JP2000081681A - Heat developable photosensitive material, its production and image forming method using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a heat developable photosensitive material (in particular a black-and-white heat developable photosensitive material) having enhanced stability of photographic performance during long-term preservation (shelf stability), also having enhanced stability of photographic performance to variation in developing conditions and excellent in production stability and to provide an image forming method using the photosensitive material. SOLUTION: The heat developable photosensitive material contains photosensitive silver halide grains, org. silver salt particles, a silver ion reducing agent and a binder on the substrate. The grain diameter distribution of all the photosensitive silver halide grains contained in the photosensitive material has at least two peaks and transition metal ions are contained in >=80% by number of the grains.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, a method for producing the same, and an image forming method using the same.
More particularly, the present invention relates to a photothermographic material (particularly, black-and-white photothermographic material) having excellent storage stability and production stability, a method for producing the same, and an image forming method using the same.

[0002]

2. Description of the Related Art In the medical field and the printing plate-making field, waste liquids caused by wet treatment of image forming materials have become a problem in terms of workability. Is strongly desired. Therefore, laser
There is a need for technology relating to photothermographic materials for photographic technology applications that enable efficient exposure with imagers and laser imagesetters and can form high-resolution, clear black images. As this technique, for example, US Pat. Nos. 3,152,904 and 3,487,075
And D. Morgan (Dry Silver Photog)
graphic Materials) "(Handbo
ok of Imaging Materials,
Marcel Dekker, Inc. Page 48, 19
91) are well known. Since these photosensitive materials are developed at a high temperature of 80 ° C. or higher, they are called photothermographic materials. Since these photothermographic materials do not use any solution processing chemicals, it is possible to provide the user with a system that is simpler and does not damage the environment.

A photothermographic material containing photosensitive silver halide particles comprises a support, photosensitive silver halide particles, an organic silver salt, a reducing agent, and a binder.

However, if these photothermographic materials are kept unused, problems such as changes in fog, sensitivity, and gradation, and fluctuations in development conditions such as development time and temperature during thermal development can be avoided. There is a problem that fog, sensitivity, and gradation change. As a countermeasure against this, a response by an exposure and development apparatus is disclosed, but is not essential. In addition, correspondence of photosensitive materials is disclosed, but is not sufficient, and further improvement has been desired.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve the stability (storage stability) of photographic performance during storage of a photothermographic material over time and to stabilize the photographic performance against fluctuations in development conditions. It is an object of the present invention to provide a photothermographic material (especially a black-and-white photothermographic material) having improved production properties and excellent production stability, a method for producing the same, and an image forming method using the same.

[0006]

The above object of the present invention has been attained by the following constitutions.

[0007] 1. Photosensitive silver halide grains on a support,
In a photothermographic material containing organic silver particles, a reducing agent for silver ions, and a binder, the particle size distribution of all photosensitive silver halide particles contained in the photosensitive material has at least two peak values, A photothermographic material characterized in that at least 80% (number) of the photothermographic material contains a transition metal ion.

[0008] 2. Out of all the photosensitive silver halide grains, 20% or more (number) of grains having a particle size of less than 0.01 μm exist, and transition metal ions are contained in 80% or more (number) of the grains. 2. The photothermographic material according to item 1,

3. 3. The photothermographic material according to items 1 or 2, wherein the photosensitive silver halide grains include silver halide grains prepared after forming organic silver grains.

[0010] 4. Photosensitive silver halide grains on a support,
In a method for producing a photothermographic material containing organic silver particles, a reducing agent for silver ions, and a binder, at least 80% (by number) of all photosensitive silver halide particles contained in the photosensitive material contain a transition metal ion. A method for producing a photothermographic material.

5. 5. The method for producing a photothermographic material according to 4, wherein the silver halide particles prepared after the formation of the organic silver particles contain a transition metal ion.

6. The photothermographic material according to any one of 1 to 3 above,
An image forming method comprising exposing to light with an exposure time of less than 0 to ⁵ seconds and subjecting it to heat development to form an image.

Hereinafter, the present invention will be described in detail.

The photothermographic material of the present invention basically contains a photosensitive silver halide, a non-photosensitive reducible silver source, and a reducing agent for the silver source. This forms a photographic image. For details of the photothermographic material, see, for example, US Pat. Nos. 3,152,904 and 3,45.
7,075, and D.C. "Dry Silver Photographic Materials (Dry Silver) by Morgan
Photographic Material) "and D.C. Morgan and B.A. Sherry (She
ly) "Silver systems treated by heat (Th
thermally Processed Silver
Systems) "(Imaging Processes
And Materials (Imaging Procedures)
ses and Materials) Neblett
e, 8th edition, Sturge, V.E. Walworth, A .; Shep
p) Edit, page 2, 1969).

Next, the photosensitive silver halide grains in the present invention will be described.

In the photothermographic material of the present invention, the particle size distribution of the photosensitive silver halide grains has at least two peak values, but preferably two or more and less than five.
If the particle size distribution has one peak, the sensitivity and gradation are poor.
In the case of 5 or more, the gradation is particularly softened, which is not preferable. The particle size giving the smallest particle size peak is preferably 0.001 μm or more and less than 0.01 μm. The particle size giving the peak on the largest particle size side is 0.2 μm or less, more preferably 0.01 μm or more and less than 0.17 μm, particularly 0.02 μm.
m and less than 0.14 μm. The grain size referred to here means the length of the ridge of the silver halide grains when the silver halide grains are cubic or octahedral, and the same volume as the grains when the grains are polyhedral or spherical grains of 14 or more. Refers to the diameter of a sphere. In the case where the silver halide grains are tabular grains, the diameter means a diameter when converted into a circular image having the same area as the projected area of the main surface.

In the present invention, the number of silver halide grains having a grain size of 0.001 μm or more and less than 0.01 μm is preferably 20% or more of the total silver halide grains, more preferably, the photosensitive silver halide grains are more preferably. It is present at least 30%, most preferably at least 50%.

The shape of the silver halide grains is cubic,
Octahedral, tetradecahedral particles, tabular particles, spherical particles, rod-like particles, potato-like particles, and the like can be mentioned. In the present invention, cubic particles, tetrahedral particles, and tabular particles are particularly preferable. When tabular silver halide grains are used, the average aspect ratio is preferably from 2 to 100, more preferably from 3 to 50. These are U.S. Patent Nos. 5,264,337 and 5,314,798,
No. 5,320,958 and the like, and desired tabular grains can be easily obtained. Further, grains having rounded corners of silver halide grains can also be preferably used. The outer surface of the silver halide grains is not particularly limited, but it is preferable that the ratio occupied by the Miller index [100] plane is high, and this ratio is 50% or more, and more preferably 70%.
It is preferably at least 80%. The ratio of the Miller index [100] plane is [11] in the adsorption of the sensitizing dye.
T] utilizing the adsorption dependency between the [1] plane and the [100] plane. T
ani, J .; Imaging Sci. , 29,165
(1985).

The silver halide grains of the present invention may be prepared after forming the organic silver grains, or the silver halide grains may be prepared in advance and added to a solution for preparing an organic silver salt. Well, or a combination of these methods is also possible. The silver halide grains of the present invention are preferably prepared at least after grain formation. Furthermore, it is particularly preferable to combine both methods. That is, in the present invention, it is particularly preferable that silver halide grains prepared in advance are added to form organic silver grains, and then silver halide grains are further formed.

In the present invention, silver halide grains are preferably prepared after forming organic silver grains. Especially particle size 0.0
Silver halide grains of less than 1 μm are preferably prepared after forming the organic silver grains. As a method for adjusting after the formation of the organic silver particles, a method of adding a halogen compound to the preparation liquid after the formation of the organic silver particles and reacting with silver ions in the solution to form silver halide, or a method of forming silver of the formed organic silver A method of converting a part or all of the compound into a silver halide by a conversion reaction is preferably used.

In the case of preparing silver halide grains in advance in the present invention, P.I. Chi by Glafkids
Mie et Physique Photograph
hique (published by Paul Montel, 1967)
Year), G. F. Photographi by Duffin
c Emulsion Chemistry (TheF
ocal Press, 1966); L. Ze
Making and C by likman etal
eating PhotographicEmulsi
on (The Focal Press, 1964)
Year)). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halide may be any one of a one-sided mixing method, a double-sided mixing method, a combination thereof and the like. Good.

In the present invention, the halogen composition of the silver halide grains is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. You may.

The photosensitive silver halide grains of the present invention can be desalted by a known desalting method such as a noodle method, flocculation method, ultrafiltration method, and electrodialysis method.

The light-sensitive material of the present invention is characterized in that transition metal ions are contained in 80% or more (number) of all photosensitive silver halide grains contained therein, but preferably 85%.
Not less than 100%. If it is less than 80%, the performance stability during development deteriorates, which is not preferable.

In the light-sensitive material of the present invention, silver halide grains having a particle size of less than 0.01 .mu.m are preferably present in an amount of 20% or more (number) of all the photosensitive silver halide grains. % (Number), more preferably 30% or more and less than 100%, and most preferably 50% or more and less than 100%. In addition, 80 of the particles
% (Number) of transition metal ions is preferably contained, and more preferably 85% or more and 100% or less.

The transition metal ions contained in the photosensitive silver halide grains contained in the light-sensitive material of the present invention (hereinafter sometimes referred to as silver halide grains of the present invention) are selected from Group 6 of the Periodic Table of the Elements. An ion or a complex ion of a metal belonging to Group 10 is preferable, and specific metals include W, F
e, Co, Ni, Cu, Ru, Rh, Pd, Re, O
s, Ir, Pt, and Au are preferred. These may be used alone or in combination of two or more of the same or different metal complexes. The preferred content is 1 × 1 per mol of silver halide.
The range is preferably from 0 ^-9 mol to 1 × 10 ^-2 mol, and 1 × l
More preferably, the range is from 0 ^-8 mol to 1 × 10 ^-4 . In the present invention, the transition metal complex is represented by the following general formula 6:
Coordination complexes are preferred.

In the formula [ML ₆ ] ^m , M is a transition metal selected from elements of Groups 6 to 10 of the periodic table, L is a bridging ligand, and m is 0, -1, -2 or-.
3 is represented. 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.

Preferred specific examples of the transition metal complex used in the present invention are shown below.

[0029] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [CrCl _6] ^{4 -} 7: [IrCl6] ^4- 8: [IrCl6] ^3- 9: [Ru (NO) Cl _5] ^2- 10: [RuBr ₄ (H ₂ O) _2] ^2- 11: [Ru (NO) (H ₂ O) Cl _4] ^- 12: [RhCl ₅ (H ₂ O)] ^2- 13: [Re (NO) Cl _5] ^2- 14: [Re (NO) CN _5] ^2- 15: [Re (NO ) ClCN _4] ^2- 16: [Rh (NO) ₂ Cl _4] ^- 17: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 18: [Ru (NO) CN _5] ^2- 19: [Fe (CN) _6] ^4- 20: [Fe (CN) _6] ^{3- 21: [Co (CN)} 6] 3- 22: [Rh (NS) Cl _5] ^2- 23: [Os (NO) Cl ₅ ] ^2-24: [Cr NO) Cl _5] ^2- 25: [Re (NO) Cl _5] ^- 26: _{[Os (NS) Cl 4 (TeCN} ) ] ^2- 27: [Ru (NS) Cl _5] ^2- 28: [Re ( NS) Cl ₄ (SeCN)] ² -29: [Os (NS) Cl (SCN) ₄ ] ^2-30 : [Ir (NO) Cl ₅ ] ^2- Among these, particularly preferred metal ions are Ir ions and their ions. Complex.

It is preferred that the compound providing these metal ions or complex ions is incorporated into silver halide grains when forming silver halide grains.

When the silver halide grains of the present invention are formed after the formation of the organic silver grains, the metal ions may be added to the reaction vessel in advance as a solution of the metal ions or the complex ions during the formation of the organic silver. , May be added at any stage thereafter. In this case, the solution may be a single solution or a mixed solution with another compound. In the addition, it may be added in several divided portions, may be contained uniformly in the silver halide grains, or may be contained with a distribution within the grains. It is preferable that the content near the surface and / or the content be higher than the content inside the particle. In particular, it is preferable to include it on the particle surface.

When the silver halide grains of the present invention are formed separately from the formation of the organic silver grains, metal ions can be formed at any stage before and after the preparation of the silver halide grains, that is, before nucleation, growth, physical ripening, and chemical sensitization. Although it may be added, it is preferably added at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth, and most preferably at the stage of growth. In the addition, it may be added in several divided portions, and may be uniformly contained in the silver halide grains.
3, JP-A-2-306236, JP-A-3-167545
Nos. 4-76534, 6-110146, 5
As described in, for example, JP-A-273683, it is also possible to include the particles with a distribution, but it is preferable to include the particles with a distribution. When a distribution is provided in the particles, it is preferable that the content on the particle surface and / or near the surface is higher than the content inside the particles. In particular, it is preferable to include it on the particle surface.

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 a metal ion or complex ion in advance during silver halide preparation 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 at the end of physical ripening, or at the time of chemical ripening.

The photosensitive silver halide grains in the present invention are preferably chemically sensitized. Examples of the sensitization method include known methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization, and reduction sensitization. A sensitization method can be used. These sensitization methods can be used in combination of two or more. For sulfur sensitization, thiosulfates, thiourea compounds, inorganic sulfur and the like can be used. Compounds preferably used for selenium sensitization and tellurium sensitization are described in JP-A-9-2.
The compounds described in No. 30527 can be mentioned. Compounds preferably used in the noble metal sensitization method include, for example, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, US Pat. No. 2,448,060, and British Patent 618,061
And the like. Ascorbic acid, 2
Thiourea oxide, stannous chloride, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds, and the like can be used. When the pH of the emulsion is 7 or more or pAg
Can be reduced and sensitized by keeping at 8.3 or less.

In the photothermographic material of the present invention, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye,
Holographic polar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used. For example, Japanese Unexamined Patent Application Publication No.
No., 60-140335, 63-231437
No., 63-259,651 and 63-304242
No. 63-15245, U.S. Pat. No. 4,639,4
No. 14, No. 4,740,455, No. 4,741,
No. 966, No. 4,751,175, No. 4,83
Sensitizing dyes described in U.S. Pat. No. 5,096 can be used. Useful sensitizing dyes for use in the present invention include, for example, Research
h Disclosure Item 17643 IV-A
Item (p.23, December 1978), Item 1831
It is described in the literature described or cited in section X (p. 437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various laser imagers and scanners can be advantageously selected. For example, JP-A Nos. 9-34078, 9-54409, and 9
The compounds described in -80679 are preferably used.

Useful cyanine dyes are, for example, cyanine dyes having a basic nucleus such as a thiazoline nucleus, an oxazoline nucleus, a pyrroline nucleus, a pyridine nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus and an imidazole nucleus. Preferred useful merocyanine dyes include, in addition to the above basic nuclei, acidic nuclei such as thiohydantoin nucleus, rhodanine nucleus, oxazolidinedione nucleus, thiazolinedione nucleus, barbituric acid nucleus, thiazolinone nucleus, malononitrile nucleus and pyrazolone nucleus. Including.

In the present invention, it is particularly preferable to use a sensitizing dye having a spectral sensitivity in the infrared.

It is preferable that the sensitizing dye having spectral sensitivity in the infrared ray contains at least one compound represented by the following general formulas [Ia] to [Id].

[0039]

Embedded image

[In the general formulas [Ia] to [Id], Z ₁₁ , Z ₁₂ , Z ₂₁ , Z ₂₂ , Z ₃₁ , Z ₄₁ and Z ₄₂ are
Each represents a nonmetallic atom group necessary to complete a monocyclic or condensed 5- or 6-membered nitrogen-containing heterocyclic ring, and Q ₃₁ ,
Q ₃₂ and Q ₄₁ are each an oxygen atom, a sulfur atom, a selenium atom or -N (R) - represents, wherein R represents an alkyl group, an aryl group or a heterocyclic group. R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ ,
R _31, R ₄₁ and R _43, each represent an aliphatic group, R _32,
R ₃₃ and R ₄₂ each represent an alkyl group, an aryl group or a heterocyclic group. _{R 13, R 14, R 15} , R 16, R 17, R 23,
R ₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , R ₂₈ , R ₂₉ , R ₃₄ , R ₃₅ , R
₃₆ , _R37 , _R38 , _R39 , _R44 , _R45 , _R46 , _R47 , _R48
And R ₄₉ are each a hydrogen atom, a substituted or unsubstituted,
Alkyl group, an alkoxy group, an aryloxy group, an aryl _{group, -N (W 1, W 2} ) -, - representing the SR or heterocyclic group.
Here, R represents an alkyl group, an aryl group or a heterocyclic group, W ₁ and W ₂ each represent a substituted or unsubstituted alkyl group or an aryl group, and W ₁ and W ₂ A 6-membered or 6-membered nitrogen-containing heterocycle can also be formed.
R ₁₁ and R _13, R ₁₄ and R _16, R ₁₇ and R _12, R ₂₁ and R _23, R
₂₄ and R ₂₆ , R ₂₅ and R ₂₇ , R ₂₆ and R ₂₈ , R ₂₂ and R ₂₉ , R ₃₁
And R ₃₄ , R ₃₅ and R ₃₇ , R ₄₁ and R ₄₄ , R ₄₅ and R ₄₇ and R _49.
And R ₄₃ can be linked together to form a 5- or 6-membered ring. X ₁₁ , X ₂₁ and X ₄₁ each represent an ion necessary for canceling an intramolecular charge, and m ₁₁ , m ₂₁ and m ₄₁
Each represents the number of ions required to offset the charge in the molecule.

N ₁₁ , n ₁₂ , n ₂₁ , n ₂₂ , n ₃₁ , n ₄₁ and n ₄₂ each represent 0 or 1, and l ₃₁ , l ₃₂ , l ₃₃ ,
l ₄₁ , l ₄₂ and l ₄₃ each represent 0 or 1. The compound represented by the general formula [Ia] is preferably a compound represented by the following general formula [Ie] or [If].

[0042]

Embedded image

[The general formula [Ie] and the general formula [If]]
In the formula, Y ₅₁ , Y ₅₂ , Y ₆₁ and Y ₆₂ each represent an oxygen atom, a sulfur atom, a selenium atom or — (NR ₀ ) —, wherein R ₀ represents an aliphatic group. R ₅₁ and R ₅₂ each represent an aliphatic group, and R ₆₁ represents a nonmetallic atom group necessary for bonding to the aliphatic group or R ₆₅ to complete a 5- or 6-membered fused ring. R ₅₃ and R ₅₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₅₅ and R ₆₂ each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group or an amino group, R ₆₃ and R ₆₄
Each represents a hydrogen atom, an alkyl group or a group of non-metallic atoms necessary for forming a 5- or 6-membered ring by bonding between R ₆₃ and R ₆₄ . R ₆₅ represents a hydrogen atom or a bond to R ₆₁ . A _{51 to} A ₅₈ and A _{61 to} A ₆₈ each represent a hydrogen atom or a substitutable group, and A ₅₁ and A ₅₂ , A ₅₂ and A ₅₃ , A ₅₃ and A
₅₄ , _A55 and _A56 , _A56 and _A57 , _A57 and _A58, and _A61 and A
_62, at least one pair of A ₆₂ and A _63, A ₆₃ and A _64, A ₆₅ and A _66, A ₆₆ and A _67, A ₆₇ and A ₆₈ may form a fused naphthol ring by linking each other. _M51 and _M61
Each represents an ion required to cancel the intramolecular charge, and m ₅₁ and m ₆₁ each represent the number of ions required to cancel the intramolecular charge. p represents 2 or 3. The compound represented by the general formula [Ib] is preferably a compound represented by the following general formula [Ig], [Ih] or [Ii].

[0044]

Embedded image

[General formula [Ig], [Ih] or [I
-I], Y ₇₁ , Y ₇₂ , Y ₈₁ , Y ₈₂ , Y ₉₁ and Y
₉₂ is an oxygen atom, a sulfur atom, a selenium atom or-(N
R ₀ ) —, wherein R ₀ represents an aliphatic group. R ₇₁ , R
₇₂ , R ₈₁ , R ₈₂ , R ₉₁ and R ₉₂ each represent an aliphatic group. R ₇₃ and R ₇₄ and R ₉₃ and R ₉₄ each represent a nonmetallic atom group necessary to form a 5- or 6-membered ring, and R ₇₅ and R ₉₅ each represent a hydrogen atom , An alkyl group,
Aryl group, heterocyclic group, halogen atom, alkoxy group,
Represents an aryloxy group, an alkylthio group, an arylthio group or an amino group. A _{71 to} A ₇₈ , A _{81 to} A ₈₈ and A ₉₁ to
A ₉₈ represents a hydrogen atom or a substitutable group, and A ₇₁ and A ₇₂ , A ₇₂ and A ₇₃ , A ₇₃ and A ₇₄ , A ₇₅ and A ₇₆ , A ₇₅ and A ₇₆ , A ₇₆ and A
_77, A ₇₇ and A ₇₈ and A ₈₁ and A _82, A ₈₂ and A _83, A ₈₃ and A
₈₄ , _A85 and _A86 , _A86 and _A87 , _A87 and _A88, and _A91 and A
_92, A ₉₂ and A _93, A ₉₃ and A _94, A ₉₅ and A _96, A ₉₆ and A _97, at least one pair of A ₉₇ and A ₉₈ may be linked to form a fused naphthol ring. M ₇₁ , M _81, and M ₉₁ each represent an ion necessary to cancel the charge in the molecule, and m ₇₁ , m _81, and m ₉₁ each represent the number of ions required to cancel the charge in the molecule. Represent. Hereinafter, the general formulas [Ia] to [Id] and [Ie]
Alternatively, the photosensitive dye represented by [Ii] will be described.

In the above general formulas [Ia] to [Id], a 5- or 6-membered member represented by Z ₁₁ , Z ₁₂ , Z ₂₁ , Z ₂₂ , Z ₃₁ , Z ₄₁ and Z ₄₂ respectively. Examples of the nitrogen-containing heterocyclic ring include an oxazole nucleus (for example, an oxazolidine ring, an oxazoline ring, a benzoxazole ring, a tetrahydrobenzoxazole ring, a naphthoxazole ring, a benzonaphthoxazole ring, and the like), and an imidazole nucleus (for example, an imidazolidine ring, an imidazoline ring, a benz) Imidazole ring, tetrahydrobenzimidazole ring, naphthoimidazole ring,
Benzonaphthoimidazole ring, etc.), thiazole nucleus (for example, thiazolidine ring, thiazoline ring, benzothiazole ring, tetrahydrobenzothiazole ring, naphthothiazole ring, benzonaphthothiazole ring, etc.), selenazole nucleus (for example, selenazolidine ring, selenazoline ring, benzo) Selenazole ring, tetrahydrobenzoselenazole ring,
A naphthoselenazole ring, a benzonaphthoselenazole ring, etc.), a tellurazole nucleus (eg, a tellurazolidine ring, a tellurazoline ring, a benzotellurazole ring, etc.), a pyridine nucleus (eg, pyridine, quinoline, etc.), a pyrrole nucleus (eg, a pyrrolidine ring, Pyrroline ring, pyrrole ring, 3,3-
Dialkyl indolenine ring), and on these rings, any group described as a substitutable group represented by A _{51 to} A ₉₈ described below can be substituted.

R ₀ , R ₁₁ , R ₁₂ , R ₂₁ , R ₂₂ , R ₃₁ , R
₄₁ , _R43 , _R51 , _R52 , _R61 , _R71 , _R72 , _R81 ,
Examples of the aliphatic group represented by R ₈₂ , R ₉₁ and R ₉₂ include, for example, a branched or straight-chain alkyl group having 1 to 10 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group) A pentyl group, an iso-pentyl group, a 2-ethyl-hexyl group, an octyl group, a decyl group, etc.), an alkenyl group having 3 to 10 carbon atoms (for example, a 2-propenyl group,
3-butenyl group, 1-methyl-3-propenyl group, 3-
A pentenyl group, a 1-methyl-3-butenyl group, a 4-hexenyl group, etc.) and an aralkyl group having 7 to 10 carbon atoms (eg, a benzyl group, a phenethyl group, etc.).

The above-mentioned groups further include a lower alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.), a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.),
Vinyl group, aryl group (for example, phenyl group, p-tolyl group, p-bromophenyl group, etc.), trifluoromethyl group, alkoxy group (for example, methoxy group, ethoxy group,
Methoxyethoxy group etc.), aryloxy group (for example,
Phenoxy group, p-tolyloxy group, etc.), cyano group, sulfonyl group (eg, methanesulfonyl group, trifluoromethanesulfonyl group, p-toluenesulfonyl group, etc.), alkoxycarbonyl group (eg, ethoxycarbonyl group, butoxycarbonyl group, etc.) An amino group (eg, amino group, biscarboxymethylamino group, etc.), an aryl group (eg, phenyl group, carboxyphenyl group, etc.), a heterocyclic group (eg, tetrahydrofurfuryl,
-Pyrrolidinone-1-yl group and the like), acyl group (for example,
Acetyl group, benzoyl group, etc.), ureido group (for example,
Ureido group, 3-methylureido group, 3-phenylureido group, etc.), thioureido group (eg, thioureido group, 3-methylthioureido group, etc.), alkylthio group (eg, methylthio, ethylthio group, etc.), arylthio group (eg, A phenylthio group, etc.), a heterocyclic thio group (e.g., a 2-thienylthio group, a 3-thienylthio group, etc.),
Carbonyloxy group (eg, acetyloxy group, propanoyloxy group, benzoyloxy group, etc.), acylamino group (eg, acetylamino, benzoylamino group, etc.), thioamide group (eg, thioacetamido group, thiobenzoylamino group, etc.) Groups, or, for example,
Sulfo group, carboxy group, phosphono group, sulfate group, hydroxy group, mercapto group, sulfino group, carbamoyl group (for example, carbamoyl group, N-methylcarbamoyl group, N, N-tetramethylenecarbamoyl group, etc.), sulfamoyl group (for example, , A sulfamoyl group,
N, N-3-oxapentamethyleneaminosulfonyl group, etc.), sulfonamide group (eg, methanesulfonamide, butanesulfonamide group, etc.), sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl, ethanesulfonylaminocarbonyl group, etc.) ), An acylaminosulfonyl group (eg, acetamidosulfonyl, methoxyacetamidosulfonyl group, etc.), an acylaminocarbonyl group (eg, acetamidocarbonyl,
It may be substituted with a hydrophilic group such as a methoxyacetamidocarbonyl group or a sulfinylaminocarbonyl group (for example, a methanesulfinylaminocarbonyl group or an ethanesulfinylaminocarbonyl group). Specific examples of the aliphatic group in which these hydrophilic groups are substituted include carboxymethyl, carboxyethyl, carboxybutyl, carboxypentyl, 3-sulfatobutyl,
Sulfopropyl, 2-hydroxy-3-sulfopropyl group, 4-sulfobutyl, 5-sulfopentyl, 3-sulfopentyl, 3-sulfinobutyl, 3-phosphonopropyl, hydroxyethyl, N-methanesulfonylcarbamoylmethyl, 2 -Carboxy-2-propenyl, O
-Sulfobenzyl, P-sulfophenethyl, P-carboxybenzyl and the like.

R, R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ ,
_{R 23, R 24, R 25} , R 26, R 27, R 28, R 29, R 32, R
₃₃ , _R34 , _R35 , _R36 , _R37 , _R38 , _R39 , _R42 ,
_R44 , _R45 , _R46 , _R47 , _R48 , _R49 , _R53 , _R54 , R
Examples of the alkyl group represented by ₅₅ , _R62 , _R63 , _R64 , _R75 and _R95 include, for example, a methyl group, an ethyl group, a butyl group, an iso-butyl group, and the like. Including monocyclic and polycyclic groups, examples include groups such as a phenyl group and a naphthyl group, and examples of the heterocyclic group include groups such as thienyl, furyl, pyridyl, carbazolyl, pyrrolyl, and indolyl.

These groups can be substituted with the groups described in the description of the aliphatic groups represented by R ₀ , R _{11 and} R _92. Specific examples of the substituted alkyl group include, for example, 2-methoxyethyl , 2-hydroxyethyl, 3-ethoxycarbonylpropyl, 2-carbamoylethyl, 2-methanesulfonylethyl, 3-methanesulfonylaminopropyl, benzyl, phenethyl, carboxymethyl, carboxyethyl, allyl, 2-furylethyl And specific examples of the substituted aryl group include, for example,
p-carboxyphenyl, p-N, N-dimethylaminophenyl, p-morpholinophenyl, p-methoxyphenyl, 3,4-dimethoxyphenyl, 3,4-methylenedioxyphenyl, 3-chlorophenyl, p-nitrophenyl And specific examples of the substituted heterocyclic group include, for example, 5-chloro-2-pyridyl, 5-
Each group such as ethoxycarbonyl-2-pyridyl, 5-carbamoyl-2-pyridyl and the like can be mentioned.

Examples of the alkyl group and aryl group represented by W ₁ and W ₂ include the groups described above for R and the like.

R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₂₃ , R
_{24, R 25, R 26,} R 27, R 28, R 29, R 34, R 35,
_R36 , _R37 , _R38 , _R39 , _R44 , _R45 , _R46 , _R47 , R
Each in _{48, R 49, R 55,} R 62, R 75 and R _95, the alkoxy group represented, for example, a methoxy group, an ethoxy group, a 2-methoxyethoxy group, 2-hydroxyethoxy group and the like, As the aryloxy group, for example,
Phenoxy group, 2-naphthoxy group, 1-naphthoxy group,
Examples include a p-tolyloxy group and a p-methoxyphenyl group.

Examples of the halogen atom represented by R ₅₅ , R ₆₂ , R ₇₅ and R ₉₅ include, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and examples of the alkylthio group include a methylthio group and an ethylthio group. And the like. As the arylthio group, for example, a phenylthio group,
Examples of the amino group include substituted and unsubstituted groups. Examples of the amino group include an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a diphenylamino group, and N, N-tetramethyleneamino. Group,
And an N, N-pentamethyleneamino group.

R ₁₄ and R ₁₆ , R ₂₄ and R ₂₆ , R ₂₅ and R ₂₇ , R
₂₆ and R ₂₈ , R ₃₅ and R ₃₇ , R ₄₅ and R ₄₇ , R ₄₉ and R ₄₃ , R ₆₃
And R ₆₄ , R ₇₃ and R _74, and R ₉₃ and R ₉₄ may be each connected to each other to form a condensed ring, for example, 5
And 6-membered saturated or unsaturated fused carbocycles.
Any of these condensed rings can be substituted at any position, and examples of these substituted groups include the groups described above as the groups that can be substituted with the aliphatic group.

R ₁₁ and R ₁₃ , R ₁₂ and R ₁₇ , R ₂₁ and R ₂₃ , R
₂₂ and R ₂₉ , R ₃₁ and R ₃₄ , R ₄₁ and R ₄₄ may be each connected to each other to form a condensed ring, for example, 5
And 6-membered saturated or unsaturated nitrogen-containing condensed rings. Examples of the 5- or 6-membered nitrogen-containing heterocyclic ring formed by connecting W ₁ and W ₂ together with a nitrogen atom include, for example,
Examples include a pyrrolidine ring, a morpholine ring, a piperidine ring and the like.

A _{51 to} A ₅₈ , A _{61 to} A ₆₈ , A _{71 to} A ₇₈ , A
Each Examples of the group can be substituted represented by ₈₁ to A ₈₈ and A ₉₁ to A _98, a lower alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), a halogen atom (e.g., fluorine atom, chlorine atom, bromine Atom), vinyl group, styryl group,
Aryl group (for example, phenyl group, p-tolyl group, p-
Bromophenyl group), trifluoromethyl group, alkoxy group (eg, methoxy group, ethoxy group, etc.), aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), carbonyloxy group (eg, acetyloxy group, Propanoyloxy group, benzoyloxy group, etc.),
An amino group (for example, amino, dimethylamino, anilino, etc.), a heterocyclic group (for example, pyridyl group, pyrrolyl group, furyl group, thienyl group, imidazolyl group, thiazolyl group, pyrimidinyl group, etc.), an acyl group (for example, Acetyl group, benzoyl group, etc.), cyano group, sulfonyl group (eg, methanesulfonyl group, benzenesulfonyl group, etc.), carbamoyl group (eg, carbamoyl group, N,
N-dimethylcarbamoyl group, morpholinocarbonyl group, etc.), sulfamoyl group (eg, sulfamoyl group, N-phenylsulfamoyl group, morpholinosulfonyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino, ortho- Hydroxybenzoylamino group, etc., sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, trifluoroethoxycarbonyl group, etc.), hydroxyl group , A carboxyl group or the like.

In the compounds represented by the general formulas [Ia] to [Ii], when a group having a cationic or anionic charge is substituted, the charge in the molecule is canceled out. Thus, a counter ion is formed with an equivalent amount of an anion or cation. For example, X ₁₁ , X ₂₁ , X ₄₁ , M ₅₁ , M
Specific examples of cations required for canceling the intramolecular charge represented by ₆₁ , M ₇₁ , M ₈₁ and M ₉₁ include a proton and an organic ammonium ion (for example,
Triethylammonium, triethanolammonium, etc.), inorganic cations (eg, cations such as lithium, sodium, potassium, etc.). Specific examples of acid anions include, for example, halogen ions (eg, chloride ion, bromine ion, Iodine ion), p-toluenesulfonic acid ion, perchlorate ion, boron tetrafluoride ion, sulfate ion, methyl sulfate ion, ethyl sulfate ion, methanesulfonic acid ion, trifluoromethanesulfonic acid ion and the like.

In the sensitizing dyes represented by formulas [Ia] to [Id], the sensitizing dyes represented by formulas [Ie] and [I-
sensitizing dyes represented by formula (f) are preferably used, and sensitizing dyes represented by formulas (Ig) to (Ii) are more preferably used.

The following formulas [Ia] to [I-
Representative examples of the photosensitive dye (compound) represented by i) are shown below, but the present invention is not limited to these compounds.

[0060]

Embedded image

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

[0068]

Embedded image

[0069]

Embedded image

[0070]

Embedded image

The above-mentioned infrared-sensitive dyes are described, for example, by FM Hammer, The Chemistry of
Heterocyclic Compounds 18th
Volume, The Cyanine Dyes and Re
lated Compounds (A. Weisshe
rger ed. Published by Interscience, Ne
w York 1964).

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure (Research).
Discosure) 176 Volume 17643 (197
(Issued December 2008), page 23, IV, J, or the aforementioned Japanese Patent Publication Nos. 9-25500 and 43-4933;
Nos. 9-19032 and 59-192242.

In the present invention, the organic silver salt is a reducible silver source, and a silver salt of an organic acid or a heteroorganic acid containing a reducible silver ion source, especially a long chain (10 to 30, preferably 15 to 28) The silver salt of an aliphatic carboxylic acid having (the number of carbon atoms) is preferred. Organic or inorganic silver salt complexes wherein the ligand has a complex stability constant for silver ions of 4.0 to 10.0 are also useful. Examples include: silver salts of organic acids (eg, gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid, oleic acid,
Silver salts such as caproic acid, myristic acid, palmitic acid, maleic acid, and linoleic acid); carboxyalkylthiourea salts of silver (eg, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3 Silver complexes of aldehydes and hydroxy-substituted aromatic carboxylic acids (e.g., aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.) and hydroxy-substituted acids (e.g., salicylic acid) Benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid, etc.), and silver complexes of the polymer reaction products); silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thioene, 3-carboxymethyl-4-thia Silver salts or complexes, such as phosphorus-2 thioene); imidazole, pyrazole, urazole,
Complexes or salts of silver with a nitrogen acid selected from 1,2,4-thiazole, 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; saccharin, 5-chlorosalicyl Silver salts such as aldoxime; and silver salts of mercaptides. Examples of suitable silver salts are described in Research Disclosure No. 1
7029 and 29996, and particularly preferred silver sources are silver behenate, silver arachidate and / or silver stearate.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and can be obtained by a forward mixing method, a reverse mixing method, a simultaneous mixing method, or a method disclosed in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used. For example, an organic acid alkali metal salt soap (eg, sodium hydroxide, potassium hydroxide, etc.)
After preparing sodium behenate and sodium arachidate, the above-mentioned soap and silver nitrate are added by a control double jet to prepare crystals of an organic silver salt. At this time, silver halide grains separately prepared in advance may be mixed. Also, a silver nitrate solution is added to a solution of an organic acid alkali metal salt soap to produce organic silver salt crystals. At this time, silver halide grains separately prepared in advance may be mixed.

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. The monodispersion has the same meaning as that of silver halide, and preferably has a coefficient of variation of 1 to 30.
%. In the present invention, the organic silver salt has an average particle size of 1 μm.
It is more preferable that the particles be monodisperse particles having a particle size of m or less. Further, the organic silver salt preferably has tabular grains having 60% or more of the total organic silver. In the present invention, the term “tabular grains” refers to a ratio of an average particle diameter to a thickness, that is, an aspect ratio (AR) represented by the following formula.
Abbreviation) means three or more.

AR = average particle size (μm) / thickness (μm) In order to form organic silver into these shapes, conditions such as the temperature at the time of organic silver formation, the concentration of each liquid, the addition speed, and the stirring speed are set. It can be obtained by controlling it optimally, or by dispersing and pulverizing the organic silver crystal together with a binder, a surfactant and the like using a ball mill or a high-pressure homogenizer.

In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably from 0.5 g to 2.5 g per m ² in terms of silver. . With this range, a high-contrast image can be obtained. The amount of silver halide relative to the total amount of silver is 50% or less, preferably 25% or less, more preferably 0.1% to 15% by weight of silver.

The photothermographic material of the present invention contains a reducing agent. Examples of suitable reducing agents for the photothermographic material of the present invention are described in U.S. Pat. Nos. 3,770,448 and 3,77.
No. 3,512, No. 3,593,863, and Res
Ear Disclosure No. 17029 and 2
9963, and includes the following.

Aminohydroxycycloalkenones (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) Aminooxins; Azines (for example, a combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; Hydroxanoic acids Combinations of azines 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 ,
Chromanes; 1,4-dihydropyridines (for example, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, 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. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0080]

Embedded image

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

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

[0083]

Embedded image

[0084]

Embedded image

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, for example: gelatin, gum arabic, poly (Vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid) Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal) s (eg, poly (vinyl formal) and poly (vinyl butyral)), poly (ester) Kind, poly ( Urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). It may be hydrophilic or non-hydrophilic.

In the present invention, the binder amount of the photosensitive layer is preferably from 1.5 to 20 g / m ² . More preferably, it is 2.0 to 15 g / m ² . 1.5g /
If it is less than m ² , a sufficient optical density cannot be obtained after development.

In the present invention, a matting agent is preferably contained on the photosensitive layer side, and in order to prevent damage to the image after thermal development, it is preferable to provide a matting agent on the surface of the photosensitive material. The matting agent is preferably contained in a weight ratio of 0.5 to 30% based on all binders on the emulsion 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
No. 0,158, polystyrene or polymethacrylate; U.S. Pat. No. 3,079,257; polyacrylonitrile; U.S. Pat. No. 3,022,16.
An organic matting agent such as polycarbonate described in No. 9 or the like 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 has an average particle size of 0.5 μm to 10 μm.
μm, more preferably 1.0 μm
８8.0 μm. The matting agent has a coefficient of variation of the particle size distribution of preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less.

Here, the variation coefficient 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 can be contained in any constituent layer, but is preferably a constituent layer other than the photosensitive layer, more preferably The outermost layer viewed from the support.

The method of adding the matting agent may be a method in which the matting agent is dispersed in a coating solution in advance, or a method in which the matting agent is sprayed before the drying is completed after applying the coating solution. Is also good. When a plurality of types of matting agents are added, both methods may be used in combination.

The photothermographic material of the present invention, which forms a photographic image by heat development, comprises a reducible silver source (organic silver salt), a catalytically active amount of silver halide, a hydrazine derivative,
It is preferable that the photothermographic material contains a reducing agent and, if necessary, a color tone agent for suppressing the color tone of silver in a state of being 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 to 140 ° C) after exposure. Heating generates 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 accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. Silver produced by the reaction of the organic silver salt in the exposed areas provides a black image,
This is in contrast to the unexposed areas, where the image is formed. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only a 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 as the photosensitive layer and / or on the opposite side to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or pigment. Is also good. As the dye to be used, any compound may be used as long as it has a desired absorption in a desired wavelength range. For example, JP-A-59-6481 and JP-A-59-182436 may be used.
No. 4,271,263, U.S. Pat.
No. 4,312, European Patent Publication Nos. 533,008, 65
2,473, JP-A-2-216140, 4-34
No. 8339, No. 7-191432, No. 7-30189
The compounds described in No. 0 and the like are preferably used. These non-photosensitive layers preferably contain the binder or matting agent described above, and may further contain a sliding agent such as a polysiloxane compound, wax or liquid paraffin.

The light-sensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation. Various additives are photosensitive layer, non-photosensitive layer,
Alternatively, it may be added to any of the other forming layers. The photothermographic material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

It is preferable to add a color tone agent to the photothermographic material of the present invention. Toning agents are disclosed in US Pat.
As shown in U.S. Pat. Nos. 0,254, 3,847,612 and 4,123,282, these materials are well known in the photographic art. An example of a suitable toning agent is Resea
rc Disclosure No. 17029, which includes:

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and , 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 (for example,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isoth
uronium) derivatives and certain photobleaching combinations (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (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 + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalate Acid combinations; phthalazine (including phthalazine adducts) and maleic anhydride,
And phthalic acid, 2,3-naphthalenedicarboxylic acid or o
At least one selected from phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (E.g., 2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (e.g., 3,
6-dimercapto-1,4-diphenyl-1H, 4H-
2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained in order to control development by suppressing or accelerating development, to improve spectral sensitization efficiency, and to improve storage stability before and after development. be able to. When a mercapto compound is used in the present invention, it may be of any structure,
Those represented by SS-Ar are preferred. In the formula, M is a hydrogen atom or an alkali metal atom, and Ar is an aromatic ring or a condensed aromatic ring having one or more nitrogen, sulfur, oxygen, selenium or tellurium atoms. Preferably, the heteroaromatic ring is benzimidazole, naphthymidazole, benzothiazole, naphthothiazole, benzoxazole, naphthoxazole, benzoselenazole, benzoterzole, imidazole, oxazole,
Pyrazole, triazole, thiadiazole, tetrazole, triazine, pyrimidine, pyridazine, pyrazine, pyridine, purine, quinoline or quinazolinone. This heteroaromatic ring is, for example, a halogen (for example,
Br and Cl), hydroxy, amino, carboxy,
Alkyl (eg one or more carbon atoms, preferably 1
May also have a substituent selected from the group consisting of those having from 1 to 4 carbon atoms) and alkoxy (e.g., having at least one carbon atom, preferably having from 1 to 4 carbon atoms). Good mercapto-substituted heteroaromatic compounds include 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2-mercapto-5-methylbenzimidazole, 6-ethoxy-2-mercaptobenzothiazole, 2,2'-dithiobisbenzothiazole, 3-mercapto-1,2,4-triazole, 4,5-diphenyl-2-imidazolethiol, 2-mercaptoimidazole, 1-ethyl-2-mercaptobenzimidazole, 2- Mercaptoquinoline, 8-mercaptopurine,
2-mercapto-4- (3H) quinazolinone, 7-trifluoromethyl-4-quinolinethiol, 2,3,5
6-tetrachloro-4-pyridinethiol, 4-amino-6-hydroxy-2-mercaptopyrimidine monohydrate, 2-amino-5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto- 1,2,
4-triazole, 4-hydroxy-2-mercaptopyrimidine, 21-mercaptopyrimidine, 4,6-diamino-2mercaptopyrimidine, 2-mercapto-4-methylpyrimidine hydrochloride, 3-mercapto-5
Examples thereof include phenyl-1,2,4-triazole and 2-mercapto-4-phenyloxazole, but the present invention is not limited thereto. The addition amount of these mercapto compounds is 0.001 per mole of silver in the emulsion layer.
Preferably, the amount is from 0.01 to 0.3 mole, more preferably from 0.01 to 0.3 mole per mole of silver.

What is known as an effective antifoggant is mercury ion. The use of a mercury compound as an antifoggant in a light-sensitive material is disclosed in, for example, US Pat. No. 3,589,903. But,
Mercury compounds are environmentally undesirable. Examples of the non-mercury antifoggant include, for example, U.S. Pat. Nos. 4,546,075 and 4,452,885 and JP-A-59-57234.
Antifoggants such as those disclosed in US Pat.

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 halogen, X ₃ is hydrogen or halogen) and is a heterocyclic compound having one or more substituents. Examples of suitable antifoggants include:
JP-A-9-288328, paragraph numbers [0030] to [0
036] are preferably used. Examples of another preferred antifoggant include paragraphs [0062] to JP-A-9-90550.
[0063] and the like. Still other suitable antifoggants are disclosed in US Pat. No. 5,028,5.
No. 23 and British Patent Application Nos. 92221383.4, 9300147.7 and 9311790.1.

The most effective antifoggant is represented by the following general formula 1:
Which are compounds represented by the following formulas:

[0104]

Embedded image

[Wherein X ₁ and X ₂ represent a halogen atom. Y represents a divalent linking group. A represents a hydrogen atom, a halogen atom, or another electron-withdrawing group. m is 3 or more and 4
Represents the following integers. Q represents a heterocyclic group, an aryl group, or an aliphatic group. n represents an integer of 0 or more and 3 or less. When Q is an aliphatic group, the number of halogen atoms in the whole molecule is 6 or more and 1
It is less than 0. ]

[0106]

Embedded image

[Wherein X ₁ , X ₂ and A have the same meanings as those described in formula 1. Q represents an aromatic hetero 5-membered ring having one oxygen atom and 2 to 3 nitrogen atoms, a furan ring, a thiophene ring, and a pyrrole ring. However, when Q is a thiophene ring, X ₁ represents a bromine atom. ]

[0108]

Embedded image

[Wherein X ₁ , X ₂ and A have the same meanings as those described in formula 1. Y is -SO-, -CO-, -N
(R ₁₁ ) -SO _2- , -N (R ₁₁ ) -CO-, -N (R
₁₁ ) -COO-, -COCO-, -COO-, -OCO
-, -OCOO-, -SCO-, -SCOO-, -C
(Z ₁ ) (Z ₂ ) —, alkylene, arylene, divalent heterocyclic ring and 2 formed by any combination thereof
Represents a valent substituent. R ₁₁ represents a hydrogen atom or an alkyl group. Z ₁ and Z ₂ represent a hydrogen atom or an electron-withdrawing group. Z ₁ and Z ₂ are not hydrogen atoms at the same time. Q represents an aliphatic group, an aromatic group, or a heterocyclic group. However, when Y is -SO-, Q represents a 5-membered aromatic heterocyclic group or a pyridine ring group having at least one heteroatom other than N. First, the compound represented by Formula 1 will be described in detail.

The halogen atoms represented by X ₁ and X ₂ may be the same or different and are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom, a bromine atom and an iodine atom. More preferred are a chlorine atom and a bromine atom, and particularly preferred is a bromine atom.

Y represents a divalent linking group, specifically, -S
O ₂ —, —SO—, —CO—, —N (R ₁₁ ) —SO ₂ —,
_{-N (R 11) -CO -,} - N (R 11) -COO -, - C
OCO-, -COO-, -OCO-, -OCOO-,-
SCO -, - SCOO -, - C (Z 1) (Z 2) -, represents an alkylene, arylene, a divalent heterocyclic, and divalent substituents formed by any combination thereof. R ₁₁
Represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. Z ₁ and Z ₂ represent a hydrogen atom or an electron-withdrawing group, but they are not a hydrogen atom at the same time. The electron withdrawing group is preferably a substituent having a Hammett's substituent constant σp value of 0.01 or more, and more preferably 0.1 or more.
These are the above substituents. Regarding Hammett's substituent constant, see Journal of Medicinal Ch.
chemistry, 1973, Vol. 16, No. 1
1, 1207-1216 and the like can be referred to.
Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06), a chlorine atom (σp value: 0.2
3), bromine atom (σp value: 0.23), iodine atom (σ
p value: 0.18)), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp
Value: 0.33), trifluoromethyl (σp value: 0.5)
4)), cyano group (σp value: 0.66), nitro group (σ
p value: 0.78), an aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0.
72)), an aliphatic / aryl or heterocyclic acyl group (eg, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), an alkynyl group (eg, C ₃
H ₃ (σp value: 0.09)), aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σ
p value: 0.45)), carbamoyl group (σp value: 0.3
6) and a sulfamoyl group (σp value: 0.57). Z ₁ and Z ₂ are preferably a halogen atom, a cyano group or a nitro group. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferred, a chlorine atom and a bromine atom are more preferred, and a bromine atom is particularly preferred.

Y is preferably -SO _2- , -SO
-, - it represents a CO-, more preferably -SO ₂ - represents a. n is preferably 1.

The electron-withdrawing group represented by A is preferably a substituent having a Hammett's substituent constant σp value of 0.01 or more, more preferably 0.1 or more.
Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06), a chlorine atom (σp value: 0.2
3), bromine atom (σp value: 0.23), iodine atom (σ
p value: 0.18)), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp
Value: 0.33), trifluoromethyl (σp value: 0.5)
4)), cyano group (σp value: 0.66), nitro group (σ
p value: 0.78), an aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0.
72)), an aliphatic / aryl or heterocyclic acyl group (eg, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), an alkynyl group (eg, C ₃
H ₃ (σp value: 0.09)), aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σ
p value: 0.45)), carbamoyl group (σp value: 0.3
6) and a sulfamoyl group (σp value: 0.57). A is preferably an electron-withdrawing group, more preferably a halogen atom, an aliphatic / aryl or heterocyclic sulfonyl group, an aliphatic / aryl or heterocyclic acyl group, an aliphatic / aryl or heterocyclic oxycarbonyl group. And particularly preferably a halogen atom. Among halogen atoms, preferably chlorine atom, bromine atom,
It is an iodine atom, more preferably a chlorine atom or a bromine atom, and particularly preferably a bromine atom.

The aliphatic group represented by Q is a linear, branched or cyclic alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20, more preferably 1 to 12; Ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, cyclopropyl, cyclopentyl, cyclohexyl, etc., and alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, furthermore Preferably it is 2-12, for example, vinyl, allyl, 2-butenyl, 3-pentenyl etc.), alkynyl group (preferably having 2-3 carbon atoms)
0, more preferably 2 to 20, even more preferably 2 to 12
And for example, propargyl, 3-pentenyl and the like. ), And may have a substituent. Examples of the substituent include a carboxy group, an acyl group, an acylamino group, a sulfonylamino group, a carbamoyl group, a sulfamoyl group, an oxycarbonylamino group, and a ureido group. The aliphatic hydrocarbon group is preferably an alkyl group, and more preferably a chain alkyl group. The aryl group represented by Q preferably has 6 to 30 carbon atoms.
A monocyclic or bicyclic aryl group (e.g., phenyl, naphthyl, etc.), more preferably a phenyl group having 6 to 20 carbon atoms, and still more preferably a phenyl group having 6 to 12 carbon atoms.
The aryl group may have a substituent, and as the substituent,
For example, a carboxy group, an acyl group, an acylamino group, a sulfonylamino group, a carbamoyl group, a sulfamoyl group,
An oxycarbonylamino group or a ureido group;
The heterocyclic group represented by Q is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O and S atoms, which may be a single ring, And a fused ring may be formed. The heterocyclic group is preferably a 5- to 6-membered aromatic heterocyclic group, more preferably a 5- to 6-membered aromatic heterocyclic group containing a nitrogen atom, and further preferably a nitrogen atom having 1 to 2 atoms. And a 5- or 6-membered aromatic heterocyclic group. Specific examples of the heterocycle include, for example, pyrrolidine, piperidine,
Piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, purine, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine , Acridine, phenanthroline, phenazine, tetrazole, thiazole, oxazole, benzimidazole,
Benzoxazole, benzothiazole and the like can be mentioned. Preferably as a heterocycle, thiophene, furan,
Pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, tetrazole, thiazole, oxazole, benzimidazole,
Benzoxazole, benzothiazole and indolenine are more preferable, and triazine, quinoline, thiadiazole, benzothiazole and oxadiazole are particularly preferable, and pyridine, quinoline, thiadiazole and oxadiazole are particularly preferable. Q is preferably an aromatic nitrogen-containing heterocyclic group. m represents an integer of 3 or more and 4 or less, and preferably m is 3. When Q is an aliphatic group, the number of halogen atoms in the whole molecule is 6 or more and less than 10, but is preferably 6.

Next, the compound represented by Formula 2 will be described in detail.

In the formula, X ₁ , X ₂ and A have the same meanings as those described in formula 1.

Q represents one oxygen atom and two or more nitrogen atoms,
Represents a 5-membered aromatic heterocyclic ring, a furan ring, a thiophene ring, and a pyrrole ring having the following structure. And oxatriazole.
Preferred is oxadiazole. Preferred among the rings represented by Q is oxadiazole.

Next, the compound represented by Formula 3 will be described in detail.

In the formula, X ₁ , X ₂ and A have the same meanings as those described in formula 1.

Y is -SO-, -CO-, -N (R ₁₁ )-
SO _2- , -N (R ₁₁ ) -CO-, -N (R ₁₁ ) -CO
O-, -COCO-, -COO-, -OCO-, -OC
OO -, - SCO -, - SCOO -, - C (Z 1)
(Z ₂ ) — represents an alkylene, an arylene, a divalent heterocyclic ring, and a divalent substituent formed by any combination thereof. R ₁₁ represents a hydrogen atom or an alkyl group, preferably a hydrogen atom. Z ₁ and Z ₂ represent a hydrogen atom or an electron-withdrawing group, but they are not a hydrogen atom at the same time. The electron-withdrawing group is preferably a substituent having a Hammett's substituent constant σp value of 0.01 or more, more preferably 0.1 or more. Regarding the Hammett's substituent constant, see Journal of Medic.
internal Chemistry, 1973, Vol. 1
6, No. 11, 1207-1216 etc. can be referred to. Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp value: 0.06), a chlorine atom (σp
Value: 0.23), bromine atom (σp value: 0.23), iodine atom (σp value: 0.18), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value) Value: 0.33), trifluoromethyl (σp
Value: 0.54)), cyano group (σp value: 0.66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σ
p value: 0.72)), aliphatic / aryl or heterocyclic acyl group (eg, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), alkynyl group (eg, C ₃ H) ₃ (σp value: 0.09)), aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σp value: 0.45)), carbamoyl group ( σp value:
0.36), a sulfamoyl group (σp value: 0.57) and the like.

Z ₁ and Z ₂ are preferably a halogen atom, a cyano group or a nitro group. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferred, a chlorine atom and a bromine atom are more preferred, and a bromine atom is particularly preferred. Y is preferably -SO
-, - CO -, - N (R 11) -SO 2 -, - N (R 11)
_{-CO -, - C (Z 1} ) (Z 2) - ; more preferably, _{-SO -, - C (Z 1} ) (Z 2) - represents a. n is preferably 1.

Q represents an aliphatic group, an aromatic group, or a heterocyclic group. However, when Y is -SO-, Q represents a 5-membered aromatic heterocyclic group having at least one heteroatom other than N and a pyridine ring. These rings may be further condensed with other rings. Specific examples of the aromatic 5-membered heterocyclic group having at least one heteroatom other than N include thiazole,
Q represents an oxazole, a thiophene, a furan, a pyrrole, a thiadiazole, an oxadiazole, a thiatriazole, or an oxatriazole.

Specific examples of the compounds represented by formulas 1 to 3 will be shown below.

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

The compounds represented by formulas 1 to 3 are described, for example, in JP-A-54-165, JP-A-6-340611, JP-A-7-27881, JP-A-7-5621, and JP-B-7-119.
No. 953; U.S. Pat. Nos. 5,369,000;
374,514, 5,460,938, 5,464,737, EP 605,981,
Compounds can be synthesized according to the method described in JP-A-631,176 and the like.

The amount of the compounds represented by the general formulas 1 to 3 is not particularly limited, but may be 10 ^-4 mol / mol Ag to 1 mol / mol.
Molar Ag is preferred, especially from 10 ^-3 mol / mol Ag to 0.1 mol.
3 mol / mol Ag is preferred.

The compounds represented by formulas (1) to (3) can be added to a photosensitive layer or a non-photosensitive layer. Preferably, it is a photosensitive layer. The compounds represented by the general formulas 1 to 3 are different depending on the desired purpose, but may be 10 ^-4 mol / mol Ag to 1 mol / mol Ag, preferably 10 ^-3 mol / mol Ag to 0.3 mol / mol.
It is good to add mole Ag. Further, it is preferable that the compounds represented by the general formulas 1 to 3 are added after being dissolved in an organic solvent.

In the photosensitive layer of the present invention, a polyhydric alcohol (for example, US Pat.
Glycerin and diols of the type described in U.S. Pat. No. 960,404), the fatty acids or esters described in U.S. Pat. Nos. 2,588,765 and 3,121,060, and those described in British Patent No. 955,061. Silicone resin or the like can be used.

A hardener may be used for each layer such as the photosensitive layer, the protective layer, and the back layer of the present invention. Examples of the hardener include:
Isocyanate compounds, US Pat. No. 4,791,04
No. 2, etc., epoxy compounds
Vinyl sulfone compounds described in 2-89048 and the like are used.

In the present invention, a surfactant may be used for the purpose of improving coating properties and charging. As an example of the surfactant, any of anionic, cationic, betaine, nonionic, and fluorine-based surfactants can be appropriately used. Specifically, JP-A-62-170950, U.S. Pat.
No. 382,504, etc., fluorine polymer surfactants described in JP-A-60-244945 and JP-A-63-188.
135, a polysiloxane surfactant described in U.S. Pat. No. 3,885,965, a polyalkylene oxide and an anionic surfactant described in JP-A-6-301140. Agents and the like.

The photographic emulsion for heat development in the present invention can be prepared by various methods including a dip coating method, an air knife coating method, a flow coating method, and an extrusion coating method using a hopper of the type described in US Pat. No. 2,681,294. A coating method can be used. If necessary, US Pat. No. 2,761,79
Two or more layers can be coated simultaneously by the methods described in US Pat.

The support used in the present invention may be a plastic film (for example, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate) in order to obtain a predetermined optical density after development and to prevent deformation of the image after development. , Polyethylene naphthalate).

Among them, preferred supports include plastics (hereinafter abbreviated as SPS) containing polyethylene terephthalate (hereinafter abbreviated as PET), polyethylene naphthalate (hereinafter abbreviated as PEN), and a styrene polymer having a syndiotactic structure. Support.
The thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm.

Further, a heat-treated plastic support may 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 applied, at a temperature higher than the glass transition point of the support by 30 ° C. or more,
Preferably at a temperature higher than 35 ° C., more preferably 40 ° C.
It is preferable to heat at a temperature higher than ℃. However, the effect of the present invention cannot be obtained by heating at a temperature exceeding the melting point of the support.

Next, the plastic used will be described.

PET is a polyester in which all of the polyester components are made of polyethylene terephthalate. In addition to polyethylene terephthalate, terephthalic acid, naphthalene-2,6-dicarboxylic acid, isophthalic acid, butylene dicarboxylic acid, and 5-sodium sulfo acid are used as acid components. A polyester containing a modified polyester component of isophthalic acid, adipic acid or the like and a glycol component such as ethylene glycol, propylene glycol, butanediol, cyclohexanedimethanol or the like in an amount of 10 mol% or less of the entire polyester may be used.

As PEN, polyethylene-2,6-
Naphthalate and terephthalic acid and naphthalene-2,6
-Copolyesters consisting of dicarboxylic acid and ethylene glycol, and polyesters whose main constituent is a mixture of two or more of these polyesters are preferred. Further, another copolymerization component may be copolymerized, or another polyester may be mixed.

SPS is polystyrene having steric regularity unlike ordinary polystyrene (atactic polystyrene). The regular stereoregular structure part of SPS is called a racemo chain, and it is preferable that there are more regular parts such as two, three, five or more. In the present invention, the racemo chain is 2 It is preferably 85% or more in the chain, 75% or more in the three chains, 50% or more in the five chains, and 30% or more in the further chains. The polymerization of SPS can be carried out according to the method described in JP-A-3-131843.

As the method for forming a support and the method for producing an undercoat according to the present invention, known methods can be used. Preferably, paragraphs [0030] to [0] of JP-A-9-50994 are used.
070].

[0148]

(Preparation of undercoated photographic support)

<Preparation of PET undercoated photographic support> A corona discharge treatment of 8 W / m ² · min. Was applied to both surfaces of a commercially available biaxially stretched and heat-fixed PET film having a thickness of 175 μm, and one surface was subjected to the following undercoating. The coating liquid a-1 is applied so as to have a dry film thickness of 0.8 μm and dried to form an undercoat layer A-1. It was applied so as to have a thickness of 8 μm and dried to obtain an undercoat 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 << Undercoat coating solution b-1 >> Butyl acrylate (40% by 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) 0.8 g Finish 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.
As the undercoat layer A-2, the undercoat layer B-1 is coated on the undercoat layer B-1 with the following undercoat layer coating solution b-2 so as to have a dry film thickness of 0.8 μm. Coated as B-2.

<< Coating Solution a-2 for Lower Substrate >> 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 upper layer coating solution b-2 >> (C-4) 60 g Latex solution containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 5 g (C-6) 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finish to 1 liter with water

[0151]

Embedded image

[0152]

Embedded image

(Preparation of Photosensitive Silver Halide Emulsion 1) Water 9
6. Ossein gelatin having an average molecular weight of 100,000 in 00 ml
5 g and 10 mg of potassium bromide were dissolved at a temperature of 35 ° C.
After adjusting the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and (98/2) of potassium bromide, potassium iodide and iridium chloride in a molar ratio of 1 × 1 per mole of silver were used.
0 ^-5 mol containing aqueous solution was added over 8 minutes by the controlled double jet method while maintaining the pAg 7.7.
Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7
-Adding 0.3 g of tetrazaindene and adjusting the pH to 5 with NaOH to obtain cubic silver iodobromide grains having an average grain size of 0.04 µm, a grain size variation coefficient of 12%, and a [100] face ratio of 87%. Was. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting treatment, and then 0.1 g of phenoxyethanol.
Was adjusted to pH 5.9 and pAg 7.5 to obtain photosensitive silver halide emulsion 1.

(Preparation of silver behenate) JP-A-9-1276
No. 43 Silver behenate was prepared according to the method of Example 1 in the following manner.

Preparation of Na Behenate Solution 34 g of behenic acid was added to 340 ml of isopropanol for 65 days.
Dissolved at ° C. 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 aqueous sodium behenate solution was concentrated under reduced pressure to adjust the concentration of sodium behenate to 8.9% by weight.

Preparation of Silver Behenate A 2.94M silver nitrate solution was added to a solution of 30 g of ossein gelatin dissolved in 750 ml of distilled water, and the silver potential was increased to 4%.
00 mV. To this, 374 ml of the above sodium behenate solution was added at a speed of 44.6 ml / min at a temperature of 78 ° C. by using a controlled double jet method, and simultaneously a 2.94 M silver nitrate aqueous solution was supplied with a silver potential of 400 mV.
It was added so that it became. The amounts of sodium behenate and silver nitrate used at the time of addition were 0.092 mol and 0.101 mol, respectively.
Mole. After completion of the addition, the mixture was further stirred for 30 minutes, and the water-soluble salts were removed by ultrafiltration.

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

(Preparation of Photosensitive Material 1) The following layers were sequentially formed on the support to prepare Photosensitive Material 1. The drying was performed at 75 ° C. for 5 minutes.

Back side coating: A solution having the following composition was applied to a dry film thickness of 5 μm.

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

[0161]

Embedded image

Coating on photosensitive layer side Photosensitive layer: The following additives were added in the stated order to prepare a coating solution for the photosensitive layer, and the coating amount of silver was adjusted to 2.4 g / m ² , and a binder as a binder was prepared. Polyvinyl butyral was applied to a dry film thickness of 20 μm.

[0163] Photosensitive amount sensitizing dye-1 (0.1% DMF solution) becomes 2.4g as Emulsion A silver amount 2 ml CaBr ₂ 2 dihydrate (1% methanol solution) 9 ml antifoggant -1 (1% Methanol solution) 12 ml Antifoggant-2 (1.5% methanol solution) 8 ml Antifoggant-3 (2.4% DMF solution) 15 ml Phthalazine (4.5% DMF solution) 8 ml Developer-1 (10% acetone Solution) 30ml

[0164]

Embedded image

[0165]

Embedded image

Surface protective layer: A solution having the following composition was applied on the photosensitive layer so that the film thickness after drying was 2.5 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 matting agent (average particle size 4 μm 2 g of monodisperse silica) The particle size distribution of the silver halide particles contained in the obtained photosensitive material 1 was confirmed by electron micrographs to have peak values of 0.04 μm and 0.008 μm. In addition, it was confirmed that the number of particles having a particle diameter of 0.001 μm or more and less than 0.01 μm was 88% of all the particles.

Further, AgX particles were isolated from the light-sensitive material,
AgX was separated at a particle size of 0.010 μm as a boundary, and the Ir content of each was measured.
It was confirmed that the content was below the detection limit for particles having a particle size of less than 0 μm, and 0.9 × 10 ⁻⁵ mol / mol Ag for particles having a particle size of 0.010 μm or more.

(Preparation of Photosensitive Material 2) Photosensitive material 2 was prepared in the same manner as in Preparation of photosensitive material 1, except that the coating solution for the photosensitive layer was changed as follows.

Photosensitive layer: A coating solution for a photosensitive layer was prepared by adding the following additives in the order described, and the coated silver amount was 2.4 g / g.
m ² and polyvinyl butyral as a binder was applied so as to have a dry film thickness of 20 μm.

Photosensitive Emulsion A Amount of 2.4 g as silver amount K ₂ IrCl ₆ (0.01% methanol solution (containing NaCl)) 1.2 ml Sensitizing dye-1 (0.1% DMF solution) 2 ml CaBr ₂ Dihydrate (1% methanol solution) 9 ml Antifoggant-1 (1% methanol solution) 12 ml Antifoggant-2 (1.5% methanol solution) 8 ml Antifoggant-3 (2.4% DMF solution) 15 ml Phthalazine (4.5% DMF solution) 8 ml Developer-1 (10% acetone solution) 30 ml The particle size distribution of the silver halide particles contained in the obtained photosensitive material 2 has peak values of 0.04 μm and 0.008 μm. Was confirmed by an electron micrograph. In addition, it was confirmed that the number of particles having a particle diameter of 0.001 μm or more and less than 0.01 μm was 88% of all the particles.

Further, AgX particles were isolated from the light-sensitive material,
Ir content was measured in each particle size range fractionated by particle size.
It was confirmed that it was 0.9 × 10 ⁻⁵ mol / mol Ag. The number of particles that could not be measured without being within the fractionation range was 5% of the total particles, indicating that at least 95% of the particles contained Ir.

(Preparation of Photosensitive Material 3) Photosensitive material 3 was prepared in the same manner as in preparation of photosensitive material 1, except that the method of preparing photosensitive emulsion A was changed to the method of preparing photosensitive emulsion B described below.

(Preparation of Photosensitive Emulsion B) 0.01 mol of the above-mentioned photosensitive silver halide emulsion 1 was added to the above-mentioned silver behenate dispersion, and K ₂ IrCl ₆ (0.01% methanol solution (NaCl 1) was added in an amount of 1 × 10 ⁻⁶ mol. 100 g of an n-butyl acetate solution of polyvinyl acetate (1.2 wt%) was gradually added with stirring to form a floc of the dispersion, and then water was removed. 60 g of a 1: 2 mixed solution of 2.5 wt% of butyl acetate and isopropyl alcohol of polyvinyl butyral (average molecular weight 3000) as a binder was added thereto with stirring, and the thus obtained gel-like behenic acid and silver halide were added. Polyvinyl butyral (average molecular weight: 4000) and isopropyl alcohol were added and dispersed as a binder to the mixture.

The particle size distribution of the silver halide grains contained in the obtained light-sensitive material 3 has a peak value of 0.04 μm and 0.00
It was confirmed by an electron micrograph that the particle size was 8 μm.
In addition, it was confirmed that the number of particles having a particle diameter of 0.001 μm or more and less than 0.01 μm was 88% of all the particles.

Further, AgX particles were isolated from the light-sensitive material,
Ir content was measured in each particle size range fractionated by particle size.
It was confirmed that it was 0.9 × 10 ⁻⁵ mol / mol Ag. The number of particles that could not be measured without being within the fractionation range was 5% of the total particles, indicating that at least 95% of the particles contained Ir.

[0177]

[Table 1]

<Evaluation of Photographic Performance> The photosensitive material was exposed to light using a laser sensitometer equipped with an 810 nm diode for an exposure time of 10 ⁻⁷ seconds, and then processed (developed) at 120 ° C. for 15 seconds. The image was evaluated by a densitometer. The result of the measurement was Dmin, sensitivity (from Dmin, 1.
0, the reciprocal of the ratio of the exposure amount giving a high density), and γ (the slope between densities of 1.0 and 2.0 in the sensitometric curve). Note that the sensitivity was measured for sample No. Sensitivity of 1 to 1
The relative sensitivity was shown as 00.

<Evaluation of storage stability with time> After storing the photosensitive material for 7 days under the following conditions, processing (development) at 120 ° C. for 15 seconds.
Then, the obtained image was evaluated by a densitometer and determined by the following equation.

(Dmin (B) -Dmin (A)) / D
min (A) × 100 Condition A 25 ° C. 55% Condition B 40 ° C. 80% <Evaluation of development stability> After exposing the photosensitive material for 10 ⁻⁶ seconds using a laser sensitometer equipped with an 810 nm diode, the photosensitive material was exposed. Was processed (developed) at 115 ° C. and 125 ° C. for 15 seconds, and the obtained image was measured with a densitometer. The evaluation was made based on the fluctuation width of the sensitivity (the reciprocal of the ratio of the exposure amount giving a density 2.0 higher than Dmin), It is represented by a relative value when the sensitivity variation width of 1 is 100.

Table 2 shows the results.

[0182]

[Table 2]

It can be seen that the light-sensitive material of the present invention has low fog and high sensitivity, and is excellent in storage stability over time and development stability.

Example 2 In the preparation of the light-sensitive material 1 of Example 1, the addition amount of the photosensitive silver halide emulsion and the addition amount of calcium bromide were changed.
Photosensitive material 4 having a particle number ratio as shown in Table 3
-1.5-1.6-1 was prepared. Correspondingly, in the production of the photosensitive material 2, the amount of the photosensitive silver halide emulsion and the amount of the calcium bromide were changed so that the number ratio of the particles as shown in Table 3 was obtained. 4-2.
5-2.-2 was produced.

[0185]

[Table 3]

The storage stability over time and the development stability were evaluated for each. The results are shown as relative values when 4-1 is set to 100.

[0187]

[Table 4]

It can be seen that the light-sensitive material of the present invention has excellent storage stability over time and development stability.

[0189]

According to the present invention, the stability (storage stability) of photographic performance during storage of a photothermographic material over time is improved.
Further, the present invention provides a photothermographic material (especially a black-and-white photothermographic material) having improved photographic performance stability against fluctuations in development conditions and excellent production stability, a method for producing the same, and an image forming method using the same. I was able to.

Claims (6)

[Claims] 1. A photothermographic material comprising a support containing photosensitive silver halide particles, organic silver particles, a reducing agent for silver ions, and a binder, wherein all the photosensitive silver halide particles contained in the photosensitive material are included. Has a peak value of at least two peak values, and 80% or more (number) of the particles contain transition metal ions. 2. Among all photosensitive silver halide grains, 20% or more (number) of grains having a grain size of less than 0.01 μm are present,
2. The photothermographic material according to claim 1, wherein 80% or more (number) of the particles contain transition metal ions. 3. The photothermographic material according to claim 1, wherein the photosensitive silver halide grains include silver halide grains prepared after forming organic silver grains. 4. A method for producing a photothermographic material comprising a support containing photosensitive silver halide particles, organic silver particles, a reducing agent for silver ions, and a binder, wherein all photosensitive halogens contained in the photosensitive material are contained. 80% or more of silver halide particles (number)
A method for producing a photothermographic material, characterized by comprising a transition metal ion. 5. The method for producing a photothermographic material according to claim 4, wherein the silver halide grains prepared after the formation of the organic silver grains contain transition metal ions. 6. The photothermographic material according to claim 1, wherein
An image forming method comprising exposing to light with an exposure time of less than 0 to ⁵ seconds and subjecting it to heat development to form an image.