JPH1010672A - Heat developing photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat developing photosensitive material having high sensitivity and Dmax by incorporating a specified compd. and a hydrazine deriv. SOLUTION: This photosensitive material contains a compd. expressed by formula I and a hydrazine deriv. In formula I, R is a hydrogen atom or alkyl group having 1 to 10 carbon atoms (e.g. -C4 H9 , 2,4,4-trimethylpentyl) and R' and R" are alkyl groups having 1 to 5 carbon atoms (e.g. methyl, ethyl and t-butyl groups). As for the hydrazine deriv., a compd. expressed by formula II is preferable. In formula II, R1 is an aliphatic group or aromatic heterocyclic group, R2 is a hydrogen atom, alkyl group, etc., G1 represents -CO-, -SO2 -, etc., and A1 , A2 are hydrogen atoms or one of these is hydrogen atom and the other is an alkylsulfonyl group, arylsulfonyl group, etc.

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.C. Morgan and B.A. "Thermally Processed Silver Systems" by Shely
(Imaging Processes and Materials Neblette 8
Edition, Sturge, V. Walworth
th), A. Shepp, page 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 reducing agent in a binder matrix. It is contained in a dispersed state. 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. Silver produced by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas,
An image is formed. Such a photothermographic material is
Although it has been used for micro-sensitive materials and X-rays, it is only used in some printing 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. On the other hand, with the development of lasers and light emitting diodes in recent years,
Scanners and imagesetters having an oscillation wavelength of 0 to 800 nm have become widespread, and there has been a strong demand for the development of a sensitive material having high sensitivity, high Dmax, and high contrast suitable for these output devices. Also, demands for simple processing and dry processing are increasing.

[0003] By the way, US Patent No. 3,667,958.
Describes that a photothermographic material using a combination of polyhydroxybenzenes and hydroxylamines, reductones or hydrazines has high image quality discrimination and resolution. It turned out that it was easy to cause a rise.

[0004]

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 a high Dmax.
SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive material for printing plate making having good image quality. Another object of the present invention is to provide a photosensitive material for printing plate making of a completely dry process which does not require a wet process.

[0005]

The above objects of the present invention have been attained by the following inventions 1) to 7). 1) A photothermographic material containing a silver salt of an organic acid and silver halide, which comprises a compound represented by the following general formula (A) and a hydrazine derivative.

[0006]

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In the formula, R is a hydrogen atom or a group having 1 to 1 carbon atoms.
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-trimethyl pentyl) represents, R 'and R "is an alkyl group (e.g., methyl 1 to 5 carbon atoms, ethyl, t- butyl 2) In a photothermographic material containing a silver salt of an organic acid and silver halide, the following general formula (RI), (R-II), (R-III) or (RI)
A photothermographic material comprising the compound represented by formula (V) and a hydrazine derivative.

[0008]

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

[0010]

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

[0012]

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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. Wherein R _{1 to} R ₁₀ , R ₁ ′ to R ₅ ′, R _{11 to} R ₁₃ , R ₁₁ ′ to
R ₁₃ ′, R _{21 to} R ₂₈ , R ₂₁ ′ to R ₂₈ ′ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom,
It is a group represented by an amino group or -OA. Where R
At least one of the ₁ to R ₅ is a group represented by -OA, at least one of R _{1 '~R 5'} is a group represented by -OA, at least one of R ₇ to R ₁₀ Is a group represented by -OA. Also, R _{1 to} R ₁₀ , R ₁ ′ to R ₅ ′, R _{11
~R 13, R 11 '~R 13} ', R 21 ~R 28, R 21 '~R 28'
May be bonded to each other to form a ring. A and A 'represent a hydrogen atom, an alkyl group, an acyl group, an aryl group, a phosphate group, and a sulfonyl group. R
_{1 ~R 10, R 1 '~R} 5', R 11 ~R 13, R 11 '~
_{R 13 ', R 21 ~R 28} , R 21' ~R 28 'A, A' may be substituted. However, in the general formula (R-III), R ₁
At least one of to R _5, if the group in which at least one of R ₁ '~R _5' is represented by -OA, L ₁ is a sulfur atom. 3) The photothermographic material according to 1) or 2), wherein the hydrazine derivative is represented by the following general formula (I).

[0014]

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In the formula, R ₁ represents an aliphatic group or an aromatic hetero ring, 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 is -CO-
Group, -SO ₂ - group, -SO- group,

[0016]

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A —CO—CO— group, a thiocarbonyl group,
Or 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 group. 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. 4) The photothermographic material according to any one of 1) to 3), wherein the hydrazine derivative is a compound represented by the following general formulas (II) to (V).

[0018]

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In the formula, R _{10 to} R ₁₃ represent an aromatic group or an unsaturated heterocyclic group, and A _{10 to} A ₁₃ and A _{20 to} A ₂₃ represent A ₁ ,
Represent the same meaning as A _2. In the general formula (III), R ₂₁ is an alkyl group substituted with at least one electron-withdrawing group,
Represents an aryl group, a heterocyclic group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, a hydrazino group, an alkoxy group, or an aryloxy group substituted with at least one electron-withdrawing group. In the general formula (V), G ₁₃ represents a —SO 2 — group, a —SO— group,

[0020]

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(R ₃₀ is a group having the same meaning as R _{3 in} formula (I)), a thiocarbonyl group or an iminomethylene group, and R ₂₃ is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group. , An alkylamino group, an arylamino group, a heterocyclic amino group or a hydrazino group. 5) The photothermographic material according to any one of 1) to 4), wherein the gradation γ after the heat development processing is γ> 5.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrazine derivative used in the present invention is preferably a compound represented by the following general formula (I). General formula (I)

[0023]

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In the formula, R ₁ represents an aliphatic group or an aromatic telocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an unsaturated heterocyclic group, an alkoxy group, an aryloxy group, an amino group or A hydrazino group, G ₁ is —C
O- group, -SO ₂ - group, -SO- group,

[0025]

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A —CO—CO— group, a thiocarbonyl group,
Or 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 group. 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.

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, there are a benzene ring, a naphthalene ring, 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. Among them, those containing a benzene ring are preferable. Particularly preferred as R ₁ is an aryl group.
The aliphatic group or the aromatic group of R ₁ may be substituted, and typical substituents include, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocyclic ring,
Pyridinium group, hydroxy group, alkoxy group, aryloxy group, acyloxy group, alkyl or arylsulfonyloxy group, amino group, carbonamide group, sulfonamide group, ureido group, thioureido group, semicarbazide group, thiosemicarbazide group, urethane group, hydrazide Group having a quaternary ammonium structure, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, carboxyl group, sulfo group, acyl group, alkoxy or aryloxycarbonyl group, carbamoyl group, sulfamoyl Group, halogen atom, cyano group, phosphoric acid amide group, diacylamino group, imide group, group having an acylurea structure, group containing a selenium atom or tellurium atom, tertiary sulfonium structure, etc. Is a group having a quaternary sulfonium structure. Preferred examples of the substituent include a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms) and an aralkyl group (preferably having an alkyl moiety having a carbon number of 1 to 20). Monocyclic or bicyclic one to three), an alkoxy group (preferably one having 1 to 20 carbon atoms), a substituted amino group (preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino Group (preferably having 2 to 30 carbon atoms), sulfonamide group (preferably having 1 to 3 carbon atoms)
0), a ureido group (preferably having 1 to 3 carbon atoms)
0), a phosphoric amide group (preferably having 1 carbon atom)
To 30).

In the general formula (I), R_Two Represented by
The alkyl group is preferably an alkyl having 1 to 4 carbon atoms.
A monocyclic or bicyclic aryl
Are preferred, for example those containing a benzene ring.
You. At least one nitrogen, oxygen,
And a 5- to 6-membered ring compound containing a sulfur atom, for example,
Ruforino, piperidino, pyrrolinyl, imidazo
Ryl, pyrazolyl, triazolyl, tetrazolyl
Group, pyridyl group, pyridinium group, quinolinium group,
Examples include a norinyl group and an indazolyl group. Indazolyl
Groups or pyridinium groups are particularly preferred. Alkoxy group
Is preferably an alkoxy group having 1 to 8 carbon atoms
The aryloxy group is preferably a monocyclic one,
As the amino group, an unsubstituted amino group and 1 to 10 carbon atoms
Are preferably an alkylamino group and an arylamino group. R
_Two May be substituted, and a preferred substituent is R
₁ The above-mentioned substituents are applicable. R_Two In table
Preferred among the groups mentioned are G₁ Is a -CO- group
In such a case, a hydrogen atom, an alkyl group (for example, a methyl group,
Trifluoromethyl group, 3-hydroxypropyl group, 3
-Methanesulfonamidopropyl group, phenylsulfoni
Aralkyl group (e.g., o-hydro
An aryl group (eg, phenyl)
Group, 3,5-dichlorophenyl group, o-methanesulfone
An amidophenyl group, a 4-methanesulfonylphenyl group,
2-hydroxymethylphenyl group), -C_TwoF_FourCOOM
(M: hydrogen atom, alkali metal atom), heterocyclic group (d
Troindazolyl, imidazolyl, etc.). Ma
G₁ Is -SO _Two -In the case of a group_Two Is an alkyl group
(Eg, a methyl group), an aralkyl group (eg, o
-Hydroxybenzyl group), an aryl group (for example,
A phenyl group or the like or a substituted amino group (eg, dimethyl
And the like are preferred. G₁ Is -COCO-
In the case of a group, an alkoxy group, an aryloxy group, an amino group
Is preferred. In the general formula (I), G represents a -CO- group,-
A COCO- group is preferred, and a -CO- group is most preferred.
Also, R_Two Is G₁ -R_Two Is split from the remaining molecules,
-G₁ -R_Two Rings that form cyclic structures containing partial atoms
Which may cause a chemical reaction,
As described in, for example, JP-A-63-29751.
Things.

A ₁ and A ₂ represent a hydrogen atom, an alkyl or aryl sulfonyl group having 20 or less carbon atoms (preferably a phenyl sulfonyl group or a Hammett having a sum of substituent constants of-
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; ))). A ₁ , A ₂
Is most preferably a hydrogen atom.

The substituents of R ₁ and R _{2 in} the general formula (I) 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 also include those exemplified as the substituent of R ₁ .

R ₁ or R _{2 in} the formula (I) may have a ballast group or a polymer commonly used in immobile photographic additives such as couplers incorporated therein. A ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, for example, an alkyl group,
It can be selected from aralkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups, alkylphenoxy groups and the like. Examples of the polymer include those described in JP-A-1-100530.

R ₁ or R _{2 in} the general formula (I) may have incorporated therein a group which enhances the adsorption to the surface of the silver halide grains. Examples of such an adsorbing group include U.S. Pat. Nos. 4,385,108 and 4,459,34 such as an alkylthio group, an arylthio group, a thiourea group, a heterocyclic thioamide group, a mercapto heterocyclic group, and a triazole group.
7, JP-A-59-195233 and JP-A-59-2002.
No. 31, No. 59-201045, No. 59-20104
No. 6, No. 59-201047, No. 59-201048
No. 59-201049, JP-A-61-17073.
Nos. 3, 61-270744, 62-948, 63-234244, 63-234245, and 6
Groups described in JP-A-3-234246.

The hydrazine derivative particularly preferred in the present invention will be described below.

Further, among the hydrazine derivatives used in the present invention, more preferred ones are represented by the following general formulas (II) to (II).
It is a compound represented by (V).

[0035]

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In the formula, R _{10 to} R ₁₃ represent an aromatic group or an unsaturated heterocyclic group, specifically an aryl group or an unsaturated heterocyclic group, and A _{10 to} A ₁₃ and A _{20 to} A ₂₃ represent A ₁ and A ₂ have the same meaning. In the general formula (III), R ₂₁ represents an alkyl group substituted with at least one electron-withdrawing group, an aryl group substituted with at least one electron-withdrawing group, a heterocyclic group, an amino group, an alkylamino group, an arylamino group. A heterocyclic amino group, a hydrazino group, an alkoxy group or an aryloxy group. In the general formula (V), G ₁₃ represents a —SO 2 — group, a —SO— group,

[0037]

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(R ₃₀ is a group having the same meaning as R _{3 in} formula (I)), a thiocarbonyl group or an iminomethylene group, and R ₂₃ is an alkyl group, an aryl group, an alkoxy group, an aryloxy group, or an amino group. , An alkylamino group, an arylamino group, a heterocyclic amino group or a hydrazino group. Among the compounds represented by the general formula (II), more preferred are the compounds represented by the following general formula (II-1).

[0039]

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Where X_TenIs a sulfonamide group, ureido
Group, thioureido group, oxycarbonyl group, sulfone
Amide group, phosphonamide group, alkylamino group, halogen
Atom, cyano group, alkoxy group having 2 or more carbon atoms,
Reeloxy, alkylthio, arylthio, f
Telocyclic thio group, acylamino group having 3 or more carbon atoms,
Bamoyl group, sulfamoyl group, or alkyl or
Represents an arylsulfonyl group, m_TenRepresents an integer of 0 to 5
You. Y_TenIs X_TenOr a nitro group or methoxy
Group, alkyl group or acetamido group, n_Ten
Represents an integer of 0 to 4. Where m_TenAnd n_TenSum exceeds 5
Never get_TenWhen is 0, A ₁₀₀Or A₂₀₀No
It is not a hydrogen atom. A₁₀₀, A₂₀₀Is the general formula (I)
A in₁, A_TwoIs synonymous with m_TenIs preferably one or
Is 2, n_TenIs preferably 0 or 1, most preferably
Is m_TenIs 1, n_TenIs 0.

In the general formula (III), R ₂₁ is preferably a heterocyclic group (for example, morpholino, indazolyl, imidazolyl, pyridyl, etc.), an alkyl group substituted with at least one electron-withdrawing group, or at least one electron-withdrawing group. Represents an aryl group substituted with a functional group. Here, the electron-withdrawing group refers to a substituent having a positive Hammett's substituent constant σm, and specifically includes a halogen atom, a nitro group, a cyano group, an acyl group, an oxycarbonyl group, and a sulfonamide. Group, sulfamoyl group, carbamoyl group, acyloxy group (alkyl or arylsulfonyl group,
Represents an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an imide group, or the like. R ₂₁ is more preferably an alkyl group substituted with at least one electron-withdrawing group, wherein the electron-withdrawing group is a fluorine atom,
An alkoxy group and an aryloxy group are particularly preferred. In the general formula (IV), R ₂₂ is preferably an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, or an alkoxy group. In the general formula (V), G ₁₃ is preferably —SO ₂ —, a thiocarbonyl group,

[0042]

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(R ₃₀ is the same as R _{3 in} formula (I)). R ₂₃ is, G ₁₃ is -SO ₂ - when, preferably an alkyl group, an aryl group, also G ₁₃ is the (Formula 2
In the case of 1), an aryloxy group or an alkyl or arylamino group is preferable, and when G ₁₃ is a thiocarbonyl group, an alkyl or arylamino group or a hydrazino group is preferable. Particularly preferred among the hydrazine derivatives used in the present invention are compounds represented by formulas (III) to (V).

The following are specific examples of the hydrazine derivative that can be used in the present invention, but the present invention is not limited thereto.

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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The hydrazine derivatives used in the present invention include, in addition to the above, RESEARCH DISCLOSURE Item 2
No. 3516 (November 1983, P. 346) and references cited therein, as well as U.S. Pat. No. 4,080,20.
No. 7, 4,269,929, 4,276,364
Nos. 4,278,748 and 4,385,108
No. 4,459,347 and 4,478,928
Nos. 4,560,638 and 4,686,167
Nos. 4,912,016 and 4,988,604
No. 4,994,365, No. 5,041,355
No. 5,104,769, British Patent 2,011,
391B, EP 217,310, EP 301,310,
No. 799, No. 356, 898, JP-A-60-1797.
No. 34, No. 61-170733, No. 61-27074
No. 4, 62-178246, 62-270948
Nos. 63-29751, 63-32538, 63-110407, 63-121838, and 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
No. 234246, No. 63-294552, No. 63-3
Nos. 06438 and 64-10233, JP-A-1-90
No. 439, No. 1-100530, No. 1-1095941
No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2
No. 83549, No. 1-285940, No. 2-2541
No. 2-77057, No. 2-139538, No. 2
196234, 2-196235, 2-19
No. 8440, No. 2-198441, No. 2-19844
No. 2, 2-220042, 2-221953,
2-221954, 2-285342, 2-
No. 285343, No. 2-289843, No. 2-302
No. 750, No. 2-304550, No. 3-37642
No. 3-54549, No. 3-125134, No. 3
Nos. -184039, 3-240036, 3-24
No. 0037, No. 3-259240, No. 3-28003
No. 8, 3-282536, 4-51143, 4-56842, 4-84134, 2-230
No. 233, No. 4-96053, No. 4-216544
Nos. 5-45761, 5-45762, 5-
No. 45763, No. 5-45764, No. 5-45765
And Japanese Patent Application No. 5-94925 can be used.

In addition, the compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, the compounds described on pages 3 and 4 of the same publication. Compounds represented by the general formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. JP 6
General formulas (4) and (5) described in JP-A-230497
And compounds represented by formula (6), specifically, compounds 4-1 to 4-
Compounds 5-1 to 5-4 described on page 10, pages 28 to 36
2, and compounds 6-1 to 6-7 described on pages 39 and 40. Compounds represented by formulas (I) and (2) described in JP-A-6-289520, specifically, compounds 1-1) to 1-1 described on pages 5 to 7 of the same publication
7) and 2-1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. JP-A-6-3
A compound represented by (Chemical Formula 1) described in No. 13951, specifically, a compound described on pages 3 to 5 of the same publication. JP-A-7-
A compound represented by the general formula (I) described in No. 5610,
Specifically, Compounds I-1 to I-5 described on pages 5 to 10 of the publication are described.
I-38. The general formula (I) described in JP-A-7-77783.
Compounds represented by I), specifically, pages 10 to 2 of the publication
Compounds II-1 to II-102 described on page 7. JP-A-7-1
General formula (H) and general formula (H
Compounds represented by a), specifically, pages 8 to 15 of the same publication.
Compounds H-1 to H-44 described on page p. Can be used.

In the present invention, the amount of the hydrazine derivative to be added is 1 × 10 ^-6 mol to 1 × 10 ⁶ mol / mol silver.
^-1 mol is preferable, and a range of 1 × 10 ⁻⁵ mol to 5 × 10 ⁻² mol is particularly preferable.

The hydrazine derivative of the present invention can be prepared by using a suitable organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like. Also, by an already well-known emulsification dispersion method, dissolution using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsifying and dispersing. An object can be prepared and used. Alternatively, the hydrazine derivative powder 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. In the present invention, it is preferable to use indazoles (for example, nitroindazole) as an antifoggant in combination with a hydrazine derivative.

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 photographic material in combination with the hydrazine derivative. Examples of compounds for the nucleation accelerator are given below.

[0066]

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[0067]

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The nucleation accelerator of the present invention is preferably added in an amount of 1 × 10 ⁻⁶ to 2 × 10 ⁻² mol per mol of silver, more preferably 1 × 10 ⁻⁵ mol.
２2 × 10 ⁻² mol is more preferred, and 2 × 10 ^-5 −1 × 1
0 ^-2 mol is most preferred.

In one embodiment of the present invention, a compound represented by the following general formula (A) is contained in the photothermographic material as a reducing agent.

[0070]

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In the formula, R is a hydrogen atom or a group having 1 to 1 carbon atoms.
10 alkyl group (e.g., -C ₄ H _9, 2,4,4-trimethyl pentyl) represents, R 'and R "is an alkyl group (e.g., methyl 1 to 5 carbon atoms, ethyl, t- butyl ).

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

[0073]

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[0074]

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The amount of the compound represented by the general formula (A)
Is preferably 1 × 10 per mole of silver. ^-2-10 mol, especially
1 × 10^-2１．５1.5 mol.

In one embodiment of the present invention, a compound represented by the following general formula (RI), (R-II), (R-III) or (R-IV) is used as a reducing agent in a photothermographic material. To be included.

[0077]

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

[0079]

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

[0081]

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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. Wherein R _{1 to} R ₁₀ , R ₁ ′ to R ₅ ′, R _{11 to} R ₁₃ , R ₁₁ ′ to
R ₁₃ ′, R _{21 to} R ₂₈ , R ₂₁ ′ to R ₂₈ ′ represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a halogen atom,
It is a group represented by an amino group or -OA. Where R
At least one of the ₁ to R ₅ is a group represented by -OA, at least one of R _{1 '~R 5'} is a group represented by -OA, at least one of R ₇ to R ₁₀ Is a group represented by -OA. Also, R _{1 to} R ₁₀ , R ₁ ′ to R ₅ ′, R _{11
~R 13, R 11 '~R 13} ', R 21 ~R 28, R 21 '~R 28'
May be bonded to each other to form a ring. A and A 'represent a hydrogen atom, an alkyl group, an acyl group, an aryl group, a phosphate group, and a sulfonyl group. R
_{1 ~R 10, R 1 '~R} 5', R 11 ~R 13, R 11 '~
_{R 13 ', R 21 ~R 28} , R 21' ~R 28 'A, A' may be substituted. However, in the general formula (R-III), R ₁
At least one of to R _5, if the group in which at least one of R ₁ '~R _5' is represented by -OA, L ₁ is a sulfur atom. _{R 1 ~R 10, R 1 '} ~R 5', R 11 ~R 13, R 11 '~
_{R 13 ', R 21 ~R 28} , R 21' as the substituent of ~R ₂₈ 'A, A', for example (including an active methylene group) alkyl group, a nitro group, an alkenyl group, an alkynyl group, an aryl group, Groups containing heterocycles, groups containing quaternary nitrogen-containing heterocycles (eg, pyridinio groups), hydroxy groups, alkoxy groups (including groups that repeatedly contain ethyleneoxy and propyleneoxy units), aryloxy groups ,
Acyloxy group, acyl group, alkoxy or 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, group containing hydrazino group, group containing quaternary ammonium group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group Group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, sulfo group, acyl group, sulfamoyl group, acylsulfamoyl group, alkyl or arylsulfonylureido group, alkyl or arylsulfonylcarbamoyl group, halogen atom, cyano group, phosphorus Examples thereof include an acid amide group, a group containing a phosphate ester structure, a group containing an acylurea structure, a group containing a selenium atom or a tellurium atom, and a group having a tertiary sulfonium structure or a quaternary sulfonium structure. These substituents may be further substituted, and further substituents include those described above. Specific examples of the compounds represented by formulas (RI) to (R-IV) are described below, but the present invention is not limited thereto.

[0083]

[Table 1]

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

[Table 4]

[0087]

[Table 5]

[0088]

[Table 6]

[0089]

[Table 7]

[0090]

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[0091]

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The amount of the reducing agent represented by any of formulas (RI) to (R-IV) is preferably 1 × 10 ^-3 to 1 mol per silver.
The amount is 10 mol, more preferably 1 × 10 ^{-2 to} 1.5 mol. Compounds of general formula (A), general formulas (RI) to (RI)
The compounds of V) may be used alone or in combination. When mixed, the auxiliary reducing agent is used in a molar number of 1/1000 to 1/1, preferably 1 to the main reducing agent.
It is used in the range of / 100 to 1/1.

The photothermographic material of the present invention forms a photographic image using a photothermographic processing method. Such a photothermographic material is disclosed in, for example, US Pat.
No. 152904, 3457075, and D.C. Morgan and B.A. "Thermally Processed SilverSy" by Shely
stems) "(Imaging Processors and
Materials (Imaging Processes and Materials) Neb
lette 8th edition, Sturge, V. Walworth, A .; Edited by Shepp, page 2,
1969).

The photothermographic material of the present invention forms a photographic image using a heat development process, and includes a reducible silver source (organic silver salt), a catalytically active amount of a photocatalyst (for example, silver halide), It is preferable that the photothermographic material contains a color tone agent and a reducing agent for suppressing the color tone of silver, which are usually dispersed in an (organic) binder matrix. The photothermographic material of the present invention is stable at room temperature, but is developed by heating to a high temperature (for example, 80 ° C. or higher) after exposure. 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.

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. In order to control 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-sensitive layer / low-sensitive layer or a low-sensitive layer / high-sensitive layer for adjusting the 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 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 include natural polymer synthetic resins and polymers and copolymers, and other film-forming media such as: gelatin, gum arabic,
Poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), 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 (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (ester) ), Poly (urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxide),
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.

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);
Blocked pyrazoles, isothiuronium (isot
hiuronium) derivatives and certain photobleaching combinations (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 (benzpthiazolinylidene) -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 (for example, ,
6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); a combination of phthalazine + phthalic acid; phthalazine (including an adduct of phthalazine), maleic anhydride, and phthalic acid , 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and anhydrides thereof (for example,
A combination with at least one compound selected from phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); 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 halides useful as photocatalysts in catalytically active amounts can be any photosensitive silver halide (eg, silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, chloroiodobromide). Silver iodide), but preferably contains iodine ions. The silver halide may be added to the image forming layer by any method, in which case the silver halide is arranged close 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 organic and heteroorganic acids containing a reducible silver ion source, especially 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 nitrogen acids selected from triazoles and benzotriazoles; silver salts such as saccharin, 5-chlorosalicylaldoxime; and silver salts of mercaptides, the preferred silver source being silver behenate. Silver source is preferably 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 unfriendly. 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 US
Patents 3,874,946 and 4,756,999 disclose
A compound such as -C (X¹) (X^Two) (X^Three)(here
And X ¹ And X^Two Is a halogen (eg, F, Cl, Br and
And I) with X^Three Is hydrogen or halogen)
It is a heterocyclic compound having a substituent. Suitable cover
Examples of inhibitors include:

[0101]

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[0102]

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Even 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 Nos. 63-159841, 60-140335, 63-231437, 63-259651, and 6
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 include, for example, RESEARCH DISCLOSURE Item 1
7643 IV-A (p.23, December 1978), I
tem 1831X (August 1978, p. 437). 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 discloses an argon laser light source.
JP-A-2-48653, U.S. Pat. No. 2,161,3
No. 31, West German Patent 936,071, Japanese Patent Application No. 3-189
No. 532, simple merocyanines, and B) a helium-neon laser light source.
No. 25, No. 54-18726, No. 59-102229
No. 6-1032
JP-B-48-42172 discloses merocyanines, C) LED light sources and red semiconductor lasers described in
Thiacarbocyanines described in JP-A-62-284343 and JP-A-2-105135; Tricarbocyanines described in JP-A-59-19032 and JP-A-60-80841; JP-A-59-192242; JP-A-3-6724.
4- (4-) described in the general formulas (IIIa) and (IIIb) of No. 2
Dicarbocyanines containing a quinoline nucleus are advantageously selected. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly 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.

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

In the photothermographic material of the present invention, a layer containing a dye can be provided as an antihalation layer.
For an Ar laser, a He-Ne laser, and a red semiconductor laser, a dye is added so as to absorb at least 0.3 or more, preferably 0.8 or more at an exposure wavelength within a range of 400 nm to 750 nm. For an infrared 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 750 nm to 1500 nm. 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 may be 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), paper or a plastic film on which the above-mentioned metal is laminated or vapor-deposited, or the like is used. On the other hand, when a 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 becomes 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, polyethersulfone, polyarylate and the like can be used.

[0108]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

[0109] Example 1 Photosensitive emulsion A mixed solution NaOH 89 g Distilled water 1.5 l solution prepared solution stearate 131g behenic acid 635g of distilled water 13 liters 90 ° C. 15 minutes of concentrated HNO ₃ 19 ml of distilled water 50ml solution AgNO ₃ 365 g Distilled water 2.5 liter solution polyvinyl butyral 86 g ethyl acetate 4.3 liter solution polyvinyl butyral 290 g isopropanol 3.6 liter solution N-bromosuccinimide 9.7 g acetone 690 ml

While maintaining the temperature of the solution at 90 ° C., the solution was added over 5 minutes with vigorous stirring.
Add over 5 minutes. After stirring for 20 minutes as it is, 35
Cool down to ° C. Add the solution over 5 minutes with more vigorous stirring at 35 ° C. and continue stirring for 90 minutes.
Thereafter, the solution was added, the stirring was stopped, and the mixture was left to stand. The aqueous layer was removed together with the salt contained therein to obtain an oil phase. After removing the solvent and removing the remaining water, the solution was added and the mixture was stirred vigorously at 50 ° C. Thereafter, the solution was added over 20 minutes and stirred for 105 minutes to obtain Emulsion A.

The following layers were sequentially formed on a heat-treated polyethylene terephthalate support to prepare a sample.
The drying was performed at 75 ° C. for 5 minutes.

Back side coating: A solution having the following composition was applied to a wet thickness of 80 microns. Polyvinyl butyral (10% isopropanol solution) 150 ml Dye-B 70 mg Dye-C 70 mg

[0113]

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Photosensitive layer side coating Photosensitive layer 1: A solution having the following composition was applied to a wet thickness of 140 μm. Photosensitive emulsion A 73 g Sensitizing dye-1 (0.1% DMF solution) 2 ml Antifoggant-1 (0.01% methanol solution) 3 ml Antifoggant-2 (0.85% methanol solution) 10 ml Antifoggant -3 (0.85% methanol solution) 10 ml Phthalazone (4.5% DMF solution) 8 ml Developer-1 (10% acetone solution) 13 ml Nucleation promoter-1 (1% methanol solution) 1 ml Antifoggant-4 (1% methanol solution) 2 ml Hydrazine derivative (1% methanol / DMF = 4: 1 solution: kind of Table 8) 2 ml

[0115]

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[0116]

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[0117]

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[0118]

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Photosensitive Layer 2 For the above-mentioned photosensitive layer, developer-1 was changed from the compound of the present invention to developer-2, which is a compound not of the present invention.
Other than that, photosensitive layer 2 was formed in the same manner as photosensitive layer 1.

[0120]

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Surface protective layer: A solution having the following composition was wetted to a thickness of 1
It was applied so as to be 00 microns. Acetone 175 ml 2-propanol 40 ml methanol 15 ml cellulose acetate 8.0 g phthalazine 1.0 g 4-methylphthalic acid 0.72 g tetrachlorophthalic acid 0.22 g tetrachlorophthalic anhydride 0.5 g

Sensitometry The photothermographic material prepared above is processed into half-cut sizes,
An 830 nm laser diode was exposed with a beam tilted 13 ° from the vertical. Then use a heat drum for 1
Heat development was performed at 20 ° C. for 10 seconds. The reciprocal of the exposure amount giving a density of 0.3 is defined as the sensitivity, and the relative sensitivity is defined as a density of 0.1 or 3.0.
Table 8 shows the inclination of the straight line connecting the points (1) and (2) with Dmax.

Evaluation of Image Quality Using the same exposure machine as for sensitometry, image quality was evaluated by generating halftone dots. The dot quality when exposing our scanner film LS555 with our color scanner MAGNASCAN is 4 points, and 5 points if better. If it was not good, it was evaluated by a 5-point method of 3, 2, and 1 points. Note that three or more points are at a practical level as a printing photosensitive material.

[0124]

[Table 8]

As can be seen from Table 8, the sensitivity, D
Both max are high. Also, it can be seen that among them, those having a large gradation have good image quality. In addition, it can be seen that only those using the developer of the present invention have good image quality.

Example 2 Photosensitive Layer Side Coating Photosensitive layer: The sensitizing dye was changed to the following sensitizing dye-2 (0.1% DMF).
Solution), and a solution for a photosensitive layer was prepared and coated in the same manner as in Example 1 except that 2 ml of a hydrazine derivative (1% methanol / DMF = 4: 1 solution) was added as shown in Table-9. .

[0127]

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[0128]

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Surface protective layer: Coating was performed in the same manner as in Example 1.

Coating on back side: Coating was performed in the same manner as in Example 1.

Sensitometry The photothermographic material prepared above was exposed with a 780 nm laser diode. Other than that, it carried out similarly to Example 1. Image quality evaluation was performed in the same manner as in Example 1 except that the photothermographic material prepared above was exposed with a 780 nm laser diode.

[0132]

[Table 9]

As can be seen from Table 9, the sensitivity, D
Both max are high. Also, it can be seen that among them, those having high gradation have high Dmax.

Example 3 (Preparation of silver halide particles B) 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, the temperature was adjusted to 35 ° C. and the pH was adjusted to 3.0.
g of an aqueous solution containing 370 ml of an aqueous solution containing potassium bromide and potassium iodide in a molar ratio (96/4) of pAg 7.7.
, And added over 10 minutes by the control double jet method. At this time, the hexacyanoferrate (III) and hexachloroiridium (I
II) 1 × 10 ⁻⁵ mol / Ag mol of complex salt was added. Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-
0.3 g of tetrazaindene was added, the pH was adjusted to 5 with sodium hydroxide, and the average particle size was 0.06 μm.
Coefficient of variation of projected diameter area 8%, [100] face ratio 87%
Of cubic silver iodobromide grains were obtained. This emulsion was coagulated and precipitated using a gelatin coagulant, and desalted, and adjusted to pH 5.9 and pAg 7.5 with 0.1 g of phenoxyethanol.

(Preparation of Organic Fatty Acid Silver Emulsion B) 300 m of water
10.6 g of behenic acid was added to the mixture, dissolved at 90 ° C. with heating, and sufficiently stirred.
1.1 ml was added and left as it was for 1 hour. Thereafter, the mixture was cooled to 30 ° C., and 7.0 ml of 1N phosphoric acid was added.
Was added and, with sufficient stirring, 0.13 g of N-bromosuccinimide was added. Thereafter, the silver halide grains B prepared in advance were added to behenic acid in a silver amount of 1%.
It was added while stirring at a temperature of 40 ° C. so as to be 0 mol%. Further, 25 ml of a 1N aqueous silver nitrate solution was continuously added over 2 minutes, and the mixture was allowed to stand for 1 hour with stirring. While stirring this aqueous mixture, 37 g of a 1.2 wt% solution of polyvinyl acetate in n-butyl acetate was gradually added to form a floc of the dispersion, water was removed, and water was washed twice and water was removed. After the addition, 20 g of a 1: 2 mixed solution of 2.5 wt% of butyl acetate and isopropyl alcohol of polyvinyl butyral (average molecular weight: 3000) was added with stirring, and the thus obtained gel-like silver behenate and halide were obtained. 12.5 g of polyvinyl butyral (average molecular weight 4000) and 57 g of isopropyl alcohol were added to the silver mixture and dispersed.

The following layers were sequentially coated on the heat-treated polyethylene terephthalate support to prepare a sample. In addition, each drying was performed at 75 ° C. for 5 minutes.

Back side coating: A solution having the following composition was applied to the surface opposite to the surface on which the photosensitive layer was provided so that the wet thickness was 100 μm. Polyvinyl butyral # 4000-2 (manufactured by Denki Kagaku Kogyo KK) (10% isopropanol solution) 60 g isopropyl alcohol 10 g 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (manufactured by Wako Pure Chemical Industries, Ltd.) Dye S-1 was added to a solution of 8 g or more of an 8% solution of ethyl acetate.
A solution obtained by dissolving 2 g in a mixed solvent of 10 g of methanol and 20 g of acetone has an absorption at the exposure wavelength of the back layer of 0.
8).

[0138]

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Photosensitive layer side coated photosensitive layer B: A solution having the following composition was applied to the opposite side of the back layer so that the coated silver amount was 1.5 g / m ² to form a photosensitive layer. The hydrazine derivatives were changed as shown in Table 10, and various samples shown in Table 10 were produced. Organic fatty acid silver salt emulsion B 73 g Sensitizing dye D-1 (0.05% methanol solution) 4 ml Phthalazine (5% methanol solution) 2.5 ml Antifoggant-1 (1.7% DMF solution) 2.5 ml Developer -1 (10% acetone solution) 13 ml hydrazine derivative Those listed in Table 10 (1% methanol solution) 2 ml 2-mercapto-5-methylbenzotriazole (0.5% DMF solution) 5 ml CaBr ₂ (0.3% methanol solution) ) 6.5 ml

[0140]

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Photosensitive layer C: A photosensitive layer C was prepared in the same manner as the photosensitive layer B, except that the developer-1 was changed to the developer-2 outside the present invention.

[0142]

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Surface protective layer: A solution having the following composition was wetted to a thickness of 1
It was applied on the photosensitive layer so as to be 00 microns. Acetone 175 ml Methanol 15 ml Cellulose acetate 8.0 g 4-methylphthalic acid 0.72 g Tetrachlorophthalic acid 0.22 g Tetrachlorophthalic anhydride 0.5 g

Sensitometry The photothermographic material prepared above was exposed to xenon flash light with an emission time of 10 ^-3 seconds through an interference filter having a peak at 670 nm. Thereafter, heat development was performed at 115 ° C. for 15 seconds using a heat drum. The sensitivity is 3.
The reciprocal of the exposure amount giving 0 was taken as the sensitivity and indicated by relative sensitivity.
The slope of the straight line connecting the points of density 0.1 and 1.5 in the characteristic curve is shown as the gradation (γ) indicating the cut of the leg. The dye in the back layer was erased by irradiating a halogen lamp for 15 seconds after the heat development treatment.

[0145]

[Table 10]

[0146]

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As can be seen from Table 10, the sample of the present invention shows high values for both sensitivity and γ.

Embodiment 4

The following layers were sequentially coated on the heat-treated polyethylene terephthalate support to prepare a sample. In addition, each drying was performed at 75 ° C. for 5 minutes.

Back side coating: A coating solution having the same formulation as the back layer of Example 3 was applied in the same manner.

Photosensitive layer side coated photosensitive layer D: A solution having the following composition was applied to the opposite side of the back layer so that the applied silver amount was ga1.5 g / m ² to form a photosensitive layer. Various samples shown in Table 11 were prepared by changing the developer as shown in Table 11. Organic fatty acid silver salt emulsion B 73 g Sensitizing dye D-1 (0.05% methanol solution) 4 ml Phthalazine (5% methanol solution) 2.5 ml Antifoggant-1 (1.7% DMF solution) 2.5 ml Developer (See Table 11) (10% acetone solution) 13 ml Hydrazine derivative (see Table 11) (1% methanol solution) 2 ml 2-mercapto-5-methylbenzotriazole (0.5% DMF solution) 5 ml CaBr ₂ (0.3 6.5% methanol solution)

[0152]

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Surface protective layer: A coating solution having the same formulation as the surface protective layer of Example 3 was applied in the same manner. Sensitometry The photothermographic material prepared above was exposed to xenon flash light with an emission time of 10 ^-3 seconds through an interference filter having a peak at 670 nm. Thereafter, heat development was performed at 115 ° C. for 15 seconds using a heat drum. The sensitivity is 3.
The reciprocal of the exposure amount giving 0 was taken as the sensitivity and indicated by relative sensitivity.
The slope of the straight line connecting the points of density 0.1 and 1.5 in the characteristic curve is shown as the gradation (γ) indicating the cut of the leg. The dye in the back layer was erased by irradiating a halogen lamp for 15 seconds after the heat development treatment.

[0154]

[Table 11]

As can be seen from Table 11, the sample of the present invention shows high values for both sensitivity and γ.

[Procedure amendment]

[Submission date] March 28, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0015

[Correction method] Change

[Correction contents]

In the formula, R ₁ represents an aliphatic group or an aromatic group, 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 is a —CO— group, —SO ₂
— Group, —SO— group,

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction contents]

In the formula, R ₁ represents an aliphatic group or an aromatic group, 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 is a —CO— group, —SO ₂
— Group, —SO— group,

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction contents]

In the general formula (III), R ₂₁ is preferably a heterocyclic group (for example, morpholino, indazolyl, imidazolyl, pyridyl, etc.), an alkyl group substituted with at least one electron-withdrawing group, or at least one electron-withdrawing group. Represents an aryl group substituted with a functional group. Here, the electron-withdrawing group refers to a substituent having a positive Hammett's substituent constant σm, and specifically includes a halogen atom, a nitro group, a cyano group, an acyl group, an oxycarbonyl group, and a sulfonamide. Group, sulfamoyl group, carbamoyl group, acyloxy group, (alkyl or aryl) sulfonyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, imide group and the like. R ₂₁ is more preferably an alkyl group substituted with at least one electron-withdrawing group, and as the electron-withdrawing group, a fluorine atom, an alkoxy group, and an aryloxy group are particularly preferable. In the general formula (IV), R ₂₂ is preferably an amino group,
It is an alkylamino group, an arylamino group, a heterocyclic amino group, or an alkoxy group. G ₁₃ in the general formula (V)
Is preferably -SO ₂ -, thiocarbonyl group,

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kosaburo Yamada 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Photo Film Co., Ltd.

Claims (5)

[Claims] 1. A photothermographic material containing a silver salt of an organic acid and silver halide, comprising a compound represented by the following general formula (A) and a hydrazine derivative. Embedded image In the formula, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ′ and R ″ represent an alkyl group having 1 to 5 carbon atoms. 2. A thermal developing sensation containing an organic acid silver salt and a silver halide.
In optical materials, the following general formulas (R-I), (R-II), (R-III)
Or the compound represented by (R-IV) and a hydrazine derivative
A photothermographic material characterized by containing: Embedded imageThe ring structure formed by Z in the general formula (R-III) is
It is the one of the note. Embedded imageIn the general formula (R-IV), the ring structure formed by Z is
It is the one of the note. Embedded imageWhere L₁, L_TwoIs> CH (R₆)
Is a sulfur atom. n represents a natural number. Where R₁ ~ R
_Ten, R₁'~ R_Five', R₁₁~ R₁₃, R₁₁'~ R₁₃', R_{twenty one}
~ R₂₈, R_{twenty one}'~ R₂₈′ Represents a hydrogen atom, an alkyl group,
Reel group, aralkyl group, halogen atom, amino group
Or a group represented by -OA. Where R₁ ~ R_FiveLittle
At least one is a group represented by -OA,₁'~
R_FiveAt least one is a group represented by -OA;
R₇~ R_TenAt least one is a group represented by -OA
You. Also, R₁ ~ R_Ten, R₁'~ R_Five', R₁₁~ R₁₃, R
₁₁'~ R₁₃', R _{twenty one}~ R₂₈, R_{twenty one}'~ R₂₈′ In each
A plurality of substituents of the above may be bonded to each other to form a ring.
No. A and A 'represent a hydrogen atom, an alkyl group, an acyl group,
Represents a reel group, a phosphate group, or a sulfonyl group. R₁ ~
R_Ten, R₁'~ R_Five', R₁₁~ R₁₃, R₁₁'~ R₁₃', R
_{twenty one}~ R₂₈, R_{twenty one}'~ R₂₈', A, A' are substituted
Is also good. However, in the general formula (R-III), R₁ ~ R_Fiveof
At least one, R₁'~ R_Five 'Is at least one of-
In the case of a group represented by OA, L₁Is a sulfur atom. 3. The photothermographic material according to claim 1, wherein the hydrazine derivative is represented by the following general formula (I). Embedded image In the formula, R ₁ represents an aliphatic group or an aromatic group, 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 is —CO— group, —SO ₂ — group, —SO
-Group, , -CO-CO-, thiocarbonyl, or iminomethylene, wherein 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; Represents a substituted 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. 4. A hydrazine derivative represented by the following general formula (II):
2. A compound represented by the formula (V):
4. The photothermographic material according to any one of items 1 to 3, Embedded image In the formula, R _{10 to} R ₁₃ represent an aromatic group or an unsaturated heterocyclic group, and A _{10 to} A ₁₃ and A _{20 to} A ₂₃ have the same meaning as A ₁ and A ₂ . In the general formula (III), R ₂₁ represents an alkyl group substituted with at least one electron-withdrawing group, an aryl group substituted with at least one electron-withdrawing group, a heterocyclic group, an amino group, an alkylamino group, an arylamino group. Group,
Represents a heterocyclic amino group, hydrazino group, alkoxy group or aryloxy group. In the general formula (V), G ₁₃ is -S
O2- group, -SO- group, (R ₃₀ represents a group having the same meaning as R _{3 in} formula (I)), a thiocarbonyl group or an iminomethylene group, and R ₂₃ represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group,
Represents an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group or a hydrazino group. 5. The photothermographic material according to claim 1, wherein the gradation γ after the heat development processing is γ> 5.