JP2000098533A - Novel halogen radical releasing agent, heat-developable photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the novel halogen radical releasing agent superior in storage stability and capable of rapidly releasing a halogen radical by allowing the radical releasing agent to be caused to change its chemical structure by being oxidized. SOLUTION: The halogen radical releasing agent is caused to change its chemical structure by being oxidized and it is represented by the formula in which L is a reducing agent functioning in accordance with the Kendall-Pervtz Rules; Q is a divalent bonding electron withdrawing group; each of X1 and X2 is a halogen atom; A is a group having a Hammett's substituent constant σp of >=0.15; each of (n) and (m) is 0 or 1. When this halogen radical releasing agent is added to the heat-developable photographic sensitive material, its addition is not especially limited but it is preferred to add it in an amount of 10-4-1 mol/mol Ag, especially, 10-3-0.3 mol/mol Ag.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel halogen radical releasing agent, a photothermographic material and an image forming method.

[0002]

2. Description of the Related Art Halogen radical releasing agents are widely used as an exposure visible image forming agent for printing plates, photoresist materials, or acid generators for direct printing plates. In recent years, an image is formed by a heat development process collectively called "dry silver" containing a reducible silver source (for example, an organic silver salt), a catalytic amount of a photocatalyst (for example, silver halide), and a reducing agent in a binder matrix. The photographic light-sensitive material that forms the ink is widely used especially as a light-sensitive material for output of a laser imager for medical use, and a halogen radical releasing agent plays a very important role as an image stabilizer and an antifoggant. . However, conventionally used halogen radical releasing agents have a disadvantage that they easily release halogen radicals during storage, and the raw preservability of the material is poor. In addition, when used in "dry silver" heat-developable photographic light-sensitive materials, there is a disadvantage that the effect of image stabilization is insufficient. In particular, when applied to a heat-developable photographic light-sensitive material for a medical laser imager or a heat-developable photographic light-sensitive material for output of a printing imagesetter containing a high contrast agent and having an oscillation wavelength of 600 nm to 800 nm. Further has the disadvantage that the silver tone of the silver halide tends to deteriorate.

[0003]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a halogen radical releasing agent which is excellent in storage stability and rapidly releases a halogen radical.

A second object of the present invention is to provide a heat-developable photographic material having good raw storability and an image forming method thereof.

A third object is to contain a heat-developable photographic light-sensitive material for a laser imager for medical use or a high-contrast agent which has good raw storability and image storability and good color tone of image silver. The present invention provides a photothermographic material for output of a printing imagesetter having an oscillation wavelength of 600 nm to 800 nm, and an image forming method thereof.

[0006]

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

[0007] 1. A halogen radical releasing agent characterized in that a chemical structure is changed by being oxidized.

[0008] 2. The halogen radical releasing agent according to 1, wherein the halogen radical releasing agent is represented by the following general formula (1).

[0009]

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[Wherein, L represents a reducing group according to the Kendall-Peltz rule, Q represents a divalent linking group, and EWG represents an electron-withdrawing divalent linking group. X ₁ and X ₂ represent a halogen atom, and A represents a Hammett's substituent constant σp value of 0.3.
Represents 15 or more groups. n and m represent 0 or 1, and k represents an integer of 1 to 3. ] 3. 3. The halogen radical releasing agent according to 2, wherein the reducing group according to the Kendall-Perz rule has at least one partial structure selected from benzenediol, aminophenol, hydrazine and aminopyrazolone.

4. A heat-developable photographic light-sensitive material comprising, on a support, at least one of an organic silver salt, a binder, a photosensitive silver halide, and a halogen radical-releasing agent as described in any one of 1 to 3 above.

5. At least one photosensitive layer containing an organic silver salt, a binder and a photosensitive silver halide is provided on a support.
In a heat-developable photographic light-sensitive material having a layer,
4. A photothermographic material comprising at least one halogen radical-releasing agent according to any one of claims 1 to 3.

6. 6. The photothermographic material according to item 4 or 5, further comprising a hydrazine compound.

7. 7. An image forming method for a photothermographic material, comprising exposing the photothermographic material according to any one of the above items 4 to 6 using a laser light source.

Hereinafter, the present invention will be described in detail.

The halogen radical releasing agent of the present invention will be described in more detail.

In the present invention, the phrase “the chemical structure is changed by being oxidized” preferably means that “a part of the structure of the halogen radical releasing agent is oxidized to be more electron-withdrawing than before it is oxidized. It is preferable for the expression of the effects of the present invention that the halogen radical is more easily released as compared to before the oxidation.

Next, the compound represented by formula (1) will be described in detail.

In the general formula (1), L represents a reducing group conforming to the Kendall-Peltz rule.
More specifically about the Peltz rule, The Theory o
fthe Photographic Process
4th. Edition (1977) H. Ja
It is shown in mes chapter 11, pages 298 et seq. As the reducing group according to the Kendall-Peltz rule represented by L, a group represented by the following general formula (2) is preferably mentioned.

Formula (2) a- (Y ₁ = Y ₂ ) _n2 -a 'wherein a and a' each independently represents a group selected from a hydroxyl group, a salt of a hydroxyl group, and an amino group. May be further substituted. Y ₁ and Y ₂ each independently represent a carbon atom or a nitrogen atom. n2 represents an integer of 0 or more. As the reducing group according to the Kendall-Peltz rule, for example, preferably benzenediol, naphthalene diol, aminophenol, bisphenol,
3-pyrazolidone, hydrazine, hydroxylamine,
Reductone, aminopyrazolone, phenylenediamine,
Pyrogallol, gallate, hydroxycoumarin and the like. Particularly preferred are benzenediol, aminophenol, hydrazine and aminopyrazolone.

A group bonded to L in the general formula (1)

[0022]

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Represents a group directly bonded to at least one of a, a 'and carbon atoms Y ₁ and Y _{2 in} the general formula (2).

The divalent linking group represented by Q preferably includes groups such as alkylene, arylene and heterocycle. Particularly preferred is a heterocyclic group, and among them, a nitrogen-containing 6-membered heterocyclic ring is particularly preferred. Specific examples include heterocycles such as pyridine, pyrimidine, pyrazine, pyridazine, triazine, and benzene ring condensates thereof. n represents 0 or 1, but is preferably 0.

The electron-withdrawing divalent linking group represented by EWG is preferably -SO _2- , -SO-, -CO
_{-, - N (R 11)} -SO 2 -, - N (R 11) -CO-,
_{-N (R 1 1) -COO -} , - COCO -, - COO-,
-OCO-, -OCOO-, -SCO-, -SCOO
—, —C (Z ₁ ) (Z ₂ ) — and a divalent substituent or the like formed by any combination thereof (here, R ₁₁
Represents a hydrogen atom or an alkyl group. Z ₁ and Z ₂ represent a hydrogen atom or an electron-withdrawing group. Z ₁ and Z ₂ are not hydrogen atoms at the same time. ). Particularly preferably,
—SO ₂ —, —N (R ₁₁ ) —SO ₂ —, or —C (Z ₁ )
(Z ₂ ) −. The electron-withdrawing group represented by Z ₁ and Z ₂ is preferably a substituent having a Hammett's substituent constant σp value of 0.01 or more, more preferably 0.1 or more. Regarding Hammett's substituent constant,
Journal of Medicinal Chem
istry, 1973, Vol. 16, No. 11,1
207-1216 can be referred to. Examples of the electron-withdrawing group include a halogen atom (a fluorine atom (σ
p value: 0.06), chlorine atom (σp value: 0.23), bromine atom (σp value: 0.23), iodine atom (σp value:
0.18)), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σp value:
0.33), trifluoromethyl (σp value: 0.5)
4)), cyano group (σp value: 0.66), nitro group (σ
p value: 0.78), an aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0.
72)), an aliphatic / aryl or heterocyclic acyl group (eg, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), an alkynyl group (eg, C ₃
H ₃ (σp value: 0.09)), aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σ
p value: 0.45)), carbamoyl group (σp value: 0.3
6) and a sulfamoyl group (σp value: 0.57). m represents 0 or 1, and preferably m is 1. Z ₁ and Z ₂ are preferably a halogen atom, a cyano group or a nitro group. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferred, a chlorine atom and a bromine atom are more preferred, and a bromine atom is particularly preferred.

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

The electron-withdrawing group represented by A is a substituent having a Hammett's substituent constant σp value of 0.15 or more, more preferably 0.2 or more. Examples of the electron-withdrawing group include a halogen atom (a chlorine atom (σp value: 0.
23), bromine atom (σp value: 0.23), iodine atom (σp value: 0.18), trihalomethyl group (tribromomethyl (σp value: 0.29), trichloromethyl (σ
p value: 0.33), trifluoromethyl (σp value: 0.
54)), cyano group (σp value: 0.66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value:
0.72)), an aliphatic aryl or heterocyclic acyl group (for example, acetyl (σp value: 0.50), benzoyl (σp value: 0.43)), an aliphatic aryl or heterocyclic oxycarbonyl group ( For example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σp value
Value: 0.45)), carbamoyl group (σp value: 0.3
6) and a sulfamoyl group (σp value: 0.57).

A is preferably a halogen atom, an aliphatic group,
An aryl or heterocyclic sulfonyl group, an aliphatic / aryl or heterocyclic acyl group, an aliphatic / aryl or heterocyclic oxycarbonyl group, particularly preferably a halogen atom. Among the halogen atoms, a chlorine atom, a bromine atom and an iodine atom are preferred, a chlorine atom and a bromine atom are more preferred, and a bromine atom is particularly preferred.

K represents an integer of 1 to 3, preferably k
Is 1.

Hereinafter, specific examples of the halogen radical releasing agent of the present invention will be listed, but the present invention is not limited thereto.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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Next, the method for synthesizing the halogen radical releasing agent of the present invention will be described in detail with reference to examples. Further, halogen radical releasing agents of the present invention other than those described above can be easily synthesized by the same method.

(Synthesis Example 1: Synthesis of Exemplified Compound R-1) "Reaction Scheme"

[0044]

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10.8 g of phenylhydrazine (I) was dissolved in 50 ml of acetonitrile, and 8.0 g of pyridine was added. The mixture was cooled so that the internal temperature became 10 ° C. or lower, and 35.2 g of tribromomethanesulfonyl chloride (II) was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 2 hours as it was, and insoluble materials were removed by filtration and then concentrated under reduced pressure. The residue was recrystallized from ethyl acetate to obtain 34 g of Exemplified Compound R-1. (Yield 8
0%) The structure was identified by NMR spectrum and MASS spectrum.

(Synthesis Example 2: Synthesis of Exemplified Compound R-23) "Reaction Scheme"

[0047]

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The benzoquinone derivative (III) (17.4 g) and sodium mercaptoacetate (IV) (11.4 g) were dissolved in ethanol (200 ml), and the mixture was heated under reflux for 3 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was recrystallized from methanol to obtain 22.3 g of an intermediate (V). (Yield 8
4%) Next, 27.0 g of caustic soda was dissolved in 200 ml of water, and 18.0 g of the intermediate (V) obtained above was dissolved therein.
After cooling to 5 ° C. or lower, 108 g of bromine was slowly added dropwise. After stirring for 3 hours, the mixture was slowly neutralized with dilute hydrochloric acid until it became approximately neutral. The precipitated crystals were collected by filtration, washed sufficiently with water, and dried. The crude crystals were recrystallized from ethyl acetate to obtain 23.0 g of Exemplified Compound R-23. (Yield 75
%) The structure was identified by an NMR spectrum and a MASS spectrum.

(Synthesis Example 3: Synthesis of Exemplified Compound R-29) “Reaction Scheme”

[0050]

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17.9 g of 2,6-dichloro-4-aminophenol (VI) was dissolved in 50 ml of acetonitrile,
8.0 g of pyridine were added. The internal temperature was cooled to 10 ° C or less, and tribromomethanesulfonyl chloride (I
I) 35.2 g was slowly added dropwise. After completion of the dropwise addition, the mixture was stirred for 2 hours as it was, and insoluble materials were removed by filtration and then concentrated under reduced pressure. The residue was recrystallized from ethyl acetate to give Exemplified Compound R-2.
33.7 g of 9 were obtained. (Yield 68%) The structure was identified by NMR spectrum and MASS spectrum.

(Synthesis Example 4: Synthesis of Exemplified Compound R-46) "Reaction Scheme"

[0053]

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Dissolve 10.8 g of sodium bicarbonate in 100 ml of water,
To this, 14.6 g of mercaptopyridine (VII) was added and dissolved. To this was added 9.8 g of chloroacetic acid,
For 3 hours. After completion of the reaction, the mixture was acidified with diluted hydrochloric acid and extracted with ethyl acetate. The solvent was evaporated to dryness under reduced pressure to obtain 18.7 g of mercaptoacetic acid derivative (VIII) (yield 92).
%).

Next, 40 g of sodium hydroxide was dissolved in 300 ml of water, and 20.4 g of (VIII) was dissolved therein. After cooling to 5 ° C. or lower, 180 g of bromine was slowly added dropwise. 3
After stirring for an hour, the mixture was slowly neutralized with dilute hydrochloric acid until it was approximately neutral. The precipitated crystals were collected by filtration, washed sufficiently with water, and dried. The crude crystals were recrystallized from ethyl acetate to obtain 38.5 g of a bromo compound (IX) (89% yield).

Next, 42.9 g of (IX) was added to 50 parts of ethanol.
The mixture was dissolved in 0 ml, 5.5 g of hydrazine hydrate was added, and the mixture was heated and stirred at 50 ° C. for 5 hours. The solvent was distilled off, and the residue was recrystallized from methanol to give the hydrazino compound (X) in an amount of 40.0%.
g (94% yield).

Next, 42.4 g of (X) was added to ethanol 60
The solution was dissolved in 0 ml, and 26.7 g of the β-ketoester (XI) was added, followed by heating under reflux for 8 hours. The reaction solution was cooled, and the precipitated crystals were collected by filtration to obtain 57.5 g of a pyrazolone compound (XII) (yield 84%).

Next, 68.6 g of (XII) was added to 700 m of acetic acid.
and 7.5 g of sodium nitrite was added slowly. The mixture was stirred vigorously for 3 hours, and the resulting yellow suspension was filtered off, washed with water and then with acetonitrile to obtain 60.7 g of a nitroso compound (XIII) (yield: 85%).

Next, 71.5 g of (XIII) was added to methanol 8
And 5 g of 5% palladium on carbon, concentrated hydrochloric acid 2
0 ml was added and catalytic hydrogenation was performed at normal pressure. After completion of the reaction, the catalyst was filtered off, concentrated under reduced pressure, and the residue was recrystallized from methanol to obtain 54.7 g of Exemplified Compound R-46 (yield: 74%). Structure is NMR spectrum and MASS
Identified by spectrum.

When the halogen radical releasing agent of the present invention is added to a photothermographic material, the amount thereof is not particularly limited, but is preferably from 10 ^-4 mol to 1 mol / mol Ag, particularly preferably 10 ^-3 mol / mol Ag. Molar to 0.3 mole / mole Ag is preferred.

The halogen radical releasing agent of the present invention can be added to a photosensitive layer or a non-photosensitive layer. Preferably, it is a photosensitive layer. Further, it is preferable that the halogen radical releasing agent of the present invention is added after being dissolved in an organic solvent.

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

The silver halide grains are preferably monodisperse grains. The monodisperse particles referred to herein are particles having a degree of monodispersity of 40% or less, more preferably 30% or less, particularly preferably 0.1% or more and 20% or less.
% Or less.

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

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

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

The average particle diameter of the tabular grains is preferably 0.1 μm or less, more preferably 0.01 μm to 0.08 μm.
μm is more preferred. These are disclosed in U.S. Pat.
No. 337, 5,314,798, 5,320,9
No. 58 and the like, and the desired tabular grains can be easily obtained. In the present invention, when these tabular grains are used, the sharpness of an image is further improved.

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

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

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

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

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

The silver halide used in the present invention preferably contains an ion or complex ion of a metal belonging to VIB, VIIB, VIII or IB belonging to a transition metal of the periodic table. The above metals include Cr, W (above VIB
Group): Re (Group VIIB): Fe, Co, Ni, Ru, R
h, Pd, Os, Ir, Pt (above, group VIII): Cu, A
u (more than IB group) is preferable, and when it is used for a photosensitive material for printing plate making, it is preferably selected from Rh, Re, Ru, Ir, and Os.

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

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

Specific examples of the ligand represented by L include halides (fluorides, chlorides, bromides and iodides), cyanides, cyanates, thiocyanates, selenocyanates, tellurocyanates, azides and alcohols. Each ligand of
Nitrosyl, thionitrosyl and the like can be mentioned, and preferred are aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

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

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

[0079] ^{_{1: [RhCl 6] 3- 2}} : [RuCl 6] 3- 3: [ReCl 6] 3- 4: [RuBr 6] 3- 5: [OsCl 6] 3- 6: [CrCl 6] 4 ^{- 7: [Ru (NO)} Cl 5] 2- 8: [RuBr 4 (H 2 O) 2] 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: [ ^{_{u (NS) Cl 5] 2-}} 24: [Re (NS) Cl 4 (SeCN)] 2- 25: [Os (NS) Cl (SCN) 4] 2- 26: [Ir (NO) Cl 5] 2 ^- may be used in ion or complex ion is 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 mol per mol of silver halide.
The amount is suitably from ^10-9 to ^1-10-2 mol, preferably 1 mol.
X 10 ^-8 to 1 X 10 ^-4 mol.

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

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

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

The organic silver salt used in the present invention is a reducible silver source, and a silver salt of an organic acid and a hetero organic acid containing a reducible silver ion source, particularly a long chain (preferably having 10 to 30 carbon atoms). , An aliphatic carboxylic acid having 15 to 25 carbon atoms, and a nitrogen-containing heterocyclic ring are more 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. An example of a suitable silver salt is Research Discl
Osure 17029 and 29996, and include: salts of organic acids (eg, gallic acid,
Salts of oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkylthiourea salts (eg, 1- (3-carboxypropyl) thiourea,
1- (3-carboxypropyl) -3,3-dimethylthiourea); 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 (e.g., salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,
5-thiodisalicylic acid)); silver salts or complexes of thioenes (for example, 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thioene, and 3-
Carboxymethyl-4-thiazoline-2-thioene)); imidazole, pyrazole, urazole, 1,
Complexes or salts of nitrogen acids with silver selected from 2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; saccharin, 5-chlorosalicylaldoxime And silver salts of mercaptides. The preferred silver salt is silver behenate.

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

The organic silver salt can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and is described in a forward mixing method, a reverse mixing method, a simultaneous mixing method, and JP-A No. 9-127643. The controlled double jet method is preferably used.

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

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

The photothermographic material of the present invention preferably contains a reducing agent. Examples of suitable reducing agents are described in U.S. Patent Nos. 3,770,448, 3,773,512,
No. 3,593,863 and Research D
No. 17029 and 29996, and include the following:

Aminohydroxycycloalkenones (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductone esters (eg, piperidinohexose reductone monoacetate) as precursors of reducing agents An N-hydroxyurea derivative (for example, Np-methylphenyl-N
Hydrazones of aldehydes or ketones (e.g. anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (e.g.
Hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone, and (2,5-dihydroxy-phenyl) methylsulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamidoanilines (eg, 4- (N- Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (eg, 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (eg, 1,2,3,4-tetrahydro) Aminooxins; Azines (for example, a combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; Hydroxanoic acids Combinations of azines and sulfonamide phenols; α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives; 5-pyrazolones; sulfonamide phenol reducing agents; 2-phenylindane-1 ,
Chromanes; 1,4-dihydropyridines (for example, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-hydroxy-3- t-butyl-5
-Methylphenyl) methane, bis (6-hydroxy-m
-Tri) mesitol, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
4,5-ethylidene-bis (2-t-butyl-6-methyl) phenol); UV-sensitive ascorbic acid derivatives; 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols.

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

[0092]

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

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

[0095]

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[0096]

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The amount of the reducing agent including the compound represented by the formula (A) is preferably 1 × per mole of silver.
10 ^-2 to 10 mol, particularly preferably 1 × 10 ^{-2 to} 1.5
Is a mole.

Binders suitable for the photothermographic material of the present invention are transparent or translucent, generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic,
Polyvinyl alcohol, hydroxyethyl cellulose,
Cellulose acetate, cellulose acetate butyrate, polyvinylpyrrolidone, casein, starch, polyacrylic acid, polymethylmethacrylic acid, polyvinyl chloride, polymethacrylic acid, copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly ( Styrene-butadiene), polyvinyl acetals (e.g., polyvinyl formal and polyvinyl butyral), polyesters, polyurethanes, phenoxy resins, polyvinylidene chloride, polyepoxides, polycarbonates, polyvinyl acetate, cellulose esters, and polyamides. These may be hydrophilic or non-hydrophilic.

[0099] In the present invention, the binder of the photosensitive layer is preferably 1.5~6g / m ^2, more preferably from 1.7~5g / m ^2. 1.5 g / m ²
If it is less than 1, the density of the unexposed portion is significantly increased, and may not be usable.

In the present invention, a matting agent is preferably contained on the photosensitive layer side. In order to improve the dimensional repetition accuracy of the present invention, a polymer matting agent or an inorganic matting agent is added to all binders on the emulsion layer side. , 0.5 to 10 by weight
%.

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, but is preferably used in order to achieve the object of the present invention. Is a constituent layer other than the photosensitive layer, and is more preferably the outermost layer as viewed from the support.

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

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

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

[0109]

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[Wherein A ₀ represents an aliphatic group, an aromatic group, a -G ₀ -D ₀ group or a heterocyclic group which may have a substituent, B ₀ represents a blocking group, and A ₁ , a ₂ are both hydrogen atoms, or one is a hydrogen atom and the other represents an acyl group, a sulfonyl group or an oxalyl group. G ₀ is a -CO- group,-
A COCO— group, a —CS— group, a —C (＝ NG ₁ D ₁ ) — group,
—SO— group, —SO ₂ — group or —P (O) (G ₁ D ₁ ) —
G ₁ represents a simple bond, —O— group, —S— group or —N (D ₁ ) — group, D ₁ represents an aliphatic group, an aromatic group,
Represents a heterocyclic group or a hydrogen atom, and 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. In the general formula [H], the aliphatic group represented by A ₀ preferably has 1 to 30 carbon atoms, and particularly preferably has 1 to 30 carbon atoms.
Preferred are 20 linear, branched or cyclic alkyl groups such as methyl, ethyl, t-butyl, octyl,
Cyclohexyl group and benzyl group, which are further suitable substituents (for example, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, sulfoxy group, sulfonamide group, sulfamoyl group, acylamino group, ureido group, etc. ) May be substituted.

In the general formula [H], the aromatic group represented by A ₀ is preferably a monocyclic or condensed ring aryl group, for example, 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, and a furan ring; particularly preferred as A ₀ are an aryl group and a heterocyclic group; and the aromatic and heterocyclic groups of A ₀ have a substituent. And particularly preferred groups include pKa7 to
Examples of the substituent having an acidic group of 11 include a sulfonamide group, a hydroxyl group, and a mercapto group.

In the general formula [H], represented by A _0-
The G ₀ -D ₀ group will be described.

G ₀ represents a —CO— group, a —COCO— group,
CS-group, -C (= NG ₁ D ₁ ) -group, -SO- group, -S
Represents an O ₂ — group or a —P (O) (G ₁ D ₁ ) — group, and preferred G ₀ is a —CO— group or a —COCO— group, and particularly preferably a —COCO— group. G ₁ represents a mere bond, —O— group, —S— group or —N (D ₁ ) — group; D ₁ represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom; When a plurality of D ₁ are present, they may be the same or different.

D ₀ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group,
Represents an alkylthio group or an arylthio group, and is preferably D ₀
Examples thereof include a hydrogen atom, an alkyl group, an alkoxy group, an amino group, an aryl group and the like.

In the general formula [H], A ₀ preferably contains at least one diffusion-resistant group or silver halide-adsorbing group. As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. As the ballast group, a photographically inactive alkyl group having 8 or more carbon atoms, alkenyl group, alkynyl group, alkoxy group Group, phenyl group, phenoxy group, alkylphenoxy group and the like.

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.

[0117] In formula (H), B ₀ represents a blocking group, preferably a -G ₀ -D _0, is synonymous with -G ₀ -D ₀ group in A _0, A ₀ and B ₀ are It may be the same or different.

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

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

[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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As the hydrazine compound used in the present invention, the following compounds can be used in addition to the above.

Research Disclosure
Item 23516 (November 1983, p. 3)
46) and references cited therein, as well as U.S. Pat. Nos. 4,080,207, 4,269,929, 4,276,364, 4,278,748, and 4,385. No. 4,108,347, No. 4,478,928, No. 4,560,638, No. 4,686,167, No. 4,912,016, No. 4,988,604 Nos. 4,994,365, 5,041,355, 5,104,769, British Patent No. 2,011,391B, and European Patent No. 217,3
No. 10, No. 301,799, No. 356,898, JP-A-60-179834, JP-A-61-170733,
Nos. 61-270744, 62-178246, 62-270948, 63-29751, 63
No. 32538, No. 63-104047, No. 63-1
Nos. 21838, 63-129337, 63-22
No. 3744, No. 63-234244, No. 63-234
No. 245, No. 63-234246, No. 63-2945
No. 52, No. 63-306438, No. 64-10233
No., JP-A-1-90439, JP-A-1-100530,
No. 1-1055941, No. 1-105943, No. 1-
No. 276128, No. 1-280747, No. 1-283
No. 548, No. 1-283549, No. 1-285940
No. 2-2541, No. 2-77057, No. 2-1
39538, 2-196234, 2-1962
No. 35, No. 2-198440, No. 2-198441
No. 2-198442, No. 2-220042, No. 2-221953, No. 2-221954, No. 2-2
No. 85342, No. 2-285343, No. 2-2898
No. 43, No. 2-302750, No. 2-304550
No. 3-37642, 3-54549, 3-
No. 125134, No. 3-184039, No. 3-240
No. 036, No. 3-240037, No. 3-259240
No. 3-2820038, No. 3-282536, No. 4-51143, No. 4-56842, No. 4-841
No. 34, No. 2-230233, No. 4-96053,
4-216544, 5-45761, 5-4
No. 5762, No. 5-45763, No. 5-45764
No. 5-45765, No. 6-289524, No. 9
-160164 and the like.

Other than these, compounds represented by (Chemical Formula 1) described in JP-B-6-77138, specifically, compounds described on pages 3 and 4 of the same publication. Compounds represented by formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication. JP 6
General formulas (4) and (5) described in JP-A-230497
And compounds represented by formula (6), specifically, compounds 4-1 to 4-
Compounds 5-1 to 5-4 described on page 10, pages 28 to 36
2, and compounds 6-1 to 6-7 described on pages 39 and 40. Compounds represented by formulas (I) and (2) described in JP-A-6-289520, specifically, compounds 1-1) to 1-1 described on pages 5 to 7 of the same.
7) and 2-1). Compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically, compounds described on pages 6 to 19 of the same. JP-A-6-3
Compounds represented by Chemical Formula 1 described in No. 13951, specifically, compounds described on pages 3 to 5 of the same publication. JP-A-7-
A compound represented by the general formula (I) described in No. 5610,
Specifically, Compounds I-1 to I-5 described on pages 5 to 10 of the publication are described.
I-38. The general formula (I) described in JP-A-7-77783.
Compounds represented by I), specifically, pages 10 to 2 of the publication
Compounds II-1 to II-102 described on page 7. JP-A-7-1
General formula (H) and general formula (H
Compounds represented by a), specifically, pages 8 to 15 of the same publication
The compounds described in Compounds H-1 to H-44 on the page can be used.

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

The hydrazine compound of the present invention can be prepared by using a suitable organic solvent such as alcohols (methanol, ethanol,
Propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide,
It can be used by dissolving it in dimethyl sulfoxide, methyl cellosolve or the like. In addition, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, a hydrazine compound powder can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method and used.

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

The photothermographic material of the present invention is stable at normal temperature, but is developed by heating to a high temperature (for example, 80 ° C. to 140 ° C.) after exposure. Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated on the photosensitive 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, and only the photosensitive layer may be formed on the support. It is preferable to form at least one non-photosensitive layer. A filter layer may be formed on the same side as or opposite to the photosensitive layer to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or pigment. . As the dye, a compound described in Japanese Patent Application No. 7-11184 is preferred.
The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitive layer / low-sensitive layer or a low-sensitive layer / high-sensitive layer for adjusting the gradation. Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers. The photothermographic material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

It is preferable to add a color tone agent to the photothermographic material of the present invention. An example of a suitable toning agent is Resea
rc Disclosure No. 17029, which includes:

Imides (for example, phthalimide); cyclic imides, pyrazolin-5-ones and quinazolinones (for example, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,2) Naphthalimides (eg, N-hydroxy-1,8-naphthalimide); Cobalt complexes (eg, hexamine trifluoroacetate of cobalt); Mercaptans (eg, 3-thiazolidinedione);
-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); a combination of phthalazine + phthalic acid; phthalazine (including adducts of phthalazine) 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 (For example, 2,4-dihydroxypyrimidine and tetraazapentalene derivatives (for example, 3,6-dimercapto-1,4-diphenyl-1H, 4H-2,3
a, 5,6a-Tetraazapentalene). Preferred toning agents are phthalazone or phthalazine.

The photothermographic materials of the present invention include, for example, US Pat. Nos. 3,874,946 and 4,756,999.
No. 5,340,712, European Patent No. 605,981A
No. 1, 622, 666A1, 631, 176A1
JP-B-54-165, JP-A-7-2781, JP-A-9-160164, JP-A-9-244178, and JP-A-9-244178
-258367, 9-265150, 9-28
The polyhalogen compounds described in Nos. 1640 and 9-319022 can be preferably used.

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-6-259651.
3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, 4,741,966, 4,751,175, and 4,835. No. 096 can be used. Useful sensitizing dyes for use in the present invention include, for example, Res
ear Disclosure Item1764
Section 3IV-A (p.23, December 1978), Item
m 1831X (August 1978, p. 437). 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, A) Japanese Patent Application Laid-Open No. 60-162247 discloses an argon laser light source.
JP-A-2-48653, U.S. Pat.
No. 331, West German Patent No. 936,071, Japanese Patent Application No. 3-1
JP-A-50-689 discloses simple merocyanines described in JP-A-89532 and B) a helium-neon laser light source.
No. 2425, No. 54-18726, No. 59-1022
Trinuclear cyanine dyes disclosed in JP-A-29-29, Japanese Patent Application No. 6-10
No. 3272, for merocyanines, C) LED light sources and red semiconductor lasers.
Nos. 172, 51-9609 and 55-39818
JP-A-62-284343, JP-A-2-1051
No. 35, No. 35, and D) an infrared semiconductor laser light source.
No. 2, tricarbocyanines described in JP-A-60-80841, JP-A-59-192242, JP-A-Hei 3
The dicarbocyanines containing a 4-quinoline nucleus described in General Formula (IIIa) and General Formula (IIIb) of No. 67267 are advantageously selected. Further, when the wavelength of the infrared laser light source is 750 nm or more, more preferably 800 nm or more.
Sensitizing dyes described in JP-A-6-52387, JP-B-6-52387 and JP-A-3-10931, U.S. Pat. No. 5,441,866, and JP-A-7-13295 are preferably used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Exposure of the photothermographic material of the present invention is performed by using an Ar laser (488 nm) and a He-Ne laser (633n).
m), a red semiconductor laser (670 nm), an infrared semiconductor laser (780 nm, 830 nm) and the like.

[0139]

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

Example 1 (Preparation of silver halide 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, sensitizing dyes SD-1 and SD-2 were added in an amount of 5 × 10 ⁻⁵ mol per mol of silver halide. 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, silver halide grains prepared in advance were added with stirring while heating at 40 ° C. so that the silver amount was 10 mol% with respect to behenic acid. Further, 25 ml of a 1N 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, and the mixture was sufficiently stirred, and allowed to stand still to separate into an ethyl acetate phase containing silver behenate grains and silver halide grains and an aqueous phase. After removing the aqueous phase, silver behenate grains and silver halide grains were collected by centrifugation. Thereafter, 20 g of synthetic zeolite A-3 (spherical) manufactured by Tosoh Corporation and 22 cc of isopropyl alcohol were added, and the mixture was allowed to stand for 1 hour and filtered. Further, 3.4 g of polyvinyl butyral and 23 cc of isopropyl alcohol were added, and the mixture was sufficiently stirred at 35 ° C. at a high speed for dispersion to complete the preparation of the organic fatty acid silver emulsion.

(Composition of photosensitive layer) Organic fatty acid silver emulsion 1.75 g (in silver) / m ² pyridinium hydrobromide perbromide 1.5 × 10 ^-4 mol / m ² Calcium bromide 1.8 × 10 ^-4 mol / m ² 2- (4-chlorobenzoyl) benzoic acid 1.5 × 10 ⁻³ mol / m ² sensitizing dye-1 4.2 × 10 ⁻⁶ mol / m ² developer (reducing agent A-3) 0 × 10 ⁻² mol / m ² 2-mercaptobenzimidazole 3.2 × 10 ⁻³ mol / m ² Halogen radical releasing agent of the present invention, comparative compound (described in Table 1) 6.0 × 10 ⁻⁴ mol / m ^{As the two} solvents, methyl ethyl ketone, acetone, and methanol were appropriately used.

[0144]

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

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

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

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

[0149]

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Thickness 1 biaxially stretched with the above composition
A 75 μm polyethylene terephthalate film was applied and dried to obtain a coated sample.

<< Evaluation Method >>"Evaluation of Sensitometry"
Process the photothermographic material prepared above to half-cut size,
An 830 nm laser diode was exposed with a beam tilted 13 ° from the vertical. Then use a heat drum for 1
Heat development was performed at 20 ° C. for 15 seconds. The fog value at that time was measured. Further, the sensitivity (reciprocal of the ratio of the exposure amount giving a density higher than fog by 1.0) was measured. Sample No. in Table 1 When the sensitivity of 1 was set to 100, the sensitivity of each sample was evaluated by a relative value. Table 1 shows the results.

[Evaluation of Raw Preservation]
After putting three coated samples in a closed container maintained at 5%, 5
Aged at 0 ° C. for 7 days (forced aging). The second sample in this and a sample for comparison with time (stored in a light-shielding container at room temperature) were subjected to the same treatment as that used for the evaluation of sensitometry, and the concentration of the fog portion was measured. Table 1 shows the results.

(Increase in fog 1) = (fog during forced aging) − (fog during aging for comparison) “Evaluation of image preservability”: 25 samples of two samples treated in the same manner as in the sensitometric evaluation The other sheet was stored for 7 days at 25 ° C. and 55% light-shielded, and the other sheet was exposed to natural light at 25 ° C. and 55% for 7 days. Table 1 shows the results.

(Increase in fog 2) = (Fog when exposed to natural light)-(Fog when preserved from light) A sample treated in the same manner as in the "Evaluation of silver tone of image" sensitometric evaluation is visually evaluated. did. A sample having a preferable "cool black tone" was judged as "O", and a sample having an unfavorable "warm black tone" in image diagnosis or appreciation was judged as "x". Table 1 shows the results
Shown in

[0155]

[Table 1]

As is clear from Table 1, the sample of the present invention has sufficient sensitivity, low fog, good raw storability and image storability of the photographic material, and a silver color tone of the image silver is preferable. Black tone ”.

Example 2 [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 was coated on both sides with 8 W / m 2. Apply a corona discharge treatment for ² minutes, apply the following undercoating coating solution a-1 on one surface so as to have a dry film thickness of 0.8 μm, and dry to form an undercoating layer A-1. Was coated with the following undercoating coating solution b-1 so as to have a dry film thickness of 0.8 μm and dried to obtain an undercoating layer B-1.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30% by weight) t-butyl acrylate (20% by weight) Styrene (25% by weight) 2-hydroxyethyl acrylate (25% by weight) copolymer latex liquid (Solid content 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish to 1 liter with water << 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 Subbing Upper Layer >> Gelatin 0.4 g / m ² Weight (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g Silica particles ( (Average particle size: 3 μm) 0.1 g Finished to 1 liter with water << Lower 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

[0160]

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[0161]

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(Preparation of Photosensitive Emulsion A) Preparation of Silver Halide Emulsion 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, the temperature was adjusted to 35 ° C. and the pH was adjusted to 3.0. 370 ml of an aqueous solution containing 74 g, an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (98/2), and rhodium chloride were added in an amount of 1 × 10 6 per mole of silver.
^-4 mol was added over 10 minutes by a controlled double jet method, keeping the pAg at 7.7. Then 4-
0.3 g of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, the average particle size was 0.06 μm, the variation coefficient of the projected diameter area was 8%, and [100 ] Cubic silver iodobromide grains having an area ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting, and then 0.1 g of phenoxyethanol was added.
H5.9 and pAg7.5 were adjusted to obtain a silver halide emulsion.

According to the method of Example 1 of JP-A-9-127463, silver behenate was prepared by the following method.

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

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

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

Preparation of Photosensitive Emulsion A To this silver behenate dispersion, 0.01 mol of each of the above-mentioned silver halide emulsions was added, and 100 g of a solution of polyvinyl acetate in n-butyl acetate (1.2 wt%) was further added with stirring. After gradually adding to form a floc of the dispersion, remove the water,
After two further water washes and removal of water, polyvinyl butyral (average molecular weight 3000) was used as a binder.
5wt% butyl acetate and isopropyl alcohol 1:
2 After adding 60 g of the mixed solution with stirring, polyvinyl butyral (average molecular weight of 40) was added as a binder to the gel-like mixture of behenic acid and silver halide thus obtained.
00) and isopropyl alcohol, and dispersed to prepare a photosensitive emulsion A.

The following layers were sequentially formed on a support to prepare a sample. The drying was performed at 75 ° C. for 5 minutes.

Coating on back side: A liquid having the following composition was applied to a wet thickness of 80 μm.

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

[0171]

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Photosensitive layer surface side coating Photosensitive layer 1: A solution having the following composition was coated at a silver amount of 2.0 g /
m ² , polyvinyl butyral as a binder.
It was applied so as to be ² g / m ² .

Photosensitive Emulsion A Amount of 3 g / m ² in terms of silver sensitizing dye-1 (0.1% DMF solution) 2 mg Halogen radical releasing agent of the present invention, comparative compound (described in Table 2) (2% acetone Solution) 3 ml Phthalazone (4.5% DMF solution) 8 ml Developer (reducing agent A-3) (10% acetone solution) 13 ml Hardening agent H-33 (1% methanol / DMF = 4: 1 solution) 2 ml Surface protection Layer: A solution having the following composition was applied on each photosensitive layer so as to have a wet thickness of 100 μm.

Acetone 175 ml 2-propanol 40 ml methanol 15 ml cellulose acetate 8.0 g phthalazine 1.0 g 4-methylphthalic acid 0.72 g tetrachlorophthalic acid 0.22 g tetrachlorophthalic anhydride 0.5 g monodisperse having an average particle size of 4 μm 1% (W / W) with respect to silica binder << Evaluation Method >>"Evaluation of sensitometry" The photothermographic material prepared above was interposed with an interference filter having a peak at 633 nm, and emitted for 10 ^-3 seconds. Exposure was performed with xenon flash light. Thereafter, heat development was performed at 115 ° C. for 15 seconds using a heat drum. The reciprocal of the exposure amount giving a density of 3.0 was defined as the sensitivity, and the sample No. The sensitivity was indicated by relative sensitivity with the sensitivity of 21 being 100. Also, the slope of the straight line connecting the points of density 0.1 and 1.5 in the characteristic curve is shown as a gradation (γ0115) that represents leg separation. Table 2 shows the results.

[Evaluation of Raw Preservability]
After putting three coated samples in a closed container maintained at 5%, 5
Aged at 0 ° C. for 7 days (forced aging). The second sample in this and a sample for comparison with time (stored in a light-shielding container at room temperature) were subjected to the same treatment as that used for the evaluation of sensitometry, and the concentration of the fog portion was measured. Table 2 shows the results.

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

(Increase in fog 2) = (Fog when exposed to natural light)-(Fog when preserved from light) A sample which has been subjected to the same processing as the "Evaluation of silver tone of image" sensitometric evaluation is visually evaluated. did. A sample having a preferable "cool black tone" was judged as "O", and a sample having an unfavorable "warm black tone" in image diagnosis or appreciation was judged as "x". Table 2 shows the results
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[0178]

[Table 2]

As is clear from Table 2, the sample of the present invention has sufficient sensitivity, high gamma, good contrast,
Further, the fog is low, the raw storability of the photosensitive material and the image storability are good, and the silver tone of the image silver is "cool black tone".

[0180]

According to the present invention, it is possible to provide a halogen radical releasing agent which is excellent in storage stability and rapidly releases a halogen radical. Secondly, a heat-developable photographic light-sensitive material having good raw storability and an image forming method thereof can be provided. Third, a heat-developable photographic light-sensitive material for a laser imager for medical use, which has good raw storability and image storability and a good color tone of image silver, or a high contrast agent, and has a wavelength of 600 nm to 800 nm. Thus, a photothermographic material for output of a printing imagesetter having an oscillation wavelength can be provided and a method for forming an image thereof.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 213/74 C07D 213/74 4C048 213/76 213/76 4C054 215/40 215/40 4C055 217/22 217 / 22 4C063 217/24 217/24 4C204 231/22 231/22 Z 239/54 241/22 241/22 251/24 251/24 295/12 Z 295/12 303/27 303/27 307/62 307 / 62 401/04 231 401/04 231 239/55 F term (reference) 2H025 AA02 AA11 AB08 AC08 BE08 CC02 CC20 2H123 AB00 AB03 AB23 AB29 BB00 BB02 BB31 CA00 CA22 CB00 CB03 4C031 KA05 4C034 AL03 AM12 4C037A03 CC03A03 CC XX01 4C054 AA02 BB03 CC01 DD04 DD08 EE01 FF30 4C055 AA01 BA01 BA02 BA03 BA46 BA52 BB02 BB07 BB17 CA01 CA02 CA16 CA27 CA52 CA53 CB02 CB15 CB17 DA01 DA46 DB07 4C063 AA01 BB02 BB07 CC42 DD10 DD12 DD03 DD12

Claims (7)

[Claims] 1. A halogen radical releasing agent characterized in that a chemical structure is changed by being oxidized. 2. The halogen radical releasing agent according to claim 1, wherein the halogen radical releasing agent is represented by the following general formula (1). Embedded image [In the formula, L represents a reducing group according to the Kendall-Peltz rule, Q represents a divalent linking group, and EWG represents an electron-withdrawing divalent linking group. X ₁ and X ₂ represent a halogen atom, and A represents a group having a Hammett's substituent constant σp value of 0.15 or more. n and m represent 0 or 1, and k represents an integer of 1 to 3. ] 3. The halogen radical releasing agent according to claim 2, wherein the reducing group according to the Kendall-Peltz rule has at least one partial structure selected from benzenediol, aminophenol, hydrazine and aminopyrazolone. . 4. A support comprising at least one of an organic silver salt, a binder, a photosensitive silver halide, and a halogen radical releasing agent according to claim 1 on a support. Heat developed photographic photosensitive material. 5. A photothermographic material having at least one photosensitive layer containing an organic silver salt, a binder and a photosensitive silver halide on a support, wherein the photosensitive layer is any one of claims 1 to 3. A photothermographic material comprising at least one halogen radical releasing agent according to claim 1. 6. The photothermographic material according to claim 4, further comprising a hydrazine compound. 7. A method for forming an image on a photothermographic material, comprising exposing the photothermographic material according to claim 4 to light using a laser light source.