JP2000019680A - Heat-developable photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the heat-developable photographic sensitive material for a printing plate having superhigh contrast and scratch resistance and superior in the reproducibility of minute dots by incorporating a hydrazine derivative in the photosensitive layer and/or its adjacent layer and a fluorinated surfactant and a lubricating agent in the outermost layer of the photosensitive material. SOLUTION: The photosensitive material contains photosensitive silver halide and an organic silver salt and a reducing agent for silver ions and a binder, and the photosensitive layer or its adjacent layer contains the hydrazine derivative and the outermost layer of the photosensitive material contains at least ones of the lubricating agent and the fluorinated surfactants so that at least one of the surfactants has one or more 2-20 C hydrophilic hydrocarbon chains and one or more hydrophilic anionic or nonionic or betaine groups, and one part or the total parts of the H atoms of the one or more hydrocarbon chains are substituted with F atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a black and white photothermographic material for printing plate making.

[0002]

2. Description of the Related Art Conventionally, in the field of printing plate making, waste liquid caused by wet processing of an image forming material has become a problem in terms of workability. In recent years, the amount of treated waste liquid has been reduced from the viewpoint of environmental protection and space saving. It is strongly desired. Therefore, there is a need for a technique relating to photothermographic materials for photographic technology, which enables efficient exposure with a laser imagesetter and can form a high-resolution, clear black image. As this technique, for example, US Pat. No. 3,152,904,
No. 3,487,075 and D.C. Morgan
n) "Dry Silver Photographic Material (Dry Sil)
ver Photographic Material
s) "(Handbook of Imaging M
materials, Marcel Dekker, I
nc. 48, 1991) are well known. Since these photosensitive materials are usually developed at a temperature of 80 ° C. or higher, they are called photothermographic materials.

In recent years, in the photographic light-sensitive material for printing plate making, a screening method for forming an image with a smaller halftone dot than before, such as high definition and FM screening, has begun to spread. For such a screening method, a super-hard contrast type photosensitive material in which the density of minute halftone dots is easy to be applied is preferable.

As a photographic technique for obtaining such an ultra-high contrast image, there is disclosed, for example, US Pat. No. 4,269,929 in which a hydrazine derivative is contained in a silver halide photographic light-sensitive material or JP-A-Hei. No. 4-98239 is disclosed.

However, in the conventional photothermographic material as described above, a sufficiently super-high-contrast image has not been obtained. There is a problem that a failure is likely to occur.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a heat-developable photographic material for printing plate making which is super-hard and has excellent scratch resistance and excellent reproducibility of fine halftone dots. is there.

[0007]

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

(1) In a heat-developable photographic material containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions and a binder, a hydrazine derivative is added to a photosensitive layer of the photosensitive material and / or a layer adjacent thereto. And a heat-developable photographic light-sensitive material characterized in that the outermost layer of the light-sensitive material contains at least one or more fluorine-based surfactants and at least one or more sliding agents.

(2) The photothermographic material according to (1), wherein the photosensitive layer and / or its adjacent layer contains at least one kind of amine compound and / or quaternary onium compound.

(3) The photothermographic material according to (1) or (2), which forms a hard image having a gamma of 10 or more.

Hereinafter, the present invention will be described in detail.

First, the fluorine-based surfactant used in the present invention will be described.

Examples of the fluorine-based surfactant used in the present invention include British Patent Nos. 1,330,356 and 1,542,631, and US Pat. No. 3,666,478.
No. 3,888,678 and No. 3,589,906
No., JP-B-52-26687, JP-A-48-4313.
No. 0, No. 49-46733, No. 51-32322,
One hydrocarbon chain in which at least one is a hydrophilic hydrocarbon chain having 2 to 20 carbon atoms as described in JP-A-2-12145, JP-A-3-24657, and JP-B-3-27099. Or more than one, and contains at least one hydrophilic anion group or hydrophilic nonionic group or hydrophilic betaine group, wherein all or part of one or more hydrogen atoms of the hydrocarbon chain is fluorine. A fluorine-containing surfactant characterized by being substituted with an atom.

Preferred examples of these are shown below.

[0015]

Embedded image

[0016]

Embedded image

[0017]

Embedded image

[0018]

Embedded image

In the present invention, the outermost layer of the light-sensitive material contains a fluorinated surfactant.

The amount of addition is generally 1 m ^{2 of} photographic light-sensitive material.
0.5 mg to 100 mg, preferably 1 m
g to 50 mg.

Next, the slipper used in the present invention will be described.

Representative examples of the sliding agent used in the present invention include, for example, US Pat. No. 3,042,522, British Patent 955,061, US Pat. No. 3,080,317.
Nos. 4,004,927 and 4,047,958
No. 3,489,576, British Patent 1,143,1
18, silicon-based sliding agents described in JP-A-60-140341, U.S. Pat.
732,305, 2,976,148, 3,20
No. 6,311; German Patent 1,284,295;
No. 284,294, etc., higher fatty acid-based, alcohol-based, acid amide-based slip agents, British Patent 1,263,722
, Metal soaps described in U.S. Pat. Nos. 3,933,516, and U.S. Pat. Nos. 2,588,765 and 3,121,0.
No. 60, UK Patent No. 1,198,387, etc., ester type and ether type slip agents, US Pat. No. 3,502,43
No. 7 and 3,042,222.

The following are specific examples of compounds of the slip agent used in the present invention, but the present invention is not limited to these.

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

The optimum amount of the slipping agent varies depending on the amount of gelatin in the outermost layer, the type of matting agent, and the like, but is generally 5 mg to 200 mg, preferably 15 mg to 150 mg per 1 m ² per side of the photographic material. It is.

The photosensitive layer of the photographic material of the present invention and / or its adjacent layer contains a hydrazine derivative.

In the present invention, as the hydrazine derivative, a compound represented by the following general formula [H] is preferable.

[0031]

Embedded image

In the formula, A represents an aryl group or a heterocyclic ring containing at least one sulfur atom or oxygen atom, and G represents a-(CO) n- group, a sulfonyl group, a sulfoxy group, a -P
(＝ O) represents an R ₂ — group or an iminomethylene group;
Represents an integer of 1 or 2; A ₁ and A _{2 each} represent a hydrogen atom or one of them is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group or a substituted or unsubstituted acyl group; Represents a substituted or unsubstituted alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, amino group, carbamoyl group, or oxycarbonyl group. R ₂ is a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group,
Represents an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, an amino group, or the like.

Among the compounds represented by the general formula [H], more preferred are the compounds represented by the following general formula [Ha].

[0034]

Embedded image

In the formula, R ¹ is an aliphatic group (eg, octyl group, decyl group), an aromatic group (eg, phenyl group, 2-hydroxyphenyl group, chlorophenyl group) or a heterocyclic group (eg, pyridyl group, chenyl group, Furyl group),
As these groups, those further substituted with a suitable substituent are preferably used. Further, R ¹ preferably contains at least one ballast group or silver halide adsorption promoting group.

As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, an alkyl group having a carbon number of 8 or more which is relatively inert to photographic properties, for example, an alkyl group Alkenyl group, alkynyl group, alkoxy group, phenyl group, phenoxy group, alkylphenoxy group and the like.

The silver halide adsorption promoting groups include thiourea, thiourethane, mercapto, thioether,
Examples include a thione group, a heterocyclic group, a thioamide heterocyclic group, a mercapto heterocyclic group, and an adsorptive group described in JP-A-64-90439.

In the general formula [Ha], X represents a group that can be substituted on a phenyl group, m represents an integer of 0 to 4,
Is 2 or more, X may be the same or different.

In the general formula [Ha], A ₃ and A ₄ have the same meaning as A ₁ and A ₂ in the general formula [H], and preferably both are hydrogen atoms.

In the general formula [Ha], G represents a carbonyl group, a sulfonyl group, a sulfoxy group, a phosphoryl group or an iminomethylene group, and G is preferably a carbonyl group.

In the general formula [Ha], R ² represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an allyl group, a heterocyclic group, an alkoxy group, a hydroxyl group, an amino group,
Represents a carbamoyl group or an oxycarbonyl group. Most preferred R ² includes a —COOR ₃ group and —CON (R ₄ )
(R ₅₎ groups (R ₃ represents an alkynyl group or a saturated heterocyclic group, R ₄ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, R ₅ is alkenyl A alkynyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group).

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

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

Specific examples of other preferred hydrazine derivatives are (1) to (252) described in US Pat. No. 5,229,248, columns 4 to 60.

The hydrazine derivative according to the present invention can be synthesized by a known method. For example, US Pat.
It can be synthesized by a method as described in columns 59 to 80 of No. 29,248.

The amount of addition may be any amount that makes the contrast high (the amount of the contrast enhancement).
Although the optimum amount varies depending on the degree of chemical sensitization, the type of the inhibitor, etc., it is generally 10 ^-6 to 10 ^-1 per mol of silver halide.
Molar range, preferably from 10 ^-5 to 10 ^-2 mol.

In order to effectively promote the contrast enhancement by the hydrazine derivative, a quaternary onium compound having a quaternary nitrogen compound and / or a quaternary phosphorus compound in the structure, an amine compound, or an alcohol compound having a molecular weight of 120 or more is selected. It is preferable to use at least one nucleation accelerator used.

In the present invention, in order to effectively promote hardening by the hydrazine derivative, the following general formula [Na]
Alternatively, it is preferable to use an amine compound represented by [Nb].

[0054]

Embedded image

In the general formula [Na], R ₁₁ , R ₁₂ , R
₁₃ is a hydrogen atom, an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, an aryl group,
Represents a substituted aryl group. R ₁₁ , R ₁₂ and R ₁₃ can form a ring. Particularly preferred are aliphatic tertiary amine compounds. These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. In order to have diffusion resistance, a compound having a molecular weight of 100 or more is preferable, and a compound having a molecular weight of 300 or more is more preferable.

Preferred examples of the silver halide-adsorbing group include a heterocyclic group-containing compound, a mercapto group, a thioether group, a thione group, and a thiourea group. General formula [Na]
Particularly preferred are compounds having at least one thioether group as a silver halide adsorptive group in the molecule.

Hereinafter, specific examples of these amine compounds represented by the general formula [Na] will be described.

[0058]

Embedded image

[0059]

Embedded image

[0060]

Embedded image

[0061]

Embedded image

In the general formula [Nb], Ar represents a substituted or unsubstituted aromatic or heterocyclic group, and R ₁₄ represents a hydrogen atom, an alkyl group, an alkynyl group or an aryl group.
Ar and R ₁₄ may be linked by a linking group to form a ring.
These compounds preferably have a diffusion-resistant group or a silver halide adsorption group in the molecule. The molecular weight for imparting preferable diffusion resistance is preferably 120 or more, and particularly preferably 300 or more. Specific compounds of the general formula [Nb] include the following.

[0063]

Embedded image

[0064]

Embedded image

Specific examples of other preferred amine compounds are described in JP-A-6-258751, page (13), “006”.
2) to (15), “0065” (2-
Compounds 1) to (2-20) and 3-1 to 3-6 described in JP-A-6-2587551, page (15), "0067" to page (16), "0068".

The above-mentioned amine compound preferably used in the present invention may be a photographic constituent layer on the side of a silver halide emulsion layer,
It may be used for any layer and can be used in the same manner as the hydrazine derivative described above. Also, two or more kinds may be used in combination.

The optimum amount to be added varies depending on the particle size of the silver halide grains, the halogen composition, the degree of chemical sensitization, the type of the inhibitor, and the like, but is generally 10 ^-6 per mol of silver halide.
The range is preferably 10 to 10 ^-1 mol, particularly preferably 10 ^-5 to 10 ^-2 mol.

Next, 4 used in the photographic light-sensitive material of the present invention
The onium salt compound is described. 4 used in the present invention
The onium salt compound is a compound having a quaternary cation group of a nitrogen atom or a phosphorus atom in the molecule, and is preferably a compound represented by the following general formula (P).

[0069]

Embedded image

In the general formula (P), Q represents a nitrogen atom or a phosphorus atom, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X ⁻ represents an anion. Further, R _{1 to} R ₄ may be linked to each other to form a ring.

The substituents represented by R _{1 to} R ₄ include an alkyl group (eg, methyl, ethyl, propyl, butyl, hexyl, cyclohexyl group, etc.), an alkenyl group (eg, allyl, butenyl group, etc.), an alkynyl group (eg, For example, propargyl, butynyl group, etc.), aryl group (phenyl, naphthyl group, etc.), heterocyclic group (eg, piperidinyl, piperazinyl, morpholinyl, pyridyl, furyl, thienyl, tetrahydrofuryl, tetrahydrothienyl, sulfolanyl group, etc.), amino group and the like. No. R _{1 to} R ₄ may be connected to each other to form a piperidine ring, morpholine ring, piperazine ring, quinuclidine ring, pyridine ring,
Examples include a pyrrole ring, an imidazole ring, a triazole ring, and a tetrazole ring. The groups represented by R _{1 to} R ₄ may have a substituent such as a hydroxyl group, 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.

The quaternary onium salt compounds used in the present invention include the following general formulas (Pa), (Pb) and (Pc)
Or a compound represented by the following general formula [T] can be preferably used.

[0075]

Embedded image

In the formula, A ¹ , A ² , A ³ , A ⁴ and A ⁵ represent a group of non-metallic 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. A ¹ , A ² ,
Preferred examples of A ³ , A ⁴ and A ⁵ include 5- to 6-membered rings (rings such as pyridine, imidazole, thiazole, oxazole, pyrazine and 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. Bp is preferably an alkylene group or an alkenylene group.

R ¹ , R ² and R ⁵ each represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. R ¹ and R ² may be the same or different. As the substituent,
The substituents are the same as those described as the substituents for A ¹ , A ² , A ³ , A ⁴ and A ⁵ . Preferred examples of R ¹ , R ² and R ⁵ are each an alkyl group having 4 to 10 carbon atoms. More preferred examples include a substituted or unsubstituted aryl-substituted alkyl group.

[0079] X _p ^- is a counter ion necessary to balance the charge of the whole molecule, for example chloride, bromide,
It represents iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, oxalate and the like. np represents the number of counter ions required to balance the charge of the entire molecule, and np is 0 in the case of an internal salt.

[0080]

Embedded image

The substituents R ₅ and R ₆ of the phenyl group of the triphenyltetrazolium compound represented by the above 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 ([sigma] P = -0.17 or less, and any group having a negative sigma value) can be seen in reports by C. Hansch et al.
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.

The following are specific examples of the quaternary onium salt compounds, but the present invention is not limited thereto.

[0085]

Embedded image

[0086]

Embedded image

[0087]

Embedded image

[0088]

Embedded image

[0089]

Embedded image

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

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

The addition amount of these quaternary onium salt compounds is as follows:
The amount is about 1 × 10 ^-8 to 1 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-1 mol, per mol of silver halide. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol. 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. The amount added to the hydrophilic colloid layer may be an amount according to the above silver halide emulsion layer.

The quaternary onium salt compounds may be used alone or in combination of two or more. Preferably, it is added to the photosensitive layer and / or its adjacent layer.

The details of the photothermographic material are described in, for example, US Pat. Nos. 3,152,904 and 3,457,
No. 075, and D.A. “Dry Silver Photographic Materials (Dry Silver P) by Morgan
photographic Material) ”and D.C.
Morgan and B.A. Shelley
y) "Heat treated silver system (The
rmally Processed Silver-S
systems) "(Imaging Processes and Materials)
es and Materials) Neblette
Eighth Edition, Sturge, V.S. Walworth, A .; Shep
p) Edit, page 2, 1969).
Among them, in the present invention, the photosensitive material is 80 to 140
It is characterized in that an image is formed by heat development at a temperature of ° C. and no fixing is performed. Therefore, the silver halide and the organic silver salt remaining in the unexposed area remain in the photosensitive material without being removed.

In the present invention, after the heat development processing,
The optical transmission density of the light-sensitive material containing the support at 400 nm is preferably 0.2 or less. A more preferable value of the optical transmission density is 0.02 or more and 0.2 or less.

In the present invention, the silver halide grains function as a light sensor. In the present invention, in order to suppress white turbidity after image formation and to obtain good image quality, it is preferable that the average particle size is small, and the average particle size is 0.1 μm or less, more preferably 0.01 μm or less.
m 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 equation is 40 or less. The particle size is more preferably 30 or less, and particularly preferably 0.1% or more and 20% or less.

Monodispersity = (standard deviation of particle size) / (average value of particle size) × 100 In the present invention, the silver halide particles have an average particle size of 0.1.
μm or less and more preferably monodisperse particles,
By setting it in this range, the granularity of the image is also improved.

The shape of the silver halide grains is not particularly limited, but the ratio occupied by the Miller index [100] plane is preferably high, and this ratio is 50% or more, and more preferably 7% or more.
It is preferably at least 0%, particularly preferably at least 80%. The ratio of the Miller index [100] plane is determined by the T.M. Tani, J .; Imaging Sci. , 29,
165 (1985).

Another preferred form of silver halide is tabular grains. The term "tabular grain" as used herein means a vertical thickness h μm where the square root of the projected area is a particle size r μm.
Means that the aspect ratio = r / h is 3 or more. Among them, the aspect ratio is preferably 3 or more and 50 or less. The particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.08 μm.
These are disclosed in U.S. Patent Nos. 5,264,337 and 5,31.
No. 4,798, 5,320,958, and the like, the desired tabular grains can be easily obtained. When these tabular grains are used in the present invention, the sharpness of an image is further improved.

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide. The photographic emulsion used in the present invention is 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, etc. may be used.
Any of a one-side mixing method, a simultaneous mixing method, a combination thereof and the like may be used. The silver halide may be added to the image forming layer by any method, 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 ions or complex ions of a metal belonging to Groups 6 to 10 of the periodic table. The above metals include W, Fe, Co, Ni, Cu, Ru, Rh, P
d, Re, Os, Ir, Pt, and Au are preferred.

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 transition metal selected from the elements of Groups 6 to 10 of the periodic table, L is a bridging ligand, and m is 0, -1, -2 or-.
3 is represented. Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

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

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

[0110] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [IrCl _6] ^{4 -} 7: [Ru (NO) Cl _5] ^2- 8: [RuBr ₄ (H ₂ O)] ^2- 9: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 10: [RhCl ₅ (H ₂ O)] ^2- 11: [Re (NO) Cl _5] ^2- 12: [Re (NO) CN _5] ^2- 13: [Re (NO) ClCN _4] ^2- 14: [Rh (NO) ₂ Cl _4] ^- 15: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 16: [Ru (NO) CN _5] ^2- 17: [Fe (CN) _6] ^3- 18: [Rh (NS) Cl _5] ^2- 19: [Os (NO) Cl _5] ^2- 20: [Cr (NO) Cl _5] ^2- 21: [Re (NO) Cl _5] ^- 22: [Os (NS) Cl ₄ (TeCN )] ^2-23 : [ Ru (NS) Cl _5] ^2- 24: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 25: [Os (NS) Cl (SCN) 4 ] ^2- 26: [Ir (NO) Cl _5] ^{2 -} 27: [Ir (NS) Cl _5] ^2- also may with ions or complex ions one kind of these metals, the metal of the same kind of metal or different may be used alone or in combination. The content of these metal ions or complex ions is generally 1 × 10 ⁻⁹ per mol of silver halide.
~ 1 × 10 ^-2 mol is suitable, preferably 1 × 10 ^-8 mol.
１1 × 10 ^-4 mol. The compound that provides the ion or complex ion of these metals is preferably added during silver halide grain formation and incorporated into the silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, and physical ripening It may be added at any stage before and after chemical sensitization, but is particularly preferably added at the stage of nucleation, growth, and physical ripening, more preferably at the stage of nucleation and growth. Preferably, it is added at the stage of nucleation.
In the addition, it may be added in several portions, may be added uniformly in the silver halide grains, or may be added to the silver halide grains as described in JP-A-63-29603 and JP-A-2-3062.
No. 36, No. 3-167545, No. 4-76534,
As described in JP-A-6-110146, JP-A-5-273683, and the like, 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 or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution are mixed at the same time. To prepare silver halide grains by a method of simultaneous mixing of three liquids, a method of charging a required amount of an aqueous solution of a metal compound into a reaction vessel during grain formation, or a method of preparing silver halide. There is a method in which another silver halide grain doped with a metal ion or a complex ion in advance is sometimes added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound and NaCl and KCl are dissolved together is added to a water-soluble halide solution. When adding to the particle surface, a required amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or at the end of physical ripening, or at the time of chemical ripening.

The photosensitive silver halide grains can be desalted by washing with water by a method known in the art such as a noodle method or a flocculation method, but in the present invention, it may or may not be desalted. .

The photosensitive silver halide grains in the present invention are preferably chemically sensitized. As a preferred chemical sensitization method, a sulfur sensitization method, a selenium sensitization method, and a tellurium sensitization method are well known in the art. Further, a noble metal sensitization method or a reduction sensitization method of a gold compound, platinum, palladium, an iridium compound or the like can be used. As the compound preferably used in the sulfur sensitization method, the selenium sensitization method, and the tellurium sensitization method, known compounds can be used, and the compounds described in JP-A-7-128768 can be used. Examples of tellurium sensitizers include diacyl tellurides, bis (oxycarbonyl) tellurides, bis (carbamoyl) tellurides, diacyl tellurides, bis (oxycarbonyl) ditellurides, bis (carbamoyl) ditellurides, and P = Te Compounds having a bond, tellurocarboxylates, Te-organyltellurocarboxylates, di (poly) tellurides, tellurides, tellurols, telluroacetals, tellurosulfonates, compounds having a P-Te bond, including Te
Heterocycles, tellurocarbonyl compounds, inorganic tellurium compounds, colloidal tellurium, and the like can be used. Compounds preferably used in the noble metal sensitization method are described, for example, in chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide, gold selenide, and US Pat. No. 2,448,060 and British Patent 618,061. The compounds described above can be preferably used. As specific compounds of the reduction sensitization method, in addition to ascorbic acid and thiourea dioxide, for example, stannous chloride, aminoiminomethanesulfinic acid, hydrazine derivatives, borane compounds, silane compounds, polyamine compounds and the like can be used. . When the pH of the emulsion is 7 or more or pAg
Can be reduced and sensitized by keeping at 8.3 or less. Further, reduction sensitization can be achieved by introducing a single addition portion of silver ion during grain formation.

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, particularly 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
And salts thereof: organic acid salts (eg, salts of gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkylthiourea salts (Eg, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.); a silver complex of a polymer reaction product of an aldehyde and a hydroxy-substituted aromatic carboxylic acid ( For example, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.), hydroxy-substituted acids (eg, salicylic acid, 4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid)) and silver of thiones Salts or complexes (eg,
3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thione, and 3-carboxymethyl-4-thiazoline-2-thione), imidazole,
Pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-
A complex or salt of silver and a nitrogen acid selected from 1,2,4-triazole and benzotriazole; saccharin,
Silver salts such as 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are silver behenate, arachidic acid and / or stearic acid.

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. For example, an organic acid alkali metal salt soap (eg, sodium hydroxide, potassium hydroxide, etc.)
After preparing sodium behenate and sodium arachidate, the above-mentioned soap and silver nitrate are added by a control double jet to prepare crystals of an organic silver salt. At that time, silver halide grains may be mixed.

In the present invention, the organic silver salt has an average particle size of 1
It is preferably not more than μm and monodispersed. The average particle size of the organic silver salt refers to the diameter of a sphere equivalent to the volume of the organic silver salt particles when the particles of the organic silver salt are, for example, spherical, rod-shaped, or tabular particles. The average particle size is preferably 0.01 μm to 0.8 μm, particularly 0.05 μm
０．５0.5 μm is preferred. Monodispersion has the same meaning as that of silver halide, and preferably has a monodispersity of 1 to 30.
It is. In the present invention, the organic silver salt has an average particle diameter of 1 μm.
The following monodisperse particles are more preferable, and an image having a high density can be obtained by setting the content in this range. Further, the organic silver salt preferably has tabular grains having 60% or more of the total organic silver. In the present invention, the tabular grains mean those having an aspect ratio (abbreviated as AR) of 3 or more, which is a ratio between the average particle diameter and the thickness, that is, the following formula.

AR = average particle size (μm) / thickness (μm) In order to form organic silver into these shapes, the organic silver crystal is obtained by dispersing and grinding a binder, a surfactant and the like with a ball mill or the like. Can be

In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably 0.5 g or more and 2.2 g or less per m ² in terms of silver. . With this range, a high-contrast image can be obtained. The amount of silver halide relative to the total amount of silver is at most 50% by weight, preferably at most 25%, more preferably between 0.1% and 15%.

The photothermographic material of the present invention preferably contains a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448, 3,773,512,
No. 3,593,863 and Research D
No. 17029 and 29996, and include the following: Aminohydroxycycloalkenones (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents; N- Hydroxyurea derivatives (eg, Np-methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (eg, anthracenaldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (E.g., hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (e.g., benzenesulfhydroxamic acid) ;
Sulfonamidoanilines (for example, 4- (N-methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (Eg, 1,2,3,4-tetrahydroquinoxaline); amideoxins; azines (eg, a combination of an arylcarboxylic 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; Phenol reducing agents; 2-phenylindane-1,3-dione and the like; chromans; 1,4-dihydropyridines (for example, 2,6-dimethoxy-3,5-
Dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-hydroxy-3-t)
-Butyl-5-methylphenyl) methane, bis (6-hydroxy-m-tri) mesitol,
2,2-bis (4-hydroxy-3-methylphenyl)
Propane, 4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols. Examples of the hindered phenols include compounds represented by the following general formula (A).

[0119]

Embedded image

In the general formula (A), R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, -C ₄ H ₉ , 2,
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.

[0122]

Embedded image

[0123]

Embedded image

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

Binders suitable for the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media, for example: gelatin, gum arabic, poly (Vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid) , Copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinylacetal) s (eg, poly (vinylformal) and poly (vinylbutyral)), poly (ester) Kind, poly ( Urethane), phenoxy resin, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). It may be hydrophilic or non-hydrophilic. In order to protect the surface of the light-sensitive material and prevent abrasion, a non-light-sensitive layer may be provided outside the light-sensitive layer. The binder used for these non-photosensitive layers may be the same as or different from the binder used for the photosensitive layers.

In the present invention, in order to increase the speed of thermal development, the amount of the binder in the photosensitive layer is 1.5 to 10 g / m ^2.
It is preferred that More preferably, 1.7 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 30% based on all binders on the emulsion layer side.

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, as inorganic substances, silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkali described in British Patent No. 1,173,181 etc. An earth metal or a carbonate such as cadmium or zinc can be used as a matting agent. As organic matter,
Starch described in U.S. Pat. No. 2,322,037, Belgian Patent No. 625,451 and British Patent No. 981,19
No. 8 and the like, and starch derivatives described in JP-B-44-3643.
No. 33, Swiss Patent No. 33
No. 0,158, polystyrene or polymethacrylate; U.S. Pat. No. 3,079,257; polyacrylonitrile; U.S. Pat. No. 3,022,16.
An organic matting agent such as polycarbonate described in No. 9 or the like can be used.

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

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

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

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

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

The photothermographic material of the present invention, which forms a photographic image by heat development, comprises a reducible silver source (organic silver salt), a photosensitive silver halide, a reducing agent and, if necessary, silver. It is preferable that the photothermographic material contains a color toning agent which suppresses the color tone of the present invention 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 exposed to a high temperature (for example, 80 ° C. to 14 ° C.).
(0 ° 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.

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 dye layer on the same side as the photosensitive layer and / or an antihalation dye layer, a so-called backing layer, may be formed on the opposite side. A dye or a pigment may be included in the active layer. As the dye used, any compound may be used as long as it has a desired absorption in a desired wavelength range.
For example, JP-A-59-6481, JP-A-59-1824
No. 36, U.S. Pat. No. 4,271,263, U.S. Pat.
594,312, European Patent Publication 533,008, European Patent Publication 652,473, JP-A-2-216140.
JP-A-4-348339, JP-A-7-19143
No. 2, JP-A-7-301890 and the like are preferably used.

It is preferable that these non-photosensitive layers contain the binder and the matting agent described above.

The light-sensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation.

It is preferable to add a toning agent to the photothermographic material of the present invention for the purpose of improving the silver tone after development. Examples of suitable toning agents are Research Discl
No. 17029, which includes the following:

Imides (eg, phthalimide); cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and , 4-thiazolidinedione); naphthalimides (eg, N-hydroxy-1,8-naphthalimide); cobalt complexes (eg, hexamine trifluoroacetate of cobalt), mercaptans (eg, 3
-Mercapto-1,2,4-triazole); N- (aminomethyl) aryldicarboximides (for example,
N- (dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium (isoth
uronium) derivatives and certain photobleaching combinations (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
A combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl -2-benzothiazolinylidene (benzothiazolinylidene))-1-methylethylidene) -2-thio-2,4
-Oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (for example, 4-
(1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3
-Dihydro-1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (for example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); phthalazine + phthalate Acid combinations; phthalazine (including phthalazine adducts) and maleic anhydride,
And phthalic acid, 2,3-naphthalenedicarboxylic acid or o
At least one selected from phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (E.g., 2,4-dihydroxypyrimidine) and tetraazapentalene derivatives (e.g., 3,
6-dimercapto-1,4-diphenyl-1H, 4H-
2,3a, 5,6a-tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

In the present invention, a mercapto compound, a disulfide compound, and a thione compound are contained in order to suppress or accelerate development to control development, to improve spectral sensitization efficiency, to improve storage stability before and after development, and the like. be able to.

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

The photothermographic material of the present invention may contain an antifoggant. What is known as the most effective antifoggant is mercury ion. The use of a mercury compound as an antifoggant in a light-sensitive material is disclosed in, for example, US Pat. No. 3,589,903. 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 4,756,99.
No.9, -C (X ₁ )
(X ₂ ) A heterocyclic compound having one or more substituents represented by (X ₃ ) (where X ₁ and X ₂ are halogen and X ₃ is hydrogen or halogen). Examples of suitable antifoggants include JP-A-9-288328, paragraph [0030].
To [0036] are preferably used. Examples of another preferred antifoggant include paragraphs [0062] to JP-A-9-90550.
[0063] The compound described in [0063]. Still other suitable antifoggants are disclosed in US Pat. No. 5,028,5.
No. 23 and British Patent Application Nos. 9221383.4, 9300147.7 and 9311790.1.

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.

Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and the other forming layers. In the photothermographic material of the present invention, for example, a surfactant, an antioxidant,
Stabilizers, plasticizers, ultraviolet absorbers, coating aids, and the like may be used. These additives and the other additives mentioned above are Research Disclosure Item 1
Compounds described in No. 7029 (pp. 9-15, June 1978) can be preferably used.

The support used in the present invention may be a plastic film (for example, polyethylene terephthalate, polycarbonate, or the like) in order to prevent deformation of an image after development processing.
Polyimide, nylon, cellulose triacetate, polyethylene naphthalate) are preferred.

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 thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm.

A plastic support which has been heat-treated can also be used. The plastics to be employed include the above-mentioned plastics. The heat treatment of the support means that after forming these supports and before the photosensitive layer is applied, at a temperature higher than the glass transition point of the support by 30 ° C. or more,
Preferably at a temperature higher than 35 ° C., more preferably 40 ° C.
It is preferable to heat at a temperature higher than ℃. However, the effect of the present invention cannot be obtained by heating at a temperature exceeding the melting point of the support.

Next, the plastic used will be described.

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

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

In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer can be contained in the constituent layer in order to improve the chargeability. These may be contained in any layer, but are preferably contained in an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat, and the like.
In the present invention, the conductive compounds described in U.S. Pat. No. 5,244,773, columns 14 to 20, are preferably used.

[0154]

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 Photographic Support] <Preparation of PET Subbed Photographic Support> A commercially available biaxially stretched and heat-fixed PET film having a thickness of 100 μm and 8 w / m on both sides. Apply a corona discharge treatment for ² minutes, apply the following undercoating coating solution a-1 on one surface to a dry film thickness of 0.8 μm, and dry to form an undercoating layer A-1. The following antistatic coating undercoating solution b-1 was applied to the surface of
m 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 Finish to 1 liter with water << Undercoat coating solution b-1 >> Butyl acrylate (40% by weight) ) Styrene (20% by weight) Glycidyl acrylate (40% by weight) copolymer latex liquid (solid content 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish to 1 liter with water Then, on the upper surface of the undercoat layer A-1 and the undercoat layer B-1,
A corona discharge of 8 w / m ² · min. Was performed, and the following lower coating liquid a-2 was coated on the lower coating layer A-1 with a dry film thickness of 0.1 μm.
As the undercoat layer A-2, the undercoat layer B-1 is coated on the undercoat layer B-1 with the following undercoat layer coating solution b-2 so as to have a dry film thickness of 0.8 μm. Coated as B-2.

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

[0158]

Embedded image

[0159]

Embedded image

(Heat treatment of support) In the 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.
An aqueous solution (equimolar to silver) containing potassium bromide and potassium iodide in the molar ratio of 2) and K [Ir (NO) Cl ₅ ]
The salt was added by a controlled double jet method at 1 × 10 ^-6 mol per silver mol and the rhodium chloride salt at 1 × 10 ^-4 mol per silver mol while maintaining the pAg at 7.7.
Thereafter, 4-hydroxy-6-methyl-1,3,3a, 7
Cubic iodobromide having an average particle size of 0.06 μm, a monodispersity of 10%, a variation coefficient of the projected diameter area of 8%, and a [100] face ratio of 87% by adding tetrazaindene and adjusting the pH to 5 with NaOH. Silver particles 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 to obtain a silver halide emulsion. Further, it was chemically sensitized with chloroauric acid and inorganic sulfur to obtain a silver halide emulsion A.

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

(Preparation of Preform Emulsion of Organic Acid Silver and Silver Halide Emulsion A) 15.1 g of the above silver halide emulsion A was added to the above organic acid Na solution, and the pH was adjusted to 8.1 with a sodium hydroxide solution. Later 147m of 1M silver nitrate solution
was added over 7 minutes, and the mixture was further stirred for 20 minutes, and the water-soluble salts were removed by ultrafiltration. The resulting organic acid silver particles had an average particle size of 0.8 μm and a monodispersity of 8%. After the floc of the dispersion was formed, water was removed, washed with water six times and water was removed, and dried to obtain a preform emulsion.

(Preparation of photosensitive emulsion) Polyvinyl butyral (average molecular weight: 300
544 g of 0) methyl ethyl ketone solution (17 wt%)
And 107 g of toluene were gradually added and mixed.
Dispersed at 000 psi.

The following layers were sequentially formed on the support,
A sample was prepared. The drying was performed at 60 ° C. for 15 minutes.

Coating on back side: A liquid having the following composition was applied.

Cellulose acetate (10% methyl ethyl ketone solution) 15 ml / m ² dye-B 7 mg / m ² dye-C 7 mg / m ² Matting agent: monodispersity 15% Average particle size 10 μm monodisperse silica 30 mg / m ² C _{9 H 17 -C 6 H 4 -SO 3} Na 10mg / m 2

[0168]

Embedded image

Photosensitive Layer Side Coating Photosensitive Layer 1: A solution having the following composition was coated and the silver amount was 2.1 g / m ^2.
It was applied so that it became.

Preform emulsion 240 g Sensitizing dye-1 (0.1% methanol solution) 1.7 ml Pyridinium bromide perbromide (6% methanol solution) 3 ml Calcium bromide (0.1% methanol solution) 1.7 ml Antifogging Agent-2 (10% methanol solution) 1.2 ml 2- (4-chlorobenzoyl) benzoic acid (12% methanol solution) 9.2 ml 2-mercaptobenzimidazole (1% methanol solution) 11 ml tribromomethylsulfoquinoline (5 % Methanol solution) 17 ml Reducing agent A-4 (20% methanol solution) 29.5 ml Hydrazine compounds shown in Table 1 Quaternary onium compounds shown in Table 1

[0171]

Embedded image

Surface protective layer: A solution having the following composition was applied on the photosensitive layer.

Acetone 35 ml / m ² Methyl ethyl ketone 17 ml / m ² Cellulose acetate 2.3 g / m ² Methanol 7 ml / m ² Phthalazine 250 mg / m ² 4-Methylphthalic acid 180 mg / m ² Tetrachlorophthalic acid 150 mg / m ² Tetrachlorophthale Acid anhydride 170 mg / m ² Matting agent: Monodispersity 10% Average particle size 4 μm Monodispersed silica 70 mg / m ² C ₉ H ₁₇ —C ₆ H ₄ —SO ₃ Na 10 mg / m ² Sliding agent R-20 20 mg / m ² Fluorine-based surfactant F-16 20 mg / m ² Fluorine-based surfactant F-17 2 mg / m ² << Exposure and development treatment >> 1.5 × 10 5 with a laser sensitometer using a semiconductor laser of 810 nm as a light source. Step exposure was performed while changing the amount of light in ^-7 seconds, and heat development was performed at 110 ° C. for 15 seconds. At that time, exposure and development were performed at 23 ° C and 50 ° C.
Performed in a room conditioned to% RH.

The obtained developed sample was subjected to PDA-
The blackening density was measured with a 65 (Konica Digital Densitometer).

Further, in order to evaluate the reproducibility of minute dots of the sample obtained in this way, an imager having a semiconductor laser of 810 nm was used to evaluate the reproducibility of 3000 dots.
Set to output a small point (5% halftone dot), a middle point (50% halftone dot), a large point (95% halftone dot), and a solid (100% halftone dot) at / 300 lpi. Exposure is performed while changing the temperature, and using an automatic developing machine having a heat drum,
Heat development was performed at 10 ° C. for 15 seconds.

The obtained developed sample was subjected to X-Ri
The net% was measured by te361T.

Further, in order to evaluate the scratch resistance,
Middle point at 2400 dpi / 200 lpi (50% halftone dot)
Is set to be output to a large size, and 610 mm × 6
One 1-meter sample roll was continuously processed, and the occurrence of scratches was visually evaluated.

(Evaluation of Gamma) Gamma is represented by the tangent of density 0.1 and 3.0, and it is shown that a super-high contrast image can be obtained only when the gamma value in the table is 10 or more.

(Evaluation method of dot reproducibility of small dot) Small dot (target dot% 5%) at an exposure amount giving a solid density of 5.0
Shows the% of dots actually reproduced on the sample. The value in the table is 5
The closer to%, the better.

(Evaluation of Scratch Resistance) 610 mm × 61
One m roll sample was processed (approximately 100 sheets in total), and the total number of blackened flaws generated was counted. Naturally, the smaller the number, the better. If it exceeds 8, it is a practically problematic level.

Table 1 shows the results of the evaluation.

[0182]

[Table 1]

The outermost layer contains a fluorinated surfactant and a slipping agent, and the photosensitive layer contains a hydrazine compound.
By containing a high-grade onium compound, a heat-developable photographic light-sensitive material for printing plate making having an ultra-high contrast, excellent scratch resistance and excellent reproducibility of fine halftone dots could be obtained.

Example 2 A sensitizing dye, a hydrazine compound,
The quaternary onium compounds were changed to the following compounds, and the slip agent and the fluorinated surfactant in the surface protective layer were changed to the compounds shown in Table 2.

2. Sensitizing dye d-1 (0.5% methanol solution) 2.0 ml Sensitizing dye d-10 (0.5% methanol solution) 1.5 ml Hydrazine compound H-31 (2% methanol solution) 0 ml Amine compound Na-21 (5% methanol solution) 2.0 ml

[0186]

Embedded image

<< Exposure and Development Processing >> 633 n as a light source
1.5 × with a laser sensitometer using a semiconductor laser
Step exposure is performed while changing the amount of light in 10 ^-7 seconds.
The film was thermally developed at 0 ° C. for 15 seconds. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH.

The obtained developed sample was subjected to PDA-
The blackening density was measured with a 65 (Konica Digital Densitometer).

Further, in order to evaluate the reproducibility of minute halftone dots of the sample obtained in this way, an imager having a 633 nm semiconductor laser was used to evaluate the reproducibility of 3000 dots.
Set to output a small point (5% halftone dot), a middle point (50% halftone dot), a large point (95% halftone dot), and a solid (100% halftone dot) at / 300 lpi. Exposure is performed while changing the temperature, and using an automatic developing machine having a heat drum,
Heat development was performed at 10 ° C. for 15 seconds.

The developed sample thus obtained was subjected to X-Ri
The net% was measured by te361T.

Further, in order to evaluate the scratch resistance,
Middle point at 2400 dpi / 200 lpi (50% halftone dot)
Is set to be output to a large size, and 610 mm × 6
One 1-meter sample roll was continuously processed, and the occurrence of scratches was visually evaluated.

(Evaluation of Scratch Resistance) 610 mm × 61
One m roll sample was processed (approximately 100 sheets in total), and the total number of blackened flaws generated was counted. Naturally, the smaller the number, the better. If it exceeds 8, it is a practically problematic level.

The same evaluation as in Example 1 was performed.
Shown in

[0194]

[Table 2]

By containing a fluorinated surfactant and a slippery agent in the outermost layer and a hydrazine compound and an amine compound in the photosensitive layer, a super-high contrast, excellent scratch resistance, and a finer A heat-developable photographic photosensitive material for printing plate making having excellent halftone dot reproducibility was obtained.

[0196]

According to the constitution of the present invention, a heat-developable photographic photosensitive material for printing plate making which has a super-high contrast, excellent scratch resistance and excellent reproducibility of fine halftone dots can be obtained.

Claims (3)

[Claims] 1. A photothermographic material containing a photosensitive silver halide, an organic silver salt, a reducing agent for silver ions and a binder, wherein a hydrazine derivative is contained in a photosensitive layer of the photosensitive material and / or a layer adjacent thereto. A photothermographic material comprising at least one fluorine-based surfactant and at least one sliding agent in the outermost layer of the light-sensitive material. 2. The photothermographic material according to claim 1, wherein the photosensitive layer and / or its adjacent layer contains at least one kind of amine compound and / or quaternary onium compound. 3. The photothermographic material according to claim 1, wherein a high-contrast image having a gamma of 10 or more is formed.