JP2000169741A - Thermally developable silver salt photographic photosensitive material containing novel photosensitive colorant, and compound therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermally developable photosensitive material improved in sensitivity, fog, and storage stability by incorporating a specific photosensitive colorant into the same. SOLUTION: This photosensitive material contains at least one compound selected from the group of compounds represented by the formula (wherein R1 and R2 are each an aliphatic group; L1 to L9 are each a methine group; a, b, c, d, and f are each 0 or 1; X is an ion necessary for neutralizing the electric charge in the molecule; n is a number necessary for neutralizing the electric charge in the molecule; Q1 and Q2 are each a group of nonmetallic atoms necessary for forming a 5- or 6-membered nitrogen-containing heterocycle which may be a condensed ring; -CR3=CR4R5 is a substituent on the nitrogen-containing heterocycle formed by Q1; -CR6=CR7R8 is a substituent on the nitrogen-containing heterocycle formed by Q2; R3 to R8 are each independently H, a halogen, or a monovalent substituent provided each of R3 to R5 does not form an aromatic ring together with atoms forming Q1 and each of R6 to R8 does not form an aromatic ring together with the atoms forming Q2; and n1 and n2 are each 0-4).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a heat-developable silver salt photographic material containing a novel photosensitive dye and having improved photographic properties.

[0002]

2. Description of the Related Art Various dyes are used as dyes and pigments for various uses such as dyeing materials for fibers, coloring materials for resins and paints, image forming materials for photographs, printing, copying machines, printers, and light absorbing materials for color filters. It is widely used in In recent years, various image forming dyes for color hard copy using inkjet, electrophotography, silver halide photography, thermal transfer, etc. have been proposed, and with the development of electronic imaging,
The demand for filter dyes for solid-state image pickup tubes and color liquid crystal televisions, dyes for optical recording media using semiconductor lasers, and the like is increasing, and the use fields of dyes are expanding.

In a silver halide photographic application, when a certain dye is added to a photosensitive silver halide emulsion (hereinafter also referred to as a silver halide emulsion or simply an emulsion), the photosensitive wavelength range of the silver halide emulsion is expanded, Optical sensitization is a well-known fact.

[0004] A large number of compounds have been known as dyes used for this purpose. For example, the theory of the photographic process, 4th edition (1977, Macmillan) by TJ James Co., N.
Y. ) P. 194-234, "The Cyanine Soy and Related Compounds" by Francis M. Harmer (1964, John Willy and
Sands, N. Y. ), Dem Stammer, "The Chemistry of Heterocyclic Compounds, Vol. 30," p. 441- (1977, John Willy and Sons, NY).
Among these, styryl dyes, hemicyanine dyes, cyanine dyes, merocyanine dyes, xanthene dyes, etc. are selected from various types of heterocyclic mother nuclei or aromatic rings and conjugated chains, and the substituents, from near ultraviolet by selecting and combining. It is derived into a dye having an arbitrary absorption maximum wavelength in the near infrared region.

[0005] Slight differences in the structure of photosensitive dyes greatly affect photographic performance such as sensitivity, fogging, and storage stability. However, it is difficult to predict the effects in advance, and there have been many conventional methods. Researchers have tried to synthesize a number of photosensitive dyes and examine their photographic performance. However, it is still impossible to predict the photographic performance.

In recent years, in order to generate a final image,
There is a growing demand for so-called dry photosensitive materials, in particular, heat-developable silver salt photosensitive materials that do not use a liquid developer, from the viewpoint of workability free of liquid preparation and environmental protection by eliminating waste liquid. However, a silver image obtained from a heat-developable silver halide photographic material has a lower sensitivity than a silver image obtained from a silver halide photographic material obtained by liquid development. There was a problem that the fog increased greatly when stored. For this reason, a new photosensitive dye has been demanded.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a heat-developable silver salt photographic material having a specific photosensitive dye and improved sensitivity, fog and storage stability.

[0008] The second object is to use pharmaceuticals, dyeing materials for fibers, coloring materials for resins and paints, image forming materials in photographs, printing, copying machines, printers, ink jets, electrophotography, silver halide photography, thermal transfer, and the like. Image forming dyes for color hard copy, electrophotography, photosensitive dyes in photographs such as silver halide photographs,
It is an object of the present invention to provide a compound which can be widely applied to a light absorbing material of a color filter, a filter dye for a solid-state image pickup tube or a color liquid crystal television, and a dye for an optical recording medium using a semiconductor laser.

[0009]

The above objects of the present invention have been attained by the following constitutions.

[0010] 1. A heat-developable silver salt photographic material comprising at least one compound represented by the following general formula (1).

[0011]

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[Wherein R ¹ and R ² each represent an aliphatic group;
L ^{1 to} L ⁹ represent a methine group, and a, b, c, d, e, and f each represent 0 or 1. X represents an ion necessary to neutralize the intramolecular charge, and n represents a number required to neutralize the intramolecular charge. Q ¹ and Q ² each represent a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may form a condensed ring, and —CR ³ ＣＲCR ⁴ R ⁵ is represented by Q ¹ Represents a substituent that is substituted on the formed nitrogen-containing heterocyclic ring,
—CR ⁶ ＣＲCR ⁷ R ⁸ represents a substituent that is substituted on the nitrogen-containing heterocyclic ring formed by Q ² , and R ^{3 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, and a monovalent substituent. Represents However, R ^{3 to} R ⁵ do not form an aromatic ring together with the atoms forming Q ¹ , and R ^{6 to} R ⁸ do not form an aromatic ring together with the atoms forming Q ² . n1 and n2 are 0 to 4
, But do not become 0 at the same time. ) 2. A heat-developable silver salt photographic material comprising at least one compound represented by the following general formulas (2) to (6).

[0013]

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Wherein R ¹ and R ² each represent an aliphatic group;
L ^{1 to} L ⁹ represent a methine group, and Y ¹ and Y ² represent an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom or a carbon atom. X
Represents the ion necessary to neutralize the charge in the molecule, and n
Represents the number necessary to neutralize the charge in the molecule. Q ³ ,
Q ⁴ represents a group of nonmetallic atoms necessary for forming an aromatic ring or a heterocyclic ring, and —CR ³ ＣＲCR ⁴ R ⁵ is substituted with the aromatic ring or the heterocyclic ring formed by Q ³ represents a substituent, -CR ⁶ = CR ⁷ R ⁸ represents a substituent which is substituted on the aromatic ring or heterocyclic ring formed by Q ^4, R ³
To R ⁸ each independently represent a hydrogen atom, a halogen atom, or a monovalent substituent. However, R ^{3 to} R ⁵ do not form an aromatic ring together with the atoms forming Q ³ , and R ^{6 to} R ⁸ represent Q ⁴
Does not form an aromatic ring with the atoms forming
n1 and n2 represent 0 to 4, but do not become 0 at the same time. ) 3. 3. The heat-developable silver salt photographic material as described in 1 or 2 above, further comprising a photosensitive silver halide and an organic silver salt.

4. 4. A heat-developable image forming method, comprising exposing the heat-developable silver halide photographic material as described in 1, 2, or 3 to a laser.

5. In the above formula (1), at least one of L ^{1 to} L ⁹ is involved in ring formation.

6. In the above formula (2), L ¹ is involved in ring formation.

[7] A compound according to the above formula (3), wherein at least one of L ^{1 to} L ³ is involved in ring formation.

8. In the above formula (4), at least one of L ^{1 to} L ⁵ is involved in ring formation.

9. In the above formula (5), at least one of L ^{1 to} L ⁷ has a monovalent substituent.

10. In the general formula (5), L ^{1 to} L ⁷
Wherein at least one of the above is involved in ring formation.

11. A compound represented by the general formula (6).

12. In the general formula (6), L ^{1 to} L ⁹
A compound having a monovalent substituent in at least one of the above.

13. In the general formula (6), L ^{1 to} L ⁹
Wherein at least one of the above is involved in ring formation.

Hereinafter, the present invention will be described more specifically.

The present invention has been made in view of the current state of the heat-developable silver salt photographic light-sensitive material described above,
The fact that the compound represented by formula (6) is very effective in spectral sensitization of a heat-developable silver salt photographic light-sensitive material containing a silver halide or an organic silver salt as a photosensitive dye. I found it.

Among heat-developable silver halide photographic materials (hereinafter sometimes simply referred to as heat-developable light-sensitive materials), those generally referred to as dry silver are different from ordinary light-sensitive materials. Instead, those which are insoluble in water such as polyvinyl butyral, cellulose acetate butyrate and cellulose acetate and are soluble in organic solvents such as toluene, acetone or isopropanol are mainly used. This is because the binder layer itself is used as a reaction medium during thermal development to soften and progress the development reaction, so that the binder layer is formed so as to form a matrix convenient for diffusion of various reagents necessary for the development reaction. For this reason, the adsorption equilibrium of the photosensitive dye with respect to the silver halide contained in the photothermographic layer is significantly different from that of the gelatin matrix. It is considered that this resulted in disadvantages such as poor storage stability. The present inventors have intensively studied to improve the above-mentioned disadvantages, and as a result, the general formula (1)
It has been found that compounds having the structures of (6) to (6) are useful as photosensitive dyes. As a result, fog, sensitivity, and high illuminance failure characteristics were improved, and storage stability was also improved. Although it is not possible to fully explain why these compounds give good results, it seems that the compounds of the present invention have improved the above-mentioned disadvantages by having a group effective for silver halide adsorption. That is, the photosensitive dye of the present invention has 2
Although the group having a heavy bond is directly substituted, these substituents enhance the π-electron interaction between the compounds, which makes it easier for the dye molecules to form an aggregated structure, and as a result, the adsorption becomes stronger. The present inventors presume that these photographic properties and storage stability have been improved.

These sensitizing dyes may have a substituent on the methine chain in the structure, and preferably, these methine compounds represented by L ^{1 to} L ⁹ in the general formulas (1) to (6). At least one chain is involved in ring formation, eg, L ¹ forms a ring with the N-position alkyl group on the dye nucleus, eg, three adjacent methines, eg, L ² , L ³ , L ⁴ Are compounds forming an isophorone ring or a dehydrodecalin ring. This has the effect of further improving the stability of the compound itself by making the dye structure rigid, especially when the methine chain is long and absorbs to the infrared region.

As described above, the photosensitive dye of the present invention is presumed to have stronger adsorption than conventional ones, and is useful when used in a heat-developable photographic material. Therefore, the presence of an organic silver salt such as silver behenate is not essential, and any silver halide photographic light-sensitive material that can be developed by heat can be used.
It is effective. For example, US Pat. No. 3,220,84
No. 6, No. 3,523,795, No. 3,301,6
No. 78, No. 3,506,444 and the like. These are photothermographic materials of a type not containing an organic silver salt, but the present invention is particularly effective and useful in the case of a so-called dry silver containing an organic silver salt.

The compound of the present invention is a so-called photosensitive dye, and is effective in addition to a heat-developable photographic light-sensitive material containing silver halide. The photosensitive dye according to the present invention can be used in a photosensitive system other than the system using silver halide, and can be used in other systems such as electrophotography and radical photography which form any latent image by light absorption thereof.
Further, it can be used as an image forming agent for forming various images by utilizing its light absorption characteristics. In particular, these cyanine dyes are advantageous in vivid color reproduction when used as an image forming agent because they have a narrow absorption band and a large extinction coefficient. These applications include inkjet, electrophotography,
There are image forming dyes for color hard copy using silver salt photography, thermal transfer and the like. In addition, it is widely used in various applications such as color filter materials utilizing the above characteristics, filter dyes such as filter dyes for solid-state image pickup tubes and color liquid crystal televisions, and dyes for optical recording media using semiconductor lasers. Is possible. It can also be used as a coloring material for pharmaceuticals, fibers, and resins and paints.

In the compounds represented by the general formulas (1) to (6), the aliphatic groups represented by R ¹ and R ² include, for example,
A branched or straight-chain alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, iso-pentyl group, 2-ethyl-hexyl group, octyl group, decyl group) Alkenyl group having 3 to 10 carbon atoms (for example, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4- Hexenyl group) and an aralkyl group having 7 to 10 carbon atoms (eg, benzyl group, phenethyl group, etc.).

In the general formulas (1) to (6), R ¹ and R ²
Further includes a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.) and an alkyl group (eg,
Methyl group, ethyl group, propyl group, butyl group, pentyl group, iso-pentyl group, 2-ethyl-hexyl group, octyl group, decyl group, etc., aryl group (eg, phenyl group, carboxyphenyl group, etc.), complex Ring group (for example,
Imidazolyl group, thiazolyl group, benzoxazolyl group, pyridyl group, pyrrolyl group, indolyl group, pyrimidinyl group, etc.), alkenyl group (for example, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group,
3-pentenyl group, 1-methyl-3-butenyl group, 4-
Hexenyl group), alkynyl group (eg, 1-propynyl group), alkoxy group (eg, methoxy group, ethoxy group, propoxy group, etc.), aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), hetero Aryloxy group (for example, 2-pyridyloxy group), alkylthio group (for example, methylthio group, trifluoromethylthio group, etc.), arylthio group (for example, phenylthio group, 2-naphthylthio group), heteroarylthio group (for example, 3- Thienylthio), aralkyl groups (for example,
Benzyl group, 3-chlorobenzyl group, etc.), carboxyl group, acylamino group (eg, acetylamino group, benzoylamino group, etc.), acyl group (eg, acetyl group,
A benzoyl group, a sulfonyl group (eg, a methanesulfonyl group, a trifluoromethanesulfonyl group, etc.), a carbamoyl group (eg, a carbamoyl group, an N, N-dimethylcarbamoyl group, an N-morpholinocarbonyl group, etc.),
Sulfamoyl group (sulfamoyl group, N, N-dimethylsulfamoyl group, morpholinosulfamoyl group, etc.), hydroxyl group, styryl group, nitro group, cyano group, sulfonamide group (for example, methanesulfonamide group, butanesulfonamide Group, benzenesulfonylamino group, etc.), amino group (eg, amino group, N, N-dimethylamino group, N, N-diethylamino group, etc.), sulfo group, phosphono group, sulfate group, sulfino group, sulfonylaminocarbonyl group ( For example, methanesulfonylaminocarbonyl, ethanesulfonylaminocarbonyl group, etc.), acylaminosulfonyl group (eg, acetamidosulfonyl, methoxyacetamidosulfonyl group, etc.), acylaminocarbonyl group (eg, acetamidocarbonyl, methoxy Etc. acetamido group), sulfinyl aminocarbonyl group (e.g., methanesulfinyl aminocarbonyl, may be substituted with a substituent ethanesulfinyl aminocarbonyl group) or the like.

In the general formulas (1) to (6), R ^{3 to} R ⁸
Each independently represents a hydrogen atom, a halogen atom or a monovalent substituent, and examples of the monovalent substituent include the aforementioned R ¹ , R ²
And a substituent that may be substituted.

In the general formulas (2) to (6), Q ³ and Q ⁴
Examples of the aromatic or heterocyclic ring formed by include a benzene ring, a naphthalene ring, a thiophene ring, a thiazole ring, a furan ring, a pyridine ring, a pyrrole ring, an oxazole ring, a thiadiazole ring, and a pyrazine ring.

The ring formed by Q ³ and Q ⁴ may further be substituted with a substituent which may be substituted on R ¹ and R ² , and may further contain a saturated carbon ring, a benzene ring, a naphthalene ring, The ring may form a condensed ring.

In the general formulas (1) to (6), L ^{1 to} L ⁹
Each independently represents a substituted or unsubstituted methine carbon,
Examples of the group substituted on the methine carbon include the aforementioned R ¹ ,
Substituents and the like which may be substituted on R ² can be mentioned.

As described above, the methine carbon can be bonded to an adjacent methine carbon or a separated methine carbon via an alkylene group to form a 5- or 6-membered carbon ring, It may be bonded to R ¹ or R ² to form a 5- or 6-membered nitrogen-containing heterocyclic ring. The following are specific examples.

[0038]

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In the formula, Y ¹ and Y ² each represent an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom or a carbon atom;
V ¹ and V ² represent hydrogen and a group which may be substituted with R ¹ or R ^2, and V ¹ and V ² may together form an aromatic ring or a heterocyclic ring . Examples of the aromatic ring and hetero ring formed include a benzene ring, a naphthalene ring, a thiophene ring, a thiazole ring, a furan ring, a pyridine ring, a pyrrole ring, an oxazole ring, a thiadiazole ring, and a pyrazine ring. The ring formed by V ¹ and V ² may be further substituted with a substituent which may be substituted on R ¹ and R ² , and may be a saturated carbon ring, a benzene ring, a naphthalene ring or a heterocyclic ring. May form a condensed ring. Z ^A represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic group, and may be condensed with a saturated carbon ring, a benzene ring, a naphthalene ring or a heterocyclic ring. R ^A, R ^B, R ^D and R ^E are each a hydrogen atom, an alkyl group or an aryl group, R ^C
And R ^F are each a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an arylthio group,
Represents a heterocyclic thio group, an aryl group, an amino group, a heterocyclic group or a halogen atom, and t is an integer of 2 or 3. R ^A ,
Examples of the alkyl group represented by R ^B , R ^C , R ^D , R ^E, and R ^F include lower alkyl groups having 1 to 3 carbon atoms such as methyl, ethyl, propyl, and isopropyl. Examples of the group include a phenyl group and a p-tolyl group. Examples of the alkoxy group include a methoxy group and an ethoxy group. Examples of the alkylthio group include a group such as a methylthio group, and an aralkyl group. Examples thereof include a benzyl group, a phenethyl group, an m-bromobenzyl group and the like, and examples of the heterocyclic group include a morpholinyl group, a piperidyl group, a pyrrolidinyl group,
Examples include an imidazolinyl group and a pyrrolyl group.

Examples of the amino group represented by R ^C and R ^F include, for example, N, N-dimethylamino group and N, N-diethylamino group. Examples of the halogen atom include fluorine, chlorine and the like. Each atom.

X represents a cation or an acid anion;
Specific examples of the cation include a proton, an organic ammonium ion (for example, each ion such as triethylammonium and triethanolammonium), and an inorganic cation (for example, each cation such as lithium, sodium, and potassium). For example,
Examples include halogen ions (for example, chloride ion, bromine ion, iodine ion, etc.), p-toluenesulfonic acid ion, perchlorate ion, boron tetrafluoride ion, sulfate ion and the like. n is 0 when an internal salt is formed and the charge is neutralized.

The compounds represented by the general formulas (1) to (6) used in the silver halide emulsion, silver halide photographic light-sensitive material, heat-developable silver salt photographic light-sensitive material and the like of the present invention have at least one azole nucleus. With a structure that has two basic cores,
In the ultimate structure of the resonance system, an azolylidene structure and an azolium ion structure can be taken.

Specific examples of the compounds represented by formulas (1) to (6) used in the present invention are shown below, but the present invention is not limited thereto.

[0044]

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[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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The above-mentioned infrared photosensitive dye is described in, for example, FM Hammer, The Chemistry of H.
Ethecyclic Compounds, Vol. 18,
The Cyanine Dyes and Rela
ted Compounds (A. Weissberg
er ed. Published by Interscience, NewY
Ork 1964), JP-A-3-13838, JP-A-10-73900, JP-T-Hei 9-500222, U.S. Pat. No. 2,734,900, British Patent 774,77.
No. 9, J.I. Gen. Chem. USSR (Engl. T
ransl. 34; 1964; 2455; U.S. Patent No. 2,455,420; Org. Chem. US
SR (Engl. Transl.); 15; 1979;
774, Dokl. Chem. (Engl. Trans
l. 177; 1967; 1136, Chemish
e. Berichte. 119 (10); 1986;
The compound can be easily synthesized by the method described in 3102.

The photosensitive dye of the present invention may be used alone, or two or more photosensitive dyes may be used in combination. When the sensitizing dyes of the present invention are used alone or in combination, the total of 1 × 10 ^-6 mol to 5 × 10 ^-3 mol, preferably 1 × 10 ^-3 mol, per mol of silver halide is obtained.
10 ⁻⁵ mol to 2.5 × 10 ⁻³ mol, more preferably 4 ×
It is contained in the silver halide emulsion at a ratio of 10 ⁻⁵ mol to 1 × 10 ⁻³ mol.

When two or more photosensitive dyes are used in combination in the present invention, the photosensitive dyes can be contained in the silver halide emulsion at any desired ratio. The photosensitive dye of the present invention can be directly dispersed in an emulsion. Also, these are firstly suitable solvents such as methyl alcohol, ethyl alcohol, n
-Dissolved in propanol, methyl cellosolve, acetone, water, pyridine or a mixture thereof,
It can also be added to the emulsion in the form of a solution. Ultrasound can also be used for lysis.

As a method of adding the photosensitive dye, as described in US Pat. No. 3,469,987, the dye is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. A method of adding this dispersion to an emulsion, as described in JP-B-46-24185, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to the emulsion; Patent No. 3,822
No. 135, the dye is dissolved in a surfactant,
A method of adding the solution to an emulsion;
No. 4, as described in JP-A-50-80826, a method of dissolving using a compound that shifts to a longer wavelength side and adding the solution to an emulsion; For example, a method of dissolving in an acid and adding the solution to an emulsion is preferably used. Other additions to emulsions include U.S. Pat. Nos. 2,912,343 and 3,342,6.
No. 05, No. 2,996,287, No. 3,429,
No. 835 or the like. The photosensitive dye may be dispersed uniformly in the silver halide emulsion before it is coated on a suitable support, but may be dispersed in any step of the preparation of the silver halide emulsion.

A When two or more photosensitive dyes of the present invention are used in combination, the photosensitive dyes can be dispersed in a silver halide emulsion independently or in advance by mixing them in advance by the method described above. A dye having an absorption in the visible region for the purpose of supersensitization, a dye having no spectral sensitizing effect or a substance which does not substantially absorb visible light together with the photosensitive dye of the present invention, A substance exhibiting a feeling may be contained in the emulsion. Useful photosensitive dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (hereinafter abbreviated as RD) 176, 17643 (published in December 1978), page 23, J, p. Clause or Japanese Patent Publication No. 49-255
No. 00, No. 43-4933, JP-A-59-19032
No. 59-192242, No. 62-123454
And JP-A-3-15049.

The photothermographic material according to the present invention is described, for example, in US Pat. Nos. 3,152,904 and 3,457,07.
No. 5, and D.E. "Dry Silver Photo Material" by Morgan
Ophthalmic Material) and D.C. Morgan and B.A. "The Silver System Treated by Heat (Thermal)" by Shelly
ly Processed Silver System
ms) "(Imaging Processes and Materials
nd Materials) Neblette No. 8
Plate, Sturge, V.S. Walworth, A .; Shepp, 2nd page, 1969) and the like. Among them, the present invention is characterized in that an image is formed by thermally developing a photosensitive material at 80 to 140 ° C., and no fixing is performed.

The silver halide grains of the photosensitive silver halide according to the present invention can be used in such a photothermographic material.
It functions as an optical sensor. In order to suppress white turbidity after image formation and obtain good image quality, it is preferable that the average particle size is small, and the preferable average particle size is 0.20 μm or less, more preferably 0.1 μm or less.
03 μm to 0.15 μm, especially 0.03 μm to 0.11
μm is preferred. Here, the average grain size refers to the length of the edge of the silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal.
In the case of non-normal crystals, for example, in the case of spherical, rod-like, or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The silver halide grains are preferably monodisperse grains. The term “monodisperse particles” as used herein means particles having a monodispersity of 40% or less, more preferably 30% or less, and particularly preferably 0.1% or more.
The particles are 0% or less.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 Regarding the shape of silver halide grains,
Although there is no particular limitation, the ratio occupied by the Miller index [100] plane is preferably high, and this ratio is preferably at least 50%, more preferably at least 70%, particularly preferably at least 80%.
The ratio of the [100] plane of the Miller index is determined by the T.M. Tani, J .; Imaging Sci. , 2
9, 165 (1985).

Another preferred form of silver halide is tabular grains. The term “tabular grain” as used herein means a thickness hμ in the vertical direction, where the square root of the projected area is a particle size rμm.
It means that the aspect ratio = r / h when m is 3 or more. Among them, the aspect ratio is preferably 3 or more and 50 or more.
It is as follows.

The average particle diameter of the tabular grains is preferably 0.1 μm or less, and more preferably 0.01 μm to 0.08 μm.
m is more preferred. These are disclosed in US Pat. No. 5,264,3.
No. 37, No. 5,314,798, No. 5,320,
No. 958, etc., and the desired tabular grains can be easily obtained. In the present invention, when these tabular grains are used, the sharpness of an image is further improved.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide.

The photographic emulsion used in the present invention is described in US Pat. Gl
Chimie et Physique by Afkids
e Photographique (Paul Mon
tel, 1967); F. By Duffin
Photographic Emulsion Chem
istry (published by The Focal Press, 19
66); L. M by Zelikman et al
aking andCoating Photogra
phi Emulsion (The Focal P
Ress, published in 1964) and the like.

That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method for reacting a soluble silver salt and a soluble halide salt may be any one of a one-sided mixing method, a double-sided mixing method, a combination thereof and the like. May be used.

The silver halide may be added to the image forming layer by any method, and the silver halide is arranged so as to be close to the reducible silver source. The silver halide may be prepared in advance and added to a solution for preparing an organic silver salt, and a part of the organic acid silver is produced by a reaction between the organic acid silver and a halogen ion. Or may be prepared by converting all to silver halide,
Although a combination of these methods is also possible, the former method of preparing silver halide in advance and adding it to a solution for preparing an organic silver salt is preferable.

In general, the silver halide is preferably contained in an amount of 0.75 to 30% by weight based on the organic silver salt.

The silver halide used in the present invention preferably contains metal ions belonging to groups 6 to 11 of the periodic table. As the above metals, W, Fe, Co,
Ni, Cu, Ru, Rh, Pd, Re, Os, Ir, P
t and Au are preferred.

These metal ions can be introduced into silver halide in the form of a metal complex or a metal complex ion. As these metal complexes or metal complex ions, hexacoordinate metal complexes represented by the following general formula are preferable.

In the formula [ML ₆ ] ^m , M is a transition metal selected from elements of Groups 6 to 11 of the periodic table, L is a ligand, and m is 0,-, 2-, 3- or 4-
Represents Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

Particularly preferred examples of M are rhodium (Rh), ruthenium (Ru), rhenium (Re), iridium (Ir) and osmium (Os).

Specific examples of transition metal complex ions are shown below, but the present invention is not limited to these.

[0075] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [IrCl _6] ^{4 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2- 11: [Re (NO) Cl _5] ^2- 12: [Re (NO) CN _5] ^2- 13: [Re (NO) ClCN _4] ^2- 14: [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) CN _5] ^2- 17: [Fe (CN) _6] ^3- 18: [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN )] ^2-23 : [R u (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO) Cl _5] ^{2 -} 27: [Ir (NS) Cl _5] ^2- these metal ions may be a metal complex or metal complex ions one type, the metal of the same kind of metal or different may be used alone or in combination. The content of these metal ions, metal complexes or metal complex ions, generally is suitably 1 × 10 ^-9 ~1 × 10 ^-2 mol per mol of silver halide, preferably 1 × 10 ^{- It is 8} to 1 × 10 ^-4 mol.

The compounds providing these metals are preferably added during silver halide grain formation and incorporated into silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, physical ripening, and chemical ripening Although it may be added at any stage before and after sensitization, it is particularly preferable to add at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth, and most preferably. It is added at the stage of nucleation.

In the addition, it may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added to silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in Japanese Patent Application Laid-Open No. H11-157, etc., the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles.

These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution of a powder or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution are used. When they are mixed simultaneously, they are added as a third aqueous solution to prepare silver halide grains by a three-liquid simultaneous mixing method, a method in which a required amount of an aqueous solution of a metal compound is charged into a reaction vessel during grain formation, or a method in which halogen is added. There is a method in which another silver halide grain doped with metal ions or complex ions in advance during the preparation of silver halide is added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution.

When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or during physical ripening, or at the time of chemical ripening.

In the present invention, the organic silver salt is a reducible silver ion source, and is a silver salt of an organic acid or a hetero organic acid, particularly a long chain (10 to 30, preferably 15 to 25 carbon atoms).
The aliphatic carboxylic acids and nitrogen-containing heterocycles 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. Examples of suitable silver salts are described in RD 17029 and 29996 and include: silver salts of organic acids (eg, gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid) A silver salt such as an acid); a carboxyalkylthiourea salt of silver (for example, a silver salt such as 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea); Silver complexes of polymer reaction products with hydroxy-substituted aromatic carboxylic acids (eg, aldehydes (silver complexes with formaldehyde, acetaldehyde, butyraldehyde, etc.), silver salts of hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3, 5-dihydroxybenzoic acid, 5,5
Silver salts such as -thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thioene, and 3-carboxymethyl-4- Silver salts or silver complexes such as thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole A complex or salt of silver and a nitrogen acid selected from the group consisting of: silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. Among them, a preferred silver ion source is silver behenate.

The amount of the organic silver salt added was 3 g / m
^The content is preferably ² or less, more preferably 2 g / m ² or less.

The organic silver salt can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver. The organic silver salt is described in Japanese Patent Application Laid-Open No. Hei 9-127463, which describes a forward mixing method, a reverse mixing method, and a simultaneous mixing method. Controlled double jet method or the like is preferably used.

In the present invention, the organic silver salt has an average particle size of 1
It is preferably not more than μm and monodispersed. The average particle size of the organic silver salt refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles when the particles of the organic silver salt are, for example, spherical, rod-shaped, or tabular particles. The average particle size is preferably 0.01 μm to 0.8 μm, particularly 0.05 μm
０．５0.5 μm is preferred. Monodispersion has the same meaning as that of silver halide, and preferably has a monodispersity of 1 to 30.
It is. In the present invention, the organic silver salt has an average particle diameter of 1 μm.
The following single molecule is more preferable, and an image having a high density can be obtained by setting the molecular weight within this range.

In the present invention, in order to obtain a predetermined optical transmission density, the total amount of silver halide and organic silver salt is preferably from 0.3 g to 1.5 g per m ² in terms of silver amount. preferable. With this range, a high-contrast image can be obtained. By setting it in this range, a high-contrast image can be obtained.

The photothermographic material of the present invention preferably contains a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448, 3,773,512,
No. 3,593,863, and RD17029 and 29963, and there are the following.

Aminohydroxycycloalkenonone compounds (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents An N-hydroxyurea derivative (for example, Np-methylphenyl-N
Hydrazones of aldehydes or ketones (e.g. anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g.
Hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamidoanilines (eg, 4- (N- Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (eg, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (eg, 1,2,3,4-tetrahydro) Amide oximes; azines (for example, a combination of an aliphatic carboxylic acid aryl hydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; hydroxamic acids; Combinations of gins and sulfonamide phenols; α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamide phenol reducing agents; 2-phenylindane-1 ,
3-dione and the like; chroman; 1,4-dihydropyridines (eg, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (eg, bis (2-hydroxy-3- t-butyl-5
-Methylphenyl) methane, bis (6-hydroxy-m
-Tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Particularly preferred reducing agents are bisphenols.

Examples of bisphenols include compounds represented by the following general formula (A).

[0088]

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In the formula, R represents a hydrogen atom or a group having 1 to 1 carbon atoms.
Represents an alkyl group of 10 (eg, butyl group, 2,4,4-trimethylpentyl group, etc.), and R ′ and R ″ represent an alkyl group having 1 to 5 carbon atoms (eg, methyl group, ethyl group, t- Butyl group).

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

[0091]

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[0092]

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The amount of the reducing agent including the compound represented by formula (A) is preferably 1 × 1 per mol of silver.
It is from 0 ^-2 to 10 mol, especially from 1 x 10 ^{-2 to} 1.5 mol.

Binders suitable for the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic, and polyvinyl. Alcohol, hydroxyethylcellulose, cellulose acetate, cellulose acetate butyrate, polyvinylpyrrolidone, casein, starch, polyacrylic acid, polymethylmethacrylic acid, polyvinyl chloride, polymethacrylic acid, copoly (styrene-maleic anhydride), copoly (styrene- Acrylonitrile), copoly (styrene-butadiene), polyvinylacetals (eg, polyvinylformal and polyvinylbutyral), polyesters, polyurethanes, phenoxy resins, polyvinylidene chloride Emissions, polyepoxides, polycarbonates, polyvinyl acetate, cellulose esters, and polyamides. These may be hydrophilic or non-hydrophilic.

[0095] In the present invention, the binder of the photosensitive layer is preferably ^{1.5g / m 2 ~6g / m 2} , more preferably from ^{1.7g / m 2 ~5g / m 2} . If it is less than 1.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

In the present invention, a matting agent is preferably contained on the photosensitive layer side. In order to prevent the image after thermal development from being damaged, it is preferable to provide a matting agent on the surface of the photosensitive material. It is preferred that the matting agent is contained in a weight ratio of 0.5 to 10% based on all binders on the photosensitive layer side.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, as inorganic substances, silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkali described in British Patent No. 1,173,181 etc. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. As organic matter,
Starch described in U.S. Pat. No. 2,322,037, Belgian Patent No. 625,451 and British Patent No. 981,19
No. 8 and the like, and starch derivatives described in JP-B-44-3643.
No. 33, Swiss Patent No. 33
Organic matting agents such as polystyrene or polymethacrylate described in U.S. Pat. No. 0,158, polyacrylonitrile described in U.S. Pat. No. 3,079,257, and polycarbonate described in U.S. Pat. No. 3,022,169. Can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical. The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a sphere. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere.

The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm. The matting agent preferably has a variation coefficient of the particle size distribution of 50% or less, more preferably 40% or less, and particularly preferably 30% or less.

Here, the coefficient of variation of the particle size distribution is a value represented by the following equation.

(Standard deviation of particle size) / (average value of particle size) × 100 The matting agent according to the present invention can be contained in any constituent layer, but is preferably used to achieve the object of the present invention. Is a constituent layer other than the photosensitive layer, and is more preferably the outermost layer as viewed from the support.

The method of adding the matting agent according to the present invention may be a method of dispersing in a coating solution in advance and applying the solution.
A method of spraying a matting agent after the application liquid is applied and before the drying is completed may be used. When a plurality of types of matting agents are added, both methods may be used in combination.

In the present invention, when the photothermographic material is a photothermographic material for printing an image setter having an oscillation wavelength of 600 to 800 nm, a hydrazine compound is preferably contained in the photothermographic material. .

The preferred hydrazine compound used in the present invention is a compound represented by the following formula [H].

[0105]

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In the formula, A represents an aliphatic group, an aromatic group, a -GD group or a heterocyclic group which may have a substituent, B represents a blocking group, and A ₁ and A ₂ are both A hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. G is a -CO- group, -COCO-
Group, -CS- group, -C (= NG ₁ D ₁ )-group, -SO-
A —SO ₂ — group or a —P (＝ O) (G ₁ D ₁ ) — group, wherein G ₁ is a mere bond, a —O— group, a —S— group, or a —N (D ₁ ) — group Represents D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, D represents a hydrogen atom, an aliphatic group,
Represents an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.

In the general formula [H], the aliphatic group represented by A preferably has 1 to 30 carbon atoms, and particularly has a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Preferred are, for example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group, benzyl group,
These may be further substituted with a suitable substituent (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc.).

In the general formula [H], the aromatic group represented by A is preferably a monocyclic or heterocyclic aryl group, such as a benzene ring or a naphthalene ring. Is a monocyclic or condensed ring, preferably a heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur, and oxygen atoms, such as a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, and a quinoline ring. , A thiazole ring, a benzothiazole ring, a thiophene ring, and a furan ring.
Are particularly preferably an aryl group and a heterocyclic group, and the aromatic group and the heterocyclic group of A may have a substituent, and a particularly preferable group is a substituent having an acidic group having a pKa of 7 to 11. Specific examples include a sulfonamide group, a hydroxyl group, and a mercapto group.

In the general formula [H], -G represented by A
The -D group will be described.

G represents a —CO— group, a —COCO— group, a —C
S-group, -C (= NG ₁ D ₁ ) -group, -SO- group, -SO
₂ - group or a _{-P (= O) (G 1} D 1) - group, wherein preferred examples of G -CO- group, in -COCO- group, especially preferably include -COCO- group. G ₁ represents a mere bond, —O— group, —S— group or —N (D ₁ ) — group;
D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in a molecule, they may be the same or different.

D represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. Preferred D is a hydrogen atom, an alkyl group, an alkoxy group. Group, amino group, aryl group and the like.

In the general formula [H], A preferably contains at least one diffusion-resistant group or a silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable, and as the ballast group, a photographically inactive alkyl group having 8 or more carbon atoms, an alkenyl group, an alkoxy group, or a phenyl group is used. Group, phenoxy group, alkylphenoxy group and the like.

In the general formula [H], the thiourea, thiourethane, mercapto,
Thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, or JP-A-64-090
No. 439, and the like.

In the general formula [H], B represents a blocking group, preferably -GD, and -G in A
It has the same meaning as the -D group, and A and B may be the same or different.

A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (eg, acetyl, trifluoroacetyl, benzoyl, etc.), a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.) ),
Or an oxalyl group (such as an ethoxalyl group).

Next, specific examples of the compound represented by the formula [H] are shown below, but the present invention is not limited thereto.

[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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As the hydrazine compound used in the present invention, the following compounds can be used in addition to the above. RD23516 (November 1983, P.34)
6) and the references cited therein, as well as U.S. Pat.
Nos. 080,207, 4,269,929, 4,276,364, 4,278,748, 4,385,108, 4,459,347,
Nos. 4,478,928 and 4,560,638
No. 4,686,167 and No. 4,912,01
No. 6, No. 4,988,604, No. 4,994, 3
No. 65, No. 5,041,355, No. 5,104,
No. 769, British Patent No. 2,011,391B, European Patent Nos. 217,310, 301,799, and 3
No. 56,898, JP-A-60-179834, and JP-A-60-17934.
-170733, 61-270744, 62-
No. 178246, No. 62-270948, No. 63-2
Nos. 9751, 63-32538, 63-1040
No. 47, No. 63-121838, No. 63-12933
No. 7, 63-223744, 63-234244
No. 63-234245, No. 63-234246
Nos. 63-294552 and 63-306438
No. 64-10233, JP-A-1-90439,
1-1100530, 1-1105594, 1-
No. 105943, No. 1-276128, No. 1-280
Nos. 747, 1-283548, 1-283549
No. 1-285940, No. 2-2541, No. 2-
77057, 2-153838, 2-1962
No. 34, No. 2-196235, No. 2-198440
No. 2-198441, No. 2-198442, No. 2-220042, No. 2-221953, and No. 2-2
No. 21954, No. 2-285342, No. 2-2853
No. 43, No. 2-289843, No. 2-302750
No. 2-304550, No. 3-37642, No. 3
-54549, 3-125134, 3-184
No. 039, No. 3-240036, No. 3-240037
Nos. 3-259240, 3-280038, 3-282536, 4-511143, 4-56
No. 842, No. 4-84134, No. 2-230233
No. 4-96053, No. 4-216544, No. 5
No. 455761, No. 5-45762, No. 5-4576
No. 3, 5-45764, 5-45765, 6
-289524 and 9-160164.

Further, in addition to 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, and JP-B-6-93082 Compounds represented by the general formula (I) described above, specifically, compounds 1 to 38 described on pages 8 to 18 of the same publication;
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 pages 10, 28 to 36
2, compounds 39-1 to 6-7 described on pages 39 and 40, and compounds represented by formulas (1) and (2) described in JP-A-6-289520. Are 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 publication, 6-3
Compounds represented by (Chemical Formula 1) described in JP-A-13951, specifically, compounds described on pages 3 to 5 of the same publication;
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 and 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 the page can be used.

The hydrazine derivative-added layer is a photosensitive layer and / or a constituent layer adjacent to the photosensitive layer. The optimum amount is not uniform depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of reducing agent, the type of inhibitor, etc., but it is 10 ^-6 per mol of silver halide. Mol ~
The range is preferably about 10 ^-1 mol, particularly preferably 10 ^-5 mol to 10 ^-2 mol.

The hydrazine compound of the present invention can be prepared by using a suitable organic solvent such as alcohols (methanol, ethanol,
It can be used by dissolving it in propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve and the like. Also, by a well-known emulsification dispersion method, together with a high boiling point solvent such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and dissolved using an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically. An emulsified dispersion can be prepared and used. Alternatively, a hydrazine compound 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.

The light-sensitive material of the present invention may contain a nucleation accelerator such as an amine derivative, an onium salt compound, a disulfide derivative and a hydroxylamine derivative in combination with the hydrazine compound.

The photothermographic material of the present invention is stable at room temperature, but is developed by heating (for example, 80 ° C. to 140 ° C.) after exposure. Heating produces silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated on the photosensitive silver halide by 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 to form an image. This reaction process proceeds without supplying any processing liquid such as water from the outside.

The photothermographic material of the present invention preferably contains a toning agent. An example of a suitable toning agent is RD170
No. 29, which includes the following.

Imides (for example, succinimide, phthalimide); pyrazolin-5-ones and quinazolinones (for example, 3-phenyl-2-pyrazolin-5-one,
1-phenylurazole, quinazoline and 2,4-thiazolidinedione); naphthalimides (for example, N-
Hydroxy-1,8-naphthalimide); cobalt complex (for example, hexaamminetrifluoroacetate of cobalt); mercaptans (for example, 3-mercapto-1,2,4-triazole); N- (aminomethyl)
Aryldicarboximides (eg, N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium
um) derivatives and certain photobleaches (eg, N, N'-hexamethylene (1-carbamoyl-
3,5-dimethylpyrazole), 1,8- (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate), and 2- (tribromomethylsulfonyl) benzothiazole combinations); merocyanine dyes (e.g., , 3-ethyl-5-((3-ethyl-2-benzothiazolinylidene (benzothiazolinylidene))-
1-methylethylidene) -2-thio-2,4-oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 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 and sodium benzenesulfinate or 8-methylphthalazinone and sodium p-tolylsulfinate);
A combination of phthalazine and phthalic acid; phthalazine (including an adduct of phthalazine) and maleic anhydride, and phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivative and its anhydride (for example, phthalic acid, 4 −
A combination with at least one compound selected from methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazolinediones, benzoxazine, naphthoxazine derivatives; benzoxazine-2,
4-diones (for example, 1,3-benzoxazine-
Pyrimidines and asymmetric-triazines (eg, 2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (eg, 3,6-dimercapto-1,4-diphenyl-1H, 4H) −2,3a,
5,6a-tetraazapentalene). Preferred toning agents are phthalazinone or phthalazine.

The photothermographic material of the present invention includes, for example, US Pat. Nos. 3,874,946 and 4,756,999.
No. 5,340,712, European Patent No. 605,9
No. 81A1, No. 622, 666A1, No. 631,
176A1, JP-B-54-165, JP-A-07-2
No. 781, No. 9-160164, No. 9-244178
, 9-258367, 9-265150, 9-281640, and 9-319022 can be preferably used.

In the present invention, a mercapto compound, a disulfide compound and a thione compound are used for suppressing or accelerating the development and controlling the development, and for improving the spectral sensitization efficiency and the preservability before and after the development. Can be contained.

When a mercapto compound is used in the present invention, it may be of any structure,
Those represented by -SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring, a heteroaromatic ring or a condensed aromatic ring having at least one nitrogen, sulfur, oxygen, selenium or tellurium atom. Preferably a heteroaromatic ring, benzimidazole, naphthymidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole,
Heterocycles such as benzoselenazole, benzotellurazole, imidazole, oxazole, pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone are preferred. The heteroaromatic ring can be, for example, halogen (eg, Br and Cl), hydroxy, amino, carboxy, alkyl (eg, 1
And at least one carbon atom, preferably having 1 to 4 carbon atoms, and alkoxy (for example, having at least one carbon atom, preferably having 1 to 4 carbon atoms).
And a substituent selected from the group consisting of:
Examples of the mercapto-substituted heteroaromatic compound include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzothiazole, 3-mercapto-1,2,4-triazole, 2-mercaptoquinoline, 8-mercaptopurine, 2,3,5,6-tetrachloro-4-pyridinethiol, 4-hydroxy-2-mercaptopyrimidine, 2-mercapto-4-phenyloxazole, etc. The invention is not limited to these.

The photothermographic material of the present invention may contain an antifoggant. A mercury compound is known as an effective antifoggant, for example, in U.S. Pat. No. 3,589,903. However, since this is environmentally unfavorable, studies on non-mercury antifoggants have been conducted for a long time. . Non-mercury antifoggants include, for example, U.S. Pat.
Nos. 75 and 4,452,885 and JP-A-59-5959.
Antifoggants such as those disclosed in US Pat.

Particularly preferred non-mercury antifoggants are disclosed in US Pat. Nos. 3,874,946 and 4,756,9.
No. 99, -C (X ₁ )
(X ₂ ) A heterocyclic compound having one or more substituents represented by (X ₃ ) (where X ₁ and X ₂ are halogen and X ₃ is hydrogen or halogen). Examples of suitable antifoggants include JP-A-9-288328, paragraph [0030].
To [0036] are preferably used.

As another example of a preferred antifoggant, JP-A-9-90550, paragraph [0062]
To [0063], and other suitable antifoggants are described in U.S. Pat.
8,523 and European Patent Nos. 600,587, 6
Nos. 05,981 and 631,176.

The photothermographic material of the present invention includes, in addition to the compounds represented by formulas (1) to (6) of the present invention, for example, JP-A-63-159814 and JP-A-60-140335.
Nos. 63-231437, 63-259,651, 63-304242, 63-15245, U.S. Pat. Nos. 4,639,414 and 4,740,455
No. 4,741,966, No. 4,751,17
No. 5,835,096 and the like can be used. Useful photosensitive dyes for use in the present invention are described, for example, in RD 17643 IV-A (p. 23, December 1978) and 18431X (p. 4 in August 1979).
37) or in the literature cited.

In particular, photosensitive dyes having spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078 and JP-A-9-5440
Compounds described in Nos. 9 and 9-80679 are preferably used.

The photothermographic material of the present invention has at least one photosensitive layer on a support, and only the photosensitive layer may be formed on the support. It is preferable to form at least one non-photosensitive layer. A filter layer may be formed on the same side as or opposite to the photosensitive layer to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or content. . The photosensitive layer may be a plurality of layers, or the sensitivity may be a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and the other forming layers. In the photothermographic material of the present invention, for example, a surfactant, an antioxidant,
Stabilizers, plasticizers, ultraviolet absorbers, coating aids and the like may be added.

As these additives and the other additives described above, the compounds described in RD17029 (pp. 9-15, June 1978) can be preferably used.

The support used in the present invention may be formed of a plastic film (for example, polyethylene terephthalate, polycarbonate, or the like) in order to prevent deformation of an image after development processing.
Polyimide, nylon, cellulose triacetate, polyethylene naphthalate) are preferred. The thickness of the support is about 50 to 300 μm, preferably 7 to
0 to 180 μm. Further, a heat-treated plastic support can also be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support means that after forming these supports and before the photosensitive layer is coated, at a temperature higher than the glass transition point of the support by 30 ° C. or more, preferably at a temperature higher by 35 ° C. or more, More preferably, the heating is performed at a temperature higher than 40 ° C. However, heating at a temperature exceeding the melting point of the support is not preferred. .

As the method for forming a film and the method for producing an undercoat according to the present invention, known methods can be used, and preferably, paragraphs [0030] to [0] of JP-A-9-50094 are used.
070].

In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be contained in the constituent layer in order to improve the chargeability. These may be contained in any layer, but are preferably contained in an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat layer, and the like.

In the present invention, US Pat.
The conductive compounds described in No. 773 columns 14 to 20 are preferably used.

The exposure source of the photothermographic material of the present invention includes an Ar ion laser (488 nm), a He—Ne laser (633 nm), and a red semiconductor laser (670 n).
m), infrared semiconductor laser (780 nm, 830 nm)
Are preferred.

[0147]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 << Preparation of Silver Halide Particles >> 7.5 g of gelatin and 10 mg of potassium bromide were dissolved in 900 ml of pure water, and the temperature was adjusted to 3%.
After adjusting the pH to 5 ° C. and pH 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and 370 ml of an aqueous solution containing potassium bromide and potassium iodide (equimolar to silver) in a molar ratio of (96/4).
ml was added over 10 minutes by a controlled double jet method while keeping pAg at 7.7. Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, the average particle size was 0.06 μm, and the variation coefficient of the projected diameter area was 8
% And [100] face ratio of 86% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting treatment, and then 0.1 g of phenoxyethanol was added.
After adjusting the pAg to 5.9 and pAg 7.5, silver halide grains were obtained.

<< Preparation of Organic Fatty Acid Silver Emulsion >> 300 ml of water
10.6 g of behenic acid was put therein, dissolved by heating at 90 ° C., and 31.1 ml of 1N sodium hydroxide was sufficiently stirred.
Was added and left as it was for 1 hour. Then 3
After cooling to 0 ° C., 7.0 ml of 1N phosphoric acid was added, and 0.01 g of N-bromosuccinimide was added with sufficient stirring. Thereafter, the silver halide grains prepared in advance are mixed with behenic acid so that the silver amount becomes 10 mol% in terms of silver amount.
The mixture was added with stirring while being heated to ℃. Further, 25 ml of a 1N silver nitrate aqueous solution was continuously added over 2 minutes, and the mixture was allowed to stand for 1 hour with stirring.

To this emulsion, polyvinyl butyral dissolved in ethyl acetate was added, and the mixture was sufficiently stirred, and allowed to stand still to separate into an ethyl acetate phase containing silver behenate grains and silver halide grains and an aqueous phase. After removing the aqueous phase, silver behenate grains and silver halide grains were collected by centrifugation. Thereafter, 20 g of synthetic zeolite A-3 (spherical) manufactured by Tosoh Corporation and 22 cc of isopropyl alcohol were added, and the mixture was allowed to stand for 1 hour and filtered. Further, 3.4 g of polyvinyl butyral and 23 cc of isopropyl alcohol were added, and the mixture was sufficiently stirred at 35 ° C. at a high speed for dispersion to complete the preparation of the organic fatty acid silver emulsion.

<< Composition of photosensitive layer >> Organic fatty acid silver emulsion 1.75 g (in terms of silver) / m ² pyridinium hydrobromide perbromide 1.5 × 10 ^-4 mol / m ² Calcium bromide 1.8 × 10 ^-4 mol / m ² 2- (4-chlorobenzoyl) benzoic acid 1.5 × 10 ⁻³ mol / m ² Photosensitive dye SD-1 4.2 × 10 ⁻⁶ mol / m ² 2-mercaptobenzimidazole 3.2 × 10 ^{− 3} mol / m ² 2-tribromomethylsulfonylpyridine 6.0 × 10 ⁻⁴ mol / m ^{2 As a} solvent, methyl ethyl ketone, acetone, and methanol were appropriately used.

<< Surface Protective Layer Composition >> A surface protective layer coating solution was prepared as follows.

Cellulose acetate 4 g / m ² 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 4.8 × 10 ⁻³ mol / m ² Phthalazine 3.2 × 10 ⁻³ mol / m ² 4-methylphthalic acid 1.6 × 10 ⁻³ mol / m ² Tetrachlorophthalic acid 7.9 × 10 ⁻⁴ mol / m ² Tetrachlorophthalic anhydride 9.1 × 10 ^{− 4} mol / m ² silicon dioxide (particle size: 2 μm) 0.22 g / m ^{2 As a} solvent, methyl ethyl ketone, acetone, and methanol were appropriately used.

<< Composition of Backing Layer >> A coating solution for the backing layer was prepared as follows.

Cellulose acetate 4 g / m ² Anti-halation dye Dye D-2 0.06 g / m ² Dye D-3 0.018 g / m ² Polymethyl methacrylate (particle size 10 μm) 0.02 g / m ²

[0156]

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[0157]

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Thickness 1 biaxially stretched with the above composition
A sample 101 was obtained by coating on a 75 μm polyethylene terephthalate film and drying. Next, samples 102 to 102 were prepared in the same manner as in fabric sample 101 except that the photosensitive dye SD-1 in the photosensitive layer was changed to the compound used in the present invention described in Table 1.
107 was obtained.

<< Evaluation of Sensitometry >> The photothermographic material sample prepared above was processed into a half-cut size, and 830 n
m laser diode was exposed with a beam inclined by 13 ° from the vertical plane. Then use a heat drum at 120 ° C x
Heat development was performed for 15 seconds. The fog value at that time was measured. Further, the sensitivity (reciprocal of the ratio of the exposure amount giving a density higher than fog by 1.0) was measured. When the sensitivity of Sample 101 in Table 1 was set to 100, the sensitivity of each sample was evaluated by a relative value. Table 1 shows the results.

<< Evaluation of Raw Preservability >> Further, two more samples were taken from each of the above coated samples, and one of them was subjected to HT at 50 ° C.
Under the condition of 55%, stored for 7 days (forced aging condition) under shading conditions, and the other was stored at room temperature (25 ° C.)
Stored in a light-tight container under the conditions of 55% HT. After performing the same treatment as that used for the sensitometry evaluation of these two samples, the density of the fog portion was measured. Table 1 shows the results
Shown in

(Increase in fog 1) = (fog during forced aging)-(fogging during comparison for aging) << Evaluation of Image Preservation >> 25 samples were subjected to the same processing as in the sensitometric evaluation. The other sheet was stored for 7 days at 25 ° C. and 55% light-shielded, and the other sheet was exposed to natural light at 25 ° C. and 55% for 7 days. Table 1 shows the results.

(Increase in fog 2) = (fog when exposed to natural light)-(fog when preserved from light)

[0163]

[Table 1]

From Table 1, it can be seen that the sample of the present invention has sufficient sensitivity, low fog, and good raw storage stability and image storage stability of the light-sensitive material.

(Example 2) << Preparation of Substretched Photographic Support >><Preparation of PET Substretched Photographic Support> A commercially available biaxially stretched heat-fixed PET film having a thickness of 100 μm and having a thickness of 8 watts on both sides. / M ² · min. Of corona discharge treatment, and apply the following undercoating coating liquid a-1 on one surface so as to have a dry film thickness of 0.8 μm and dry to form an undercoating layer A-1. On the opposite side, the following undercoating coating solution b-1 was applied so as to have a dry film thickness of 0.8 μm and dried to obtain an undercoating layer B-1.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30% by weight) t-butyl acrylate (20% by weight) Styrene (25% by weight) 2-Hydroxyethyl acrylate (25% by weight) copolymer latex liquid (Solid content 30%) 270 g (C-1) 0.6 g hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish to 1 liter with water << Subtraction coating solution b-1 >> Butyl acrylate (40 weight %) Styrene (20% by weight) Glycidyl acrylate (40% by weight) copolymer latex liquid (solid content: 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 8g Finished to 1 liter with water Then, on the upper surface of the undercoat layer A-1 and the undercoat layer B-1,
A corona discharge of 8 w / m ² · min. Was performed, and the following lower coating liquid a-2 was coated on the lower coating layer A-1 with a dry film thickness of 0.1 μm.
The lower coating layer B-2 is coated with the following coating liquid b-2 on the lower coating layer B-1 so as to have a dry film thickness of 0.8 μm. Coated as B-2.

<< Coating Solution a-2 for Subbing Upper Layer >> Gelatin 0.4 g / m ² Weight (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g Silica particles ( (Average particle size: 3 μm) 0.1 g Finished to 1 liter with water << Lower coating solution for upper layer b-2 >> (C-4) 60 g Latex liquid containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 0 0.5 g (C-6) 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finish to 1 liter with water

[0168]

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[0169]

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<< Preparation of Silver Halide Emulsion A >> Water 900m
7.5 g of inert gelatin and 10 ml of potassium bromide
mg, and adjusted to a temperature of 35 ° C. and a pH of 3.0, and then 370 ml of an aqueous solution containing 74 g of silver nitrate (98/98).
In a controlled double jet method, 370 ml of an aqueous solution containing a molar ratio of potassium bromide and potassium iodide equal to silver nitrate and 1 × 10 ^-4 mol of rhodium chloride per mol of silver was maintained at pAg 7.7. It was added over a minute. Thereafter, 4-hydroxy-6-methyl-1,3,3
a, 7-Tetrazindene 0.3 g was added, and the pH was adjusted to 5 with NaOH to obtain a cubic iodobromide having an average grain size of 0.06 μm, a variation coefficient of the projected diameter area of 8%, and a [100] face ratio of 87%. Silver particles were obtained. A gelatin flocculant was added to this emulsion, and the mixture was flocculated and precipitated. After desalting, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5 to obtain a silver halide emulsion A.

According to the method of Example 1 of JP-A-9-127643, silver behenate was prepared in the following manner.

<< Preparation of Sodium Behenate Solution >> 340
34 g of behenic acid was dissolved at 65 ° C. in ml of isopropanol. Next, while stirring, a 0.25N aqueous sodium hydroxide solution was added so as to have a pH of 8.7. At this time, about 400 ml of the sodium hydroxide aqueous solution was required. Next, the sodium behenate aqueous solution was concentrated under reduced pressure to adjust the concentration of sodium behenate to 8.9% by weight.

<< Preparation of Silver Behenate >> 2.9 ml of a solution prepared by dissolving 30 g of ossein gelatin in 750 ml of distilled water.
A 4M silver nitrate solution was added to adjust the silver potential to 400 mV. 78 ° C using a controlled double jet method
374 ml of the sodium behenate solution was added at a speed of 44.6 ml / min.
Was added so that the silver potential became 400 mV. The amounts of sodium behenate and silver nitrate used at the time of addition were 0.092 mol and 0.101 mol, respectively.

After the addition was completed, the mixture was further stirred for 30 minutes, and water-soluble salts were removed by ultrafiltration.

<< Preparation of Photosensitive Emulsion >> To this silver behenate dispersion, 0.01 mol of the above-mentioned silver halide emulsion A was added, and while stirring, n-butyl acetate solution of polyvinyl acetate (1.2 wt%) 100 g was gradually added to form a floc of the dispersion, water was removed, water was further washed twice and water was removed, and then 2.5 wt% butyl acetate of polyvinyl butyral (average molecular weight 3000) was used as a binder. 60g of a 1: 2 mixed solution of isopropyl alcohol
Was added with stirring, and polyvinyl butyral (average molecular weight: 4000) and isopropyl alcohol were added as binders to the obtained gel-like mixture of behenic acid and silver halide to prepare a photosensitive emulsion.

The following layers were sequentially formed on a support, and the coating sample No. 201 was produced. The drying was 75 ° C,
Performed in 5 minutes.

Back side coating: A solution having the following composition was applied on the undercoat layer B-2 so as to have a wet thickness of 80 μm.

Polyvinyl butyral (10% isopropanol solution) 150 ml Dye-B 70 mg Dye-C 70 mg

[0179]

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Photosensitive layer surface side coating Photosensitive layer: A solution having the following composition is coated on the undercoating upper layer A-2 so that the amount of silver applied is 2.0 g / m ² , and polyvinyl butyral as a binder is 3.2 g / m ² . Was applied in the same manner.

Photosensitive Emulsion Amount of 3 g / m ² in terms of silver Photosensitive dye SD-1 (0.1% DMF solution) 2 mg Pyridinium hydrobromide perbromide (2% acetone solution) 1 ml 2-Tribromomethylsulfonylpyridine (2% acetone solution) 3 ml Phthalazinone (4.5% DMF solution) 8 ml 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane (10% acetone solution) 13 ml High contrast agent H (1% methanol / DMF = 4: 1 solution) 2 ml

[0182]

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Surface protective layer: A solution having the following composition was wetted to a thickness of 1
It was applied on each photosensitive layer so as to have a thickness of 00 μm.

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 monodisperse having an average particle size of 4 μm 1% (W / W) based on silica binder << Evaluation of sensitometry >> Coated sample 2 prepared above
Photothermographic materials 202 to 207 were prepared in the same manner except that the photosensitive dye SD-1 in the photosensitive layer No. 01 was changed to the compounds of the present invention shown in Table 2. These were passed through an interference filter having a peak at a wavelength of 830 nm, and the emission time was 10 ^−3.
Exposure with xenon flash light for s. Thereafter, heat development was performed at 115 ° C. for 15 seconds using a heat drum. The reciprocal of the exposure amount giving a density of 1.0 was defined as the sensitivity, and the relative sensitivity was defined assuming that the sensitivity of sample 201 was 100.

Table 2 shows the results.

<< Evaluation of Raw Preservation >> Further, two more samples were taken from each of the above coated samples, and one of them was heated at 50 ° C.
Stored under shading conditions for 7 days (forced aging condition) under the condition of T55%, and stored at room temperature (25
° C) and HT 55%. After performing the same treatment as that used for the sensitometry evaluation of these two samples, the density of the fog portion was measured. Table 2 shows the results.

(Increase in fog 1) = (fog during forced aging) − (fog during aging for comparison) << Evaluation of Image Preservation >> 25 samples were subjected to the same processing as in the sensitometric evaluation. The other sheet was stored for 7 days at 25 ° C. and 55% light-shielded, and the other sheet was exposed to natural light at 25 ° C. and 55% for 7 days. Table 2 shows the results.

(Increase in fog 2) = (fog when exposed to natural light) − (fog when preserved from light)

[0189]

[Table 2]

From Table 2, it can be seen that the sample of the present invention has sufficient sensitivity, low fog, and good raw storage stability and image storage stability of the light-sensitive material.

Example 3 Synthesis of D-7 2.0 g of compound 7A, 2.3 g of compound 7B and 0.6 g of sodium acetate were heated and refluxed for 1 hour in ethanol, and cooled to precipitate crude crystals of the dye. did. The crude crystals were taken out by filtration and recrystallized from methanol to give yellow crystals.
5 g were obtained.

[0192]

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The product was identified as the target product (compound D-7) by NMR spectrum and mass spectrum.

Example 4 Synthesis of D-16 2.0 g of compound 16A, 2.2 g of compound 16B and 0.6 g of triethylamine were added in acetic anhydride for 20 minutes.
The mixture was heated to 0 ° C., and after cooling, ethanol was added to precipitate crude pigment crystals. The crude crystals were taken out by filtration and recrystallized with ethanol to obtain 2.4 g of red crystals.

[0195]

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The product was identified as the target product (Compound D-16) by NMR spectrum and mass spectrum.

Example 5 Synthesis of D-22 A mixture of 2.0 g of compound 22A and 0.5 g of compound 22B was heated at 150 ° C. for 20 minutes, and cooled to obtain a crude dye crystal. The crude crystals were recrystallized from ethanol to obtain 1.1 g of blue crystals.

[0198]

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The product was identified as the target compound (Compound D-22) by NMR spectrum and mass spectrum.

Example 6 Synthesis of D-34 2.0 g of compound 34A and 0.55 g of compound 34B
After reacting at 120 ° C for 10 minutes, ethanol 50m
l and 0.5 g of triethylamine were added, and the mixture was heated under reflux for 30 minutes and cooled to obtain a crude crystal of the dye. The crude crystals were recrystallized from fluorinated alcohol-methanol to obtain 1.5 g of blue-green crystals.

[0201]

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The product was identified as the target product (Compound D-34) by NMR spectrum and mass spectrum.

Example 7 Synthesis of D-43 2.0 g of compound 43A and 0.90 g of compound 43B
After reacting at 120 ° C. for 10 minutes, 50 ml of methanol and 0.6 g of triethylamine were added, and the mixture was heated for 30 minutes and cooled to obtain a crude crystal of a dye. The crude crystals were recrystallized from fluorinated alcohol-methanol to obtain 1.1 g of green crystals.

[0204]

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The product was identified as the target product (Compound D-43) by NMR spectrum and mass spectrum.

Examples 3 to 7 for other dyes of the present invention
It was able to be synthesized by a method according to.

[0207]

According to the present invention, a heat-developable silver salt photographic light-sensitive material having high sensitivity, low fog, and excellent raw storage stability and image storage stability of a light-sensitive material can be provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H123 AB03 AB18 AB23 BB00 BB23 CA00 CA22 CB00 CB03 4H056 CA01 CA02 CA05 CB06 CC01 CC02 CC08 CD01 CD08 CD09 CE02 CE03 CE06 CE07 DD03 DD06 DD12 DD15 DD19 DD23 DD30 FA05

Claims (13)

[Claims] 1. A heat-developable silver salt photographic material comprising at least one compound represented by the following general formula (1). Embedded image [Wherein, R ¹ and R ² each represent an aliphatic group, L ^{1 to} L ⁹ represent a methine group, and a, b, c, d, e, and f each represent 0 or 1. X represents an ion necessary to neutralize the intramolecular charge, and n represents a number required to neutralize the intramolecular charge. Q ¹ and Q ² each represent a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring which may form a condensed ring, and —CR ³ ＣＲCR ⁴ R ⁵ is represented by Q ¹ Represents a substituent substituting the formed nitrogen-containing heterocycle, and represents -CR ⁶ ＣC
R ⁷ R ⁸ represents a substituent substituting the nitrogen-containing heterocyclic ring formed by Q ² , and R ^{3 to} R ⁸ each independently represent a hydrogen atom,
Represents a halogen atom and a monovalent substituent. However, R ³ ~
R ⁵ does not form an aromatic ring together with the atoms forming the Q ^1, R ⁶ ~R ⁸ do not form an aromatic ring together with the atoms forming the Q ^2. n1 and n2 represent 0 to 4,
It does not become 0 at the same time. ) 2. A heat-developable silver salt photographic material comprising at least one compound represented by the following general formulas (2) to (6). Embedded image [Wherein, R ¹ and R ² each represent an aliphatic group, L ^{1 to} L ⁹ represent a methine group, and Y ¹ and Y ² represent an oxygen atom, a sulfur atom, a selenium atom, a nitrogen atom or a carbon atom. . X represents an ion necessary to neutralize the intramolecular charge, and n represents a number required to neutralize the intramolecular charge. Q ³ and Q ⁴ each represent a nonmetallic atom group necessary for forming an aromatic ring or a heterocyclic ring, and —CR ³ ＣＲCR ⁴ R ⁵ is substituted with the aromatic ring or the heterocyclic ring formed by Q ³ Represents a substituent represented by -CR
⁶ = CR ⁷ R ⁸ represents a substituent substituting on the aromatic ring or heterocyclic ring formed by Q ⁴ , and R ^{3 to} R ⁸ each independently represent a hydrogen atom, a halogen atom, and a monovalent substituent. Represents
However, R ^{3 to} R ⁵ do not form an aromatic ring together with the atoms forming Q ³ , and R ^{6 to} R ⁸ do not form an aromatic ring together with the atoms forming Q ⁴ . n1 and n2 are 0
Although it represents 4, it does not become 0 at the same time. ) 3. The heat-developable silver salt photographic material according to claim 1, which contains a photosensitive silver halide and an organic silver salt. 4. A heat-developable image forming method, comprising exposing the heat-developable silver halide photographic light-sensitive material according to claim 1, 2 or 3 with a laser. 5. A compound according to the above formula (1), wherein at least one of L ^{1 to} L ⁹ is involved in ring formation. 6. A compound according to the above formula (2), wherein L ¹ is involved in ring formation. 7. A compound according to the above formula (3), wherein at least one of L ^{1 to} L ³ is involved in ring formation. 8. A compound according to the above formula (4), wherein at least one of L ^{1 to} L ⁵ is involved in ring formation. 9. A compound having a general formula (5), wherein at least one of L ^{1 to} L ⁷ has a monovalent substituent. 10. A compound according to the above formula (5), wherein at least one of L ^{1 to} L ⁷ is involved in ring formation. 11. A compound represented by the general formula (6). 12. A compound characterized by having a monovalent substituent in at least one of L ^{1 to} L ⁹ in the general formula (6). 13. A compound according to the formula (6), wherein at least one of L ^{1 to} L ⁹ is involved in ring formation.