JP2001013628A - Heat developable photosensitive material and image forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat developable photosensitive material giving a high contrast and high density image excellent in preservability, having scuffing and wear resistances, conveyability and dot reproducibility in the exposure of the resulting image as an original to a PS plate and excellent in dimensional stability before and after heat development. SOLUTION: This heat developable photosensitive material has photosenstive silver halide, an organic silver salt, a reducing agent, a binder and at least one of hydrazine and a quaternary onium salt on the substrate and contains organic powder of at least one selected from among benzoguanamine- formaldehyde resin, benzoguanamine-melamine-formaldehyde resin and melamine- formaldehyde resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a photothermographic material.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making and medical treatment, waste liquids caused by wet processing of image forming materials have become a problem in terms of workability. Weight loss is strongly desired. Thus, there is a need for a technology relating to photothermal materials for photographic applications that can be efficiently exposed by a laser imagesetter or laser imager and can form a high-resolution and clear black image. This technique includes, for example, U.S. Patent Nos. 3,152,904 and 3,487,075 and D.C. "Dry Silver Photograph" by Morgan
ic Materials) ”(Handbook o
f Imaging Materials, Marce
l Dekker, Inc. As described in, for example, page 48, 1991), a heat developing material containing an organic silver salt, photosensitive silver halide particles, a reducing agent and a binder on a support is known.

[0003] These photothermographic materials form a photographic image by a heat development process, and include a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, a silver salt. A color toning agent for suppressing color tone is usually contained in a dispersed state in an (organic) binder matrix. The photothermographic material is stable at room temperature, but is exposed to high temperature (for example, 8
(0 ° C. to 140 ° C.). 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. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

[0004] These photothermographic materials have been used for microfilms and X-ray photography. However, since the density of the obtained image is low and the gradation is soft, some of them are used for printing plate making. It is only used.

On the other hand, due to recent advances in laser and light-emitting diode technology, sensitivity and density (Dmax) that can be exposed by a scanner having an oscillation wavelength of 600 to 800 nm.
There is a strong demand for the development of a photosensitive material having high image quality and capable of obtaining a high-contrast image, and a demand for simple processing and dry processing is also increasing.

US Pat. No. 3,667,958 describes that a photothermographic material using a combination of polyhydroxybenzenes and hydroxylamines, reductones or hydrazines has high image recognizability and resolution. However, the combination of these reducing agents tends to cause an increase in fog.

US Pat. Nos. 5,464,738 and 5,496,695 disclose organic silver salts, silver halides,
A photothermographic material containing a hindered phenol and a certain hydrazine derivative is described. However, when these hydrazine derivatives are used, sufficient Dmax or ultra-high contrast cannot be obtained, and black spots are further generated. Image is degraded.

A photothermographic material containing a hydrazine derivative having an improved black pot is described in JP-A-9-292267.
And JP-A-9-304870, JP-A-9-304871, JP-A-9-304872 and JP-A-10-31282, and JP-A-10-62898 discloses a further improved image reproducibility. There are things, but all are D
They have not yet achieved all of small point reproducibility and dimensional stability in addition to max, ultra-high contrast and suppression of black spots. Further, the formed image is inferior in storage stability over time, and fog increases.

It is known to add a matting agent to improve the transportability and prevent sticking.
JP-A-136463 describes an example in which polymer particles such as polymethyl methacrylate and styrene-methacrylic acid copolymer are added as a matting agent, and JP-A-10-19983 describes an example in which a matting agent of true spherical silica is added. However, the addition of these deteriorates small-dot reproducibility when printing a thermally developed image on a PS plate as a document,
Dmax of the heat-developed image may be reduced, or high contrast may be insufficient. In addition, in recent years, there has been a tendency to reduce the thickness of the photosensitive layer and the protective layer in order to speed up the processing, and the abrasion resistance is deteriorated. Therefore, improvements have been made by adding a matting agent. It cannot be improved enough.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to obtain a high-contrast, high-density image, excellent storage stability of the image, abrasion resistance, and conveyance. It is an object of the present invention to provide a photothermographic material which is compatible with both properties and small dot reproducibility when printing an obtained image as a document on a PS plate and has excellent dimensional stability before and after thermal development.

[0011]

SUMMARY OF THE INVENTION The object of the present invention is to provide a support comprising a photosensitive silver halide, an organic silver salt, a reducing agent, a binder, and at least one selected from hydrazine and a quaternary onium salt. A photothermographic material containing at least one organic powder selected from a benzoguanamine-formaldehyde resin, a benzoguanamine-melamine-formaldehyde resin, and a melamine-formaldehyde resin, wherein the organic powder has a Mohs hardness of 5 or more and a true specific gravity of 0. 8 to 2.5, the organic powder is contained in the outermost surface layer, the outermost surface layer contains a metal oxide having a Mohs hardness of 8 or more, and the outermost surface layer is a fatty acid. And at least one selected from fatty acid esters
Containing seeds, the thickness of the support is 110 to 150 μm
And the thickness of the photosensitive layer containing silver halide is 3
To 15 μm, the amount of silver contained in the photosensitive layer is 0.3 to 1.5 g / m ² , an image forming method for exposing the photothermographic material to an image with laser light, The wavelength is in the range of 700 to 1000 nm;
Horizontally transporting the photothermographic material and performing thermal development through preheating; performing preheating and thermal development within 45 seconds in total; photosensitive silver halide, organic silver salt, reducing agent, binder on the support And a photothermographic material having at least one selected from hydrazine and a quaternary onium salt are subjected to thermal development processing by a horizontal transport type automatic developing machine in which a roller of a heating unit is an opposed roller, and a thermal dimensional change before and after the processing. Of 0.01% to 0.05%, and at least one selected from a photosensitive silver halide, an organic silver salt, a reducing agent, a binder, and hydrazine and a quaternary onium salt on a support. The heat-developable photosensitive material is subjected to thermal development processing by a horizontal transport type automatic developing machine having a belt transport type heating unit, and the thermal dimensional change before and after the processing is 0.01% to 0.05%.
Image forming method.

Hereinafter, the present invention will be described in detail.

The photothermographic material of the present invention contains a toning agent selected from hydrazine and a quaternary onium salt, and further comprises a benzoguanamine-formaldehyde resin, a benzoguanamine-melamine-formaldehyde resin, and a melamine resin.
It is characterized by containing at least one organic powder selected from formaldehyde resins.

The organic powders selected from benzoguanamine-formaldehyde resin, benzoguanamine-melamine-formaldehyde resin, and melamine-formaldehyde resin are organic and have good affinity for the binder, and therefore have a high binding strength to the binder, and have a high binding force. You can increase the resistance when you are. Compared with other organic powders such as polymethyl methacrylate and styrene resin, it has excellent abrasion resistance, has good dispersibility, and has excellent dispersion stability when used as a coating solution. Here, the benzoguanamine-formaldehyde resin refers to a thermosetting resin obtained by condensing benzoguanamine and formaldehyde under basic conditions. Benzoguanamine-melamine-formaldehyde resin refers to a thermosetting resin obtained by condensing benzoguanamine-melamine and formaldehyde under basic conditions. Melamine-formaldehyde resin refers to a thermosetting resin obtained by condensing melamine and formaldehyde under basic conditions. The structure is represented as follows:

[0015]

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These resins can be produced by the method described in Plastic Materials Course (8) Urea-Melamine Resin, etc., Nikkan Kogyo Shimbun. There are also commercial products such as Nippon Shokubai Kagaku Co., Ltd. and Eposter.

These organic powders preferably have a Mohs hardness of 5 or more and a true specific gravity of 0.8 to 2.5, and more preferably a Mohs hardness of 6 or more and a true specific gravity of 1.
0 to 2.0. It is also preferably spherical,
The particles may be elliptical or square, and particles having different shapes may be mixed and used. The average particle size is about 1 to 10 μm, preferably 2 to 8 μm. The particle size distribution may be of any type, but those with little variation are preferred, and two or more types of particles having different distributions may be used in combination.

The layer containing the organic powder may contain other additives. Preferred are metal oxides having a Mohs hardness of 8 or more, particularly α-alumina, chromium oxide, fatty acids and fatty acid esters. The addition amount of the other additives is preferably 1 to 50% by weight based on the organic powder.

In the photothermographic material of the present invention, the support preferably has a thickness of 110 to 150 μm.
More preferably, 110 to 140 μm, furthermore, 115 to 1 μm
35 μm, the thickness of the photosensitive layer is preferably 3 to 15 μm, more preferably 7 to 11 μm, and the amount of silver contained in the photosensitive layer is 0.3 to 1.5 g / m ^2. And more preferably 0.7 to 1.1 g / m ² .

In a preferred embodiment of the photothermographic material of the present invention, an undercoat layer, a photosensitive layer, and a photosensitive layer surface protective layer are provided in this order on a support and provided on the photosensitive surface side. The undercoat layer is preferably composed of two or more layers, and has a total thickness of about 0.2 to 5 μm, preferably 0.1 to 5 μm.
5 to 3 μm. The thickness of the photosensitive layer is preferably 5 to 13 μm, more preferably 7 to 11 μm. The thickness of the photosensitive layer surface protective layer is preferably 2 to 10 μm, and more preferably 4 to 8 μm. The surface protective layer of the photosensitive layer preferably contains a matting agent. The matting agent has an average particle size of about 1 to 10 μm, preferably 3 to 7 μm.

On the back coat surface side, it is preferable to provide an undercoat layer, a back coat layer, and a back coat surface protective layer on the support in this order. The undercoat layer is preferably composed of two or more layers, and the undercoat layer closest to the support is preferably an antistatic layer containing a conductive metal oxide and / or a conductive polymer. As the conductive metal oxide, SnO ₂ surface-treated with Sb is preferable, and as the conductive polymer, polyaniline is preferable. The total thickness of the undercoat layer is about 0.2 to 4 μm, preferably 0.5 to 2 μm.
m. The thickness of the back coat layer is preferably 2 to 10 μm, more preferably 4 to 8 μm. The back coat layer preferably contains an antihalation dye. The thickness of the back coat surface protective layer is preferably 2 to 10 μm, more preferably 4 to 8 μm. It is preferable that a matting agent is contained in this surface protective layer. The average particle size of the matting agent is 1-10μ
m, preferably 3 to 7 μm.

Silver halide functions as an optical sensor. Average particle size is preferably smaller,
0.1 μm or less, more preferably 0.01 μm to 0.1
μm, particularly preferably 0.02 μm to 0.08 μm. The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. In the case of non-normal crystals, for example, in the case of spherical, rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains. Further, the silver halide is preferably monodispersed.
Here, the monodispersion means that the degree of monodispersion determined by the following formula is 40% or less. More preferably 30% or less,
Particularly preferred are particles having a content of 0.1% or more and 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%. Another preferred form of silver halide is tabular grains. The term “tabular grains” as used herein means those having an aspect ratio = r / h of 3 or more, where the square root of the projected area is r μm and the vertical thickness is h μm. Among them, the aspect ratio is preferably 3 or more and 50 or less. The particle size is 0.
1 μm or less, preferably 0.01 μm
~ 0.08 µm is preferred.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion may be prepared by any method such as an acid method, a neutral method, and an ammonia method, and the method of reacting a soluble silver salt and a soluble halide salt includes a one-side mixing method, a simultaneous mixing method, and the like. May be used. The silver halide may be added to the image forming layer by any method, in which case the silver halide is arranged close to the reducible silver source.
Further, the silver halide may be prepared by converting a part or all of the silver in the organic acid silver by the reaction of the organic acid silver and the halogen ion into silver halide, or may be prepared by preparing silver halide in advance. In advance, this may be added to a solution for preparing an organic silver salt, or a combination of these methods is possible, but the latter is preferred. Generally, the silver halide is preferably contained in an amount of 0.75 to 30% by weight based on the organic silver salt.

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

The photosensitive silver halide grains can be desalted by washing with a method known in the art such as a noodle method and a flocculation method. The photosensitive silver halide grains are preferably chemically sensitized. Preferred chemical sensitization methods include sulfur sensitization, selenium sensitization, tellurium sensitization, noble metal sensitization such as gold compounds, platinum, palladium, and iridium compounds, and reduction sensitization, as is well known in the art. Sensitization can be used.

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 25) And the nitrogen-containing heterocycle is preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. Examples of suitable silver salts are Research
h Disclosure Nos. 17029 and 29963
It is described in. Preferred silver sources are silver behenate, silver arachidate and 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 includes a forward 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.

The average particle size of the organic silver particles is 0.2 to 1.2 μm.
m, more preferably 0.35 to
1 μm. The organic silver particles are preferably monodispersed, and preferably have a monodispersity of 1 to 30.

In order to prevent the light-sensitive material from being devitrified, the total amount of silver halide and organic silver salt is preferably 0.5 g to 2.2 g per m ² in terms of silver.

Examples of suitable reducing agents are described in US Pat.
No. 0,448, No. 3,773,512, No. 3,5
No. 93,863 and Research Disclo
Sure Nos. 17029 and 29996. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0032]

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

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

[0035]

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[0036]

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

Suitable binders for the heat-developable materials are transparent or translucent, generally colorless, natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, gum arabic, poly (vinyl alcohol) , Hydroxyethylcellulose, 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 (vinylacetal) s (eg, poly (vinylformal) and poly (vinylbutyral)), poly (esters),
There are poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate), cellulose esters, and poly (amides). It may be hydrophilic or hydrophobic. Preferred binders include polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, polyurethane and the like. Among them, polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, and polyester are particularly preferably used.

Another preferred binder is a soluble or dispersible binder in an aqueous solvent (aqueous solvent).
It is a polymer having an equilibrium water content of 2% by weight or less at 60 ° C. and 60% RH. When such a polymer is used, a photosensitive layer can be formed using a water solvent containing 30% by weight or more of water as a coating solvent. Examples of such a polymer include an acrylic resin, a polyester resin, a polyurethane resin, a vinyl chloride resin, a vinylidene chloride resin, a rubber-based resin (for example, S
(BR resin and NBR resin), vinyl acetate resin, polyolefin resin, polyvinyl acetal resin and the like.

The binder amount of the photosensitive layer is 1.5 to 10 g /
m ² , and more preferably 1.7 to
8 g / m ² .

As the hydrazine derivative, a compound represented by the following general formula [H] is preferable.

[0042]

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In the formula, A ₀ represents an aliphatic group, an aromatic group, a heterocyclic group or a -G ₀ -D ₀ group which may have a substituent;
B ₀ represents a blocking group, and A ₁ and A ₂ each represent a hydrogen atom, or one represents a hydrogen atom and the other represents an acyl group, a sulfonyl group, or an oxalyl group. Here, G ₀ is -CO-
Group, -COCO- group, -CS- group, -C (= NG ₁ D ₁ )
— Group, —SO— group, —SO ₂ — group or —P (O) (G ₁ D
₁ ) represents a group, G ₁ represents a mere bond, an —O— group, —S—
Group or -N (D ₁₎ - represents a group, D ₁ is an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, a plurality of D ₁ in the molecule
If they are present, they can be the same or different. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group,
Represents an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group.

In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly preferably a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, t-butyl group, octyl group, cyclohexyl group, benzyl group,
These may be further substituted with a suitable substituent (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc.).

In the general formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed-ring aryl group, such as a benzene ring or a naphthalene ring, and a heterocyclic group represented by A _0. The group is preferably a heterocyclic ring containing at least one heteroatom selected from nitrogen, sulfur, and oxygen atom in a single ring or a condensed ring, for example, a pyrrolidine ring, an imidazole ring, a tetrahydrofuran ring, a morpholine ring, a pyridine ring, a pyrimidine ring, a quinoline ring, a thiazole ring, a benzothiazole ring, a thiophene ring, a furan ring, and, in -G ₀ -D ₀ group represented by A _0, G ₀ is -CO
Group, -COCO- group, -CS- group, -C (= NG
₁ D ₁₎ - group, -SO- group, -SO ₂ - group or -P (O)
(G ₁ D ₁ ) — represents a group. G ₁ is a mere bond, -O-
A group, —S— group or —N (D ₁ ) — group, wherein D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in the molecule, They can be the same or different. D ₀ is a hydrogen atom, an aliphatic group, an aromatic group,
It represents a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferable D ₀ includes a hydrogen atom, an alkyl group, an alkoxy group, an amino group, and the like. Aromatic groups A _0, heterocyclic group or -G ₀ -D ₀ group may have a substituent.

Particularly preferred as A ₀ are an aryl group and a -G ₀ -D ₀ group.

In the general formula [H], A ₀ preferably contains at least one diffusion-resistant group or a silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable, and as the ballast group, a photographically inert alkyl group, alkenyl group, alkynyl group, alkoxy group, phenyl group, Examples thereof include a phenoxy group and an alkylphenoxy group, and the total number of carbon atoms in the substituent is preferably 8 or more.

In the general formula [H], examples of the silver halide adsorption promoting group include thiourea, thiourethane group, mercapto group, thioether group, thione group, heterocyclic group, thioamide heterocyclic group, mercapto heterocyclic group, 64-9
No. 0439.

In the general formula [H], B ₀ represents a blocking group, preferably -G ₀ -D ₀ group, and G ₀ represents -CO- group, -COCO- group, -CS- group, -C (= N
G ₁ D ₁ ) —, —SO—, —SO ₂ —, or —P
(O) A preferred (G ₀ ) representing a (G ₁ D ₁ ) — group is
C _O - group, and a -COCO- group, G ₁ is a single bond, -O- group, -S- group, or -N (D ₁₎ - group, wherein
D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom, and when a plurality of D ₁ are present in a molecule, they may be the same or different. D ₀ represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, and preferred D ₀ is a hydrogen atom, an alkyl group, an alkoxy group, And an amino group. A ₁ and A ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl group, trifluoroacetyl group, benzoyl group, etc.);
Represents a sulfonyl group (such as a methanesulfonyl group or a toluenesulfonyl group) or an oxalyl group (such as an ethoxalyl group).

Next, specific examples of the compound represented by the general formula [H] are shown below, but it should not be construed that the invention is limited thereto.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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More preferred hydrazine derivatives are represented by the following formulas (H-1), (H-2), (H-3) and (H-4)
Or a compound represented by (H-5).

[0058]

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In the formula, R ₁₁ , R ₁₂ and R ₁₃ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ₁₄ represents a heterocyclic oxy group or a heteroarylthio group. A ₁ and A ₂ both represent a hydrogen atom or one is a hydrogen atom and the other is an acyl group, an alkylsulfonyl group or an oxalyl group.

[0060]

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In the formula, R ₂₁ represents a substituted or unsubstituted alkyl group, aryl group or heteroaryl group. R ₂₂ represents hydrogen, an alkylamino group, an arylamino group, or a heteroarylamino group. A ₁ and A ₂ have the same meanings as those in formula (H-1).

[0062]

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In the formula, G ₃₁ and G ₃₂ represent a — (CO) p- group,
C (= S)-group, sulfonyl group, sulfoxy group, -P
(＝ O) represents an R ₃₃ — group or an iminomethylene group, and p is 1
Or an integer of 2, and R ₃₃ represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group or an amino group. However, when G ₃₁ is a sulfonyl group, G ₃₂ is not a carbonyl group. R ₃₁ and R ₃₂ represent a monovalent substituent. A ₁ and A ₂ have the same meanings as those in formula (H-1).

[0064]

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In the formula, R ₄₁ , R ₄₂ and R ₄₃ each represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. R ₄₄ and R ₄₅ represent a substituted or unsubstituted alkyl group. A ₁ and A ₂ have the same meanings as those in formula (H-1).

[0066]

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In the formula, R ₅₁ represents an alkyl group, alkenyl group, alkynyl group, aralkyl group, heterocyclic group, substituted amino group, alkylamino group, arylamino group, heterocyclic amino group, hydrazino group, alkoxy group, aryl group Oxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, alkylthiocarbonyl group, arylthiocarbonyl group, heterocyclic thiocarbonyl group, carbamoyl A carbamoyloxy group, a carbamoylthio group, a carbazoyl group, an oxalyl group, an oxamoyl group, an alkoxyureido group, an aryloxyureido group, or a heterocyclic oxyureido group. A ₁ and A ₂ have the same meanings as those in formula (H-1).

In the general formula (H-1), the aryl group represented by R ₁₁ , R ₁₂ and R ₁₃ is a phenyl group,
Examples include a methylphenyl group and a naphthyl group, and examples of the heteroaryl group include a triazole residue, an imidazole residue, a pyridine residue, a furan residue, and a thiophene residue. Further, R ₁₁ , R ₁₂ and R ₁₃ may be bonded via an arbitrary linking group. Examples of the substituent which R ₁₁ , R ₁₂ and R ₁₃ may have include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a heterocyclic group containing a quaternized nitrogen atom (a pyridinio group) Etc.), a hydroxy group, an alkoxy group (including a group repeatedly containing an ethyleneoxy group or a propyleneoxy group unit), an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a urethane group, Carboxyl group, imide group, amino group, carboxamide group, sulfonamide group, ureido group, thioureido group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, 4
Primary ammonium group, (alkyl, aryl or heterocycle)
Thio, mercapto, (alkyl or aryl) sulfonyl, (alkyl or aryl) sulfinyl,
A sulfo group, a sulfamoyl group, an acylsulfamoyl group, an (alkyl or aryl) sulfonyluureido group,
(Alkyl or aryl) sulfonylcarbamoyl group,
Examples include a halogen atom, a cyano group, a nitro group, and a phosphoric amide group. All of R ₁₁ , R ₁₂ and R ₁₃ are preferably phenyl groups, and more preferably all are unsubstituted phenyl groups.

The heteroaryloxy group represented by R ₁₄ includes a pyridyloxy group, an indolyloxy group, a benzothiazolyloxy group, a benzimidazolyloxy group,
A furyloxy group, a thienyloxy group, a pyrazolyloxy group, an imidazolyloxy group, and the like.Examples of the heteroarylthio group include a pyridylthio group, a pyrimidylthio group, an indolylthio group, a benzothiazolylthio group, a benzimidazolylthio group, a furylthio group, Examples include a thienylthio group, a pyrazolylthio group, and an imidazolylthio group. R ₁₄ is preferably a pyridyloxy group or a thienyloxy group.

The acyl group represented by A ₁ or A ₂ includes
Examples include an acetyl group, a trifluoroacetyl group, and a benzoyl group. Examples of the sulfonyl group include a methanesulfonyl group and a toluenesulfonyl group. Examples of the oxalyl group include an ethoxalyl group. Both A ₁ and A ₂ are preferably hydrogen atoms.

In the formula (H-2), examples of the alkyl group represented by R ₂₁ include a methyl group, an ethyl group, a t-butyl group, a 2-octyl group, a cyclohexyl group, a benzyl group and a diphenylmethyl group. And an aryl group, a heteroaryl group, and a substituent which may be present include R
₁₁ is the same as R ₁₂ and R _13. R ₂₁ is preferably an aryl group or a heteroaryl group, and particularly preferably a phenyl group. The alkylamino group represented by R _22, methylamino group, ethylamino group, propylamino group, butylamino group, dimethylamino group, diethylamino group, etc. ethylmethylamino group. Examples of the arylamino group anilino Examples of the group and heteroaryl group include a thiazolylamino group, a benzimidazolylamino group, and a benzthiazolylamino group. Preferably the R ₂₂ is dimethylamino group or diethylamino group.

In formula (H-3), the monovalent substituents represented by R ₃₁ and R ₃₂ are the same as those described in formula (H-1), but are preferably alkyl groups , An aryl group, a heteroaryl group, an alkoxy group, or an amino group, further an aryl group or an alkoxy group, particularly preferably R ₃₁ is a phenyl group, and R ₃₂ is tert.
-Butoxycarbonyl group. G ₃₁ and G ₃₂ are preferably a —CO— group, a —COCO— group, a sulfonyl group or a —CS— group, and more preferably both are —CO—.
Group or a sulfonyl group.

In formula (H-4), R ₄₁ , R ₄₂ and R ₄₃ are the same as R ₁₁ , R ₁₂ and R ₁₃ in formula (H-1).
Is synonymous with Preferably, all are phenyl groups, and all are unsubstituted phenyl groups. R ₄₄ , R ₄₅
Examples of the substituted or unsubstituted alkyl group represented by are a methyl group, an ethyl group, a t-butyl group, a 2-octyl group, a cyclohexyl group, a benzyl group, a diphenylmethyl group, and the like. Is the case.

Specific examples of the compounds represented by formulas (H-1) to (H-5) are shown below, but the invention is not limited thereto.

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Other hydrazine derivatives that can be preferably used include compounds H-1 to H-29 described in US Pat. No. 5,545,505, columns 11 to 20;
U.S. Pat. No. 5,464,738, column 9 to column 1
Compounds 1 to 12 described in 1. These hydrazine derivatives can be synthesized by a known method.

The hydrazine derivative-added layer is a photosensitive layer containing silver halide and / or a layer adjacent to the photosensitive layer.
The addition amount is the particle size of the silver halide grains, the halogen composition,
The extent of chemical sensitization, although the optimum amount is not uniform such as type of inhibitor per mole of silver halide 10 ^-6 mol to 10
^The preferred range is about ^-1 mol, particularly 10 ^-5 mol to 10 ^-2 mol.

As the quaternary onium compound, a compound represented by the following formula (P) is preferably used.

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In the formula, Q represents a nitrogen atom or a phosphorus atom;
₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Incidentally, R _{1 to} R ₄ may be connected to each other to form a ring.

In the general formula (P), the substituent represented by R _{1 to} R ₄ is an alkyl group (methyl group, ethyl group,
Propyl group, butyl group, hexyl group, cyclohexyl group, etc., alkenyl group (allyl group, butenyl group, etc.), alkynyl group (propargyl group, butynyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), heterocyclic group (Piperidinyl group, piperazinyl group, morpholinyl group, pyridyl group, furyl group, thienyl group, tetrahydrofuryl group, tetrahydrothienyl group, sulfolanyl group, etc.), amino group and the like.

The ring which may be formed by connecting R _{1 to} R ₄ to each other includes a piperidine ring, a morpholine ring, a piperazine ring,
Examples include a quinuclidine ring, a pyridine ring, a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring.

The groups represented by R _{1 to} R ₄ are hydroxyl groups,
It may have a substituent such as an alkoxy group, an aryloxy group, a carboxyl group, a sulfo group, an alkyl group and an aryl group.

As R ₁ , R ₂ , R ₃ and R ₄ , a hydrogen atom and an alkyl group are preferred.

Examples of the anion represented by X ⁻ include inorganic and organic anions such as a halogen ion, a sulfate ion, a nitrate ion, an acetate ion and a p-toluenesulfonic acid ion.

More preferably, the following general formulas (Pa) and (P
b) or a compound represented by (Pc); and a compound represented by the following general formula [T].

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In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of nonmetallic atoms for completing a nitrogen-containing heterocyclic ring, and may contain an oxygen atom, a nitrogen atom and a sulfur atom. And the benzene ring may be condensed. A ¹ , A ² , A ³ , A ⁴ and A ⁵
May have a substituent and may be the same or different. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkynyl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfo group, a carboxy group, a hydroxyl group, an alkoxy group, and an aryloxy group. Amide group, sulfamoyl group, carbamoyl group, ureido group, amino group, sulfonamide group, sulfonyl group, cyano group, nitro group, mercapto group, alkylthio group and arylthio group. Preferred examples of A ¹ , A ² , A ³ , A ⁴ and A ⁵ include a 5- to 6-membered ring (pyridine,
Imidazole, thiozole, oxazole, pyrazine,
Each ring such as pyrimidine), and a more preferred example is a pyridine ring.

_BP represents a divalent linking group, and m represents 0 or 1.
Represents Examples of the divalent linking group include an alkylene group, an arylene group, an alkenylene group, —SO ₂ —, —SO—, and —O
—, —S—, —CO—, and —N (R ⁶ ) — (R ⁶ represents an alkyl group, an aryl group, or a hydrogen atom) alone or in combination. Preferred examples of B _p include an alkylene group and an alkenylene group.

R ¹¹ , R ¹² and R ¹⁵ each have 1 to 2 carbon atoms
Represents an alkyl group of 0. R ¹¹ and R ¹² may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and examples of the substituent include A ¹ , A ² , A ³ ,
The substituents are the same as those described as the substituents for A ⁴ and A ⁵ .

Preferable examples of R ¹¹ , R ¹² and R ¹⁵ are each an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0105] X _p ^- is a counter ion necessary to refer balancing the charge of the whole molecule, expressed as chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p- toluenesulfonate, the oxalato or the like. n _p represents the number of counter ions required to balance the charge of the whole molecule, and n _p is 0 in the case of an internal salt.

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The substituents R ₅ and R ₆ of the phenyl group of the triphenyltetrazolium compound represented by the general formula [T],
R ₇ is preferably a hydrogen atom or a compound having a negative Hammett sigma value (σP) indicating the degree of electron withdrawing property.

The Hammett's sigma value for the phenyl group is described in many literatures, for example, Journal of Medical Chemistry.
Chemistry) 20, vol. 304, p. As a group having a particularly preferable negative sigma value, for example, a methyl group (σP = −0.17 or less, and
P value), ethyl group (-0.15), cyclopropyl group (-0.21), n-propyl group (-0.13), is
o-propyl group (-0.15), cyclobutyl group (-
0.15), n-butyl group (-0.16), iso-butyl group (-0.20), n-pentyl group (-0.1
5), cyclohexyl group (-0.22), amino group (-
0.66), acetylamino group (-0.15), hydroxyl group (-0.37), methoxy group (-0.27),
Ethoxy group (-0.24), propoxy group (-0.2
5), butoxy group (-0.32), pentoxy group (-
0.34), etc., each of which has the general formula [T]
Is useful as a substituent of the compound of

N represents 1 or 2, and examples of the anion represented by X _T ^n- include halogen ions such as chloride ion, bromide ion and iodide ion, nitric acid, sulfuric acid, and the like.
Acid radicals of inorganic acids such as perchloric acid, acid radicals of organic acids such as sulfonic acid and carboxylic acid, anionic activators, specifically p-
Lower alkylbenzene sulfonic acid anions such as toluene sulfonic acid anion; higher alkyl benzene sulfonic acid anions such as p-dodecyl benzene sulfonic acid anion; higher alkyl sulfate anions such as lauryl sulfate anion; boric acid anions such as tetraphenyl boron; Dialkyl sulfosuccinate anions such as 2-ethylhexyl sulfosuccinate anion,
Examples thereof include higher fatty acid anions such as cetyl polyethenoxy sulfate anion, and polymers having an acid radical attached to a polymer such as polyacrylate anion.

Hereinafter, specific examples of the quaternary onium compound will be shown below, but it should not be construed that the invention is limited thereto.

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The above quaternary onium compound can be easily synthesized according to a known method. For example, the above tetrazolium compound can be obtained from Chemical Reviews vol. 55
p. 335-483 can be referred to.

The addition amount of these quaternary onium compounds is about 1 × 10 ^-8 to 1 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-1 mol per mol of silver halide. These can be added to the light-sensitive material at any time from the time of silver halide grain formation to the time of coating.

A quaternary onium compound and an amino compound are
They may be used alone or in combination of two or more.
The compound may be added to any of the constituent layers of the photosensitive material, but is preferably added to at least one of the constituent layers on the side having the photosensitive layer, further to the photosensitive layer and / or an adjacent layer thereof.

The photothermographic material of the present invention comprises a compound represented by the following general formula (A), a hydroxylamine, an alkanolamine, an ammonium phthalate compound, a hydroxamic acid compound represented by the general formula (B), (C)
It is preferable to contain at least one selected from the group consisting of an N-acylhydrazine compound represented by Formula (I) and a hydrogen atom donor compound represented by Formula (D).

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[Wherein EWD represents an electron-withdrawing group;
₁ , R ₂ and R ₃ each represent a hydrogen atom or a monovalent substituent. However, at least one selected from R ₁ and R ₂ is a monovalent substituent. ]

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[Wherein R ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amide group, an aryl group, an aralkyl group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic group, a heterocyclic group. Represents an oxy group or a heterocyclic thio group, and R ₅ is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amide group, an aryl group, an aralkyl group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic group. , a heterocyclic oxy group, a heterocyclic thio group, a hydrazino group, an alkylamino group, a sulfonylamino group, a ureido group, an oxycarbonyl amino group, an alkynyl group or an unsubstituted amino group, R ₄ and R ₅ are bonded to each other To form a 5- to 7-membered ring. X represents a hydrogen atom, an alkyl group, a carbamoyl group or an oxycarbonyl group. ]

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[Wherein R ₆ is an alkyl group, an alkenyl group, an alkoxy group, an alkylthio group, an amide group, an aryl group, an aralkyl group, an aryloxy group, an arylthio group, an anilino group, a heterocyclic group, a heterocyclic oxy group or Represents a heterocyclic thio group. General formula (D) R ₇ —H wherein R ₇ is a benzhydrol nucleus, a diphenylphosphine nucleus, a triphenylmethane nucleus, an N, N′-dialkylpiperazine nucleus, a 3-pyrrololine nucleus, a xanthene nucleus,
9,10-dihydroanthracene nucleus, 9-hydroxyfluorene nucleus, allyl-β-ketoester nucleus, alkyl-β-ketoester nucleus, oxime nucleus, amide oxime nucleus, benzaldehyde oxime nucleus, acetophenone oxime nucleus, caprolactam oxime nucleus, It represents an ethylbenzoyl acetate nucleus, a pivalaldehyde nucleus, and an ethyl isobutyl acetate nucleus. In the general formula (A), the electron-withdrawing group represented by EWD is a substituent whose Hammett's substitution number σp can take a positive value, and specifically, a cyano group or an alkoxycarbonyl group , Aryloxycarbonyl group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, nitro group, halogen atom, perfluoroalkyl group, acyl group, formyl group, phosphoryl group, carboxy group or a salt thereof, sulfo group or its Examples thereof include a salt, a saturated or unsaturated heterocyclic group, an alkenyl group, an alkynyl group, an acyloxy group, an acylthio group, a sulfonyloxy group, and an aryl group substituted with these electron-withdrawing groups. These groups may have a substituent.

Specific examples of the compound represented by formula (A) include those described in US Pat. No. 5,545,515.

Specific examples of hydroxylamine, alkanolamine and ammonium phthalate compounds include those described in US Pat. No. 5,545,505.

In the general formula (B), R ₄ is preferably an alkyl group, and particularly preferably a methyl group or an ethyl group. R ₅ is preferably an aryl group, a heterocyclic group, a heterocyclic oxy group, or a heterocyclic thio group, and more preferably a heterocyclic oxy group or a heterocyclic thio group. Specifically, as the heterocyclic oxy group, a pyridyloxy group,
Examples include a pyrimidyloxy group, an indolyloxy group, a benzothiazolyloxy group, a benzimidazolyloxy group, a furyloxy group, a thienyloxy group, a pyrazolyloxy group, and an imidazolyloxy group. Specific examples of the heterocyclic thio group include a pyridylthio group, a pyrimidylthio group,
Examples thereof include an indolylthio group, a benzothiazolylthio group, a benzimidazolylthio group, a furylthio group, a thienylthio group, a pyrazolylthio group, and an imidazolylthio group.
Of these, a pyridyloxy group and a thienyloxy group are preferred. X is preferably a hydrogen atom.

Specific examples of the compound represented by formula (B) include those described in US Pat. No. 5,545,507.

In the general formula (C), R ₆ is preferably an aryl group, a heterocyclic group, a heterocyclic oxy group, or a heterocyclic thio group, more preferably a heterocyclic oxy group,
It is a heterocyclic thio group. Specific examples thereof include those described above, and among them, preferred are a pyridyloxy group and a thienyloxy group.

Specific examples of the compound represented by formula (C) include those described in US Pat. No. 5,558,983.

Specific examples of the compound represented by formula (D) include those described in US Pat. No. 5,637,449.

Specific examples of the compounds of the general formulas (A) to (D), hydroxylamine, alkanolamine and ammonium phthalate are shown below, but are not limited thereto.

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In the photothermographic material of the present invention, various surfactants can be used as a coating aid. Among them, a fluorine-based surfactant is preferably used for improving charging characteristics and preventing spot-like coating failure.

The photothermographic material of the present invention may optionally contain a color tone agent for suppressing the color tone of silver. Examples of suitable toning agents that can be employed are Research Disclosure
re No. 17029. In addition, a mercapto compound, a disulfide compound, and a thione compound can be contained in order to suppress or promote development to control development, to improve spectral sensitization efficiency, to improve storage stability before and after development, and the like.

The photothermographic material of the present invention may contain an antifoggant.

A sensitizing dye can be used in the photothermographic material of the present invention. Useful sensitizing dyes for use in the present invention include, for example, Research Disclosure Item 1
7643IV-A (p.23, December 1978) and Item 1831X (p.437, August 1978). In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The photothermographic material of the invention may contain, for example, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid, and the like. These additives and the other additives mentioned above are
h Disclosure Item 17029 (19
June 1978 p. Compounds described in 9 to 15) can be preferably used.

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). A heat-treated plastic support can also be used.

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

The photothermographic material of the present invention has a wavelength of 700 to 700.
Image effects are exposed by a scanner using a laser in the range of 1000 nm as a light source, and the effect is remarkably exhibited. In the heat development, it is preferable that the photosensitive material is horizontally conveyed and heat-developed through preheating.
It is effective in rapid processing of 5 seconds or less, preferably 5 to 40 seconds, and more preferably 5 to 30 seconds.

The preferred heating temperature is in the range of 30 ° C. to 150 ° C., and the preferred range of thermal development is 80 to 140 ° C.
And 100 to 140 ° C. is more preferable. A preferable range of the preheating is 30 to 130 ° C, more preferably 50 to 120 ° C.

Further, heat development is performed by a horizontal transport type automatic developing machine in which the rollers of the heating section are opposed rollers or a horizontal transport type automatic developing machine having a belt transport type heating section, and the thermal dimensional change before and after the processing is 0.01%. % To 0.05%, it is possible to obtain an image which is superior in printing plate making use.

[0151]

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

Example 1 (Preparation of Subbed PET Support) A commercially available biaxially stretched heat-fixed PET film having a thickness of 125 μm was coated on both surfaces with 8 W /
m ² · m of corona discharge treatment, the following undercoating coating liquid a-1 is applied to one side to a dry film thickness of 0.8 μm, and dried to form an undercoating layer A-1, and vice versa. On the side surface, the following antistatic coating solution b-1 was applied with a dry film thickness of 0.8 μm
And dried to form an antistatic subbing layer B-
It was set to 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 polystyrene fine particles (average particle diameter 3 μm) 0.05 g colloidal silica (average particle diameter 90 μm) 0 .1 g with water 1 l << Undercoat coating solution b-1 >> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.18 μm) Amount to become 200 mg / m ² Butyl acrylate (30% by weight) Styrene ( 20% by weight) Glycidyl acrylate (40% by weight) copolymer latex liquid (solid content 30%) 270 g (C-1) 0.6 g hexa Styrene-1,6-bis subsequently finish 1l in (ethyleneurea) 0.8 g Water, to the undercoat layer A-1 and the upper surface undercoat layer B-1,
A corona discharge of 8 W / m ² · min. Was performed, and the lower coating layer a-1 was coated on the lower coating layer A-1 with a dry film thickness of 0.9 μm.
As the undercoat layer A-2, the undercoat layer B-1 is coated with the following undercoat layer coating solution b-2 on the undercoat layer B-1 so as to have a dry film thickness of 0.2 μm. Coated as B-2.

<< Coating Solution a-2 for Subbing Upper Layer >> Gelatin 3.6 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

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(Heat Treatment of Support) In the above-mentioned undercoat drying step of the undercoated support, the support was heated at 140 ° C.
Thereafter, it was gradually cooled.

(Preparation of Silver Halide Emulsion A) 900 m of water
7.5 g of inert gelatin and 10 ml of potassium bromide
mg, and adjusted to a temperature of 35 ° C. and a pH of 3.0, and 370 ml of an aqueous solution containing 74 g of silver nitrate (60/3
1 mol of silver of an aqueous solution and [Ir (NO) Cl _5] salt per mole silver 1 × 10 ^-6 mol, and rhodium chloride salt comprises sodium chloride and potassium bromide and potassium iodide in a molar ratio of 8/2) 1 × 10 ^-6 mol per 1 g was added by the controlled double jet method while keeping the pAg at 7.7. Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7-
Add tetrazaindene, adjust pH to 8 with NaOH, pAg
By adjusting the particle size to 6.5, reduction sensitization was performed to obtain cubic silver iodobromide grains having an average grain size of 0.06 μm, a monodispersity of 10%, a variation coefficient of projected diameter area of 8%, and a [100] face ratio of 87%. Obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant and desalting treatment to obtain a silver halide emulsion A.

(Preparation of Na Behenate Solution) In 945 ml of pure water, 32.4 g of behenic acid, 9.9 g of arachidic acid and 5.6 g of stearic acid were dissolved at 90 ° C. Next, while stirring at a high speed, 98 ml of a 1.5 M aqueous sodium hydroxide solution
Was added. Next, 0.93 ml of concentrated nitric acid was added.
C. and stirred for 30 minutes to obtain a sodium behenate solution.

(Preparation of Preform Emulsion of Silver Behenate and Silver Halide Emulsion A) 15.1 g of the silver halide emulsion A was added to the above sodium behenate solution, and the pH was adjusted to 8.1 with a sodium hydroxide solution. Later, 1M silver nitrate solution 14
7 ml was added over 7 minutes, the mixture was further stirred for 20 minutes, and water-soluble salts were removed by ultrafiltration. The resulting silver behenate was grains having an average grain size of 0.8 μm and a monodispersity of 8%. After the floc of the dispersion has formed, the water is removed and an additional 6
After washing with water and removing water several times, it was dried.

(Preparation of Photosensitive Emulsion) The preform emulsion thus prepared was divided, and polyvinyl butyral (average molecular weight: 3000, Tg = 70 ° C., -SO ₃ K: 0.2
Mmol) in methyl ethyl ketone (17 wt.
%) 544 g and toluene 107 g were gradually added and mixed, and then dispersed at 30 ° C. for 10 minutes at 4000 psi with a media disperser using a 0.5 mm-size ZrO ₂ bead mill.

The following layers were simultaneously coated on both sides of the support to prepare a sample. The drying was performed at 60 ° C. for 15 minutes.

(Coating on Back Side) A liquid having the following composition was applied onto the B-1 layer of the support so that the dry film thickness became 6 μm to form a back coat layer.

Cellulose acetate butyrate 15 g (10% methyl ethyl ketone solution) Dye-A 0.007 g Dye-B 0.007 g Matting agent: monodispersity 15% Average particle size 8 μm monodisperse silica 0.09 g C ₈ F ₁₇ (CH ₂ CH ₂ O) ₁₂ C ₈ F ₁₇ 0.05 g C ₉ F ₁₉ -C ₆ H ₄ -SO ₃ Na 0.01 g

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(Coating of Backcoat Surface Protective Layer) A solution having the following composition was applied on the backcoat layer to a dry film thickness of 3.5 μm.
It was applied so that it became.

Cellulose acetate butyrate 15 g (10% methyl ethyl ketone solution) Matting agent: Compound described in Table 1 0.2 g C ₈ F ₁₇ (CH ₂ CH ₂ O) ₁₂ C ₈ F ₁₇ 0.05 g C ₉ F ₁₉ − C ₆ H ₄ —SO ₃ Na 0.01 g Stearic acid 0.1 g α-alumina (average particle size 0.4 μm) 0.2 g (coating on photosensitive layer side) Photosensitive layer 1: On top of A-1 layer of support A solution having the following composition was applied so that the applied silver amount was 1.0 g / m ² and the dry film thickness was 10.0 μm.

Preform emulsion 240 g Sensitizing dye (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml Oxidizing agent ( 10 ml methanol solution) 1.2 ml 2-4-chlorobenzoylbenzoic acid (12% methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline (5% methanol solution) 17 ml hydrazine Derivatives Described in Table 1 0.4 g Hardening accelerator Described in Table 1 0.3 g Phthalazine 0.6 g 4-Methylphthalic acid 0.25 g Tetrachlorophthalic acid 0.2 g Calcium carbonate having an average particle size of 3 μm 0.1 g A-4 (20% methanol solution) 20.5 ml isocyane 0.5 g (Desmodur N3300, manufactured by Mobay Corporation)

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Surface protective layer: A solution having the following composition was simultaneously coated on the photosensitive layer so that the dry film thickness was 6 μm.

Acetone 5 g Methyl ethyl ketone 21 g Cellulose acetate butyrate 2.3 g Methanol 7 g Phthalazine 0.25 g A-4 (20% methanol solution) 10 g Matting agent: Compound described in Table 1 0.05 g CH ₂ = CHSO ₂ CH ₂ CH 0.035 g of ₂ OCH ₂ CH ₂ SO ₂ CH = CH ₂ fluorinated surfactant C ₁₂ F ₂₅ (CH ₂ CH ₂ O) ₁₀ C ₁₂ F ₂₅ 0.01 g C ₈ F ₁₇ -C ₆ H ₄ -SO ₃ Na 0.01 g Stearic acid 0.1 g α-alumina (average particle size 0.4 μm) 0.2 g The smoother value of the surface on the photosensitive layer side is 25 mmHg, and the smoother value of the surface on the back coat layer side is 200.
mmHg. The smoother value was measured by humidifying the unexposed sample at 23 ° C. and 48% RH for 2 hours, and measuring the smoother value of the surface on the photosensitive layer side in the same environment using SM-6B manufactured by Toyo Denshi Kogyo Co., Ltd. did.

Using the prepared sample, the binder was removed, and the sample was observed by an electron microscope by a replica method. The organic silver particles had a major axis diameter of 0.5 ± 0.05 μm.
m, tabular grains having a minor axis diameter of 0.4 ± 0.05 μm and a thickness of 0.01 μm occupy 90% of the total organic silver grains.
% Particles.

The heat-developable material thus prepared was placed in a dark room for 30 cm.
Cut into a length of 50 m in width and wound around a cardboard core with an inner diameter of 10 cm to obtain a roll-shaped sample, 60 cm x 2 m
And wrapped.

<< Forced Deterioration Test >> The packaged sample was allowed to stand at 40 ° C. and 80% RH for 5 days under forced degradation conditions.

<< Exposure and development treatment >> Thereafter, 780 nm
Using a Dotex 2dry (internal drum system) manufactured by Scitex, an image setter equipped with a semiconductor laser, halftone dots were exposed at 300 ° C. so as to change the exposure amount in 5% steps, and were exposed at 90 ° C. for 10 seconds. After passing through the pre-heating section, 120 ° C while performing horizontal transfer in the oven
For 15 seconds. At that time, exposure and development,
The test was performed in a room humid at 23 ° C. and 50% RH.

(Evaluation of Reproducibility of Small Spots after Printing on PS Plate) A PS plate exposed by contacting a developed sample with a PS plate and irradiating it at 8 mW / cm ² using a metal halide lamp as a light source. Was developed with a developing solution obtained by diluting a commercially available developing solution (manufactured by Konica Corporation, SDR-1) 6 times at a developing temperature of 27 ° C. for a developing time of 20 seconds. Further, the area of the 50% halftone dot having a screen ruling of 150 lines / inch on the plate was measured to evaluate the small dot reproducibility. The area was measured with a Macbeth densitometer. The smaller the halftone dot area ratio on the plate is, the better the small dot reproducibility is.

(Evaluation of Gradation) Thermal development was carried out at 110 ° C. for 20 seconds, and evaluation of cutout was made by the gradient (gamma) of a straight line connecting the characteristic curves 1.0 and 1.5.

(Evaluation of Density Change after Thermal Development) A sample that had been subjected to forced deterioration was exposed and thermally developed. The sample was divided into two parts, and one was placed in a thermostat at 50 ° C. and 60% RH for 5 days. It was used for evaluation over time, and it was evaluated how much the density changed from 2.5 to 2.5.

(Shrinkage: Evaluation of thermal dimensional stability) 500 mm
Cut the sample to × 440mm size, 23 ℃, 50%
After humidifying for 2 hours with RH, the length of the PET support in the longitudinal stretching side was measured. Thereafter, the above-mentioned heat development processing is performed, and the humidity is again adjusted at 23 ° C. and 50% RH for 2 hours. Then, the length of the same side is measured, and the shrinkage per 1 m is (length before processing) − (heat development). (Length after treatment).

(Evaluation of transportability) Imation Company (manufactured)
A dry view heat developing machine for plate making was set to the above processing conditions, and 50 samples each of 500 mm × 440 mm size were processed, and the number of films wound around rollers or jammed in the developing machine was counted.

(Evaluation of anti-scratch resistance)
It reciprocated and evaluated the occurrence of scratches on a five-point scale.

5 No occurrences 4 Pinholes generated 3 Pinholes considerably generated 2 Streak-like flaws generated 1 Flaws generated on the entire surface Table 1 shows the above results.

[0183]

[Table 1]

The matting agent was as follows: M-1: monodispersity 15%, monodisperse melamine-formaldehyde resin having an average particle size of 5 μm (Mohs hardness 7, true specific gravity 1.3) M-2: monodispersity 15% Monodisperse benzoguanamine-formaldehyde resin with an average particle size of 5 μm (Mohs hardness 7, true specific gravity 1.3) M-3: Monodispersity 10%, monodisperse benzoguanamine-melamine-formaldehyde resin with an average particle size of 5 μm (Mohs hardness 7, True specific gravity 1.3) M-4: Monodisperse polymethyl methacrylate having a monodispersity of 10% and an average particle size of 5 μm M-5: Monodisperse spherical silica having a monodispersity of 10% and an average particle size of 5 μm.

Example 2 (Preparation of silver halide grains) In 900 ml of pure water, 7.5 g of gelatin and 10 mg of potassium bromide were dissolved and the temperature was adjusted to 3
After adjusting the pH to 5 ° C. and the pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and a controlled double jet while maintaining an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (96/4) at pAg 7.7. The method was added over 10 minutes. Thereafter, 4-hydroxy-6-methyl-1,
0.3 g of 3,3a, 7-tetrazaindene was added and Na was added.
Adjust the pH to 5 with OH and average particle size 0.06μ
m, coefficient of variation of projected diameter area 8%, {100} surface ratio 8
6% of cubic silver iodobromide grains were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and after desalting, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5. Thereafter, the temperature was raised to 60 ° C., 2 mg of sodium thiosulfate was added, the mixture was aged for 100 minutes, and then cooled to 38 ° C. to complete the chemical sensitization to obtain silver halide grains.

(Preparation of Organic Fatty Acid Silver Emulsion) 300 ml of water
10.6 g of behenic acid was put therein, dissolved by heating at 90 ° C., and 31.1 ml of 1N sodium hydroxide was sufficiently stirred.
Was added and left as it was for 1 hour. Then 3
After cooling to 0 ° C., 7.0 ml of 1N phosphoric acid was added, and 0.01 g of N-bromosuccinimide was added with sufficient stirring. Thereafter, the silver halide grains prepared at 40 ° C. were adjusted to 10 mol% as silver based on the behenic acid.
The mixture was added while stirring while heating. Further, 25 ml of a 1N aqueous solution of silver nitrate was continuously added over 2 minutes, and the mixture was allowed to stand for 1 hour with stirring.

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

(Composition of photosensitive layer) Organic fatty acid silver emulsion 1.75 g / m ^{2 of} silver pyridinium hydrobromide perbromide 1.5 × 10 ⁻⁴ mol / m ² Calcium bromide 1.8 × 10 ⁻⁴ mol / m ² 2- (4-chlorobenzoyl) benzoic acid 1.5 × 10 ⁻³ mol / m ² sensitizing dye (described above) 4.2 × 10 ⁻⁶ mol / m ² 2-mercaptobenzimidazole 3.2 × 10 ^{− 3} mol / m ² 2-tribromomethylsulfonylquinoline 6.0 × 10 ⁻⁴ mol / m ² hydrazine derivative 0.5 × 10 ⁻¹ mol / m ² shown in Table 2 As a solvent, methyl ethyl ketone, acetone and methanol were used. Used as appropriate.

(Surface Protective Layer Composition) A surface protective layer coating solution was prepared as follows.

Cellulose acetate 4 g / m ² 1,1 bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane 4.8 × 10 ⁻³ mol / m ² Phthalazine 2 × 10 ⁻³ mol / m ² 4-methylphthalic acid 1.6 × 10 ⁻³ mol / m ² Tetrachlorophthalic acid 7.9 × 10 ⁻⁴ mol / m ² Tetrachlorophthalic anhydride 9.1 × 10 ^-4 mol / m ² silicon dioxide (particle size 2 μm) 20 mg / m ^{2 As a} solvent, methyl ethyl ketone, acetone and methanol were used as appropriate.

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

Cellulose acetate 4 g / m ² Dye-A (supra) 0.06 g / m ² Dye-B (supra) 0.018 g / m ² Silicon dioxide (particle size 10 μm) 50 mg / m ² Methyl ethyl ketone, acetone and methanol were used as appropriate.

Each coating solution having the above composition was applied to a biaxially stretched polyethylene terephthalate film having a thickness of 120 μm and dried to obtain a coated sample.

<Evaluation of Thermal Dimension Change> Horizontal transport type automatic developing machine (1) in which the rollers of the heating unit are staggered rollers, horizontal transport type automatic developing machine (2) in which the rollers of the heating unit are opposing rollers, belt transport Each of the horizontal transport type automatic developing machines (3) having a mold heating section was subjected to a developing treatment at 115 ° C. for 30 seconds, and the expansion and contraction of the film before and after the heat development was measured to calculate the expansion and contraction ratio with respect to the original support. FIG. 1 shows a model diagram of the arrangement of the rollers in the heating section of each automatic developing machine.

<Evaluation of Development Stability> The photothermographic material prepared as described above was exposed to xenon flash light having a light emission time of 10 ^-3 seconds through an interference filter having a peak at 780 nm. Development is performed by Top to Top in each automatic processor.
Evaluation was made at Top 48 seconds and 40 seconds. The reciprocal of the exposure amount giving a density of 3.0 was defined as the sensitivity and indicated by relative sensitivity.

Table 2 shows the results.

[0197]

[Table 2]

[0198]

According to the photothermographic material of the present invention, a high-contrast, high-density image can be obtained by containing a high-contrast agent, and the image has excellent storability, abrasion resistance and transportability. Small dot reproducibility when printing on a PS plate as a manuscript can be compatible,
Also, it has excellent dimensional stability before and after thermal development.

[Brief description of the drawings]

FIG. 1 is a model diagram illustrating a roller arrangement of a heating unit of an automatic developing machine.

Continued on the front page F-term (reference) 2H112 AA03 AA11 BA07 BA08 BC22 2H123 AB00 AB02 AB03 AB23 AB28 BA00 BA01 BA32 BA48 BA49 BB00 BB02 BB16 BB20 BB31 CA16 CA22 CA40 CB00 CB07 EA07

Claims (14)

[Claims] 1. A support comprising a photosensitive silver halide, an organic silver salt, a reducing agent, a binder, and at least one selected from hydrazine and a quaternary onium salt, and a benzoguanamine-formaldehyde resin, benzoguanamine-melamine- A photothermographic material comprising at least one organic powder selected from a formaldehyde resin and a melamine-formaldehyde resin. 2. The photothermographic material according to claim 1, wherein the organic powder has a Mohs hardness of 5 or more and a true specific gravity of 0.8 to 2.5. 3. The photothermographic material according to claim 1, wherein the organic powder is contained in an outermost surface layer. 4. The photothermographic material according to claim 3, wherein the outermost surface layer contains a metal oxide having a Mohs hardness of 8 or more. 5. The photothermographic material according to claim 3, wherein the outermost surface layer contains at least one selected from fatty acids and fatty acid esters. 6. The photothermographic material according to claim 1, wherein the thickness of the support is 110 to 150 μm. 7. The method according to claim 1, wherein the thickness of the photosensitive layer containing silver halide is 3 to 15 μm.
7. The photothermographic material according to item 3, 4, 5 or 6. 8. The method according to claim 1, wherein the amount of silver contained in the photosensitive layer is 0.3.
The photothermographic material according to claim 7, characterized in that the to 1.5 g / m ^2. 9. An image forming method, comprising exposing the photothermographic material according to claim 1 to an image with a laser beam. 10. The laser beam has a wavelength of 700 to 10
The image forming method according to claim 9, wherein the thickness is in a range of 00 nm. 11. The photothermographic material according to claim 9, wherein the photothermographic material is horizontally conveyed and thermally developed through preheating.
0. The image forming method according to item 1. 12. A combination of preheating and thermal development, for a total of 45
The image forming method according to claim 11, wherein the method is performed within seconds. 13. A photothermographic material having a photosensitive silver halide, an organic silver salt, a reducing agent, a binder, and at least one selected from hydrazine and a quaternary onium salt on a support, and a roller in a heating section is provided. An image forming method, wherein heat development processing is performed by a horizontal transport type automatic developing machine as an opposing roller, and a thermal dimensional change before and after the processing is set to 0.01% to 0.05%. 14. A belt-conveying heating unit comprising a support and a photothermographic material comprising a photosensitive silver halide, an organic silver salt, a reducing agent, a binder and at least one selected from hydrazine and a quaternary onium salt. Heat development processing with a horizontal transport type automatic developing machine having a thermal dimensional change rate before and after processing of 0.0
An image forming method, wherein the content is 1% to 0.05%.