JPH11194446A - Heat-developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance storage stabilities of raw film and processed images by incorporating at least one kind of specified compound. SOLUTION: This heat-developable photosensitive material contains at least one kind of compounds represented by formulae I and II, and formula III: CH2 = CHSO2 -R5 -SO2 CH=CH2 , and in formulae I-III, R is an optionally substituted alkylene group with a divalent bonding group; X in formula I is a divalent bonding group; X is an O atom or a -OCO- group; each of R1 -R4 is a halogen atom or an optionally substituted hydrocarbon group, and at least one of R1 -R4 is a group having a double bond, a halogen atom, and acid anhydride residue, an epoxy or alkoxycarbonyl or amino group; each of (n) and (n') and (n") is 0 or 1 and at least n+n'+n" is 1; and R5 is an alkylene group optionally substituted with a divalent bonding group. It is preferred that this photosensitive material is provided with a photosensitive layer containing an organic silver salt and photosensitive silver halide grains and a non-photosensitive layer containing a reducing agent on a support.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material capable of significantly improving the aging stability of a so-called raw film before use and the aging stability of an image after processing.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical treatment, waste liquid caused by wet processing of an image forming material has been a problem in workability (heavy, dirty, inventory control). In addition, from the viewpoint of space saving, it is strongly desired to reduce the amount of processing waste liquid.

In order to satisfy such demands, conventionally,
Research has been made on dry silver salt photosensitive materials. A typical example is a thermally developed silver salt which uses an organic silver salt disclosed in U.S. Pat. No. 3,457,075 to form an image by a thermal reaction. Other types include a type that forms an image by reaction with heat and diffusion transfer, and a type that forms an image by melting, sublimation, ablation, or the like by the light-to-heat conversion energy of laser light. Each technique has not yet achieved the performance and handleability equivalent to current silver halide photographic materials, but some of them have been put to practical use with some technical problems left.

[0004]

Among the heat-developable silver salt types using an organic silver salt, an image forming element such as an organic silver salt, a photosensitive silver halide particle and a reducing agent is contained in a photosensitive material. Since it remains in the photosensitive material even after processing, there are many problems to be solved.According to the research of the present inventors, the stability over time of a so-called raw film before use and the stability over time of an image after processing are in principle. It turned out that there was a problem that it easily deteriorated.

Accordingly, the present invention has been made in view of the above circumstances, and an object of the present invention is to significantly improve the temporal stability of a so-called raw film before use and the temporal stability of an image after processing. An object of the present invention is to provide a photothermographic material.

[0006]

A photothermographic material according to the present invention for solving the above-mentioned problems comprises a photothermographic material containing at least an organic silver salt, photosensitive silver halide particles, a reducing agent and a binder on a support. In the material, the following general formula (1)
It is characterized by containing at least one selected from the compounds represented by (3).

[0007]

Embedded image [In the formula, R represents a divalent linking group which may have a substituent. X represents a divalent linking group. ]

[0008]

Embedded image In the formula, X represents an oxygen atom or -OCO-. R ₁ , R
₂ , R ₃ and R ₄ each represent a halogen atom or a hydrocarbon group which may be substituted, and R ₁ , R ₂ , R ₃ and R ₄
At least contains a double bond, a halogen atom, an epoxy group, an acid anhydride residue, an alkoxycarbonyl group or an amino group. n, n ′ and n ″ each represent 0 or 1,
n + n ′ + n ″ is at least 1.

General formula (3) CH ₂ ＣＨCHSO ₂ —R ₅ —S
O ₂ CH ＝ CH _{2 In the} formula, R ₅ represents an alkylene group which may be substituted with a divalent linking group.

The photothermographic material of the present invention is provided on a support.
It is preferable that the photosensitive layer has at least a photosensitive layer and a non-photosensitive layer, the photosensitive layer contains an organic silver salt and photosensitive silver halide grains, and the non-photosensitive layer contains a reducing agent.

[0011]

Embodiments of the present invention will be described below in detail.

First, the compound represented by the general formula (1) will be described.

In the general formula (1), R represents a divalent linking group which may have a substituent, and the substituent of the alkylene group representing R may be a halogen atom, a hydroxyl group, a hydroxyalkyl group or It is preferably a group selected from amino groups. It is preferable that the linking group for R has an amide linking moiety, an ether linking moiety, or a thioether linking moiety.

[0014] X represents a divalent linking group, the divalent linking group represented the _{X, -SO 2 -, - SO} 2 NH -, - S
-, -O- or -NR'- are preferred. Where R 'is 1
It is a valence linking group and preferably an electron-withdrawing group.

Specific examples of the compound represented by the general formula (1) are shown below, but it should not be construed that the invention is limited thereto.

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

The addition layer of the compound represented by the general formula (1)
Either a photosensitive layer or a non-photosensitive layer (such as an undercoat layer or a protective layer) may be used, but it is preferably added to the layer having the photosensitive layer. More preferably, it is added to a layer containing an organic silver salt and silver halide.

The amount of the compound represented by the general formula (1) is
Although not particularly limited, 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol / m
The range of ² is preferred, and more preferably 1 × 10 ^-4 to 1 ×
It is in the range of 10 ⁻³ mol / m ² .

Next, the compound represented by formula (2) will be described.

In the general formula (2), X represents an oxygen atom or -OCO
- _{represents, R 1, R 2, R} 3 and R ₄ each represent a halogen atom or an optionally substituted hydrocarbon group, R _1,
At least one of R ₂ , R ₃ and R ₄ contains a double bond, a halogen atom, an epoxy group, an acid anhydride residue, an alkoxycarbonyl group or an amino group. n, n ′ and n ″ each represent 0 or 1, and n + n ′ + n ″ is at least 1.

The halogen atom represented by R _{1 to} R ₄ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The hydrocarbon group which may be substituted includes a saturated or unsaturated chain or ring, and includes, for example, an alkyl group (eg, methyl, ethyl, propyl, etc.) and an alkenyl group (eg, vinyl, allyl, etc.). And aryl groups (for example, phenyl, tolyl, etc.).

The double bond of at least one of R _{1 to} R ₄ is a C ＝ C bond, for example, alkenyl, acryloyl, methacryloyl, vinylcarbonylamino,
Introduced as an isopropenylcarbonylamino group and the like,
Examples of the acid anhydride residue include a group such as a methylcarbonyloxycarbonylethyl group, and a halogen atom may be introduced in a form such as a haloacylamino group.

Specific examples of the compound represented by the general formula (2) are shown below, but it should not be construed that the invention is limited thereto.

[0027]

Embedded image

[0028]

Embedded image

The compound represented by the general formula (2) is disclosed in
The compound can be synthesized by the method described in JP-A-8-3565, or can be obtained as a commercial product from Toray Silicon Co., Ltd. or Chisso Corporation.

The addition layer of the compound represented by the general formula (2)
Either a photosensitive layer or a non-photosensitive layer (such as an undercoat layer or a protective layer) may be used, but it is preferably added to the layer having the photosensitive layer. More preferably, it is added to a layer containing an organic silver salt and silver halide.

The amount of the compound represented by the general formula (2) is
Although not particularly limited, 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol / m
The range of ² is preferred, and more preferably 1 × 10 ^-4 to 1 ×
It is in the range of 10 ⁻³ mol / m ² .

Next, the compound represented by formula (3) will be described.

R ₅ represents an alkylene group which may be substituted with a divalent linking group, and the linking group representing R ₅ has an amide linking moiety, an ether linking moiety or a thioether linking moiety. Is preferred.

Specific examples of the compound represented by the general formula (3) are shown below, but it should not be construed that the invention is limited thereto. Examples are the following groups 3-1 -CH ₂ - - in the general formula _{(3) -R 5 3-2 - (} CH 2) 2 - 3-3 - (CH 2) 4 - 3-4 -CH 2 _{O-CH 2 - 3-5 - (} CH 2) 2 O-CH 2 - 3-6 -CH 2 CH (OH) CH 2 - example showed total structural formula _{3-7 (CH 2 = CHSO 2 CONH} ) _2- CH ₂ CH ₂ -3-8 (CH ₂ ＣＨCHSO ₂ CONH) ₂ —CH ₂ CH ₂ CH ₂ — Among the above exemplified compounds, preferred are 3-4, 3-
6, 3-7 and 3-8.

The addition layer of the compound represented by the general formula (3)
Either a photosensitive layer or a non-photosensitive layer (such as an undercoat layer or a protective layer) may be used, but it is preferably added to the layer having the photosensitive layer. More preferably, it is added to a layer containing an organic silver salt and silver halide.

The amount of the compound represented by the general formula (3) is
Although not particularly limited, 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol / m
The range of ² is preferred, and more preferably 1 × 10 ^-4 to 1 ×
It is in the range of 10 ⁻³ mol / m ² .

The compounds represented by the general formulas (1) to (3) can be used alone or in combination of two or more. When used in combination, they may be added to the same layer or may be added separately to different layers.

The silver halide grains in the present invention function as an optical sensor. In the present invention, in order to suppress white turbidity after image formation, and to obtain good image quality, the average particle size is preferably small, specifically, the average particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.1 μm, particularly 0.02 μm to 0.0
8 μm is preferred.

In the case where the silver halide grains are cubic or octahedral so-called normal crystals, the average grain size means the length of the edge of the silver halide grains. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The silver halide grains are preferably monodisperse grains. The term “monodisperse particles” as used herein means particles having a degree of monodispersity of 40% or less, more preferably 30% or less, particularly preferably 20% or less.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 The shape of silver halide grains is not particularly limited, but the proportion occupied by the Miller index [100] plane is high. It is preferable that this ratio is 50% or more, further 70% or more,
In particular, it is preferably at least 80%. Miller index [1
The ratio of the [00] plane is determined by utilizing the dependence of the adsorption of the sensitizing dye on the [111] plane and the [100] plane. Tan
i. Imaging Sci. , 29, 165 (1
985).

The above-mentioned monodisperse particles have an average particle size of 0.1 μm.
The following is preferable, and more preferably 0.01 μm to 0.1
μm, particularly preferably 0.02 μm to 0.08 μm.

Another preferred form of silver halide grains is tabular grains. Here, the tabular grains are:
The aspect ratio (= r / h) is 3 or more when the square root of the projected area of the particle is r μm and the thickness in the vertical direction is h μm. Among them, those having an aspect ratio of 3 or more and 50 or less are preferable.

The average particle diameter of the tabular grains is preferably 0.1 μm or less, and more preferably 0.01 μm to 0.08 μm.
μm is more preferred. These are disclosed in U.S. Pat.
No. 337, 5,314,798, 5,320,9
No. 58 and the like, and the desired tabular grains can be easily obtained.

The composition of silver halide is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion used in the present invention is P.I. Chimie et by Glafkids
Physique Photographique (P
aul Montel, 1967); F. D
Photographic Emuls by uffin
ion Chemistry (The Focal P
Res., 1966); L. Zelikman
Making and Coating by et al
Photographic Emulsion (Th
e Focal Press, 1964) and the like.

That is, any of an acidic method, a neutral method, an ammonia method and the like may be used. In order to form a solution by reacting a soluble silver salt and a soluble halide, a one-side mixing method, a double-mixing method, a combination thereof and the like are used. Either may be used.

The silver halide may be added to the image forming layer by any method, and the silver halide is arranged so as to be close to the reducible silver source.

The silver halide may be prepared by converting a part or all of the silver in the organic acid silver to the silver halide by the reaction between the organic acid silver and the halide ion.
Silver halide may be prepared in advance and added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred.

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

The silver halide used in the present invention is selected from VIB, VIIB, VII belonging to transition metals of the Periodic Table of the Elements.
It preferably contains an ion or a complex ion of a metal belonging to Group I or IB. The above metals include Cr, W
(The above-mentioned VIB group): Re (VIIB group): Fe, Co,
Ni, Ru, Rh, Pd, Os, Ir, Pt (VI
II): Cu and Au (above IB) are preferable, and when used for a photosensitive material for plate making, Rh, Re, and
It is preferable to be selected from Ru, Ir, and Os.

These metals can be introduced into the silver halide in the form of a complex. In the present invention, the transition metal complex is preferably a six-coordinate complex represented by the following general formula.

In the formula [ML ₆ ] ^m , M is a group of elements of the periodic table VIB, VIIB, VIII
A transition metal selected from Group IV and IB elements, L represents a bridging ligand, and m represents 0, -1, -2 or -3.

Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and alcohol. Each ligand of
Nitrosyl, thionitrosyl and the like can be mentioned, and preferred are aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

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

Specific examples of the transition metal coordination complex are shown below.

[0056] ^{_{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: [Ru (NO)} Cl 5] 2- 8: [RuBr 4 (H 2 O)] 2- 9: [Ru (NO) (H 2 O) Cl 4] - 10: [RhCl 5 (H 2 ^{O)] 2- 11: [Re} (NO) Cl 5] 2- 12: [Re (NO) CN 5] 2- 13: [Re (NO) ClCN 4] 2- 14: [Rh (NO) 2 Cl ^{_{4] - 15: [Rh (}} NO) (H 2 O) Cl 4] - 16: [Ru (NO) CN 5] 2- 17: [Fe (CN) 6] 3- 18: [Rh (NS) Cl ^{_{5] 2- 19: [Os (}} NO) Cl 5] 2- 20: [Cr (NO) Cl 5] 2- 21: [Re (NO) Cl 5] - 22: [Os (NS) Cl 4 (TeCN )] ^2- 23: [R ^{_{(NS) Cl 5] 2- 24}} : [Re (NS) Cl 4 (SeCN)] 2- 25: [Os (NS) Cl (SCN) 4] 2- 26: [Ir (NO) Cl 5] 2-

One of these metal ions or complex ions may be used, or two or more of the same or different metals may be used in combination.

The content of these metal ions or complex ions is generally in the range of 1 to 1 mol per mol of silver halide.
The amount is suitably from ^10-9 to ^1-10-2 mol, preferably 1 mol.
X 10 ^-8 to 1 X 10 ^-4 mol.

It is preferable that the compound which provides these metal ions or complex ions is added during silver halide grain formation and incorporated into silver halide grains. Preparation of silver halide grains, that is, nucleation and growth , Physical aging,
Although it may be added at any stage before and after chemical sensitization, it is particularly preferable to add at the stage of nucleation, growth, and physical ripening,
Further, it is preferably added at the stage of nucleation and growth, most preferably at the stage of nucleation.

In the addition, the compound may be added in several divided portions, may be added uniformly in the silver halide grains, or may be added uniformly to the silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in Japanese Patent Application Laid-Open No. H10-284, etc., the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles.

These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution of a powder or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during particle formation and placed, or a silver salt solution and a halide solution are used. When mixed simultaneously, a third aqueous solution is added 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 halogen is added. There is a method in which another silver halide grain doped with a metal ion or a complex ion in advance at the time of preparing silver halide is added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

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 3 carbon atoms).
An aliphatic carboxylic acid having 0, preferably 15 to 25 carbon atoms, and a nitrogen-containing heterocyclic ring are preferred.

Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful.

Examples of suitable silver salts include Research D
No. 17029 and 29996, and include: salts of organic acids, such as salts of gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc .; silver carboxyalkylthio Urea salts (eg, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.); silver of a polymer reaction product of an aldehyde and a hydroxy-substituted aromatic carboxylic acid Complexes (e.g., aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (e.g., salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts of thioenes or Complex (for example, 3- (2-carboxyethyl) -4
-Hydroxymethyl-4- (thiazoline-2-thioene and 3-carboxymethyl-4-thiazoline-2-
Thioene), imidazole, pyrazole, urazole,
1,2,4-thiazole and 1H-tetrazole, 3-
Complexes or salts of silver and a nitrogen acid selected from amino-5-benzylthio-1,2,4-triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides.

In the present invention, a particularly preferred silver source is silver behenate.

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 includes a normal mixing method, a reverse mixing method, a simultaneous mixing method, and a method described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used.

In the present invention, the organic silver salt preferably has an average particle size of 1 μm or less and is monodispersed. The average particle size of the organic silver salt means that the particles of the organic silver salt are, for example, spherical,
In the case of rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of the organic silver salt grains. The average particle size is preferably 0.01 μm to 0.8 μm, particularly 0.05 μm.
m to 0.5 μm is preferred. The term “monodisperse” has the same meaning as in the case of silver halide grains, and the preferred monodispersity is 1%.
３０30%.

In the present invention, in order to obtain a predetermined optical density, the total amount of silver halide and organic silver salt is preferably from 0.3 g to 1.5 g per m ² in terms of silver. . The amount of silver halide relative to the total amount of silver is 50% or less by weight, preferably 25% or less, more preferably 0.1% to 15%.

The photothermographic material of the present invention contains a reducing agent. Examples of suitable reducing agents are described in U.S. Pat.
No. 0,448, No. 3,773,512, No. 3,5
No. 93,863 and Research Disclo
Sure Nos. 17029 and 29996, and include:

Aminohydroxycycloalkenonone compounds (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents An N-hydroxyurea derivative (for example, Np-methylphenyl-N
Hydrazones of aldehydes or ketones (e.g. anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g.
Hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamidoanilines (eg, 4- (N- Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (eg, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (eg, 1,2,3,4-tetrahydro) Aminooxins; Azines (eg, 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 sulfonamidophenols; α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamidophenol reducing agents; 2-phenylindane-1 ,
3-dione and the like; chroman; 1,4-dihydropyridines (eg, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (eg, bis (2-hydroxy-3- t-butyl-5
-Methylphenyl) methane, bis (6-hydroxy-m
-Tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones.

Particularly preferred reducing agents are hindered phenols.

The hindered phenols include compounds represented by the following general formula (A).

[0073]

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,}
R ′ and R ″ represent an alkyl group having 1 to 5 carbon atoms (eg, 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.

[0076]

Embedded image

[0077]

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 0 ^-2 to 10 mol, particularly preferably 1 × 10 ^{-2 to} 1.5 mol.

Binders suitable for the photothermographic material of the present invention are transparent or translucent and generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic,
Poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (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 (for example, poly (vinyl formal) and poly (vinyl butyral), poly (ester)) , Poly (urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxide),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). These may be hydrophilic or non-hydrophilic.

In the present invention, the amount of the binder in the photosensitive layer is 1.5 to 10 for the purpose of preventing dimensional fluctuation after thermal development.
g / m ² , more preferably 1.
It is 7 to 8 g / m ² . If it is less than 1.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

In the present invention, a matting agent is preferably contained on the photosensitive layer side, 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 10% with respect to 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 substances, US Pat. No. 2,322,
037 etc., Belgian Patent No. 625, 45
No. 1 and British Patent Nos. 981, 198, etc., polyvinyl alcohol described in JP-B-44-3643, etc., polystyrene or polymethacrylate described in Swiss Patent No. 330,158, U.S. Pat. Organic matting agents such as polyacrylonitrile described in 3,079,257 and the like and polycarbonate described in U.S. Pat. No. 3,022,169 can be used.

The shape of the matting agent may be either regular or irregular, but is preferably regular and spherical.

The size of the matting agent is represented by a diameter when the volume of the matting agent is converted into a spherical shape. In the present invention, the particle diameter of the matting agent indicates the diameter converted into a sphere. The matting agent used in the present invention preferably has an average particle size of 0.5 μm to 10 μm, more preferably 1.0 μm to 8.0 μm. The variation coefficient of the particle size distribution is preferably 50% or less, more preferably 40% or less, and particularly preferably 30% or less.

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

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

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

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,
The photothermographic material preferably 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 220 ° C.) after exposure. Heating produces silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is 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, which contrasts with the unexposed areas,
An 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.

In order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter layer may be formed on the same side as or opposite to the photosensitive layer, or a dye or pigment may be contained in the photosensitive layer. May be. As the dye, the compounds described in Japanese Patent Application No. 7-11184 are preferred.

The photosensitive 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.

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

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

It is preferable to add a color tone agent to the photothermographic material of the present invention. 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.

The photothermographic material of the present invention may contain an antifoggant. What is known as the most effective antifoggant is mercury ion. Regarding the use of mercury compounds as antifoggants in photosensitive materials,
For example, it is disclosed in U.S. Pat. No. 3,589,903. However, mercury compounds are environmentally unfriendly. Non-mercury antifoggants include, for example, U.S. Pat.
No. 075 and 4,452,885 and JP-A-59
Preferred are antifoggants as disclosed in US Pat.

Particularly preferred non-mercury antifoggants are described in US Pat. Nos. 3,874,946 and 4,756,993.
No. 9, compound -C (X ₁ ) (X
₂ ) 1 represented by (X ₃ ), wherein X ₁ and X ₂ are halogen atoms, and X ₃ is hydrogen or a halogen atom.
It is a heterocyclic compound having the above substituent. As examples of suitable antifoggants, compounds described in paragraphs [0062] to [0063] of JP-A-9-90550 are preferably used.

Further, more suitable antifoggants are disclosed in US Pat. No. 5,028,523 and British Patent Application No. 92221.
No. 383.4, No. 9300147.7, No. 931
No. 1790.1.

The photothermographic materials of the present invention include, for example, JP-A-63-159814, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, and JP-A-6-259561.
3-304242, 63-15245, U.S. Pat. Nos. 4,639,414 and 4,740,455,
Nos. 4,741,966 and 4,751,175
No. 4,835,096. Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure Item
Section 17643 IV-A (p. 23, December 1978),
Item 1831X (August 1978, p. 437)
Or cited in the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-34078, JP-A-9-54409, and JP-A-9-80
No. 679 is preferably used.

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

Among them, a preferred support is a support made of polyethylene terephthalate (hereinafter abbreviated as PET) and a plastic (hereinafter abbreviated as SPS) containing a styrene-based polymer having a syndiotactic structure.

The thickness of the support is preferably about 50 to 300 μm, more 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.
Heating 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 composed of polyethylene terephthalate in which all polyester components are used. In addition to polyethylene terephthalate, terephthalic acid, naphthalene-2,6-dicarboxylic acid, isophthalic acid, butylene dicarboxylic acid and 5-sodium are used as acid components. Polyesters containing modified polyester components such as sulfoisophthalic acid, adipic acid, etc., and glycol components such as ethylene glycol, propylene glycol, butanediol, cyclohexane dimethanol, etc. in an amount of 10 mol% or less of the total polyester may be used.

SPS is a 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 of forming a film and the method of producing an undercoat according to the present invention, known methods can be used. Preferably, paragraphs [0030] to [0] of JP-A No. 9-50094 are used.
070].

[0110]

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

Example 1 (Preparation of silver halide particles) 7.5 g of gelatin and 10 mg of potassium bromide were dissolved in 900 ml of pure water, and the temperature was changed to 35.
After adjusting the pH and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (96/4) maintained at pAg 7.7 by a controlled double jet method. For 10 minutes. Thereafter, 4-hydroxy-6-methyl-1,3,3
0.3 g of a, 7-tetrazaindene was added, and NaOH was added.
The pH was adjusted to 5 with an average particle size of 0.06 μm,
8% variation coefficient of projected diameter area, 86% {100} surface ratio
Of cubic silver iodobromide grains were obtained.

This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment, and then adjusted to pH 5.9 and pAg 7.5 by adding 0.1 g of phenoxyethanol.

Thereafter, sensitizing dyes SD-1 and SD-2 were added in an amount of 5 × 10 ^-5 mol per mol of silver halide. Then 6
The temperature was raised to 0 ° C, 2 mg of sodium thiosulfate was added, and 100
After aging for 3 minutes, cool to 38 ° C to complete chemical sensitization,
Silver halide grains were obtained.

[0114]

Embedded image (Preparation of organic fatty acid silver emulsion) Behenic acid 1 in 300 ml of water
0.6 g was added and dissolved by heating at 90 ° C., and 31.1 ml of 1N sodium hydroxide was added with sufficient stirring, and the mixture was left as it was for 1 hour. Then cool to 30 ° C,
After adding 7.0 ml of N phosphoric acid and stirring sufficiently,
0.01 g of bromosuccinimide was added. afterwards,
The silver halide grains prepared beforehand were added with stirring while heating at 40 ° C. so that the silver amount was 10 mol% with respect to behenic acid. Further, 25 ml of a 1N silver nitrate aqueous solution was continuously added over 2 minutes, and the mixture was left for 1 hour with stirring.

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

(Composition of photosensitive layer) A coating solution for a photosensitive layer was prepared as follows. As the solvent, methyl ethyl ketone, acetone, and methanol were appropriately used. Organic fatty acid silver emulsion 1.75 g (in silver) / m ² potassium human chlorophyllite pheromite 1.5 × 10 ^-4 4 mol / m ² Calcium bromide 1.8 × 10 ^-4 mol / m ² 2- (4-Chlorobenzoyl) benzoic acid 1.5 × 10 ^-3 mol / m ² Sensitizing dye 4.2 × 10 ^-6 mol / m ² 2-mercaphate imidazole 3.2 × 10 ^-3 mol / m ² 2-Trifluoromethylsulfonylquinoline 6.0 × 10 ^-4 mol / m ² Compound of the general formula (1) shown in Table 1.

[0117]

Embedded image

(Surface Protective Layer Composition) A surface protective layer coating solution was prepared as follows. Solvents include methyl ethyl ketone,
Acetone and methanol were used as appropriate. Cellulose acetate 4g / m ² 1,1-bis (2-hydrate proxy-3,5-di-methylphenyl) -3,5,5-trimethyl hexane (A-4) 4.8 × 10 -3 mol / m 2 phthalazine 3.2 × 10 ^{- 3} mol / m ² 4-methylphthalic acid 1.6 × 10 ^-3 mol / m ² Tetrachlorophthalic acid 7.9 × 10 ^-4 mol / m ² Tetrachlorophthalic anhydride 9.1 × 10 ^-4 mol / m ² Silicon dioxide (particles diameter 2μm) 0.22g / m ²

(Composition of Backing Layer) A coating solution for the backing layer was prepared as follows. Cellulose acetate 4 g / m ² Anti-halation dye Compound A 0.06 g / m ² Compound B 0.018 g / m ² Polymethyl methacrylate (particle size 10 μm) 0.02 g / m ²

[0120]

Embedded image

Thickness 17 biaxially stretched with the above composition
It was applied to a 5 μm polyethylene terephthalate film and dried to obtain a coated sample.

(Evaluation) The unexposed sample was stored under the following conditions, the density of the sample was measured after storage, and the change in the density was used to evaluate the aging stability of the raw film and the processed film under the following aging stability evaluation conditions. did. The raw film was evaluated after processing by a thermal drum processor of the type used to thermally develop the photothermographic element after storage.

The processed film was evaluated by processing it with a heat drum processor of the type used for thermally developing a photothermographic element, and then storing and storing.

However, in each evaluation, the drum temperature was set to 120 ° C.
The processing time for the sample to pass through the processor was 15 seconds.

Conditions for evaluating stability over time 1. 40 ° C., 50% humidity, 12 hours 2. 40 ° C., 50% humidity, 24 hours 3. 40 ° C., 50% humidity, 48 hours 4.40 ° C., 50% humidity, 72 hours

[0126]

[Table 1]

Example 2 An experiment and evaluation were conducted in the same manner as in Example 1 except that the compound of the general formula (2) was added in the photosensitive layer in place of the compound of the general formula (1) in the amount shown in Table 2. went.

Table 2 shows the results.

[0129]

[Table 2]

Example 3 An experiment and evaluation were carried out in the same manner as in Example 1 except that the compound of the general formula (3) was added in the photosensitive layer in place of the compound of the general formula (1) in the amount shown in Table 3. .

Table 3 shows the results.

[0132]

[Table 3]

[0133]

According to the present invention, it is possible to provide a photothermographic material capable of significantly improving the aging stability of a so-called raw film before use and the aging stability of an image after processing.

Claims (6)

[Claims] 1. A photothermographic material containing at least an organic silver salt, photosensitive silver halide particles, a reducing agent and a binder on a support, selected from compounds represented by the following general formulas (1) to (3): A photothermographic material comprising at least one of the following. Embedded image [In the formula, R represents a divalent linking group which may have a substituent. X represents a divalent linking group. ] [In the formula, X represents an oxygen atom or -OCO-. R ₁ , R
₂ , R ₃ and R ₄ each represent a halogen atom or a hydrocarbon group which may be substituted, and R ₁ , R ₂ , R ₃ and R ₄
At least one contains a double bond, a halogen atom, an epoxy group, an acid anhydride group, an alkoxycarbonyl group or an amino group. n, n 'and n "each represent 0 or 1;
+ N'+ n "is at least 1.] Formula _{(3) CH 2 = CHSO 2} -R 5 -SO 2 CH = C
H ₂ [wherein, R ₅ represents an alkylene group which may be substituted with a divalent linking group. ] 2. The method according to claim 1, wherein in the general formula (1), the substituent of the alkylene group representing R is a group selected from a halogen atom, a hydroxyl group, a hydroxyalkyl group and an amino group. Developed photosensitive material. 3. The compound according to claim 1, wherein in the general formula (1), the linking group representing R has an amide linking moiety, an ether linking moiety, or a thioether linking moiety.
The photothermographic material according to the above. 4. In the general formula (1), a divalent linking group representing X is
_{-SO 2 -, - SO 2 NH} -, - S -, - O- or -NR
4. The photothermographic material according to claim 1, wherein R 'is a group selected from the group consisting of'-(where R 'is a monovalent linking group). 5. The heat development method according to claim 1, wherein in the general formula (3), the linking group representing R ₅ has an amide linking moiety, an ether linking moiety or a thioether linking moiety. Photosensitive material. 6. A support having at least a photosensitive layer and a non-photosensitive layer on a support, wherein the photosensitive layer contains an organic silver salt and photosensitive silver halide grains, and the non-photosensitive layer contains a reducing agent. The photothermographic material according to claim 1, 2, 3, 4, or 5, wherein