JPH09292671A - Heat-developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the heat-developable photosensitive material high in sensitivity and ultrahigh in contrast and high in Dmax by incorporating a specified hydrazine compound in the heat-developable photosensitive material containing an organic silver salt and photosensitive silver halide and a reducing agent. SOLUTION: The heat-developable photosensitive material contains 2 kinds of the hydrazine compounds represented by formula I and II in which R1 is an aliphatic or aromatic group; both of A1 and A2 are H atoms or one of them is an H atom and the other is an alkylsulfonyl or arylsulfonyl or acyl group; R2 is a blocking group except H atom; G1 is a -CO- or -SO2 - or -SO group or a group of formula III or a -CO-CO- or thiocarbonyl or iminomethylene group; R3 is same as R2 ; when G1 is a -CO- group, R1 in formula II is an aromatic group and when G1 is not a -CO group, it is an aliphatic group.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a photothermographic material and, more particularly, to a photothermographic material suitable for printing plate making.

[0002]

2. Description of the Related Art A photothermographic material for forming a photographic image by using a heat development processing method is disclosed, for example, in US Pat. No. 3,152,904.
No. 3457075 and D.I. Morgan and B. "Thermally Processed Silver Systems" by Shely (Imaging Processes and Materials (I
maging Processes and Materials) Neblette 8th Edition, Sturge, V.I. Walworth, A.
Shepp, page 2, 1969.

[0003] Such a photothermographic material generally comprises a reducible silver source (for example, an organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide), a color tone controlling agent for controlling the color tone of silver, and a reducing agent. It is contained in a dispersed state in the matrix. Although the photothermographic material is stable at room temperature, it can be reduced by a redox reaction between a silver source (which functions as an oxidizing agent) and a reducing agent when heated to a high temperature (for example, 80 ° C. or higher) after exposure. Produces 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.

[0004] Such a photothermographic material has been used as a photosensitive material for micros and a medical photosensitive material for X-rays, but is only partially used as a photosensitive material for printing. It has a low Dmax of the obtained image,
This is because the gradation is soft and the image quality is remarkably poor as a photosensitive material for printing.

On the other hand, with the recent development of lasers and light-emitting diodes, scanners and imagesetters having an oscillation wavelength of 600 to 800 nm have become widespread, and the sensitivity, Dmax and high contrast suitable for these output machines are high. The development of wood was strongly desired. Also, demands for simple processing and dry processing are increasing.

[0006] US Patent No. 5,647,738 describes that use of sulfonyl hydrazide as a reducing agent for dry silver provides a high-contrast image. However, development does not occur unless the development temperature and the temperature of 136 to 142 ° C. are extremely high.

US Pat. No. 5,496,695 describes that a high contrast image can be obtained by using a combination of hindered phenol and formyl hydrazine or trityl hydrazine as dry silver reducing agents. However, even with such a combination of reducing agents, in order to obtain a high contrast image, 250 ° F (121 ° C) or 280 ° F (1
High temperature of 38 ° C) is required.

[0008] One of the most important performances required for a printing plate-making photosensitive material is dimensional stability. When the development temperature becomes high, the plastic film used as the support undergoes heat shrinkage, and the dimensions change. In particular, when the temperature is 120 ° C. or higher, the fluctuation becomes larger. Therefore, it is desired to obtain a high contrast image at a temperature of 120 ° C. or less.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to provide sensitivity,
An object of the present invention is to provide a photothermographic material having ultrahigh contrast and high Dmax.

An object of the present invention is to provide a photosensitive material for printing plate making which has a good image quality.

Another object of the present invention is to provide a completely dry processed photosensitive material for printing plate making which does not require wet processing.

[0012]

The above object of the present invention is to provide a photothermographic material containing an organic silver salt, a photosensitive silver halide and a reducing agent, and a hydrazine compound represented by the general formula (I) and a general formula ( And a hydrazine compound represented by II).

[0013]

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Here, R ₁ represents an aliphatic group or an aromatic group, and A ₁ and A ₂ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents an alkylsulfonyl group, an arylsulfonyl group or an acyl group.

[0015]

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A ₁ ′ and A ₂ ′ have the same definitions as R ₁ , A ₁ and A ₂ in the general formula (I), R ₂ is a block group other than a hydrogen atom, and G ₁ is —CO—. group, -SO ₂ -
Group, -SO- group,

[0017]

[Chemical 6]

It represents a --CO--CO-- group, a thiocarbonyl group, or an iminomethylene group, and R ₃ is selected from the same range as the group defined for R ₂ , provided that in R ₁ ′, G ₁ is --CO.
In the case of -group, it represents an aromatic group, and when G ₁ is other than that, it represents an aliphatic group or an aromatic group.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrazine compound represented by the general formula (I) will be described in more detail.

In the general formula (I), the aliphatic group represented by R ₁ preferably has 1 to 30 carbon atoms,
Particularly, it is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Here, the branched alkyl group may be cyclized to form a saturated heterocycle containing one or more heteroatoms therein. Further, this alkyl group may have a substituent.

In the general formula (I), the aromatic group represented by R ₁ is a monocyclic or bicyclic aryl group or an unsaturated heterocyclic group. Here, the unsaturated heterocyclic group may be condensed with a monocyclic or bicyclic aryl group to form a heteroaryl group. For example, benzene ring, naphthalene ring, pyridine ring, pyrimidine ring, imidazole ring, pyrazole ring,
Quinoline ring, isoquinoline ring, benzimidazole ring,
There are a thiazole ring, a benzothiazole ring and the like, and among them, those containing a benzene ring are preferable.

Particularly preferred as R ₁ is an aryl group.

The aliphatic group or aromatic group of R ₁ may be substituted, and typical examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocycle, a pyridinium group, Has a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, an alkyl or aryl sulfonyloxy group, an amino group, a carbonamide group, a sulfonamide group, a ureido group, a thioureido group, a semicarbazide group, a thiosemicarbazide group, a urethane group, and a hydrazide structure. Group, group having quaternary ammonium structure, alkyl or arylthio group, alkyl or aryl sulfonyl group, alkyl or aryl sulfinyl group, carboxyl group, sulfo group, acyl group,
Alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl group, halogen atom, cyano group,
A nitro group, a nitrosyl group, a phosphoric acid amide group, a diacylamino group, an imide group, a group having an acylurea structure, a group containing a selenium atom or a tellurium atom, a group having a tertiary sulfonium structure or a quaternary sulfonium structure, and the like.
Preferred substituents are a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably a monocyclic or bicyclic alkyl moiety having 1 to 3 carbon atoms), An alkoxy group (preferably having 1 carbon atom)
To 20), a substituted amino group (preferably having 1 to carbon atoms)
An amino group substituted with an alkyl group of 20), an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 30 carbon atoms),
Ureido group (preferably having 1 to 30 carbon atoms),
And a phosphoric amide group (preferably having 1 to 30 carbon atoms).

A ₁ and A ₂ are a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group, or the sum of Hammett's substituent constants is-).
A phenylsulfonyl group substituted so as to have a value of 0.5 or more; an acyl group having 20 or less carbon atoms (preferably a benzoyl group or a substituent having a sum of Hammett's substituent constants of -0.5 or more); A benzoyl group or a linear, branched or cyclic unsubstituted or substituted aliphatic acyl group (for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, a sulfonic acid group; ))).

Hydrogen atoms are most preferred as A ₁ and A ₂ .

R ₁ ′, A ₁ ′ and A ₂ ′ in the general formula (II) are selected from the same definition range as the above R ₁ . R ₂ is a block group other than a hydrogen atom, specifically, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group.

In the general formula (II), the alkyl group represented by R ₂ is preferably an alkyl group having 1 to 4 carbon atoms, and the aryl group is preferably a monocyclic or bicyclic aryl group, for example benzene. It contains a ring.

The unsaturated heterocyclic group is a compound having a 5- or 6-membered ring containing at least one nitrogen, oxygen and sulfur atom, for example, an imidazolyl group, a pyrazolyl group, a triazolyl group, a tetrazolyl group, a pyridyl group, a pyridinium group, Examples include quinolinium group and quinolyl group. Pyridyl or pyridinium 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 group, the unsubstituted amino group is an amino group, and the alkylamino group having 1 to 10 carbon atoms. A group and an arylamino group are preferred.

R ₂ may be substituted, and as the preferable substituent, those exemplified as the substituent of R ₁ are applicable.

Preferred among the groups represented by R ₂ are alkyl groups (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfone) when G ₁ is --CO-- group. Amidopropyl group, phenylsulfonylmethyl group etc.), aralkyl group (eg o-hydroxybenzyl group etc.), aryl group (eg phenyl group, 3,5-dichlorophenyl group, o-
Methanesulfonamidophenyl group, 4-methanesulfonylphenyl group, 2-hydroxymethylphenyl group, etc.), —C ₂ F ₄ COOM (M: hydrogen atom, alkali metal atom) and the like.

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

When G ₁ is a --COCO-- group, an alkoxy group, an aryloxy group and an amino group are preferred.

As G _{1 in the} general formula (II), --CO--
Group, -SO ₂ - group, -SO- group, - (P = O) R 3 -
Group, thiocarbonyl group, iminomethylene group,
A CO- group and a -COCO- group are preferable.

[0035] Also, R ₂ is be as occurring cyclization reaction to form a cyclic structure containing disrupts portion of G ₁ -R ₂ from the remainder molecule, -G ₁ -R ₂ moiety of atoms Examples thereof include those described in JP-A-63-29751.

A hydrazine derivative having at least one nitro group or nitrosyl group in R ₁ , R ₁ 'or R ₂ is preferred. Particularly, those having at least one nitro group or nitrosyl group in R ₁ and R ₁ ′ are preferable.

The substituents of R ₁ , R ₁ ′ and R ₂ may be further substituted, and preferable examples thereof include those exemplified as the substituent of R ₁ . Further, the substituents, the substituents of the substituents, the substituents of the substituents of the substituents, etc. may be multiply substituted, and preferable examples are those exemplified as the substituent of R _1. This is true.

R ₁ , R ₁ 'or R ₂ in the general formulas (I) and (II) have a ballast group or polymer incorporated therein which is commonly used in non-moving photographic additives such as couplers. But it's okay. 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 , R ₁ ′ or R ₂ in the general formulas (I) and (II) may be one in which a group for enhancing adsorption to the surface of silver halide grains is incorporated. Examples of the adsorptive group include alkylthio groups, arylthio groups, thiourea groups, heterocyclic thioamide groups, mercaptoheterocyclic groups, and triazole groups, which are disclosed in U.S. Pat. Nos. 4,385,108 and 4,459,347. Sho 59-195233,
Nos. 59-200231, 59-201045, 59-201046, 59-201047, and 5
9-201048, 59-201049, JP-A-61-170733, 61-270744 and 6
2-948, 63-234244, 63-23
The groups described in Nos. 4245 and 63-234246 are mentioned.

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

[0041]

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[0042]

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

[0044]

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[0045]

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[0046]

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[0047]

[Chemical 12]

[0048]

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[0049]

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[0050]

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The addition amount of the hydrazine compound in the present invention is preferably 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per 1 mol of total silver including the organic silver salt and silver halide, Especially 1 × 10 ⁻⁵ mol to 5
The preferable addition amount is in the range of ^{x10 -2} mol.

The addition ratio of the hydrazine compound of the general formula (I) and the hydrazine compound of the general formula (II) is 1: 1 by weight.
10 ³ to 10 ³ : 1, preferably 1:10 ² to 10 ² :
It is one.

The hydrazine derivative in the present invention is dissolved in a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like. Can be used.

By a well-known emulsification and dispersion method, oils such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are used to dissolve and mechanically dissolve them. An emulsified dispersion can be prepared and used. Alternatively, the hydrazine derivative powder may be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves according to a method known as a solid dispersion method.

In the present invention, in combination with a hydrazine derivative,
It is preferable to use indazoles (for example, nitroindazole) as an antifoggant.

It is preferable to add a nucleation accelerator such as an amine derivative, an onium salt compound, a disulfide derivative and a hydroxyamine derivative to the light-sensitive material in combination with the hydrazine derivative.

As a compound example of the nucleation accelerator, Japanese Patent Application No. 7-
A-1 to A-47 described in JP-A-266204.

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 .about.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 utilizing organic silver salts. For example, amidoximes such as phenylamidooxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehyde azine; 2,2'-bis (hydroxymethyl) propionyl. A combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid, such as a combination of -β-phenylhydrazine and ascorbic acid; polyhydroxybenzene and hydroxylamine,
A combination of reductone and / or hydrazine, such as a combination of hydroquinone with bis (ethoxyethyl) hydroxylamine, piperidinohexose reductone or formyl-4-methylphenylhydrazine;
Hydroxamic acids such as phenylhydroxamic acid, p-hydroxyphenylhydroxamic acid and β-alinine hydroxamic acid; combinations of azine and sulfonamidophenol (e.g., phenothiazine and 2,6-dichloro-
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-β as exemplified by bis (2-hydroxy-1-naphthyl) methane.
-Naphthol; a combination of bis-β-naphthol and a 1,3-dihydroxybenzene derivative (for example, 2,4-dihydroxybenzophenone or 2 ', 4'-dihydroxyacetophenone); 3-methyl-1-phenyl-5
5-pyrazolones, such as pyrazolones; reductones as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone;
Sulfonamidophenol reducing agents such as 2,6-dichloro-4-benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione and the like; 2,2-dimethyl-7-t
Chromans such as -butyl-6-hydroxychroman;
2,6-dimethoxy-3,5-dicarbethoxy-1,
1,4-dihydropyridines such as 4-dihydropyridine; bisphenols (for example, 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)
Ascorbic acid derivatives (e.g., 1-ascorbyl palmitate, ascorbyl stearate, etc.); and aldehydes and ketones such as benzyl and biacetyl; 3-pyrazolidone and certain indan-1,3-diones. and so on.

Particularly preferred reducing agents in the present invention are the following formulas (RI), (R-II), (R-III) and (RI).
Examples thereof include compounds represented by V).

[0061]

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[0062]

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[0063]

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[0064]

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The ring structure formed by Z in formula (R-III) is as follows.

[0066]

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The ring structure formed by Z in the formula (R-IV) is as follows.

[0068]

[Chemical 21]

In the formula, L ₁ and L ₂ are a group represented by CH-R ₆ or a sulfur atom. n represents a natural number.

R (R _{1 to} R ₁₀ , R ₁ ′ to R ₅ ′, R ₁₁ to
R ₁₃ , R ₁₁ ′ to R ₁₃ ′, R _{21 to} R ₂₆ R ₂₁ ′ to R ₂₄ ′) is a hydrogen atom, an alkyl group (having 1 to 30 carbon atoms), an aryl group, an aralkyl group, a halogen atom, It is a substituent represented by an amino group or -OA. However, R ₁ ~
At least one of the at least one and R ₇ to R ₁₀ in at least one and R ₁ '~R _5' of R ₅ is a group represented by -O-A. Further, R may form a ring with each other.
A and A 'each represent a hydrogen atom or an alkyl group (having 1 to 3 carbon atoms).
0), 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, alkyl groups (including active methine groups), nitro groups, alkenyl groups, alkynyl groups, aryl groups, groups containing heterocycles, A group containing a quaternary heterocycle 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 Group,
Alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, urethane group, carboxyl group, imide group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group A group containing a hydrazino group, a group containing a quaternary ammonio group, a mercapto group, a (alkyl, aryl, or heterocycle) thio group, a (alkyl or aryl) sulfonyl group, a (alkyl or aryl) sulfinyl group, a sulfo group, Sulfamoyl group, acylsulfamoyl group, (alkyl or aryl) sulfonylureido group, (alkyl or aryl) sulfonylcarbamoyl group, halogen atom, cyano group, phosphoramide group, group containing phosphate ester structure, acyl Group having a rare structure, a group containing a selenium atom or a tellurium atom, and a group having a tertiary sulfonium structure or a quaternary sulfonium structure. R,
The substituents of A and A'may be further substituted, and preferable examples thereof include those exemplified as the substituent of R. Further, the substituents, the substituents of the substituents, the substituents of the substituents of the substituents, etc. may be multiply substituted, and preferable examples are also the substituents of R, A and A ′. The examples given apply.

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

[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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

The amount of the reducing agent used in the present invention is preferably silver 1.
1 × 10 ⁻² to 10 mol per mol, particularly 1 × 10 ⁻² to 1.
5 moles.

Further, in the present invention, it is preferable to set the molar ratio of the reducing agent and the contrast-increasing agent in the range of 1:10 ^-3 to 1:10 ^-1 .

The photothermographic material of the present invention forms a photographic image by using the photothermographic processing method. Such a photothermographic material is disclosed in, for example, US Pat.
Nos. 152904, 3457075 and D.I. Morgan and B. `` Thermally Processed SilverSys '' by Shely
tems) "(Imaging Processes and Materials) Neblet
te 8th Edition, Sturge, V.T. Wallworth (W
alworth), A. Edited by Shepp, page 2, 196
9 years).

The heat-developable light-sensitive material of the present invention may be any one capable of forming a photographic image by using a heat-development treatment, including a reducible silver source (organic silver salt) and a catalytically active amount of a photocatalyst (eg, halogenated compound) It is preferable that the photothermographic material contains silver), a toning agent that suppresses the color tone of silver, and a reducing agent, usually in a state of being dispersed in an (organic) binder matrix.
The photothermographic material of the present invention is stable at normal temperature, but can be heated to a high temperature (for example, 60 ° C. or more,
Development is performed by heating to preferably 80 ° C. or higher, and preferably 120 ° C. or lower). Heating produces silver through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and the reducing agent. 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.

In the present invention, it is considered that a high contrast agent is involved in this image forming process to form an ultrahigh contrast image. Although ultra-high contrast image formation by a high contrast agent is known in a liquid processing system, it is not known at all in a heat development system using an organic silver salt and is unexpected.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer.

For controlling the amount or wavelength distribution of light passing through the photosensitive layer, a filter layer may be formed on the same side as or opposite to the photosensitive layer, or a dye or pigment may be included in the photosensitive layer. . As the dye, a compound described in Japanese Patent Application No. 7-11184 is preferred.

The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be a high sensitivity layer / low sensitivity layer or a low sensitivity layer / high sensitivity layer for adjusting gradation.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers.

The photothermographic material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

Suitable binders are transparent or translucent, generally colorless, and natural polymer synthetic resins, polymers and copolymers, and other film-forming media, for example:
Gelatin, gum arabic, poly (vinyl alcohol),
Hydroxyethyl cellulose, 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)
(Eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), There are poly (vinyl acetate), cellulose esters, and poly (amide) s. The binder may be coated from water or an organic solvent or emulsion.

The addition of toning agents is highly desirable. Examples of suitable toning agents are disclosed in Research Report No. 17029,
There are the following: imides (eg, phthalimide);
Cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline, and 2,4-thiazolidinedione); naphthalimides (eg, , N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3-mercapto-1,2,4-triazole); N
-(Aminomethyl) aryldicarboximides (eg, N- (dimethylaminomethyl) phthalimide);
The blocked pyrazoles, isothiuronium (isoth
iuronium) combinations of derivatives and certain photobleaches (eg, N, N'hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-
A combination of dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl-2-benzothia) Zolinylidene (benzothiazolinylidene) -1
-Methylethylidene) -2-thio-2,4-oxazolidinedione); phthalazinone, phthalazinone derivatives or metal salts of these derivatives (e.g.,
4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro-1,4-phthalazinedione; a combination of phthalazinone and a sulfinic acid derivative (eg, ,
6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); combination of phthalazine + phthalic acid; phthalazine (including adduct of phthalazine), maleic anhydride, and phthalic acid , 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and their anhydrides (for example,
Phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride) in combination with at least one compound; quinazolinediones, benzoxazine, naltoxazine derivatives; benzoxazine-2,4-dione (Eg 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg 2,4-dihydroxypyrimidine), and tetraazapentalene derivatives (eg
3,6-dimerocapto-1,4-diphenyl-1H, 4
H-2,3a, 5,6a-tetraazapentalene.

A preferred toning agent is phthalazone.

Silver halide useful as a catalytically active amount of photocatalyst can be any photosensitive silver halide (eg, silver bromide, silver iodide, silver silver, silver chlorobromide, silver iodobromide, chloroiodoodore). Silver iodide), but preferably contains iodine ions. The silver halide may be added to the imaging layer in any manner, with the silver halide being placed in close proximity to the reducible silver source. In general, it is preferred that the silver halide contains from 0.75 to 30% by weight, based on the reducible silver source. Silver halide may be prepared by conversion of the silver soap portion by reaction with a halide ion, may be preformed and added during the generation of the soap, or a combination of these methods is possible. The latter is preferred.

The reducible silver source is a silver salt of an organic or hetero organic acid containing a reducible silver ion source, especially a long chain (10
Aliphatic carboxylic acids of up to 30 (preferably 15 to 25 carbon atoms) are preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. An example of a suitable silver salt is Research Dis
closures described in 17029 and 29996, and include: salts of organic acids (eg, gallic acid,
Oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salt of silver (for example, 1- (3-carboxypropyl) thiourea, 1-
(3-carboxypropyl) -3,3-dimethylthiourea, etc.); silver complexes of polymer reaction products of aldehydes and hydroxy-substituted aromatic carboxylic acids (for example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids) (Eg, salicylic acid,
Benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4- (thiazoline-2). -Thioene, and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4- Complexes or salts of silver with a nitric acid selected from triazoles and benzotriazoles; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides, the preferred silver source being silver behenate. The preferable silver source is 3 g / m ^{2 in} terms of silver amount.
It is as follows. More preferably, it is 2 g / m ² or less.

Such a light-sensitive material may contain an antifoggant. The most effective antifoggant was mercury ion. The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat.
No. 03. However, mercury compounds are environmentally unfavorable. As the non-mercury antifoggant, antifoggants such as those disclosed in U.S. Pat. Nos. 4,454,075 and 4,452,885 and Japanese Patent Publication No. 59-57234 are preferred.

Particularly preferred non-mercury antifoggants are compounds such as those 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 are halogens (eg, F, Cl,
In Br and I), X ³ is represented by hydrogen or halogen) 1
It is a heterocyclic compound having the above substituents. Examples of suitable antifoggants include:

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[0099]

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Still more suitable antifoggants are disclosed in US Pat. No. 5,028,523 and British Patent Application No. 9222138.
3.4, 9300147.7, 93111790.1
Issue.

The photothermographic materials of the present invention include, for example, JP-A-63-159814, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, and JP-A-6-259561.
Nos. 3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, and 4,419.
Sensitizing dyes described in JP-A Nos. 66, 4751175 and 48335096 can be used.

Useful sensitizing dyes for use in the present invention are described, for example, in RESEARCH DISCLOSURE Item 17643 IV-A (1
December 978, p. 23), Item 1831X (1
August 978, p. 437) or in the literature cited.

In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected.

For example, A) Japanese Patent Application Laid-Open No. 60-162247 and Japanese Patent Application Laid-Open No.
No. 3, U.S. Pat. No. 2,161,331, West German Patent 93
6,071 and simple merocyanines described in Japanese Patent Application No. 3-189532; B) For helium-neon laser light sources, see JP-A-50-62425 and JP-A-54-18.
No. 726, No. 59-102229, trinuclear cyanine dyes, Japanese Patent Application No. 6-103272, merocyanines, C) LED light source and red semiconductor laser. Id. 51-9609
And JP-A-55-39818.
Thiacarbocyanines described in JP-A-2-105135 and D) Tricarbocyanines described in JP-A-59-19032 and JP-A-60-80841 for infrared semiconductor laser light sources. Kind, JP-A-59-19
2242 and the general formula (III of JP-A-3-67242)
a), dicarbocyanines containing a 4-quinoline nucleus described in the general formula (IIIb) and the like are advantageously selected.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of 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.

Exposure of the photothermographic material of the present invention is performed by using an Ar laser (488 nm) and a He-Ne laser (633n).
m), red semiconductor laser (670 nm), infrared semiconductor laser (780 nm, 830 nm) and the like are preferable.

The photothermographic material of the present invention may be provided with a dye-containing layer as an antihalation layer.
For Ar laser, He-Ne laser, and red semiconductor laser, a dye is added so as to absorb at least 0.3 or more, preferably 0.8 or more at the exposure wavelength in the range of 400 nm to 750 nm. 75 for infrared semiconductor lasers
In the range of 0 nm to 1500 nm, the exposure wavelength is at least 0.1 nm.
The dye is added so as to have an absorption of 3 or more, preferably 0.8 or more. One or more dyes may be used in combination.

The dye can be added to the dye layer near the support on the same side as the photosensitive layer or to the dye layer on the side opposite to the photosensitive layer.

The support used in the present invention is paper, synthetic paper, paper laminated with a synthetic resin (eg, polyethylene, polypropylene, polystyrene), plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate). A metal plate (for example, aluminum, an aluminum alloy, zinc, iron, or copper), a paper or a plastic film on which the above-described metal is laminated or vapor-deposited, or the like is used.

On the other hand, when the plastic film is passed through a heat developing machine, the dimensions of the film expand and contract. When used as a printing photosensitive material, this expansion and contraction is a serious problem when performing precision multicolor printing. Therefore, in the present invention, it is preferable to use a film having a small dimensional change. For example, there are a styrene-based polymer having a syndiotactic structure and a heat-treated polyethylene. Those having a high glass transition point are also preferable, and polyether ethyl ketone, polystyrene, polysulfone, polyether sulfone, polyarylate and the like can be used.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained for the purpose of suppressing or accelerating the development and controlling the development, improving the spectral sensitization efficiency, and improving the storage stability before and after the development. be able to.

When the mercapto compound is used in the present invention, it may have any structure, but Ar-SM, Ar
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, nafusuimidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzotelrazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine. , Pyrazine, pyridine, purine, quinoline or quinazolinone. The heteroaromatic ring is, for example, halogen (eg Br and Cl), hydroxy, amino, carboxy, alkyl (eg having 1 or more carbon atoms, preferably 1 to 4 carbon atoms) and alkoxy ( For example, it may have one selected from the group of substituents consisting of one or more carbon atoms, preferably having 1 to 4 carbon atoms). Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole and 2-mercaptobenzimidazole.
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-mercaptopurine 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-hydroxy-2-mercaptopyrimidine, 2-mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, 2-mercapto-
Examples include 4-methylpyrimidine hydrochloride, 3-mercapto-5-phenyl-1,2,4-triazole, 2-mercapto-4-phenyloxazole, and the like, but the 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, and more preferably 0.01 to 0.3 mol per mol of silver. Is the amount of.

The method of forming the photosensitive silver halide in the present invention is well known in the art and described in, for example, Research Disclosure, June 1978, No. 17029, and US Pat. No. 3,700,458. Can be used. As a specific method that can be used in the present invention, a method of converting a part of silver of the organic silver salt into a photosensitive silver halide by adding a halogen-containing compound to the prepared organic silver salt, gelatin, Alternatively, a method in which a photosensitive silver halide grain is prepared by adding a silver-supplying compound and a halogen-supplying compound to another polymer solution and mixed 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 to be low, specifically 0.20 μm or less, more preferably 0.1 μm or less.
01 μm or more and 0.15 μm or less, more preferably 0.01 μm or less
The thickness is preferably 2 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,
Examples thereof include octahedra, tabular grains, spherical grains, rod-shaped grains and potato-shaped grains. In the present invention, cubic grains and tabular grains are particularly preferable. The average aspect ratio when using tabular silver halide grains is preferably 100: 1 to 2: 1, more preferably 50: 1 to 3: 1.
Is good. 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 grains is not particularly limited. However, the spectral sensitization efficiency when the spectral sensitizing dye is adsorbed is high. preferable. The ratio is preferably 50% or more, and 65%
The above is more preferable, and 80% or more is further preferable. The ratio of Miller index {100} planes is based on the adsorption dependence of {111} planes and {100} planes in the adsorption of sensitizing dyes.
T. Tani; J. Imaging Sci., 29, 165 (1985)
It can be determined by the method described in. The halogen composition of the photosensitive silver halide is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide, and silver iodide. In the present invention, silver bromide or silver iodobromide can be preferably used. Particularly preferred is silver iodobromide, and the silver iodide content is preferably from 0.1 mol% to 40 mol%,
More preferably, it is at least 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 grain of the present invention preferably contains at least one metal complex selected from rhodium, rhenium, ruthenium, osmium, iridium, cobalt or iron. These metal complexes are 1
One kind may be used, or two or more kinds of same metal and different metal complexes may be used in combination. The preferred content is 1 per mol of silver
The range is preferably from nmol to 10 mmol, more preferably from 10 nmol to 100 μmol. 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. cobalt,
For the iron compound, a hexacyano metal complex can be preferably used. Specific examples include ferricyanate ion, ferrocyanate ion, hexacyanocobaltate ion, and the like, but are not limited thereto. Even if the phase containing the metal complex in the silver halide is homogeneous,
It may be contained in the core portion at a high concentration, or may be contained in the shell portion at a high concentration without any particular limitation.

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

The photosensitive silver halide grains in the 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, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, P = Te Compounds having a bond, tellurocarboxylates, Te-organyl tellurocarboxylic acid esters, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having a P-Te bond, and Te
Heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, etc. can be used. Compounds preferably used in the noble metal sensitization method are described in, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, or US Pat. No. 2,448,060 and British Patent 618,061. The compounds described above can be preferably used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . Also, the pH of the emulsion should be 7 or more or pAg
Can be sensitized by reduction by aging while maintaining the value of 8.3 or less. Further, reduction sensitization can be performed by introducing a single addition portion of silver ions during grain formation.

The photosensitive silver halide of the present invention is used in an amount of 0.00 photosensitive silver halide per mol of the organic silver salt.
The amount is preferably 1 mol or more and 0.5 mol or less, more preferably 0.02 mol or more and 0.3 mol or less, and particularly preferably 0.03 mol or more and 0.25 mol or less. Regarding the mixing method and mixing conditions of the separately prepared photosensitive silver halide and organic silver salt, the prepared silver halide grains and organic silver salt are mixed with a high-speed stirrer, a ball mill, a sand mill, a colloid mill, a vibration mill, and a homogenizer. Method of mixing with etc.,
Alternatively, there is 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, and the like. However, there is no particular limitation as long as the effects of the present invention are sufficiently exhibited. There is no.

The photothermographic material of the present invention is a so-called single-sided photosensitive 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. Preferably there is.

In the present invention, the single-sided light-sensitive material may contain a matting agent for improving the 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, US Pat. Nos. 1,939,213 and 2,701,245.
No. 2,322,037, No. 3,262,782
No. 3,539,344, No. 3,767,448 and the like, organic matting agents described in each specification, Nos. 1,260,7.
72, 2,192,241, 3,257,20
No. 6, No. 3,370,951, No. 3,523,022
Nos. 3,769,020 and the like, which are well known in the art, such as the inorganic matting agents described in the respective specifications 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,
Examples of known cellulose derivatives such as polyethylene carbonate and polytetrafluoroethylene, such as methylcellulose, cellulose acetate and cellulose acetate propionate, and examples of starch derivatives such as carboxy starch, carboxynitrophenyl starch and urea-formaldehyde-starch reactants Gelatin hardened with a hardener and hardened gelatin obtained by coacervate hardening to form hollow microcapsules can be preferably used. Examples of inorganic compounds include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum oxide, barium sulfate, calcium carbonate, silver chloride desensitized by known methods,
Similarly, silver bromide, glass, diatomaceous earth and the like can be preferably used. 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. In practicing the present invention, 0.1 μm to 3 μm
It is preferable to use one having a particle size of 0 μm. Further, the particle size distribution of the matting agent may be narrow or wide. On the other hand, since the matting agent has a great influence on the haze and surface gloss of the light-sensitive material, the particle size, shape, and particle size distribution can be adjusted to the required state during the preparation of the matting agent or by mixing a plurality of matting agents. preferable.

In the present invention, the Bekk smoothness of the matting degree of the packing layer is preferably 250 seconds or less and 10 seconds or more, more preferably 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, the layer functioning as the outermost surface layer, or the layer close to the outer surface, and also the layer acting as a so-called protective layer. It is preferably contained.

Suitable binders for the backing layer in the present invention are transparent or translucent, generally colorless, and include natural polymers such as synthetic resins, polymers and copolymers, and other film forming media such as: gelatin, gum arabic, poly (vinyl). Alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methylmethacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (Styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (for example, poly (vinyl formal) and poly (vinyl butyral)), poly (ester) s, Po (Urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides),
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.

In the present invention, the backing layer preferably has a maximum absorption of 0.3 or more and 2 or less in a desired wavelength range, more preferably 0.5 or more and 2 or less of IR absorption and in the visible region. Is preferably 0.001 or more and less than 0.5, and more preferably an antihalation layer having an optical density of 0.001 or more and less than 0.3.

When the antihalation dye is used in the present invention, the dye has a desired absorption in a desired wavelength range and has a sufficiently small absorption in the visible region, and a preferable absorbance spectrum shape of the backing layer can be obtained. Any compound can be used. For example, compounds described in JP-A-7-13295, U.S. Pat. No. 5,380,635, and JP-A-2-68.
Compounds described in JP-A-539 / 1993, page 13, lower left column, line 1 to page 14, lower left column, line 9 and JP-A-3-24539, page 14, lower left column to page 16, right lower column can be mentioned. The invention is not limited to this.

It is also possible to use backside resistive heating layers such as those shown in US Pat. Nos. 4,460,681 and 4,374,921 in a photothermographic image system. it can.

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 the like. And mixtures.

The emulsion layer or the protective layer for the emulsion layer according to the present invention is described in US Pat.
It can be used in photographic elements containing light absorbing materials and filter dyes such as those described in US Pat. Nos. 274,782, 2,527,538 and 2,956,879. See also, for example, U.S. Pat.
The dye can be mordant as described in 2,699.

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. Nos. 2,992,101 and 2,701,245. Polymer beads, including beads of the type described in 1., and the like can be included. Further, the matt degree of the emulsion surface may be any value as long as stardust failure does not occur.
0 second or less is preferable, and especially 2000 to 10000 second is preferable.

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 copolymers, maleic anhydride copolymers, polystyrene and butadiene-styrene copolymers. 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 guide when at least the organic silver salt is retained, the ratio of the binder to the organic silver salt is 1
The range of 5: 1 to 1: 2, particularly 8: 1 to 1: 1 is preferred.

As a binder for the silver halide emulsion layer and other hydrophilic colloid layers, JP-A-2-18542 is known.
The binders described in the lower right line 1st to 20th lines of page 3 of the publication are used.

[0133]

【Example】

Example 1 << Preparation of Organic Silver Salt Emulsion >> 840 g of behenic acid and 95 g of stearic acid were added to 12 liters of water and 48 g of sodium hydroxide and 63 g of sodium carbonate were dissolved in 1.5 liters of water while maintaining the temperature at 90 ° C. Stuff was added. After stirring for 30 minutes, the temperature was raised to 50 ° C., 1.1 liter of 1% aqueous solution of N-bromosuccinimide was added, and then 2.3 liter of 17% aqueous solution of silver nitrate was gradually added with stirring. Further, the liquid temperature was set to 35 ° C., 1.5 liters of a 2% aqueous solution of potassium bromide was added over 2 minutes with stirring, and then the mixture was stirred for 30 minutes, and 2.4 liters of a 1% aqueous solution of N-bromosuccinimide was added. 1.2 with stirring to this aqueous mixture
After adding 3300 g of a butyl acetate solution of polyvinyl acetate by weight, the mixture was allowed to stand for 10 minutes, separated into two layers, and the aqueous layer was removed.
Further, the remaining gel was washed twice with water. The gel-like mixture of behenic acid / silver stearate and silver bromide thus obtained was dispersed in 1800 g of a 2.6% isopropyl alcohol solution of polyvinyl butyral (Denka Butyral # 3000-K manufactured by Denki Kagaku Kogyo Co., Ltd.), Furthermore, 600 g of polyvinyl butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo KK) and 300 g of isopropyl alcohol were dispersed together to form an organic silver salt emulsion (average minor axis 0.05
μm, average major axis 1.2 μm, and coefficient of variation 25%).

<< Preparation of Emulsion Layer Coating Solution >> Each chemical was added to the organic silver salt emulsion obtained above in an amount of the following amount per mol of silver. At 25 ° C., sodium phenylthiosulfonate 10 mg, 70 mg of dye a, 2-mercapto-5-methylbenzimidazole 2 g, 4-chlorobenzophenone-
21.5 g of 2-carboxylic acid, 580 g of 2-butanone and 220 g of dimethylformamide were added with stirring, and the mixture was left for 3 hours. Then, 8 g of 5-tribromomethylsulfonyl-2-methylthiadiazole, 6 g of 2-tribromomethylsulfonylbenzothiazole, 5 g of 4,6-ditrichloromethyl-2-phenyltriazine, 2 g of disulfide compound a, and Table 1 are shown. Add the ultra-high contrast agent and reducing agent RI-35, and add tetrachlorophthalic acid 5
g, Megafax F-176P (Dainippon Ink and Chemicals, Inc. fluorinated surfactant) 1.1 g, 2-butanone 590 g, and methyl isobutyl ketone 10 g were added with stirring.

The reducing agent was added in an amount of 0.3 mol per mol of silver. The hydrazine compound C-1 of the general formula (II) for comparison is as follows.

[0136]

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[0137]

[Table 1]

<< Emulsion Surface Protective Layer Coating Solution >> 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, 12.5 g of phthalazine,
0.3 g of Megafax F-176P, Sildex H31 (average size of spherical silica manufactured by Dokai Chemical Co., Ltd., 3 μm)
2 g, 7 g of sumidur N3500 (polyisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) dissolved in 3070 g of 2-butanone and 30 g of ethyl acetate were prepared.

<< Preparation of Support Having Back Surface >> On a polyethylene terephthalate film consisting of a moistureproof undercoat containing vinylidene chloride on both sides, a back layer and a back surface surface protective layer were prepared with an aqueous solution so that the coating amount was 1 m ² or less. Was simultaneously multilayer coated. Back layer coating amount is gelatin 1.5, p
-Sodium dodecylbenzene sulfonate 30 mg, 1,
2-bis (vinylsulfonylacetamide) ethane 10
0 mg, dye a 50 mg, dye b 100 mg, dye c 30 mg,
Dye is 50 mg, proxel is 1 mg, the back surface protective layer is 1.5 g of gelatin, 20 mg of polymethylmethacrylate having an average particle diameter of 2.5 μm, 15 mg of sodium p-dodecylbenzenesulfonate, 15 mg of sodium dihexyl-α-sulfosuccinate, 50 mg sodium acetate and 1 mg proxel.

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

The compounds used in the above are shown below.

[0142]

Embedded image

<Evaluation of Photographic Performance> After exposing the photographic material with a 633 nm He-Ne laser sensitometer, the photographic material was exposed to 10
After processing (developing) at 5 ° C. for 25 seconds, the obtained image was evaluated with a densitometer. The measurement results are Dmax and sensitivity (logarithm of exposure dose that gives a density 3.0 higher than Dmin).
Was evaluated. Also, the gradient of a straight line connecting the points of density 0.3 and 3.0 on the characteristic curve is shown as gradation γ.

The results are shown in Table 2.

[0145]

[Table 2]

From this table, the sample of the present invention is Dmi
It can be seen that a significantly high-contrast image was provided with low n, high sensitivity, and high Dmax.

[0147]

As described above, according to the present invention, a photothermographic material having high sensitivity, ultrahigh contrast and high Dmax can be obtained.

Further, when used as a plate-making photosensitive material for printing, excellent image quality can be obtained.

Further, it is possible to provide a plate-making photosensitive material for printing which does not require wet processing and can be completely dry processed.

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[Procedure amendment]

[Submission date] February 25, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

[0006] US Patent No. 5,647,738 describes that use of sulfonyl hydrazide as a reducing agent for dry silver provides a high-contrast image. However, development does not occur unless the development temperature is extremely high, such as 136 ° C to 142 ° C.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction contents]

[0044]

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[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0081

[Correction method] Deleted

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0110

[Correction method] Change

[Correction contents]

On the other hand, when the plastic film is passed through a heat developing machine, the dimensions of the film expand and contract. When used as a printing photosensitive material, this expansion and contraction is a serious problem when performing precision multicolor printing. Therefore, in the present invention, it is preferable to use a film having a small dimensional change. For example, there are a styrene-based polymer having a syndiotactic structure and a heat-treated polyester. Those having a high glass transition point are also preferable, and polyether ethyl ketone, polystyrene, polysulfone, polyether sulfone, polyarylate and the like can be used.

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Claims (1)

[Claims] 1. A photothermographic material containing an organic silver salt, a photosensitive silver halide, and a reducing agent, containing a hydrazine compound represented by the general formula (I) and a hydrazine compound represented by the general formula (II). A photothermographic material which is characterized by: General formula (I) (Here, R ₁ represents an aliphatic group or an aromatic group,
₁ and A ₂ both represent a hydrogen atom, or one represents a hydrogen atom and the other represents an alkylsulfonyl group, an arylsulfonyl group or an acyl group. ) General formula (II): (Here, R ₁ ′, A ₁ ′ and A ₂ ′ have the same definitions as R ₁ , A ₁ and A ₂ in the general formula (I), R ₂ is a block group other than a hydrogen atom, and G ₁ is -CO- group, -SO ₂ -
Group, —SO— group, embedded image Represents a —CO—CO— group, a thiocarbonyl group, or an iminomethylene group, R ₃ is selected from the same range as the group defined for R ₂ , provided that R ₁ ′ is a group in which G ₁ is a —CO— group. Represents an aromatic group, and when G ₁ is other than that, represents an aliphatic group or an aromatic group. )