy, ethoxy, butoxy, substituted alkoxy groups for 2-methoxyethoxy, benzyloxy, etc.), alkylthio group (for example, methylthio, ethoxy) A substituted / unsubstituted alkyl group such as an ethylthio group, a hydroxy group, a cyano group, an aryloxy group (eg, a substituted or unsubstituted group such as phenoxy or tolyloxy), or an aryl group (eg, phenyl, p-chlorophenyl, etc.) Substituted or unsubstituted groups),
Styryl group, heterocyclic group (for example, each group such as furyl and thienyl), carbamoyl group (for example, each group such as carbamoyl and N-ethylcarbamoyl), and sulfamoyl group (for example, each group such as sulfamoyl and N, N-dimethylsulfamoyl) Group), an acylamino group (for example, each group such as acetylamino, propionylamino, and benzoylamino), an acyl group (for example, each group such as acetyl and benzoyl), an alkoxycarbonyl group (for example, a group such as ethoxycarbonyl),
Examples include an arbitrary group such as a sulfonamide group (for example, each group such as methanesulfonylamide and benzenesulfonamide), a sulfonyl group (for example, each group such as methanesulfonyl and p-toluenesulfonyl), and a carboxy group.

Examples of the group substituted on the methine carbon represented by L ¹ , L ² , L ³ and L ⁴ include a lower alkyl group (for example, each group such as methyl and ethyl) and a phenyl group (for example, phenyl and carboxy). Groups such as phenyl) and alkoxy groups (for example, groups such as methoxy and ethoxy).

N3 represents 1 or 2, and m3 represents 0 or 1. M ¹ represents a cation or an acid anion, and specific examples of the cation include a proton, an organic ammonium ion (for example, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (for example, each cation such as lithium, sodium and calcium). And specific examples of the acid anion include a halogen ion (for example, a chlorine ion, a bromine ion, an iodine ion, etc.), a p-toluenesulfonic acid ion, a perchlorine ion, a 4-boron fluoride ion and the like. n4
Is 0 when an internal salt is formed and the charge is neutralized.

Specific examples of the compound represented by formula (D-VI) are shown below, but the present invention is not limited to the following compounds.

[0166]

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[0167]

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The amount of the sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, and the like. 4 × 10 ^-6 to 8 × 10 ^-3 mol. For example, when the silver halide grain size is 0.2 to
In the case of 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains,
An addition amount of 6.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

The compounds represented by the general formulas (DI) to (D-VI) of the present invention can be prepared by using FMHamer.
Heterocyclic Compounds-Cyanine Soybean and Related Compounds (Heterocyc
lic Compounds-Cyanine Dyesand Related Compounds)
(John Wiley & Sons
s-New York, London, 1964).
DMSturmer, "Heterocyclic Compounds--Special Topics in Heterocyclic Chemistry-(Heterocycli
c Compounds --- Specialtopics in heterocyclic chemis
try ---) ", Chapter 18, Section 14, Pages 482-515, John Wiley & Sons
, New York, London, (1977)., "Rod's Chemistry of Carbon Compounds (Rodd '
S Chemistry of Carbon Compounds) '', (2nd.Ed.vol.I
V, partB, 1977), Chapter 15, pp. 369-422; (2nd Ed.
vol. IV, partB, 1985), Chapter 15, pp. 267-296,
Elsevier Science Publishing Company Inc.
It can be synthesized based on the method described in a company, New York.

The compounds represented by the general formulas (DI) to (D-VI) of the present invention may be used alone, or may be used in combination thereof. Often used for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure, Vol. 176, 17643 (Dec. 1978).
Monthly) Page 23, IV, J, or the aforementioned JP-B-49-255
00, 43-4933, JP-A-59-19032 and JP-A-59-192242.

The compounds represented by formulas (DI) to (D-VI) of the present invention may be used in combination of two or more. The compounds of the present invention can be added to a silver halide emulsion by dispersing them directly in the emulsion or by adding water, methanol, ethanol, propanol, acetone, methylcellosolve, 2, 2, 3, or 3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy
A solvent such as -1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide or the like may be dissolved alone or in a mixed solvent and added to the emulsion.

As disclosed in US Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. No. 44-23389, same method
As disclosed in 44-27555, 57-22091, etc.,
A method in which a dye is dissolved in an acid and the solution is added to the emulsion or added as an aqueous solution in the presence of an acid or base to the emulsion, as disclosed in U.S. Patent Nos. 3,822,135 and 4,006,025. As described in JP-A-53-102733 and JP-A-58-105141, a method of adding an aqueous solution or a colloidal dispersion in the coexistence of a surfactant to an emulsion is used. A method in which a dye is directly dispersed in an emulsion, and the dispersion is added to an emulsion.
As disclosed in JP-A No. 24, a method of dissolving a dye using a compound that causes a red shift and adding the solution to an emulsion can also be used. Also, ultrasonic waves can be used for the solution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful. For example, U.S. Pat.Nos. 2,735,766 and 3,628,96
No. 4, No. 4,183,756, No. 4,225,666, JP-A-58
As disclosed in the specifications of JP-A-184142 and JP-A-60-196749, chemical ripening is carried out during the step before silver halide grain formation or / and desalination, during the silver removal step and / or after desalination. Before the start of the process, as disclosed in the specification of JP-A-58-113920, etc., immediately before or during the chemical ripening, during the process, after the chemical ripening, until the application of the emulsion is applied. At any time before, it may be added in the process. Also, U.S. Pat.No.4,225,666, JP-A-58-762
As disclosed in the specification of No. 9, etc., the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle formation step and during the chemical ripening step or after the completion of the chemical ripening, The compound may be added in portions such as before aging or during the process and after completion, or may be added by changing the kind of compound to be added and the combination of compounds.

When the sensitizing dye used in the present invention is applied to a silver halide photographic light-sensitive material, if it is necessary to enhance only the sensitivity in a specific wavelength region spectrally, a sensitizing dye suitable for it is used. It is preferable that an aggregate is formed, and particularly, an aggregate that easily forms a so-called J aggregate is preferable. Also, for example, JP-B-49-46932, JP-A-58-287
No. 38, U.S. Pat. No. 3,776,738, etc. may not be used in combination with water-soluble bromides and water-soluble additives (for example, bispyridinium salt compounds, mercapto-containing heterocyclic sulfonates, alkali metal salts, etc.). Strengthens J aggregates and is preferred. These compounds are used in an amount of about 10 ^-5 to 1 mol per mol of silver halide.

The organic silver salt which can be used in the present invention includes:
Relatively stable to light, but forms a silver image when heated to 80 ° C. or higher in the presence of an exposed photocatalyst (such as a latent image of photosensitive silver halide) and a reducing agent It is a silver salt. The organic silver salt can be any organic substance including a source capable of reducing silver ions. Silver salts of organic acids, especially silver salts of long chain fatty carboxylic acids (with 10 to 30, preferably 15 to 28 carbon atoms) are preferred. Complexes of organic or inorganic silver salts whose ligands have a complex stability constant in the range of 4.0 to 10.0 are also preferred. The silver donor is preferably present in about 5 to about 5 parts of the imaging layer.
Can make up 30% by weight. Preferred organic silver salts include silver salts of organic compounds having a carboxyl group. Examples of these include, but are not limited to, silver salts of aliphatic carboxylic acids and silver salts of aromatic carboxylic acids. Preferred examples of the silver salt of an aliphatic carboxylic acid include silver behenate, silver stearate, silver oleate, silver laurate, silver caproate, silver myristate, silver palmitate, silver maleate, silver fumarate, and tartaric acid. Silver, silver linoleate, silver butyrate and silver camphorate, and mixtures thereof.

Silver salts of compounds containing a mercapto group or a thione group and derivatives thereof can also be used.
Preferred examples of these compounds include 3-mercapto-4
-Silver salt of phenyl-1,2,4-triazole, silver salt of 2-mercaptobenzimidazole, silver salt of 2-mercapto-5-aminothiadiazole, silver salt of 2- (ethylglycolamide) benzothiazole, S- Silver salts of thioglycolic acid such as silver salts of alkylthioglycolic acid (where the alkyl group has 12 to 22 carbon atoms), silver salts of dithiocarboxylic acid such as silver salts of dithioacetic acid, silver salts of thioamide, 5 Silver salt of -carboxyl-1-methyl-2-phenyl-4-thiopyridine, silver salt of mercaptotriazine, silver salt of 2-mercaptobenzoxazole, silver salt described in U.S. Pat.No. 4,123,274, for example, 3-amino-5 -Silver salts of 1,2,4-mercaptothiazole derivatives such as silver salts of benzylthio-1,2,4-thiazole; 3- (3-carboxyethyl) -4-methyl-4 described in U.S. Pat. -Silver salt of thiazoline-2-thione Includes silver salts of thione compounds. Further, compounds containing an imino group can be used. Preferred examples of these compounds include silver salts of benzotriazole and derivatives thereof, for example, silver salts of benzotriazole such as silver methylbenzotriazole, silver salts of halogen-substituted benzotriazole such as silver 5-chlorobenzotriazole,
It includes silver salts of 1,2,4-triazole or 1-H-tetrazole, imidazole and silver salts of imidazole derivatives as described in U.S. Pat. No. 4,220,709. For example, various silver acetylide compounds as described in U.S. Pat. Nos. 4,761,361 and 4,775,613 can be used.

The shape of the organic silver salt that can be used in the present invention is not particularly limited, but a needle crystal having a short axis and a long axis is preferable. As is well known in photosensitive silver halide light-sensitive materials, the inverse relationship between the size of silver salt crystal grains and their covering power also holds in the heat-developable photographic light-sensitive material of the present invention, When the size of the organic silver salt particles as the image forming portion of the photographic light-sensitive material is large, it means that the covering power is small and the image density is low. In the present invention, the minor axis is 0.01 μm or more and 0.20 μm or less, and the major axis is 0.10 μm or more and 5.0 μm or less.
μm or less is preferable, the short axis is 0.01 μm or more and 0.15 μm or less,
The major axis is more preferably 0.10 μm or more and 4.0 μm or less. The particle size distribution of the organic silver salt is preferably monodispersed. Monodispersion means the standard deviation of the lengths of the minor axis and major axis, respectively.
The percentage of the value divided by each major axis is preferably 100% or less, more preferably 80% or less, even more preferably 50% or less. The shape of the organic silver salt can be measured from a transmission electron microscope image of the organic silver salt dispersion. As another method of measuring monodispersity, there is a method of obtaining a standard deviation of a volume-weighted average diameter of an organic silver salt, and a percentage (coefficient of variation) of a value divided by a volume-weighted average diameter is preferably 100%.
Or less, more preferably 80% or less, still more preferably 50% or less. As a measuring method, for example, the organic silver salt dispersed in a liquid is irradiated with a laser beam, and the particle size (volume weighted average diameter) obtained by obtaining an autocorrelation function for a time change of the fluctuation of the scattered light is obtained. Can be.

The method of forming the photosensitive silver halide in the present invention is well known in the art, and uses, for example, the methods described in Research Disclosure No. 17029, June 1978, and US Pat. No. 3,700,458. be able to. Specific methods that can be used in the present invention include a method of converting a part of the silver of the organic silver salt to a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin. Alternatively, a method of preparing a photosensitive silver halide grain by adding a silver supply compound and a halogen supply compound to another polymer solution and mixing the resultant with an organic silver salt can be used. In the present invention, the latter method can be preferably used. The grain size of the photosensitive silver halide is preferably small for the purpose of suppressing the white turbidity after image formation.
It is preferably 0.20 μm or less, more preferably 0.01 μm or more and 0.15 μm or less, and still more preferably 0.02 μm or more and 0.12 μm or less.
Here, the grain size means the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case where the silver halide grains are tabular grains, the diameter refers to a diameter when converted into a circular image having the same area as the projected area of the main surface. In the case of other than normal crystals, for example, in the case of spherical grains, rod-shaped grains, etc., it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grains is cubic,
Octahedral, tabular particles, spherical particles, rod-like particles, potato-like particles and the like can be mentioned. In the present invention, cubic particles and tabular particles are particularly preferable. When tabular silver halide grains are used, the average aspect ratio is preferably from 100: 1 to 2: 1, more preferably from 50: 1 to 3: 1. Further, grains having rounded corners of silver halide grains can also be preferably used. The surface index (mirror index) of the outer surface of the photosensitive silver halide grain is not particularly limited, but the spectral sensitization efficiency when the spectral sensitizing dye is adsorbed is high.
The proportion occupied by the {100} plane is preferably high. The ratio is preferably at least 50%, more preferably at least 65%, even more preferably at least 80%. The ratio of the {100} plane of the Miller index is determined by T. Tani; J. Imaging Sci., 29, 165 (198) using the dependence of the adsorption of the sensitizing dye on the {111} and {100} planes.
5 years). There is no particular limitation on the halogen composition of the photosensitive silver halide,
Silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide, any of silver iodide may be used, but in the present invention, silver bromide or silver iodobromide is preferred. Can be used. Particularly preferred is silver iodobromide, and the silver iodide content is preferably from 0.1 mol% to 40 mol%,
More preferably, it is not less than 20 mol% and not more than 20 mol%. The distribution of the halogen composition in the grains may be uniform, the halogen composition may be changed stepwise, or may be changed continuously, but as a preferable example, the silver iodide content inside the grains is High silver iodobromide grains can be used. Preferably, silver halide grains having a core / shell structure can be used. As the structure, core / shell particles having preferably a 2- to 5-layer structure, more preferably a 2- to 4-layer structure, can be used.

The photosensitive silver halide grains of the present invention preferably contain at least one complex of a metal selected from rhodium, iridium, ruthenium, rhenium, osmium, cobalt or iron. These metal complexes are 1
They may be of the same kind, or two or more kinds of complexes of the same metal and different metals may be used in combination. The preferred content is 1 mole of silver.
The range is preferably from 1 nmole to 10 mmol, and from 10 nmole to 10 mmol.
A range of 0 μmol is more preferred. As a specific structure of the metal complex, a metal complex having a structure described in JP-A-7-225449 or the like can be used.

The rhodium compound used in the present invention is preferably a water-soluble rhodium compound. For example, a rhodium (III) halide compound or a rhodium complex salt having a ligand such as halogen, amines, oxalato, etc., for example, hexachlororhodium (III) complex salt, hexabromorhodium (III) complex salt, hexaaminerhodium ( III) Complex salts and trizalatrodium (III) complex salts. These rhodium compounds are used by dissolving them in water or a suitable solvent. A method generally used for stabilizing a solution of a rhodium compound, that is, an aqueous hydrogen halide solution (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid) Etc.) or alkali halides (eg KCl, NaCl, KBr, N
aBr) can be used. Instead of using water-soluble rhodium, it is also possible to add and dissolve other silver halide grains doped with rhodium during the preparation of silver halide.

The iridium compound used in the present invention includes hexachloroiridium, hexabromoiridium and hexaammineiridium. Examples of the ruthenium compound used in the present invention include hexachlororuthenium and pentachloronitrosylruthenium. As the compound of cobalt and iron, a hexacyano metal complex can be preferably used. As a specific example,
Examples include, but are not limited to, ferricyanate ion, ferrocyanate ion, and hexacyanocobaltate ion. The phase containing the metal complex in the silver halide may be uniform, may be contained in the core at a high concentration, or may be contained in the shell at a high concentration, and there is no particular limitation.

The photosensitive silver halide grains can be desalted by washing with water by a method known in the art such as a noodle method or a flocculation method, but in the present invention, it may or may not be desalted. .

The photosensitive silver halide grains in the present invention are preferably chemically sensitized. As a preferred chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method are well known in the art. Further, a noble metal sensitization method or a reduction sensitization method of a gold compound, platinum, palladium, an iridium compound or the like can be used. As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds can be used, and the compounds described in JP-A-7-128768 can be used. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides,
Bis (carbamoyl) tellurides, diacyltellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, compounds having a P = Te bond,
Tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides,
Tellurols, telluroacetals, tellursulfonates, compounds having a P-Te bond, Te-containing heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate,
Gold sulfide, gold selenide, or US Patent 2,448,060
And the compounds described in British Patent No. 618,061 can be preferably used. Specific compounds of the reduction sensitization method include, as well as ascorbic acid, thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds,
A polyamine compound or the like can be used. Reduction sensitization can be achieved by ripening the emulsion while maintaining the pH of the emulsion at 7 or more or the pAg at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ion during grain formation.

The amount of the photosensitive silver halide used in the present invention is preferably from 0.01 mol to 0.5 mol, more preferably from 0.02 mol to 0.3 mol, more preferably from 0.03 mol to 1 mol of the organic silver salt. It is particularly preferably at least 0.25 mol and not more than 0.25 mol. Regarding the mixing method and the mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide particles and organic silver salt are mixed with a high-speed stirrer, ball mill, sand mill, colloid mill, vibration mill, homogenizer, etc. There is a method of mixing, or a method of preparing an organic silver salt by mixing photosensitive silver halide prepared at any timing during the preparation of the organic silver salt, etc. There is no particular limitation as long as it appears.

In the present invention, the coating amount of silver is not more than 1
m ² per 0.1~10g is preferable, and 0.5
It is preferably 5 g.

Although not required to practice the present invention,
It may be advantageous to add a mercury (II) salt as an antifoggant to the emulsion layer. Preferred mercury (II) salts for this purpose are
Mercury acetate and mercury bromide. The photosensitive silver halide used in the present invention is generally 0.75 to 25 mol% of the organic silver salt.
, Preferably in the range of 2 to 20 mol%.

The reducing agent for the organic silver salt may be any substance which reduces silver ions to metallic silver, preferably an organic substance. Conventional photographic developers such as phenidone, hydroquinone and catechol are useful, but hindered phenol reducing agents are preferred. The reducing agent is used in one of the image forming layers.
It should be present as ~ 10% by weight. When a reducing agent is added to a layer other than the emulsion layer in a multilayer structure,
A slightly higher percentage, about 2-15%, tends to be more desirable.

A wide range of reducing agents have been disclosed for photothermographic materials using organic silver salts. For example, amide oximes such as phenylamidooxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehydeazine; 2,2′-bis (hydroxymethyl) propionyl -a combination of an aliphatic carboxylic acid aryl hydrazide such as a combination of β-phenylhydrazine and ascorbic acid and ascorbic acid; a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine (for example, hydroquinone, bis (ethoxy) Ethyl) hydroxylamine, piperidinohexose reductone or a combination of formyl-4-methylphenylhydrazine, etc.); phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-alinine hydro Hydroxamic acids such as thumb acid; combinations of azines and sulfonamidophenols (for example,
Phenothiazine and 2,6-dichloro-4-benzenesulfonamidophenol); α-cyanophenylacetic acid derivatives such as ethyl-α-cyano-2-methylphenylacetate and ethyl-α-cyanophenylacetate; 2,2′-
Dihydroxy-1,1'-binaphthyl, 6,6'-dibromo-2,
2'-dihydroxy-1,1'-binaphthyl and bis (2-
Bis-β-naphthol as exemplified by hydroxy-1-naphthyl) methane; bis-β-naphthol and 1,3-dihydroxybenzene derivatives (eg, 2,4-dihydroxybenzophenone or 2 ′, 4′-dihydroxyacetophenone 5-pyrazolone, such as 3-methyl-1-phenyl-5-pyrazolone; exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone Reductones as produced; sulfonamide phenol reducing agents such as 2,6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione; 2,2-dimethyl Chromans such as -7-t-butyl-6-hydroxychroman; 2,6-dimethoxy-3,5-dicarboe Carboxymethyl-1,4-dihydropyridine such as 1,4-dihydropyridine; bisphenols (e.g., bis (2-hydroxy -3-t
-Butyl-5-methylphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-ethylidene-bis (2-t-butyl-6-methylphenol), 1,1 ,-
Bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane and the like; ascorbic acid derivatives (for example, Such as 1-ascorbyl palmitate, ascorbyl stearate); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and certain indan-1,3-diones.

Particularly preferred reducing agents in the present invention include compounds represented by the following formulas (RI), (R-II), (R-III) and (R-IV). Can be

[0192]

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In the formula (R-III), the ring structure formed by Z is as follows.

[0194]

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In the general formula (R-IV), the ring structure formed by Z is as follows.

[0196]

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[0197] In the formula, L _1, L ₂ is a group or a sulfur atom represented by _{CH-R 6, CH-R} 6 '. n represents a natural number. R
_{(R 1 ~R 10, R 1} '~R 5', R 6 ', R 11 ~R 13, R 11' ~R
₁₃ ′ and R _{21 to} R ₂₈ ) are a hydrogen atom, an alkyl group (1 to 30 carbon atoms), an aryl group, an aralkyl group, a halogen atom, an amino group or a substituent represented by —OA. However, at least one of R _{1 to} R ₅ and R ₁ ′ to
At least one of the at least one and R ₇ to R ₁₀ of R ₅ 'is a group represented by -OA. Also, R may form a ring with each other. A 1 and A ′ represent a hydrogen atom, an alkyl group (1 to 30 carbon atoms), an acyl group (1 to 30 carbon atoms), an aryl group, a phosphate group, and a sulfonyl group. R, A and A ′ may be substituted, and typical substituents include, for example, an alkyl group (including an active methine group), a nitro group, an alkenyl group,
Groups containing alkynyl groups, aryl groups, heterocycles, groups containing quaternary nitrogen-containing heterocycles (eg, pyridinio groups), hydroxy groups, alkoxy groups (groups containing repeating units of ethyleneoxy or propyleneoxy) ), An aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a urethane group, a carboxyl group,
Imide group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, group containing hydrazino group, group containing quaternary ammonium group, mercapto group , (Alkyl, aryl, or heterocycle)
A thio group, an (alkyl or aryl) sulfonyl group,
(Alkyl or aryl) sulfinyl group, sulfo group, sulfamoyl group, acylsulfamoyl group, (alkyl or aryl) sulfonyluureido group, (alkyl or aryl) sulfonylcarbamoyl group,
A halogen atom, a cyano group, a phosphoric acid amide group, a group having a phosphate ester structure, a group having an acylurea structure, a group having a selenium atom or tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure. . The substituents of R, A and A ′ may be further substituted, and preferred examples include those exemplified as the substituents of R. Further, the substituent, the substituent of the substituent, the substituent of the substituent of the substituent,..., May be substituted multiple times, and preferred examples are also R, A,
What is illustrated as a substituent of A 'applies.

The following formulas (RI) and (RI)
Specific examples of the compounds represented by I), the general formula (R-III) and the general formula (R-IV) are shown below. However, the present invention is not limited to the following compounds.

[0199]

[Table 9]

[0200]

[Table 10]

[0201]

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[0202]

[Table 11]

[0203]

[Table 12]

[0204]

[Table 13]

[0205]

[Table 14]

[0206]

[Table 15]

The amount of the reducing agent used in the present invention is preferably 1 × 10 ⁻³ to 10 mol, more preferably 1 × 10 ^{−2 to} 1.5 mol, per 1 mol of silver.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. be able to.

When a mercapto compound is used in the present invention, it may be of any structure, but may be any of Ar-SM, Ar-SSA
Those represented by r are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic or fused aromatic ring group having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring in these groups is benzimidazole, naphthimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, Triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring can be, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy,
Alkyl (eg one or more carbon atoms, preferably 1
And those having substituents selected from the group consisting of alkoxy (e.g., having 1 to 4 carbon atoms), and alkoxy (e.g., having 1 or more carbon atoms, preferably having 1 to 4 carbon atoms). Good. As mercapto-substituted heteroaromatic compounds, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2, 2'-dithiobis-benzothiazole, 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol,
2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2-mercaptoquinoline, 8-mercaptopurine, 2-mercapto-4 (3H) -quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3 , 5,6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy
-2-mercaptopyrimidine monohydrate, 2-amino-5
-Mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-triazole, 4-hydrocyroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercapto Pyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 2-mercapto-4-phenyloxazole and the like, but the present invention is not limited thereto .

The addition amount of these mercapto compounds is preferably in the range of 0.001 to 1.0 mol per mol of silver in the emulsion layer, more preferably 0.01 to 1.0 mol per mol of silver.
The amount is 0.3 mol.

In some cases, it may be advantageous to include additives, known as "toning agents", which enhance the image, in addition to the components described above. For example, the toning agent material has a total silver holding component of 0.1 to
It may be present in an amount of 10% by weight. Toning agents are disclosed in U.S. Pat.
As shown in 080,254, 3,847,612 and 4,123,282, they are well known in the photographic art.

Examples of toning agents include phthalimide and N-hydroxyphthalimide; succinimide, pyrazoline-5-
Quinazolinone, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and
Cyclic imides such as 2,4-thiazolidinedione; naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, cobalt hexamine trifluoroacetate); 3-mercapto-1,2,4 -Triazole, 2,4-dimercaptopyrimidine, 3-mercapto-4,5
N- (aminomethyl) aryldicarboximides; mercaptans exemplified by -diphenyl-1,2,4-triazole and 2,5-dimercapto-1,3,4-thiadiazole;
(For example, (N, N-dimethylaminomethyl) phthalimide and N, N- (dimethylaminomethyl) -naphthalene-2,3-
Dicarboximides); and blocked pyrazoles, isothiuronium derivatives, and certain photobleaching agents (eg, N, N'-hexamethylenebis (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3, 6-diazaoctane) bis (isothiuronium trifluoroacetate) and 2-tribromomethylsulfonyl)-(benzothiazole)); and 3-ethyl-5 [(3-ethyl-2-benzothiazolinylidene) -1 -Methylethylidene] -2-thio-2,4-
Oxazolidinedione; phthalazinone, phthalazinone derivatives or metal salts, or 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethoxyphthalazinone and 2,3-dihydro-1,4-phthalazinedione A combination of phthalazinone and a phthalic acid derivative (such as phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride);
Phthalazine derivatives or metal salts, or derivatives such as 4- (1-naphthyl) phthalazine, 6-chlorophthalazine, 5,7-dimethoxyphthalazine and 2,3-dihydrophthalazine; phthalazine and phthalic acid derivatives (eg, phthalic acid) acid,
Quinazolinedione, such as 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride;
Benzoxazine or naphthoxazine derivatives; rhodium complexes which function not only as color tone regulators but also in situ as sources of halide ions for silver halide formation, such as ammonium hexachlororhodate (III), rhodium bromide, rhodium nitrate And potassium hexachlororhodate (III); inorganic peroxides and persulfates, such as ammonium disulfide and hydrogen peroxide; 1,3-benzoxazine-2,4-dione, 8-methyl-
1,3-benzoxazine-2,4-dione and 6-nitro-1,
Benzoxazine-2,4-dione such as 3-benzoxazine-2,4-dione; pyrimidine and asymmetric-triazines (eg, 2,4-dihydroxypyrimidine, 2-hydroxy
-4-aminopyrimidine, etc.), azauracil, and tetraazapentalene derivatives (eg, 3,6-dimercapto
-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene and 1,4-di (o-chlorophenyl) -3,6-dimercapto-1H, 4H-2,3a, 5,6a-tetraazapentalene).

The silver halide emulsion according to the invention or /
And the organic silver salts can be further protected against the formation of additional fog by antifoggants, stabilizers and stabilizer precursors, and can be stabilized against reduced sensitivity during stock storage. Suitable antifoggants, stabilizers and stabilizer precursors that can be used alone or in combination are the thiazonium salts described in U.S. Pat.Nos. 2,131,038 and 2,694,716, U.S. Pat.Nos. 2,886,437 and 2,444,605. Azaindene, U.S. Pat.
No. 728,663, mercury salts described in U.S. Pat.No. 3,287,135, sulphocatechol described in U.S. Pat.No. 3,235,652, oximes described in British Patent No.
No. 405, polyvalent metal salts, U.S. Pat.No. 3,220,839, thyuronium salts, and U.S. Pat.
Palladium, platinum and gold salts described in U.S. Patent Nos. 4,108,665 and 4,442,20
Halogen-substituted organic compounds described in No. 2, U.S. Pat.
Nos. 8,557 and 4,137,079, 4,138,365 and 4,459,350, and the phosphorus compounds described in U.S. Pat. No. 4,411,985.

The antifoggant preferably used in the present invention is a compound such as that disclosed in US Pat. Nos. 3,874,946 and 4,756,999, -C (X ₁ ) (X ₂ ) (X ₃ ) (where X ₁ and X ₂ is a heterocyclic compound having at least one substituent represented by halogen (eg, F ₂ , Cl, Br and I 2) and X 3 being a hydrogen atom or halogen. Hereinafter, specific examples of the heterocyclic compound will be shown. However, the present invention is not limited to the following compounds.

[0215]

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[0216]

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Further, a more preferred heterocyclic compound is
U.S. Pat.No. 5,028,523 and British Patent Application No.92221383.4
Nos. 9300147.7 and 9311790.1.

In the photosensitive layer according to the invention, a polyhydric alcohol (for example, US Pat.
Glycerin and diols of the type described in U.S. Pat. No. 960,404), fatty acids or esters described in U.S. Pat. Nos. 2,588,765 and 3,121,060, and silicone resins described in British Patent No. 955,061.

A hardener may be used for each layer such as the photosensitive layer, the protective layer, and the back layer of the present invention. Examples of hardeners include:
U.S. Pat.No. 4,281,060, polyisocyanates described in JP-A-6-208193, etc., epoxy compounds described in U.S. Pat.
Vinyl sulfone compounds described in No. 48 and the like are used.

In the present invention, a surfactant may be used for the purpose of improving coating properties and charging. As the surfactant, any surfactant such as nonionic, anionic, cationic, and fluorine can be used as appropriate. Specifically,
No. 62-170950, U.S. Pat.No.5,382,504, etc., fluorine polymer surfactants described in JP-A-60-244945, JP-A-63
-Fluorinated surfactants described in 188135, etc., U.S. Patent
No. 3,885,965, etc.
Examples thereof include polyalkylene oxides and anionic surfactants described in JP-A-6-301140.

The light-sensitive material of the present invention can be provided with a surface protective layer for the purpose of preventing adhesion of the image forming layer.
Any anti-adhesion material may be used as the surface protective layer. Examples of anti-adhesion materials include waxes, silica particles, styrene-containing elastomeric block copolymers (eg, styrene-butadiene-styrene, styrene
-Isoprene-styrene), cellulose acetate, cellulose acetate butyrate, cellulose propionate and mixtures thereof.

In the present invention, the emulsion layer or the protective layer of the emulsion layer may be prepared as described in US Pat. Nos. 3,253,921 and 2,274,782.
Nos. 2,527,583 and 2,956,879. Light absorbing materials and filter dyes as described in U.S. Pat. Alternatively, dyes can be mordant as described in, for example, US Pat. No. 3,282,699.

In the emulsion layer or the protective layer of the emulsion layer in the present invention, a matting agent such as starch, titanium dioxide, zinc oxide, silica, US Pat. No. 2,992,101 and US Pat.
Polymer beads, including beads of the type described in U.S. Pat. Also, the matte degree of the emulsion surface may be any value as long as stardust failure does not occur, but the Beck smoothness is preferably 1000 seconds or more and 10,000 seconds or less, particularly
It is preferably from 2000 seconds to 10,000 seconds.

As the binder for the emulsion layer in the present invention, well-known natural or synthetic resins such as gelatin, polyvinyl acetal, polyvinyl chloride,
Any one can be selected from polyvinyl acetate, cellulose acetate, polyolefin, polyester, polystyrene, polyacrylonitrile, polycarbonate and the like. Of course, copolymers and terpolymers are also included. Preferred polymers are polyvinyl butyral, butylethyl cellulose, methacrylate copolymer, maleic anhydride copolymer, polystyrene and butadiene-styrene copolymer. If necessary, two or more of these polymers can be used in combination. Such a polymer is used in an amount sufficient to hold the components therein. That is, it is used in a range effective to function as a binder. The effective range can be appropriately determined by those skilled in the art. As a guideline for at least retaining the organic silver salt, the ratio of the binder to the organic silver salt is 15:
The range of 1-1: 2, particularly 8: 1 to 1: 1 is preferred.

The photothermographic material of the present invention preferably contains a dye for the purpose of preventing halation, irradiation, and safelight fogging.

For an Ar laser, a HeNe laser, or a red semiconductor laser, a dye is added so as to absorb at least 0.3 or more, preferably 0.6 or more, at the exposure wavelength in the range of 400 to 750 nm. 750nm ~ 15 for infrared semiconductor laser
The dye is added so as to absorb at least 0.3 or more, preferably 0.6 or more at the exposure wavelength in the range of 00 nm. Further, one or more dyes may be used in combination. In addition, the dye has a visible region (300 nm) after heat development.
The absorption at 700700 nm) is preferably less than 0.5, more preferably less than 0.2.

The dye used in the present invention has a desired absorption in a desired wavelength range, has a sufficiently low absorption in a visible region,
Any compound may be used as long as a preferable absorbance spectrum shape can be obtained. For example, JP-A-7-13295, U.S. Patent
Compound described in 5,380,635, JP-A-2-68539, No. 13
From the first line on the lower left column of the page to the ninth line on the lower left column on page 14, 3-24539
Compounds described in the publication, page 14, lower left column to page 16, lower right column, are mentioned, but the present invention is not limited thereto.

For the purpose of preventing halation and irradiation, the dye is preferably added to a photosensitive layer, a non-photosensitive layer between the photosensitive layer and the support, and a non-photosensitive layer opposite to the photosensitive layer. When the purpose is to prevent safelight fogging, it is preferable to add the protective layer to the non-photosensitive layer opposite to the photosensitive layer.

The heat-developable photographic light-sensitive material of the present invention comprises
A so-called one-sided light-sensitive material having a photosensitive layer containing at least one silver halide emulsion on one side of a support and a backing layer on the other side is preferred.

In the present invention, a matting agent may be added to the single-sided photosensitive material in order to improve transportability. The matting agent is generally fine particles of an organic or inorganic compound insoluble in water. Any matting agent can be used, for example, U.S. Patent Nos. 1,939,213, 2,701,245, and 2,322,037.
No. 3,262,782, No. 3,539,344, No. 3,767,448, etc.
No. 2,192,241, No. 3,257,206, No. 3,370,951, No.
Inorganic matting agents well-known in the art, such as inorganic matting agents described in the specifications such as 3,523,022 and 3,769,020 can be used. For example, specific examples of organic compounds that can be used as a matting agent include polymethyl acrylate, polymethyl methacrylate, polyacrylonitrile, and acrylonitrile as examples of water-dispersible vinyl polymers.
-α-methylstyrene copolymer, polystyrene, styrene-divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, polytetrafluoroethylene, etc.Examples of cellulose derivatives such as methylcellulose, cellulose acetate, cellulose acetate propionate, etc. Examples of the derivative preferably include carboxystarch, carboxynitrophenyl starch, urea-formaldehyde-starch reactant, and the like, gelatin hardened with a known hardener, hardened gelatin coacervated and hardened into fine capsule hollow granules, and the like. Examples of the inorganic compound include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by a known method, silver bromide, glass, and diatomaceous earth. . The above matting agents can be used by mixing different types of substances as necessary. The size and shape of the matting agent are not particularly limited, and those having an arbitrary particle size can be used. When implementing the present invention, 0.1 μm
It is preferable to use one having a particle size of 30 μm. Further, the particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent greatly affects the haze and surface gloss of the light-sensitive material, the particle size, shape, and particle size distribution can be changed as necessary during the preparation of the matting agent or by mixing a plurality of matting agents. preferable.

In the present invention, the matting degree of the backing layer is preferably such that the Beck smoothness is 250 seconds or less and 10 seconds or more.
More preferably, the time is 180 seconds or less and 50 seconds or more.

In the present invention, the matting agent is preferably contained in the outermost surface layer of the light-sensitive material, a layer functioning as the outermost surface layer, or a layer close to the outer surface. It is preferable to be contained.

In the present invention, suitable binders for the backing layer are transparent or translucent, generally colorless, and natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, gum arabic, poly (vinyl) Alcohol), hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, poly (vinylpyrrolidone), casein,
Starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid),
Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (e.g., poly (vinyl formal) and poly (vinyl butyral)), poly (ester) s , Poly (urethane) s, phenoxy resin, poly (vinylidene chloride), poly (epoxide) s,
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). The binder may be coated from water or an organic solvent or emulsion.

US Pat. Nos. 4,460,681 and 4,374,
The backside resistive heating layer (backside re
A sistive heating layer) can also be used in a photothermographic image system.

The photographic emulsion for heat development in the present invention can be coated on various supports. Typical supports include polyester films, primed polyester films, poly (ethylene terephthalate) films, polyethylene naphthalate films, cellulose nitrate films, cellulose ester films, poly (vinyl acetal) films, polycarbonate films and related or resinous Including materials, as well as glass, paper, metal and the like. Flexible substrates, especially baryta paper, partially acetylated, coated with α-olefin polymers, especially polymers of α-olefins having 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylene-butene copolymer A paper support is typically used. The support may be transparent or opaque, but is preferably transparent.

The light-sensitive material of the present invention comprises an antistatic or conductive layer, for example, a soluble salt (eg, chloride, nitrate, etc.), a vapor-deposited metal layer, and an ionizable layer as described in US Pat. Nos. 2,861,056 and 3,206,312. Or a layer containing an insoluble inorganic salt or the like as described in US Pat. No. 3,428,451.

As a method for obtaining a color image using the heat-developable photosensitive material in the present invention, there is a method described in JP-A-7-13295, page 10, left column, line 43 to 11 left column, line 40. Examples of color dye image stabilizers include British Patent No. 1,326,889, U.S. Patent Nos. 3,432,300, 3,698,909, and 3,574,
Nos. 627, 3,573,050, 3,764,337 and 4,042,394.

The photothermographic emulsions of the present invention can be coated by various coating operations including dip coating, air knife coating, flow coating or extrusion coating using a hopper of the type described in US Pat. No. 2,681,294. If desired, two or more layers can be coated simultaneously by the methods described in U.S. Pat. No. 2,761,791 and GB 837,095.

In the heat-developable photographic material of the present invention, additional layers such as a dye-receiving layer for receiving a mobile dye image, an opaque layer if reflective printing is desired, a protective topcoat layer and photothermographic techniques It may include a known primer layer and the like. The light-sensitive material of the present invention is preferably capable of forming an image with only one light-sensitive material, and it is preferable that a functional layer required for image formation such as an image receiving layer does not become another light-sensitive material.

[0240]

【Example】

Example 1 (Preparation of Organic Acid Silver Emulsion A) Behenic acid 840 g, stearic acid
95 g was added to 12 liters of water, and while maintaining the temperature at 90 ° C., a solution prepared by dissolving 48 g of sodium hydroxide and 63 g of sodium carbonate in 1.5 liters of water was added. After stirring for 30 minutes, the temperature was raised to 50 ° C., 1.1 L of a 1% aqueous solution of N-bromosuccinimide was added, and 2.3 L of a 17% aqueous solution of silver nitrate were gradually added with stirring. Further, the solution temperature was brought to 35 ° C., 1.5 liters of a 2% aqueous solution of potassium bromide was added over 2 minutes with stirring, and the mixture was stirred for 30 minutes, and 1% of N-bromosuccinimide was added.
2.4 liters of the aqueous solution were added. While stirring the aqueous mixture, a 1.2% by weight solution of polyvinyl acetate in butyl acetate 33 was added.
After adding 00 g, the mixture was allowed to stand for 10 minutes to separate into two layers, the aqueous layer was removed, and the remaining gel was washed twice with water. The thus obtained mixture of gel-like behenic acid / silver stearate and silver bromide was dispersed in 1800 g of a 2.6% 2-butanone solution of polyvinyl butyral (Denka Butyral # 3000-K, manufactured by Denki Kagaku Kogyo Co., Ltd.). 600 g of polyvinyl butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo Co., Ltd.)
Organic acid silver salt emulsion dispersed with 300 g of isopropyl alcohol (average minor axis 0.05 μm, average major axis 1.2 μm, variation coefficient 25
% Needle-like particles).

(Preparation of Coating Solution A for Emulsion Layer) Each chemical was added to the above-obtained organic acid silver emulsion in the following amount per mole of silver. Sodium phenylthiosulfonate at 25 ° C
10 mg, the sensitizing dyes described in Table 16 in the amounts shown in Table 16,
2 g of mercapto-5-methylbenzimidazole, 1 g of 2-mercapto-5-methylbenzothiazole, 21.5 g of 4-chlorobenzophenone-2-carboxylic acid, 580 g of 2-butanone and 220 g of dimethylformamide were added with stirring and left for 3 hours. . Then, 4.5 g of 4,6-ditrichloromethyl-2-phenyltriazine, 2 g of disulfide compound A, 160 g of 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane , Phthalazine 15 g, tetrachlorophthalic acid 5 g, the hydrazine derivative shown in Table 16 in the amount shown in Table 16, Megafax F-176P (a fluorosurfactant manufactured by Dainippon Ink and Chemicals, Inc.) 1.1 g, 2 -Butanone 590
g and 10 g of methyl isobutyl ketone were added with stirring.

(Preparation of Coating Solution A for Emulsion Surface Protective Layer) CAB171-1
75 g of 5S (cellulose acetate butyrate manufactured by Eastman Chemical Co., Ltd.), 5.7 g of 4-methylphthalic acid, 1.5 g of tetrachlorophthalic anhydride, 10 g of 2-tribromomethylsulfonylbenzothiazole, 2 g of phthalazone, Megafax F-176P
0.3 g, Sildex H31 (Doukai Chemical Co., Ltd., spherical silica average size 3 μm) 2 g, sumidurN3500 (Sumitomo Bayer Urethane Co., Ltd. polyisocyanate) 5 g, 2-butanone 3070
g and 30 g of ethyl acetate.

(Preparation of Support Having Back Surface) 6 g of polyvinyl butyral (Denka Butyral # 4000-2, manufactured by Denki Kagaku Kogyo KK), Sildex H121 (average size of spherical silica 12 μm, manufactured by Dokai Chemical Co., Ltd.) 0.2 g, Sildex H51
(Average size of spherical silica manufactured by Dokai Chemical Co., Ltd., average size 5 μm) 0.2g
Was added to 64 g of 0.1 g of Megafax F-176P2-propanol while stirring, and dissolved and mixed. In addition, 42
A coating solution was prepared by adding a mixed solution of 0 mg of Dye A in 10 g of methanol and 20 g of acetone and a solution of 0.8 g of 3-isocyanatomethyl-3,5,5-trimethylhexyl isocyanate in 6 g of ethyl acetate.

A coating solution for the back side was applied to a polyethylene terephthalate film having a moisture-proof undercoat containing vinylidene chloride on both sides so as to have an optical density of 0.7 at 633 nm.

[0245]

Embedded image

The emulsion layer coating solution was coated on the support prepared as described above so that the silver content was 2 g / m ^2, and the emulsion surface protective layer coating solution was dried on the emulsion surface to a dry thickness of 5 μm. Applied.

(Evaluation of photographic performance) Helium-neon light source color scanner SG-6 manufactured by Dainippon Screen Co., Ltd.
After exposing the photographic material using 08, the photographic material is processed (developed) at 115 ° C for 25 seconds using a heat drum, and further exposed to a halogen lamp for 15 seconds. It was performed by total. The measurement results were evaluated in terms of Dmax and sensitivity (the reciprocal of the ratio of the amount of exposure that gives a density 1.5 times higher than Dmin). The gradient of the straight line connecting the points of density 0.3 and 3.0 in the characteristic curve is shown as gradation γ. Table 16 shows the results.

(Image Reproducibility: Evaluation of Sharpness of Halftone Dots) Using a helium-neon light source color scanner SG-608 manufactured by Dainippon Screen Co., Ltd., a 50% flat screen at 100 lines was used as a coated photosensitive material. Output and develop under the above processing conditions,
The sharpness of halftone dots was visually evaluated with a double magnifier. Evaluation results
(Good) 5 to 1 (bad) are shown in the table by the five-point method. Practically, three or more points are required. Table 16 shows the results.

[0249]

[Table 16]

(Results) By using the hydrazine compound of the present invention and the dye of the present invention, a heat-developable photographic light-sensitive material satisfying all of high Dmax, high contrast and image quality could be obtained.

Example 2 (Preparation of silver halide grains B) 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, the pH was adjusted to 3.0 at a temperature of 35 ° C., and 370 m of an aqueous solution containing 74 g of silver nitrate was obtained.
l, potassium bromide, and potassium iodide in a molar ratio of 94: 6, and an aqueous solution containing K4 [Fe (CN) 6] was added over 10 minutes by a control double jet method while maintaining the pAg at 7.7.
[Fe (CN) 6] -4 was added at 3 × 10 ^-5 mol per mol of silver. Then 4-hydroxy-6-methyl 1,3,3
0.3 g of a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, and the average size was 0.06 μm.
Cubic silver iodobromide grains having a 0 face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and after desalting, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5.

(Preparation of Organic Acid Silver Emulsion B) Behenic acid 10.6 g
Then, 300 ml of distilled water was mixed at 90 ° C. for 15 minutes, 31.1 ml of a 1N-NaOH aqueous solution was added over 15 minutes with vigorous stirring, and the mixture was left as it was for 1 hour and then cooled to 30 ° C. Next, 7 ml of an aqueous 1N-phosphoric acid solution was added, and 0.13 g of N-bromosuccinimide was added while stirring more vigorously, and the silver halide grains A prepared in advance were adjusted so that the silver halide amount was 2.5 mmol. Was added. In addition, 25 ml of 1N silver nitrate aqueous solution
Was added continuously over 2 minutes, and stirring was continued for 90 minutes. To this aqueous mixture was added 37 g of a 1.2% by weight butyl acetate solution of polyvinyl acetate to form a floc of the dispersion. After removing the water, water was further washed twice and water was removed. 20 g of a 2.5 wt% butyl acetate / isopropyl alcohol 1: 2 mixed solution of Denka Butyral # 3000-K (manufactured by Chemical Industry Co., Ltd.) was added with stirring, and the resulting gelled organic acid and silver halide 7.8 g of polyvinyl butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo Co., Ltd.) and 2-butanone
Add 57 g and disperse with a homogenizer. Silver behenate emulsion (average minor axis 0.04 μm, average major axis 1 μm, coefficient of variation 30%
Needle-shaped particles).

(Preparation of Emulsion Layer Coating Solution B) Each of the chemicals was added to the above-obtained organic acid silver emulsion in the following amount per mole of silver. Sodium phenylthiosulfonate at 25 ° C
10 mg, the compounds described in Table 17 in the amounts described in Table 17, 2-mercapto-5-methylbenzimidazole 2 g, 4-chlorobenzophenone-2-carboxylic acid 21.5 g and 2-butanone 580 g,
Dimethylformamide (220 g) was added with stirring and left for 3 hours. Then, 4,6-ditrichloromethyl-2-phenyltriazine 4 g, disulfide compound A (same as in Example 1) 2 g, 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5 170 g of 5,5-trimethylhexane, 5 g of tetrachlorophthalic acid, 15 g of phthalazine, the amount of the hydrazine derivative shown in Table 17 in the amount shown in Table 17, and Megafax F-1 76P (a fluorine-based interface manufactured by Dainippon Ink and Chemicals, Inc.) (Activator) 1.1 g
, 2-butanone 590 g and methyl isobutyl ketone 10 g were added with stirring.

CAB171-15S (Eastman Chemical Co., Ltd.)
Cellulose acetate butyrate) 75 g, 4-methylphthalic acid 5.7 g, tetrachlorophthalic anhydride 1.5 g, 5-tribromomethylsulfonyl-2-methylthiadiazole 8 g, 2-tribromomethylsulfonylbenzothiazole 6 g, phthalazone 3
g, 0.3 g of Megafax F-176P, Sildex H31 (Doukai Chemical's spherical silica average size 3 μm), 2 g, sumidur
N3500 (Sumitomo Bayer Urethane Co. polyisocyanate) 6
g was dissolved in 3070 g of 2-butanone and 30 g of ethyl acetate.

(Preparation of Support Having Back Surface) 6 g of polyvinyl butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo KK), Sildex H121 (average size of spherical silica 12 μm manufactured by Dokai Chemical Co., Ltd.) 0.2 g, Sildex H51
(Average size of spherical silica manufactured by Dokai Chemical Co., Ltd. 5μm) 0.2g
Was added to 64 g of 0.1 g of Megafax F-176P2-propanol while stirring, and dissolved and mixed. In addition, 42
A mixed solution of 0 mg of Dye A (same as in Example 1) in 10 g of methanol and 20 g of acetone and a solution of 0.8 g of 3-isocyanatomethyl-3,5,5-trimethylhexyl isocyanate in 6 g of ethyl acetate are added. A coating solution was prepared.

A coating solution for the back side was applied to a polyethylene terephthalate film having a moisture-proof undercoat containing vinylidene chloride on both sides so as to have an optical density of 0.7 at 633 nm.

The emulsion layer coating solution was coated on the support prepared as described above so that the silver content was 2 g / m ^2, and the emulsion surface protective layer coating solution was dried on the emulsion surface to a dry thickness of 5 μm. Applied.

(Evaluation of Photographic Performance) Evaluation was made in the same manner as in Example 1. Table 17 shows the results.

(Evaluation of Image Reproducibility) Evaluation was performed in the same manner as in Example 1. Table 17 shows the results.

[0260]

[Table 17]

(Results) By using the hydrazine compound of the present invention, a heat-developable photographic material satisfying all of high Dmax, high contrast and image quality could be obtained.

Example 3 A sample was prepared in the same manner as in Example 1 except that the sensitizing dyes shown in Table 18 were used.

(Evaluation of Photographic Performance) Evaluation was made in the same manner as in Example 1. The results are shown in Table 18.

(Evaluation of Image Reproducibility) Evaluation was performed in the same manner as in Example 1. The results are shown in Table 18.

[0265]

[Table 18]

(Results) By using the hydrazine compound of the present invention, a heat-developable photographic light-sensitive material satisfying all of high Dmax, high contrast and image quality could be obtained.

Example 4 A sample was prepared in the same manner as in Example 2 except that the sensitizing dyes shown in Table 19 were used.

(Evaluation of photographic performance) Evaluation was made in the same manner as in Example 1. The results are shown in Table 19.

(Evaluation of Image Reproducibility) Evaluation was performed in the same manner as in Example 1. The results are shown in Table 19.

[0270]

[Table 19]

(Results) By using the hydrazine compound of the present invention, a heat-developable photographic material satisfying all of high Dmax, high contrast and high image quality was obtained.

Example 5 A sample was prepared in the same manner as in Example 1 except that the sensitizing dyes shown in Table 20 were used.

(Evaluation of Photographic Performance) Evaluation was made in the same manner as in Example 1. The results are shown in Table 20.

(Evaluation of Image Reproducibility) Evaluation was performed in the same manner as in Example 1. The results are shown in Table 20.

[0275]

[Table 20]

(Results) By using the hydrazine compound of the present invention, a heat-developable photographic material satisfying all of high Dmax, high contrast and high image quality was obtained.

Example 6 A sample was prepared in the same manner as in Example 2 except that the sensitizing dyes used were those described in Table 21.

(Evaluation of Photographic Performance) Evaluation was made in the same manner as in Example 1. The results are shown in Table 21.

(Evaluation of Image Reproducibility) Evaluation was performed in the same manner as in Example 1. The results are shown in Table 21.

[0280]

[Table 21]

(Results) By using the hydrazine compound of the present invention, a heat-developable photographic material satisfying all of high Dmax, high contrast and image quality could be obtained.

Example 7 A sample was prepared in the same manner as in Example 1 except that the sensitizing dyes shown in Table 22 were used.

(Evaluation of Photographic Performance) Evaluation was made in the same manner as in Example 1. The results are shown in Table 22.

(Evaluation of Image Reproducibility) Evaluation was performed in the same manner as in Example 1. The results are shown in Table 22.

[0285]

[Table 22]

(Results) By using the hydrazine compound of the present invention, a heat-developable photographic material satisfying all of high Dmax, high contrast and high image quality was obtained.

Example 8 A sample was prepared in the same manner as in Example 2 except that the sensitizing dyes used were those described in Table 23.

(Evaluation of Photographic Performance) Evaluation was made in the same manner as in Example 1. The results are shown in Table 23.

(Evaluation of Image Reproducibility) Evaluation was performed in the same manner as in Example 1. The results are shown in Table 23.

[0290]

[Table 23]

(Results) By using the hydrazine compound of the present invention, a heat-developable photographic material satisfying all of high Dmax, high contrast and high image quality was obtained.

Example 9 The sensitizing dyes used were those described in Table 24.
Example 1 except that Dye B was used as the dye on the back surface
A sample was prepared in the same manner as in.

[0293]

Embedded image

(Evaluation of photographic performance) Evaluation was made in the same manner as in Example 1 except that exposure was performed at 810 nm and no exposure was performed using a halogen lamp. The results are shown in Table 24.

(Evaluation of Image Reproducibility) Evaluation was made in the same manner as in Example 1 except that exposure was performed at 810 nm and no exposure with a halogen lamp was performed. The results are shown in Table 24.

[0296]

[Table 24]

(Results) By using the hydrazine compound of the present invention, a heat-developable photographic light-sensitive material satisfying all of high Dmax, high contrast and image quality could be obtained.

Example 10 A sample was prepared in the same manner as in Example 2 except that the sensitizing dyes used were those described in Table 25.

(Evaluation of photographic performance) Evaluation was made in the same manner as in Example 1 except that exposure was performed at 810 nm. The results are shown in Table 25.

(Evaluation of Image Reproducibility) Evaluation was performed in the same manner as in Example 1 except that exposure was performed at 810 nm. The results are shown in Table 25.

[0301]

[Table 25]

(Results) By using the hydrazine compound of the present invention, a heat-developable photographic light-sensitive material satisfying all of high Dmax, high contrast and image quality could be obtained.

Example 11 In place of the hydrazine derivative in Example 1, H-4
3, H-49, H-50, H-40p, H-34n, H
-42p was used. Good results were obtained as in Example 1.

Example 12 In the same manner as in Example 9, samples were prepared using the sensitizing dyes described in Tables 26 and 27.

(Evaluation of Photographic Performance) The evaluation was performed in the same manner as in Example 9. The results are shown in Tables 26 and 27.

(Evaluation of Image Reproducibility) Evaluation was performed in the same manner as in Example 9. The results are shown in Tables 26 and 27.

(Evaluation of Storage Property) To estimate the change in photographic performance due to long-term storage, a sample was prepared at 50 ° C. and 40% R.
Sensitivity fluctuations after 3 days of aging under H conditions were measured.
The sensitivity was measured in the same manner as in the evaluation of photographic performance described above. Sensitivity change = sensitivity (50 ° C., 40% sample aged 3 days) −sensitivity (new sample) The closer the value is to 0, the better the performance. The results are shown in Tables 26 and 27.

[0308]

[Table 26]

[0309]

[Table 27]

By using the compound of the present invention, a heat-developable photographic light-sensitive material which satisfies all of the requirements of high Dmax, high contrast and image quality and has the same performance even after long-term storage can be obtained.

Example 13 In the same manner as in Example 10, samples were prepared using the sensitizing dyes described in Tables 28 and 29.

(Evaluation of Photographic Performance) The evaluation was performed in the same manner as in Example 9. The results are shown in Tables 28 and 29.

(Evaluation of Image Reproducibility) The evaluation was performed in the same manner as in Example 9. The results are shown in Tables 28 and 29.

(Evaluation of storage stability) The evaluation was performed in the same manner as in Example 12. The results are shown in Tables 28 and 29.

[0315]

[Table 28]

[0316]

[Table 29]

By using the compound of the present invention, a heat-developable photographic light-sensitive material satisfying all of the requirements of high Dmax, high contrast and image quality and having the same performance even after long-term storage was obtained.

Example 14 The samples prepared in Example 1 were evaluated for storage stability in the same manner as in Example 12.

The hydrazine compounds H-26e and H-34m
Samples 5 to 7 and 11 to 13 used all had a sensitivity variation of 0.01, but all samples using hydrazine compounds other than H-26e and H-34m had a sensitivity variation of 0.03 or more. became.

[0320]

According to the present invention, a heat-developable photographic light-sensitive material having a high D _max and excellent super-hard contrast images can be realized. Further, the storage stability can be improved.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07D 275/06 C07D 275/06 277/10 277/10 277/34 277/34 277/36 277/36 277/64 277/64 277/72 277/72 277/84 277/84 285/125 295/18 A 295/18 339/04 339/04 401/06 231 401/06 231 401/12 257 401/12 257 403/12 249 403/12 249 413 / 06 215 413/06 215 233 233 413/14 215 413/14 215 221 221 231 231 417 417/06 209 417/06 209 215 215 235 235 263 263 263 417/08 263 417 417 263 417 417/12 211 417/12 211 213 213 417/14 215 417/14 215 217 217 231 231 263 263 263 421/06 421/06 513/04 301 513/04 301 C09B 23/00 L C09B 23/00 C07D 213/56 // C07D 213/56 213/75 213/75 213/77 213/77 213/82 213/82 249/12 510 249/12 510 249/18 501 501 249/18 501 257/04 L 257/04 285/1 2D

Claims (10)

[Claims] In a photothermographic material having at least one photosensitive layer, an organic silver salt, a silver halide, a reducing agent, a hydrazine compound represented by the general formula (H), and a compound represented by the general formula (DI) or A photothermographic material comprising a compound represented by formula (D-II). General formula (H) [Wherein, R ¹ represents an aliphatic group, an aromatic group, or a heterocyclic group, and R ² represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group, or a hydrazino group. G ¹ represents a -CO- group, -SO ₂ -group, -SO-
Group, -P (= O) (-R ³ )-group, -CO-CO- group, thiocarbonyl group,
Or represents an imino methylene group, A ¹ and A ² are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted Represents an acyl group. R ³ is selected from the same range as the groups defined in R ^2, may be different from R ^2. General formula (DI) [Wherein, R ₃₁ and R ₃₂ may be the same or different, and each represents an alkyl group. R ₃₃ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. V represents a hydrogen atom, a lower alkyl group, an alkoxy group, a halogen atom or a substituted alkyl group. Z ₁ represents a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring. X ₁ represents an acid anion. p and q each independently represent 1 or 2. However, q is 1 when the dye forms an inner salt. General formula (D-II) In the formula, R ₃₁ ′ and R ₃₂ ′ may be the same or different, and each represents an alkyl group. R ₃₃ 'and
R ₃₄ ′ each independently represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. R ₃₅ ′ and R ₃₆ ′ each represent a hydrogen atom,
Alternatively, R ₃₅ ′ and R ₃₆ ′ are linked to form a divalent alkylene group. R ₃₇ ′ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group, or —NW ₁ ′
(W ₂ ′). Here, W ₁ ′ and W ₂ ′ each independently represent an alkyl group or an aryl group, and W ₁ ′ and W ₂ ′ may be linked to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. it can. The R _{3 3} 'and R _37' or
R ₃₄ ′ and R ₃₇ ′ may be linked to form a divalent alkylene group. Z ′ and Z ₁ ′ each independently represent a nonmetallic atom group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring. X ₁ represents an acid anion, and m ′ represents 1 or 2. However, when the dye forms an inner salt, m ′ is 1
It is. 2. A photothermographic material having at least one photosensitive layer, comprising an organic silver salt, a silver halide, a reducing agent, a hydrazine compound represented by the general formula (H), and a compound represented by the general formula (D-III). A heat-developable photographic light-sensitive material comprising a compound represented by the formula: General formula (D-III) [Wherein, R ₄₁ represents an alkyl group. Z ₂ is a 5-membered ring or 6
Represents an atom group necessary for forming a nitrogen-containing heterocyclic ring.
D and Da represent an atomic group necessary for forming an acyclic or cyclic acidic nucleus. L ₄₁ , L ₄₂ , L ₄₃ , L ₄₄ , L ₄₅ and L ₄₆ represent a methine group. M ₁ represents a charge neutralizing counter ion, and m ₁ is a number of 0 or more necessary to neutralize the charge in the molecule. i represents 0 or 1. ] 3. A photothermographic material having at least one photosensitive layer, comprising an organic silver salt, a silver halide, a reducing agent, a hydrazine compound represented by the general formula (H), and a hydrazine compound represented by the general formula (D-IV). A heat-developable photographic light-sensitive material comprising a compound represented by the formula: General formula (D-IV) [Wherein, Z ₃ and Z ₄ each represent a non-metallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic nucleus. R ₅₀ and R ₅₁ each represent an alkyl group, a substituted alkyl group, or an aryl group. Q and Q ₁ together represent the non-metallic atoms required to complete a 4-thiazolidinone, 5-thiazolidinone or 4-imidazolidinone nucleus. L ₅₀ , L ₅₁ ,
L ₅₂ , L ₅₃ and L ₅₄ each represent a methine group or a substituted methine group. L ₅₀ and L ₅₂ or L ₅₁ and L ₅₃ may form a 5- or 6-membered ring. n ₁ and n ₂ are each 0 or 1
Represents x represents an anion. r represents 0 or 1,
When an inner salt is formed, r = 0. ] 4. A photothermographic material having at least one photosensitive layer, comprising an organic silver salt, a silver halide, a reducing agent, a hydrazine compound represented by the general formula (H), and a compound represented by the general formula (DV). A heat-developable photographic light-sensitive material comprising a compound represented by the formula: General formula (D-V) [Wherein Y ₁ and Y ₂ each independently represent a group of non-metallic atoms necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and these heterocyclic rings may have a substituent. . R ₆₁ and R
₆₂ represents a substituted or unsubstituted lower alkyl group which may be the same or different. R ₆₃ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a phenyl group, a benzyl group or a phenethyl group. X ₁ represents an acid anion.
n ₁ and n ₂ independently represent 0 or 1. s represents 0 or 1, and in the case of an inner salt, s = 0. ] 5. A photothermographic material having at least one photosensitive layer, comprising an organic silver salt, a silver halide, a reducing agent, a hydrazine compound represented by the general formula (H), and a hydrazine compound represented by the general formula (D-VI). A heat-developable photographic light-sensitive material comprising a compound represented by the formula: General formula (D-VI) [Wherein, Y ¹ , Y ² and Y ³ each independently represent a —N— (R ¹⁰ ) — group, an oxygen atom, a sulfur atom or a selenium atom. R ¹⁰ , R ¹¹ ,
R ¹² and R ¹³ each represent an aliphatic group, an aryl group, or a heterocyclic group. V ¹ and V ² each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or a group bonded to V ¹ and V ² to form a condensed ring with an azole ring; L ¹ , L ² , L ³ and
L ⁴ each independently represents a substituted or unsubstituted methine carbon. n3 represents 1 or 2, and m3 represents 0 or 1. M ¹ represents an ion necessary to offset the total charge of the molecule, and n4 represents a number required to neutralize the charge of the molecule. ] 6. A photothermographic material according to claim 1, wherein the compound represented by formula (D-1) is used. 7. The method according to claim 2, wherein G ¹ in the general formula (H) is
Is -CO-, R ² is an alkyl group, an aryl group,
A heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, wherein G ¹ is a —SO ₂ — group,
An O— group, a —P (＝ O) (R ³ ) — group, a —COCO— group,
A thiocarbonyl group or an iminomethylene group;
² is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
A photothermographic material comprising an alkoxy group, an aryloxy group, an amino group or a hydrazino group. 8. The method according to claim 6, wherein G ¹ in the general formula (H) is
Is -CO-, R ² is an alkyl group, an aryl group,
A heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group, wherein G ¹ is a —SO ₂ — group,
O- group, -P (= O) (- R 3) - group, -COCO-
Wherein R ² is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group when the group is a thiocarbonyl group or an iminomethylene group; Photosensitive material. 9. The method according to claim 7, wherein G ¹ in the general formula (H) is
There represents -CO-, R ² represents an alkyl group, heat-developable photographic material, characterized in that A ¹ and A ² are both hydrogen atoms. 10. The method according to claim 8, wherein G of the general formula (H) is
¹ represents -CO-, R ² represents an alkyl group, heat-developable photographic material, characterized in that A ¹ and A ² are both hydrogen atoms.