JPH09304872A - Heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat developable photosensitive material having high sensitivity, high Dmax and satisfactory image quality by incorporating a specified hydrazine deriv. as well as an org. silver salt, silver halide and a reducing agent. SOLUTION: A hydrazine deriv. represented by the formula is incorporated into a heat developable photosensitive material contg. an org. silver salt, silver halide and a reducing agent. In the formula, R1 is alkyl substd. by at least one electron withdrawing group or electron donative group, aryl or a heterocyclic group, R2 is an aliphatic group such as 1-30C optionally substd. straight chain, branched or cyclic alkyl or alkenyl, preferably methyl substd. by three aryl groups, both A1 and A2 are H or one of them is H and the other is optionally substd. alkylsulfonyl, optionally substd. arylsulfonyl, etc., and each of A1 and2 is preferably H.

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
Plate, Sturge, V.E. Walworth
th), 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 photothermographic materials have been used for micro-sensitive materials and X-rays, but are only partially used as printing photosensitive 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 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.

In US Pat. No. 3,667,958, it is described that a photothermographic material containing polyhydroxybenzenes and hydroxylamines, reductones or hydrazines in combination with a photothermographic material has high image recognizability and resolution. However, it was found that this combination of reducing agents easily causes an increase in fog.

US Pat. No. 5,496,695 discloses a photothermographic material containing an organic silver salt, silver halide, hindered phenols, and certain hydrazine derivatives. However, when these hydrazine derivatives are used, there is a problem that a sufficiently high maximum density or super-high contrast property cannot be obtained, and black spots are generated to deteriorate the image quality.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photothermographic material having high sensitivity and Dmax and good image quality.

[0009]

The object of the present invention is to provide a photothermographic material containing an organic silver salt, a silver halide and a reducing agent, which contains a hydrazine derivative represented by the following general formula (I). It was achieved by a photothermographic material characterized in that General formula (I)

[0010]

Embedded image

In the formula, R ₂ represents an aliphatic group, and R ₁ represents an alkyl group substituted with at least one electron-withdrawing group or an electron-donating group, an aryl group, or a heterocyclic group.
A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group,
Alternatively, it represents a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the compound represented by formula (I) of the present invention will be explained in detail. The aliphatic group represented by R ₂ in the general formula (I) specifically has 1 to 1 carbon atoms.
Thirty substituted or unsubstituted linear, branched, or cyclic alkyl groups, alkenyl groups, and alkynyl groups.

When these have a substituent, examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, and a heterocyclic group containing a quaternized nitrogen atom (eg, a pyridinio group). ), A hydroxy group,
An alkoxy group (including a group containing an ethyleneoxy group or a propyleneoxy group unit repeatedly), an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a urethane group, a carboxyl group, an imide group, Amino group, carbonamido group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonio group, (alkyl, aryl, or heterocycle) thio group , Mercapto group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group, sulfamoyl group, acylsulfamoyl group, (alkyl or aryl) sulfonylureido group, (alkyl Groups include aryl) sulfonylcarbamoyl group, a halogen atom, a cyano group, a nitro group, phosphoric acid amide group, a group containing a phosphoric acid ester structure, a group having acylurea structure, a selenium atom or a tellurium atom, 3
And a group having a quaternary sulfonium structure or a quaternary sulfonium structure. These substituents may be further substituted with these substituents.

In the general formula (I), R ₂ is preferably an alkyl group, and the substituent thereof is an aryl group, a heterocyclic group, a (alkyl or aryl) thio group, a cyano group, an alkoxy group, an aryloxy group, An alkoxycarbonyl group, an aryloxycarbonyl group, or a carbamoyl group is preferable.

R ₂ is more preferably a tri-substituted methyl group, and the substituent thereof is an aryl group, a heterocyclic group,
(Alkyl or aryl) Thio group, cyano group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, or carbamoyl group is preferable.

R ₂ is particularly preferably two aryl groups, an aryl group, a heterocyclic group, a (alkyl or aryl) thio group, a cyano group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, or A methyl group having one substituent selected from a carbamoyl group. R ₂ is most preferably a methyl group substituted with 3 aryl groups.

In the general formula (I), 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 -0.5 or more). A substituted phenylsulfonyl group), an acyl group having 20 or less carbon atoms (preferably a benzoyl group, or a benzoyl group substituted so that the sum of Hammett's substituent constants is −0.5 or more, or a direct group). A chain, branched, or cyclic unsubstituted and substituted aliphatic acyl group (the substituent includes, for example, a halogen atom, an ether group, a sulfonamide group, a carbonamide group, a hydroxyl group, a carboxy group, and a sulfonic acid group)) Is. A hydrogen atom is most preferable as A ₁ and A ₂ .

In the general formula (I), R ₁ is at least 1
Represents an alkyl group, an aryl group, or a heterocyclic group in which two electron-withdrawing groups or electron-donating groups are substituted.

Here, the electron-withdrawing group or the electron-donating group means a substituent in which the Hammett's substituent constant σm takes a positive value or a negative value, respectively.

Specifically, almost all the substituents other than the hydrogen atom correspond to this, and the preferred substituents in the present invention include the following substituents.
That is, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group,
Carbamoyl group, carboxyl group, imide group, carbonamide group, sulfonamide group, ureido group, thioureido group, (alkyl, aryl, or heterocycle) thio group, (alkyl or aryl) sulfonyl group, sulfo group, sulfamoyl group, halogen Atom, cyano group, nitro group, amino group, (alkyl, aryl, or heterocycle) amino group, and the like. These groups may be further substituted with any substituent.

When the group represented by R ₁ has a substituent, the substituent may be the same as the substituent which R ₂ may have.

R ₁ or R _{2 in} the general formula (I) may have a ballast group or a polymer, which is commonly used in a non-moving photographic additive such as a coupler, 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 group, alkoxy group, phenyl group, alkylphenyl group, phenoxy group, alkylphenoxy group 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 an adsorbing group adsorbing to silver halide incorporated therein. Examples of the adsorptive group include an alkylthio group, an arylthio group, a thiourea group, a thioamide group,
U.S. Pat. Nos. 4,385,108 and 4,459,347, such as mercapto heterocyclic groups and triazole groups, JP-A-59-
Nos. 195233, 59-200231 and 59-2
No. 01045, No. 59-201046, No. 59-20
No. 1047, No. 59-201048, No. 59-201
No. 049, JP-A-61-170733 and 61-27.
Nos. 0744, 62-948 and 63-234244
And the groups described in JP-A-63-234245 and JP-A-63-234246. These adsorbing groups to silver halide may be precursors. Examples of such precursors include the groups described in JP-A-2-285344.

R ₁ or R ₂ of the general formula (I) may contain a plurality of hydrazino groups as a substituent, and at this time, the compound represented by the general formula (I) is a multimer with respect to the hydrazino group. And specifically, for example, JP-A-64-86
134, JP-A-4-16938, JP-A-5-197.
No. 091.

Next, examples of the hydrazine derivative of the present invention will be shown, but the present invention is not limited thereto.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

The compound represented by the general formula (I) of the present invention can be easily synthesized by a known method.

Specifically, for example, the compounds 1 and 3 of the present invention can be synthesized in the same manner as the synthesis examples of the compounds D-2 and D-39 in JP-A-62-86354 (pages 6 to 7). .

As the hydrazine derivative used in the present invention, in addition to the above, RESEARCH DISCLOSURE Item 2
3516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,207.
No. 4269929, No. 4276364, No. 42
No. 78748, No. 4385108, No. 4459347.
No. 4,478,928, 4560638, 46.
86167, 4912016, 4988604
No. 4,994,365, 5041355, 51
04769, British Patent No. 2011391B, European Patent Nos. 217310, No. 301799, and No. 35689.
No. 8, JP-A-60-179734 and JP-A-61-1707.
No. 33, No. 61-270744, No. 62-17824.
No. 6, No. 62-270948, No. 63-29751.
No. 63-32538, No. 63-104047,
63-121838, 63-129337, 63-223744, 63-234244, 6
3-234245, 63-234246, 63
-294552, 63-306438, 64-
10233, JP-A-1-90439, 1-100
No. 530, No. 1-105941, No. 1-105943
No. 1, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-283549, No. 1-2.
No. 85940, No. 2-2541, No. 2-77057.
No. 2, No. 2-139538, No. 2-196234, No. 2-196235, No. 2-198440, No. 2-1.
No. 98441, No. 2-198442, No. 2-2200.
42, 2-221953, 2-221954.
No. 2-285342, 2-285343, 2-289843, 2-302750, 2-3.
04550, 3-37642, 3-54549.
No. 3, No. 3-125134, No. 3-184039, No. 3-240036, No. 3-240037, No. 3-2.
59240, 3-280038, 3-2825.
No. 36, No. 4-51143, No. 4-56842, No. 4-84134, No. 2-230233, No. 4-96.
053, 4-216544, 5-45761.
No. 5, No. 5-45762, No. 5-45763, No. 5-
455764, 5-45765, and Japanese Patent Application No. 5-949.
Those described in No. 25 can be used in combination.

In addition to these, compounds represented by (Chemical formula 1) described in JP-B-6-77138, specifically, 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 the general formula (6), specifically, Compounds 4-1 to 4- described on pages 25 and 26 of the publication.
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 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)
The compound represented by I), specifically, pages 10 to 2 of the same 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. Those described in can be used in combination.

Further, in the present invention, March 2, 1991.
Various hydrazine derivatives described on pages 25 to 34 of "Public Technology (Pages 1 to 207)" (published by Aztec Co., Ltd.) issued on May 2 can be used in combination with the hydrazine derivative of the present invention.

The amount of the hydrazine derivative used in the present invention is 1 × 10 ⁻⁶ mol to 1 × 10 ⁶ mol per mol of 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 is 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.

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.

The reducing agent used in the present invention may be any substance that 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 should be present as 1 to 10% by weight of the imaging layer. In multi-layer constructions, a slightly higher proportion of about 2-15% tends to be more desirable when the reducing agent is added to layers other than the emulsion layer.

A wide range of reducing agents have been disclosed in the photothermographic materials using organic silver salts. For example, amide oximes such as phenylamidooxime, 2-thienylamidooxime and p-phenoxyphenylamidooxime; azines such as 4-hydroxy-3,5-dimethoxybenzaldehydeazine; 2,2'-bis (hydroxymethyl A) a combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid, such as a combination of propionyl-β-phenylhydrazine and ascorbic acid; polyhydroxybenzene, 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′-
Bis-β as exemplified by binaphthyl, 6,6′-bibromo-2,2′-dihydroxy-1,1′-binaphthyl and bis (2-hydroxy-1-naphthyl) methane
-Naphthol; a combination of bis-β-naphthol and a 1,3-dihydroxybenzene derivative (eg, 2,4-dihydroxybenzophenone or 2 ', 4'-dihydroxyacetophenone); 3-methyl-1-phenyl-
5-pyrazolone, such as 5-pyrazolone; reductone as exemplified by dimethylaminohexose reductone, anhydrodihydroaminohexose reductone and anhydrodihydropiperidone hexose reductone; 2,6-dichloro-4 Sulfonamidophenol reducing agents such as -benzenesulfonamidophenol and p-benzenesulfonamidophenol; 2-phenylindane-1,3-dione and the like; 2,2-dimethyl-7
Chromans such as -t-butyl-6-hydroxychroman; 2,6-dimethoxy-3,5-dicarboethoxy-
1,4-dihydropyridines such as 1,4-dihydropyridine; bisphenols (for example, bis (2-hydroxy-3-tert-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 preferable reducing agents in the present invention are the following general formulas (RI), general formulas (R-II) and general formulas (R-II).
I) and compounds represented by the general formula (R-IV).

[0043]

Embedded image

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

[0045]

Embedded image

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

[0047]

Embedded image

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
Including _{R 13, R 11 '~R 13} ', R 21 ~R 26, R 21 '~R 24') is a hydrogen atom, an alkyl group (having 1 to 30 carbon atoms),
An aryl group, an aralkyl group, a halogen atom, an amino group, or a substituent represented by -OA. However, R ₁
To R ₅ and at least one of R ₁ ′ to R ₅ ′ and at least one of R _{7 to} R ₁₀ are —OA
Is a group represented by Further, R may form a ring with each other. A and A'are hydrogen atoms and alkyl groups (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, an alkyl group (including an active methine group), a nitro group, an alkenyl group, an alkynyl group, an aryl group, a group containing a heterocyclic ring, 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 hydrazino group, a quaternary ammonium group, a mercapto group, an (alkyl, aryl, or heterocycle) thio group, an (alkyl or aryl) sulfonyl group, an (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, phosphoric amide group, group containing a phosphoric 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 preferred examples include those exemplified as the substituent of R. Further, the substituent may be substituted multiple times such as the substituent, the substituent of the substituent, the substituent of the substituent of the substituent,... The illustrations apply.

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

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.

[0052]

[Table 6]

[0053]

[Table 7]

[0054]

[Chemical 6]

[0055]

[Table 8]

[0056]

[Chemical 7]

[0057]

[Table 9]

[0058]

[Table 10]

[0059]

[Table 11]

[0060]

[Table 12]

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. Examples of onium salt-type nucleation accelerators include Japanese Patent Application No. 8-37053, pages 16 to 2
The thing described in page 1 is mentioned.

The examples will be listed below. JP 7
-77783, page 48, lines 2 to 37, specifically compound A-1), pages 49 to 58.
~ A-73). (Formula 2) described in JP-A-7-84331
1) Compounds represented by (Chemical Formula 22) and (Chemical Formula 23), specifically, compounds described on pages 6 to 8 of the same publication. Compounds represented by general formula [Na] and general formula [Nb] described in JP-A-7-104426.
Compounds of Na-1 to Na-22 and compounds of Nb-1 to Nb-12 described on pages 6 to 20. Japanese Patent Application No. 7-378
Represented by general formula (1), general formula (2), general formula (3), general formula (4), general formula (5), general formula (6) and general formula (7) described in No. 17. Compounds, specifically the compounds 1-1 to 1-19 described in the same specification, 2-1 to 2-
22 compounds, 3-1 to 3-36 compounds, 4-1 to 4
-5 compound, 5-1 to 5-41 compound, 6-1 to 6
Compounds of -58 and 7-1 to 7-38.

The amount of the nucleation accelerator added is 1 × with respect to 1 mol of silver.
10 ^{−6 to} 2 × 10 ⁻² mol is preferable, 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol is more preferable, and 2 × 10 ⁻⁵ to 1 × 10 ⁻² mol is most preferable.

The photothermographic material of the present invention forms a photographic image using a photothermographic processing method. As such a photothermographic material, as described above, for example, U.S. Pat. Nos. 3,152,904, 3457075, and D.I. Morgan and B.A. "Thermally Processed Silver System" by Shely
Systems "(Imaging Processes and Materials) N
eblette Eighth Edition, Sturge, V.I. Walworth, A. Edited by Shepp, No. 2
Page, 1969.

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 for controlling the color tone of silver, and a reducing agent 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.

A filter layer may be formed on the same side or the opposite side of the photosensitive layer in order to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or a pigment. . 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 gradation.

Various additives may be added to any of the light-sensitive layer, the non-light-sensitive 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, a coating aid and the like.

Suitable binders are transparent or translucent, generally colorless, and include natural polymeric 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 (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.

The preferred toning agent is phthalazone.

A silver halide useful as a catalytically active amount of a photocatalyst is any photosensitive silver halide (eg, silver bromide, silver iodide, silver halide, silver chlorobromide, silver iodobromide, chloroiodo odor). However, it is preferable that the iodide ion is contained. 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.

Reducible silver sources are silver salts of organic and heteroorganic acids containing a source of reducible silver ions, 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 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 the following. More preferably, it is 2 g / m ² or less.

An antifoggant may be contained in such a light-sensitive material. 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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[0079]

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Even more preferred antifoggants are US Pat. No. 5,028,523 and British patent application No. 9222138.
Nos. 3.4, 9300147.7 and 931179
No. 0.1.

The photothermographic material of the present invention includes, for example, JP-A-63-159841, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, and JP-A-63-259651.
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 used in the present invention are, for example, 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) with respect to an argon laser light source, JP-A-60-162247 and JP-A-2-4865.
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.

The exposure of the photothermographic material of the present invention is carried out by Ar laser (488 nm) and 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 invention may be provided with a layer containing a dye 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 synthetic resin (eg polyethylene, polypropylene, polystyrene), plastic film (eg polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate). A metal plate (for example, aluminum, aluminum alloy, zinc, iron, copper), paper or plastic film laminated or vapor-deposited with the above metals is used.

On the other hand, when the plastic film is passed through the heat developing machine, the size of the film expands and contracts. 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.

[0091]

【Example】

Example 1 (Preparation of Organic Silver Salt Emulsion A) 840 g of behenic acid and 95 g of stearic acid were added to 12 liters of water, and while maintaining at 90 ° C., 48 g of sodium hydroxide and 63 g of sodium carbonate.
Was dissolved in 1.5 liters of water. 30
After stirring for 50 minutes, the temperature is adjusted to 50 ° C. and N-bromosuccinimide 1%
An aqueous solution (1.1 L) was added, and then 2.3 L of a 17% silver nitrate aqueous solution was gradually added with stirring. Further, the liquid temperature was set to 35 ° C., and potassium bromide 2% while stirring.
After 1.5 liters of the aqueous solution was added over 2 minutes, the mixture was stirred for 30 minutes, and 2.4 liters of a 1% aqueous solution of N-bromosuccinimide was added. 1. Stir to this water-based mixture.
After adding 3300 g of a 2 wt% polyvinyl acetate in butyl acetate, the mixture was allowed to stand for 10 minutes to separate into two layers, the aqueous layer was removed, and the remaining gel was washed twice with water. 2.6% of polyvinyl butyral (Denka butyral # 3000-K manufactured by Denki Kagaku Kogyo Co., Ltd.) was used as a mixture of gelled behenic acid / silver stearate and silver bromide thus obtained.
Dispersed with 1800 g of 2-butanone solution, and further 600 g of polyvinyl butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo Co., Ltd.) and 3 of isopropyl alcohol.
Organic silver salt emulsion (average minor axis 0.05μ)
m, average major axis 1.2 μm, acicular particles with a coefficient of variation of 25%)
I got

(Preparation of Emulsion Layer Coating Solution A) Each chemical was added to the organic silver salt emulsion obtained above in the following amounts per mol of silver. At 25 ° C., 10 mg of sodium phenylthiosulfonate, 75 mg of sensitizing dye A, 2-mercapto-5-
2 g of methylbenzimidazole, 2-mercapto-5
Methylbenzothiazole 1 g, 4-chlorobenzophenone-2-carboxylic acid 21.5 g and 2-butanone 580
g and dimethylformamide (220 g) were added with stirring and left for 3 hours. Then, 4.5 g of 4,6-ditrichloromethyl-2-phenyltriazine, 2 g of disulfide compound A, 1,1-bis (2-hydroxy-3,5
-Dimethylphenyl) -3,5,5-trimethylhexane 160 g, phthalazine 15 g, tetrachlorophthalic acid 5 g, the hydrazine derivative shown in Table 13 in the amount shown in Table 13, Megafax F-176P (Dainippon Ink and Chemicals Incorporated) 1.1 g of Fluorosurfactant manufactured by Co., Ltd., 590 g of 2-butanone, and 10 g of methyl isobutyl ketone were added with stirring.

[0093]

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[0094]

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(Preparation of Emulsion Surface Protective Layer Coating Solution A) CAB1
71-15S (Eastman Chemical Co., Ltd. cellulose acetate butyrate) 75 g, tetrachlorophthalic anhydride 1.
5 g, 2-tribromomethylsulfonylbenzothiazole 10 g, phthalazone 2 g, Megafax F-17
6P 0.3 g, Sildex H31 (Doikai Chemical Co., Ltd. spherical silica average size 3 μm) 2 g, sumidur N3500
(Sumitomo Bayer Urethane Polyisocyanate) 5g
Was dissolved in 3070 g of 2-butanone and 30 g of ethyl acetate.

(Preparation of Support Having Back Surface) Polyvinyl butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo KK) 6 g, Sildex H121 (spherical silica average size 12 μm manufactured by Dokai Kagaku) 0 .2g,
0.2 g of Sildex H51 (average size of true spherical silica 5 μm manufactured by Dokai Chemical Co., Ltd.) and 0.1 g of Megafax F-
It was added to 64 g of 176P2-propanol with stirring to dissolve and mix. Further, a mixed solution of 420 mg of Dye A dissolved in 10 g of methanol and 20 g of acetone and a solution of 0.8 g of 3-isocyanatomethyl-3,5,5, -trimethylhexyl isocyanate dissolved in 6 g of ethyl acetate were added to the coating solution. Prepared

[0097]

[Chemical 12]

A back surface coating solution was coated on a polyethylene terephthalate film consisting of a moisture-proof undercoat containing vinylidene chloride on both sides so as to have an optical density of 633 nm of 0.7.

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 5 μm. Applied.

(Evaluation of Photographic Performance) Helium-neon light source color scanner SG manufactured by Dainippon Screen Co., Ltd.
After exposing the photographic material using -608, the sample was processed (developed) for 25 seconds at 115 ° C using a heat drum, and further exposed for 15 seconds with a halogen lamp. It was carried out by the total. The measurement results were evaluated based on Dmax and sensitivity (reciprocal of the ratio of the amount of exposure that gives a density 1.5 higher than Dmin). 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. Table 13 shows the results.

(Evaluation of Black Spots) The unexposed light-sensitive material was developed for 60 seconds at 120 ° C. using a heat drum, and the number of black spots generated was visually evaluated. "5" is the best and "1" is the worst quality. "3" is the practical limit, and "2" and "1" are not practical. Table 13 shows the results.

[0102]

[Table 13]

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

Example 2 (Preparation of silver halide grains B) 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water and the pH was adjusted to 3.0 at a temperature of 35 ° C., and then 74 g of silver nitrate was added. 370 ml of an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of 94: 6 and an aqueous solution containing K ₄ [Fe (CN) ₆ ] at a pAg of 7.7 and a control double jet method for 10 minutes. Was added. [Fe (CN)
₆ ] ^-4 was added so as to be 3 × 10 ^-5 mol per mol of silver. Thereafter, 4-hydroxy-6-methyl 1,3
0.3 g of 3a, 7-tetrazaindene was added, and NaO was added.
The pH was adjusted to 5 with H to obtain cubic silver iodobromide grains having an average size of 0.06 μm, a projected area variation coefficient of 8%, and a {100} face ratio of 87%. The emulsion was coagulated and precipitated using a gelatin coagulant, desalted, and 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and pAg to 7.5.

(Preparation of Organic Acid Silver Emulsion B) Behenic Acid 10.
6 g of distilled water and 300 ml of distilled water were mixed at 90 ° C for 15 minutes, and 31.1 ml of 1N-NaOH aqueous solution was added to 15 while stirring vigorously.
The mixture was added over a period of 1 minute, left as it was for 1 hour, and then cooled to 30 ° C. Next, 7 ml of a 1N-phosphoric acid aqueous solution was added, and N-bromosuccinimide 0.1
After the addition of 3 g, silver halide grains B prepared in advance were added so that the amount of silver halide was 2.5 mmol. Further, 25 ml of a 1N-silver nitrate aqueous solution was continuously added over 2 minutes, and stirring was continued for 90 minutes. To this aqueous mixture, 37 g of a 1.2 wt% butyl acetate solution of polyvinyl acetate was added to form flocs in the dispersion, water was removed, and water was further washed and removed twice, and then polyvinyl butyral was added. 20 g of a mixed solution of 2.5 wt% butyl acetate of Denka Butyral # 3000-K manufactured by Denki Kagaku Kogyo Co., Ltd. and 1: 2 of isopropyl alcohol was added with stirring, and then the gelled organic acid thus obtained, 7.8 g of polyvinyl butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo KK) in a mixture of silver halides,
Add 57 g of 2-butanone and disperse with a homogenizer.
Silver behenate emulsion (average particle size 0.04 μm, average major axis 1
to obtain acicular particles having a particle diameter of μm and a coefficient of variation of 30%.

(Preparation of Emulsion Layer Coating Solution B) To the organic silver salt emulsion obtained above, the respective chemicals were added in the following amounts per mol of silver. At 25 ° C., 10 mg of sodium phenylthiosulfonate, 85 mg of sensitizing dye A, 2-mercapto-5-
Methylbenzimidazole 2 g, 4-chlorobenzophenone-2-carboxylic acid 21.5 g and 2-butanone 580
g and dimethylformamide (220 g) were added with stirring and left for 3 hours. Then, 4,6-ditrichloromethyl-2-phenyltriazine (4 g), disulfide compound A (2 g), 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 1
70g, tetrachlorophthalic acid 5g, phthalazine 15g
, The amount of the hydrazine derivative shown in Table 14, the amount shown in Table 14, Megafax F-176P (Dainippon Ink and Chemicals, Incorporated Fluorine-based surfactant) 1.1 g, 2-butanone 590 g, methyl isobutyl ketone 10 g. Was added with stirring.

CAB171-15S (cellulose acetate butyrate manufactured by Eastman Chemical Co., Ltd.) 75 g, 4-methylphthalic acid 5.7 g, tetrachlorophthalic anhydride 1.5
g, 5-tribromomethylsulfonyl-2-methylthiadiazole 8 g, 2-tribromomethylsulfonylbenzothiazole 6 g, phthalazine 3 g, 0.3 g of Megafax F-176P, Sildex H31 (a true spherical silica manufactured by Dokai Kagaku Co., Ltd. Average size 3μm) 2g, sumidu
r N3500 (Polyisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) 6 g, 2-butanone 3070 g and ethyl acetate 30 g
Was prepared.

(Preparation of support having back surface) 6 g of polyvinyl butyral (Denka Butyral # 4000-2 manufactured by Denki Kagaku Kogyo KK), Sildex H121 (average spherical silica size 12 μm manufactured by Dokai Kagaku) 0.2
g, 0.2 g of Sildex H51 (average particle size 5 μm of spherical silica manufactured by Dokai Kagaku Co., Ltd.), and 0.1 g of Megafax F-176P2-propanol were added with stirring to dissolve and mix. In addition, 420 mg of Dye A
Was dissolved in 10 g of methanol and 20 g of acetone, and 0.8 g of 3-isocyanatomethyl-3,5,5-trimethylhexyl isocyanate was added to 6 g of ethyl acetate.
A solution dissolved in g was added to prepare a coating solution.

A back surface coating solution was coated on a polyethylene terephthalate film consisting of a moisture-proof undercoat containing vinylidene chloride on both sides so as to have an optical density of 633 nm of 0.7.

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 5 μm. Applied.

(Evaluation of Photographic Performance) Evaluation was made in the same manner as in Example 1. The results are shown in Table 14.

(Evaluation of black spots) Evaluation was made in the same manner as in Example 1. The results are shown in Table 14.

[0113]

[Table 14]

(Results) By using the hydrazine compound of the present invention, a photothermographic material capable of satisfying all of high Dmax, high contrast and black spots could be obtained.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location // C07C 311/37 7419-4H C07C 311/37 317/32 7419-4H 317/32 323/31 7419-4H 323/31 C07D 471/04 112 C07D 471/04 112

Claims (1)

[Claims] 1. A photothermographic material comprising an organic silver salt, a silver halide, and a reducing agent, which contains a hydrazine derivative represented by the following general formula (I). General formula (I) In the formula, R ₂ represents an aliphatic group, and R ₁ represents an alkyl group, an aryl group, or a heterocyclic group substituted with at least one electron-withdrawing group or electron-donating group. A ₁ , A ₂
Each represents a hydrogen atom, or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.