JPH09244177A - Novel polyhalomethane compound and photosensitive material containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably produce a photosensitive material having high sensitivity, ensuring low fog and less liable to variation in the photographic performance by incorporating at least one kind of specified polyhalomethane compd. SOLUTION: This polyhalomethane compd. is represented by formula I, wherein each of R1 -R7 is H or a substituent but at least one of R2 -R7 is a substituent represented by formula II (where Y is CO, SO or SO2 , each of X1 and X2 is a halogen and A is H or an electron withdrawing group). The substituent represented by each of R1 -R7 is, e.g. an alkyl, alkenyl, alkynyl, an aryl or amino, these substituents may further be substd., and in the case of two or more substituents, they may be different from each other.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyhalomethane compound and a light-sensitive material containing the same, and more particularly to a photothermographic material, which is capable of reducing fog and desensitizing the photosensitive material without deteriorating sensitivity or color tone. The present invention relates to a technique for improving storability and image storability.

[0002]

2. Description of the Related Art Polyhalomethane compounds are photopolymerization initiators,
For silver halide photographic materials (especially for photothermographic materials)
It is used for applications such as additives. Photothermographic materials for forming photographic images using the photothermographic processing method are described, for example, in U.S. Pat.
Morgan and B.A. “Thermally Processed Silver System” by Shely
Silver Systems) "(Imaging Processes
And Materials (Imaging Processes and Materi)
als) Neblette 8th Edition, Sturge, V.I. Walworth, A. Shepp editing,
Pp. 2, 1969).

In such a photothermographic material, a reducible silver source (eg organic silver salt), a catalytically active amount of photocatalyst (eg silver halide), and a reducing agent are dispersed in a usual (organic) binder matrix. It is contained in the state. The photothermographic material is stable at room temperature, but at a high temperature (for example,
When heated to 80 ° C. or higher), silver is produced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and the reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the exposure. The silver produced by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas and forms the image. A toning agent for controlling the silver tone of this silver image is optionally used in the light-sensitive material.

The most effective conventional fog prevention technique has been a method using a mercury compound as an antifoggant. The use of mercury compounds as antifoggants in light-sensitive materials is described, for example, in US Pat. No. 3,589,990.
No. 3. However, mercury compounds are not environmentally preferable, and development of a non-mercury antifoggant has been desired. As non-mercury antifoggants, various polyhalogen compounds have hitherto been disclosed (for example, US Pat. No. 3,874,946).
No. 4,756,999, No. 5,340,712, European Patent Nos. 605981A1, 622666A1, 6
31176A1, JP-B-54-165, JP-A-7-
No. 2781) is disclosed, however, the compounds described above have problems that the effect of preventing fogging is low and that the color tone of silver is deteriorated. In addition, those with a high anti-fogging effect have the problems that they cause a decrease in sensitivity, they are partially decomposed during the production of the photosensitive material, and the photographic performance tends to fluctuate due to slight differences in the production conditions. The development of agents was desired.

[0005]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a novel polyhalomethane compound which is effective for use as a photopolymerization initiator, an additive for silver halide photographic light-sensitive materials and the like. A second object of the present invention is deterioration of color tone,
It is intended to provide a light-sensitive material having a low fog without sensitivity deterioration. A third object of the present invention is to provide a light-sensitive material that is stable under the manufacturing conditions of the light-sensitive material and has little fluctuation in photographic performance.

[0006]

The above-mentioned objects can be achieved by the following means. (1) A polyhalomethane compound represented by the following general formula (I). General formula (I)

[0007]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R ₆ and R ₇ each represent a hydrogen atom or a substituent.
However, at least one of R _{2 to} R ₇ is a substituent represented by the following general formula (a). General formula (a)

[0009]

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Y represents --CO--, --SO-- or --SO _2- . X ₁ and X ₂ each represent a halogen atom.
A represents a hydrogen atom or an electron-withdrawing group. )

(2) R ₁ is a hydrogen atom, R ₄
Any one of R ₅ , R ₆ and R ₇ is a group represented by formula (a), Y is —SO ₂ —, and A is
Is a halogen atom, the polyhalomethane compound according to (1).

(3) The polyhalomethane compound according to (1) or (2), wherein R ₇ is a group represented by the general formula (a).

(4) A photosensitive material containing at least one polyhalomethane compound represented by the general formula (I) described in (1), (2) or (3).

(5) A photothermographic material containing at least one polyhalomethane compound represented by the general formula (I) described in (1), (2) or (3).

(6) The photothermographic material according to (5), which is infrared-sensitized for infrared laser exposure.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION First, the polyhalomethane compound represented by the general formula (I) will be described in detail. R ₁ , R
Examples of the substituent represented by ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ include an alkyl group (preferably having 1 to 2 carbon atoms).
0, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, Examples include cyclopentyl and cyclohexyl. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. ), Alkynyl group (preferably having 2 to 2 carbon atoms)
It preferably has 20 carbon atoms, more preferably has 2 to 12 carbon atoms, and particularly preferably has 2 to 8 carbon atoms, and examples thereof include propargyl and 3-pentynyl. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, phenyl, p-
Examples include methylphenyl and naphthyl. ), An amino group (preferably having a carbon number of 0 to 20, more preferably a carbon number of 0 to 10, particularly preferably a carbon number of 0 to 6), and examples thereof include amino, methylamino, dimethylamino, diethylamino and dibenzylamino. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, etc.), aryloxy. Group (preferably having 6 to 2 carbon atoms)
It has 0, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples include phenyloxy and 2-naphthyloxy. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, acetyl,
Examples thereof include benzoyl, formyl and pivaloyl. ), An alkoxycarbonyl group (preferably having 2 carbon atoms)
-20, more preferably 2-16 carbon atoms, particularly preferably 2-12 carbon atoms, for example, methoxycarbonyl,
Ethoxycarbonyl and the like. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, and particularly preferably having 7 to 1 carbon atoms.
0, for example, phenyloxycarbonyl and the like. ), An acyloxy group (preferably having 2 to 2 carbon atoms)
It has 0, more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably having 2 to 10 carbon atoms, for example, acetylamino, benzoylamino, etc.), an alkoxycarbonylamino group ( It preferably has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 carbon atoms.
To 12, for example, methoxycarbonylamino and the like. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 carbon atoms)
To 16, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 2 carbon atoms)
It has 0, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfonylamino and benzenesulfonylamino. ), A sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.) Carbamoyl group (preferably having 1 carbon atom).
-20, more preferably 1-16 carbon atoms, particularly preferably 1-12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio and ethylthio), and an arylthio group (preferably carbon). Number 6 to 20, more preferably carbon 6 to
16, particularly preferably 6 to 12 carbon atoms, such as phenylthio. ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl. ), A sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably having 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl. ), Ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms
12, for example, ureide, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, diethylphosphoramide, phenylphosphoramide and the like. ), Hydroxy group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group,
Heterocyclic groups (eg imidazolyl, pyridyl, furyl,
Piperidyl, morpholino and the like. ). These substituents may be further substituted. When there are two or more substituents, they may be the same or different.

The substituent is preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group. , A sulfonylamino group, a sulfamoyl group, a carbamoyl group, a ureido group, a phosphoric acid amide group, a hydroxy group,
Halogen atom, cyano group, sulfo group, carboxyl group,
Nitro group, hydroxamic acid group, sulfino group, hydrazino group, a heterocyclic group, more preferably an alkyl group,
Aryl group, alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, hydroxy group, halogen atom,
A cyano group and a heterocyclic group, more preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, a halogen atom, a cyano group and a heterocyclic group,
Particularly preferred are an alkyl group, an aryl group, a halogen atom and a heterocyclic group.

Also, R₁, R_Two, R_Three, R_Four, R_Five, R
₆, R₇Are linked to form a ring when possible.
May be. R₁Is preferably a hydrogen atom or an alkyl group.
Group, aryl group, halogen atom, heterocyclic group,
More preferably a hydrogen atom, an alkyl group or a halogen atom.
And more preferably a hydrogen atom. R_Two, R_Three, R
_Four, R_Five, R₆, R₇Preferably, a hydrogen atom,
Alkyl group, aryl group, halogen atom, heterocyclic group or
It is a substituent represented by the general formula (a). However,
R_Two, R_Three, R_Four, R_Five, R₆, R₇At least of
One is a substituent represented by the general formula (a), which is more preferable.
Preferably R_Three, R_Four, R_Five, R₆, R₇At least
And one is a substituent represented by the general formula (a), and more preferably
Or R _Four, R_Five, R₆, R₇At least one of
A substituent represented by the general formula (a), particularly preferably R
_FiveOr R₇Is a substituent represented by the general formula (a),
Yes, most preferably R₇Is represented by the general formula (a)
This is the case when the group is

Y is --CO--, --SO-- or --SO_Two-
Represents, preferably -CO-, -SO _Two− And better
More preferably-SO_Two-.

The halogen atoms represented by X ₁ and X ₂ may be the same or different from each other and include a fluorine atom, a chlorine atom,
A bromine atom or an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably a chlorine atom,
A bromine atom, particularly preferably a bromine atom.

The electron-withdrawing group represented by A is preferably a substituent having a Hammett's substituent constant σ _p value of 0.01 or more, more preferably 0.1 or more.
For Hammett's substituent constants, see Journal of Medicin.
Al Chemistry, 1973, Vol. 16, No. 11, 1207-1216 can be referred to. Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σ _p value: 0.06), chlorine atom (σ _p value: 0.23), bromine atom (σ _p value: 0.2)
3), iodine atom (σ _p value: 0.18)), trihalomethyl group (tribromomethyl (σ _p value: 0.29), trichloromethyl (σ _p value: 0.33), trifluoromethyl (σ _p value: 0.54)), cyano group (σ _p value: 0.6
6), nitro group (σ _p value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σ _p value: 0.72), aliphatic / aryl or heterocyclic acyl group (for example, , Acetyl (σ _p value: 0.5
0), benzoyl (σ _p value: 0.43)), alkenyl group (for example, 3,4- (CH = CHCH = CH) (σ _p value: 0.0
4)), an alkynyl group (for example, C ₃ H ₃ (σ _p value: 0.0
9)), an aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl (σ _p value: 0.4
5), phenoxycarbonyl (σ _p value: 0.45)),
Examples thereof include a carbamoyl group (σ _p value: 0.36) and a sulfamoyl group (σ _p value: 0.57).

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

Among the polyhalomethane compounds represented by the general formula (I), the polyhalomethane compound represented by the general formula (Ix) or the general formula (Iy) is preferable, and the general formula (I) is more preferable. A polyhalomethane compound represented by -x). General formula (I-x)

[0024]

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In the formula, R ₁ has the same meaning as in formula (I), and the preferred range is also the same. R _x2 ,
R _x3 , R _x4 , R _x5 , R _x6 , and R _x7 are each a hydrogen atom or a substituent (as the substituent, for example, those mentioned as the substituents of R _{1 to} R ₇ in the general formula (I) can be applied. Represents). However, among R _x4 , R _x5 , R _x6 , and R _x7 ,
At least one is a substituent represented by the above general formula (a), and preferably R _x7 is a substituent represented by the general formula (a). General formula (I-y)

[0026]

[Chemical 6]

In the formula, R ₁ has the same meaning as in formula (I), and the preferred range is also the same. R _y2 ,
R _y3 , R _y4 , R _y5 , R _y6 and R _y7 are each a hydrogen atom or a substituent (as the substituent, for example, those mentioned as the substituents of R _{1 to} R ₇ in the general formula (I) can be applied. ) Represents. However, at least one of R _y2 and R _y3 is a substituent represented by the general formula (a), and preferably R _y3 is a substituent represented by the general formula (a).

Among the polyhalomethane compounds represented by the general formula (I), the polyhalomethane compounds represented by the general formula (Ia) are more preferable. General formula (Ia)

[0029]

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Where Y, X₁, X_TwoAnd A are respectively
It has the same meaning as those in the general formula (a), and is also preferable.
The same applies to the range. R_a1, R_a2, R_a3, R_a4, R_a5Over
And R _a6Are each a hydrogen atom or a substituent (as a substituent
Is, for example, R in the general formula (I)₁~ R₇As a substituent of
The above can be applied. ).

Among the polyhalomethane compounds represented by the general formula (I), the polyhalomethane compounds represented by the general formula (Ib) are more preferable. General formula (Ib)

[0032]

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In the formula, R _a1 , R _a2 , R _a3 , R _a4 , R _a5 and R _a6 have the same _{meanings as} those in formula (Ia), respectively, and the preferred ranges are also the same.

Specific examples of the polyhalomethane compound represented by the general formula (I) are shown below, but the invention is not limited thereto.

[0035]

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[0036]

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[0037]

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[0038]

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The polyhalomethane compound represented by the general formula (I) of the present invention is, for example, JP-A-54-165, JP-A-6-340611, JP-A-7-2781, and JP-A-7-562.
No. 1, Japanese Patent Publication No. 7-119953, US Pat. No. 5,369.
000, 5374514, 5460938,
5464737, European Patent No. 605981, 63
It can be synthesized according to the method described in 1176 and the like.

For example, when Y is —SO— or —SO ₂ —, it can be synthesized by converting the mercapto-substituted quinoline to a mercaptoacetic acid derivative and then oxidizing / halogenating. The mercapto-substituted quinoline used as a raw material may be a commercially available product, or can be synthesized according to a usual method for synthesizing a mercapto derivative, for example, “New Experimental Chemistry Course, Vol. 14,” 1699-1711 (Chemical Society of Japan). (Ed)
The described method can be applied.

The mercaptoacetic acid derivative can be synthesized from a mercapto-substituted quinoline and a halogen-substituted carboxylic acid derivative. In this case, usual conditions for alkylation of a mercapto group can be applied. This reaction is preferably carried out in the presence of an inorganic base or an organic base, and the base is preferably a tertiary amine, a hydroxide or an alkali carbonate, and more preferably triethylamine, sodium hydroxide, potassium hydroxide, Magnesium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate. The preferred amount of the base is 1 to 10 times mol, more preferably 1 to 5 times mol, of the mercapto-substituted quinoline. Further, this reaction can be carried out without solvent or in the presence of a solvent, but is preferably carried out in the presence of a solvent. The solvent is not limited as long as it does not participate in the reaction, but preferably water, alcohols (for example, methanol, ethanol, 2-propanol, etc.),
Dimethylformamide, dimethylacetamide, nitriles (such as acetonitrile), ethers (such as diethyl ether and tetrahydrofuran), carboxylic acid esters (such as ethyl acetate), and more preferably water and alcohols.

The oxidation / halogenation reaction of the mercaptoacetic acid derivative is carried out by the reaction of hypohalous acid or a salt thereof with a basic aqueous solution as described in, for example, US Pat. No. 3,874,946 and European Patent Publication No. 60598. be able to. Alternatively, the mercaptoacetic acid derivative may be converted into a sulfonylacetic acid derivative or a sulfoacetic acid derivative in advance by using an oxidizing agent such as hydrogen peroxide, and then halogenated to synthesize. In this reaction, it is generally preferable to carry out the reaction using a solvent, and as the solvent, water and alcohols (for example, methanol, ethanol, 2-propanol etc.) are preferable, and water is more preferable.

When Y is --CO--, it can be synthesized by halogenation of an acyl-substituted quinoline. As the raw material, acyl-substituted quinoline, a commercially available product can be used, or it can be synthesized according to a usual method for synthesizing an acyl compound. For example, “New Experimental Chemistry Course Vol. 14” 751 to 875 (edited by the Chemical Society of Japan) ) The method described can be applied.

For the halogenation of the acyl-substituted quinoline, the usual conditions used in the halogenation of a ketone compound can be applied. For example, "New Experimental Chemistry Course Vol. 14" 345-3.
The method described on page 51 (edited by the Chemical Society of Japan) can be applied.

Specific examples of the synthesis of the compound represented by formula (I) are shown below. Synthesis Example 1 Synthesis of compound 1 Synthesis of 8-carboxymethylthioquinoline 8-Mercaptoquinoline (manufactured by Aldrich) 7.0
While stirring 0 g (0.0354 mol), sodium chloroacetate (manufactured by Wako Pure Chemical Industries, Ltd.) 5.8 g (0.0498 mol) and 50 ml of ethanol at room temperature,
Sodium hydroxide 4.84 g (0.121 mol) / water 1
A 5 milliliter aqueous solution was added dropwise. After stirring overnight at room temperature, concentrated hydrochloric acid was added to adjust the pH to about 1. The reaction solution was concentrated, ethanol was added, and the precipitated salt was filtered off (the same operation was repeated twice). The filtrate was concentrated and then recrystallized from ethanol / ethyl acetate to give 8-carboxymethylthioquinoline (5.6 g, 0.0255 mol).
Obtained. 72% yield

Synthesis of 8-tribromomethylsulfonylquinoline (Compound 1) 16.5 g (0.413 mol) sodium hydroxide / water 4
While stirring 40 ml at 0-5 ° C,
Bromine 10.4 ml was slowly added dropwise. Furthermore,
A solution of 5.20 g (0.0237 mol) of 8-carboxymethylthioquinoline obtained in the above reaction, 2.20 g (0.0262 mol) of sodium hydrogencarbonate and 60 ml of water in an internal temperature not to exceed 10 ° C. It was dripped slowly. After the dropping was completed, the temperature was raised to room temperature and the mixture was left overnight. The precipitated solid was collected by filtration, washed with water, and recrystallized from ethanol to give 3.10 g (6.
98 mmol) was obtained. Yield 29.5% Melting point 175-177 ° C

The compound represented by the general formula (I) of the present invention can be added in either the light-sensitive layer or the non-light-sensitive layer. It is preferably a photosensitive layer. The compound represented by the general formula (I) of the present invention varies depending on the desired purpose, but is 10 ⁻⁴ mol to 1 mol / Ag mol, preferably 10 ⁻³ mol to 0.3 mol / Ag.
It is good to add moles. The compound represented by formula (I) of the present invention is preferably added after being dissolved in an organic solvent.

The photothermographic material of the present invention forms a photographic image by using the photothermographic processing method. Such a photothermographic material is disclosed in, for example, US Pat.
No. 152904, 3457075, and D.C. Morgan and B.A. "Thermally Processed SilverSy" by Shely
stems) "(Imaging Processors and
Materials (Imaging Processes and Materials) Neb
lette 8th edition, Sturge, V. Walworth, A. Edited by Shepp, page 2,
1969) and the like.

The heat-developable light-sensitive material of the present invention may be any one capable of forming a photographic image by using a heat-development treatment, including a reducible silver source (eg organic silver salt) and a catalytically active amount of photocatalyst (eg halogen). It is preferably a photothermographic material containing silver halide) and a reducing agent usually dispersed in a (organic) binder matrix. Preferably, it further contains a toning agent for controlling the color tone of silver. The photothermographic material of the present invention is stable at room temperature, but at a high temperature (for example, 80
It is developed by heating to (° C or higher). Heating produces silver through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and the reducing agent. This oxidation-reduction reaction is promoted by the catalytic action of the latent image generated by the 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.

Therefore, a preferred embodiment of the present invention is the following photothermographic material. (A) a reducible silver source, (b) a photocatalyst, (c) a reducing agent,
A photothermographic material containing (d) a binder and (e) a compound represented by formula (I) of the present invention.

Particularly preferred embodiments are the following photothermographic materials. (A) organic silver salt, (b) reducing agent, (c) photosensitive silver halide and / or photosensitive silver halide-forming component, (d) binder and (e) represented by the general formula (I) of the present invention. Photothermographic material containing the compound described above.

The photothermographic material of the present invention is preferably a monosheet type (a type in which all the materials donated to form an image are completed as an image sheet to be observed) because of its gentleness to the earth. is there. Further, it is preferably a photothermographic material for infrared laser exposure. Further, the wavelength of infrared laser exposure is 750 nm or more, more preferably 800 nm or more. In order to be compatible with a laser in such a wavelength range, it is necessary to be spectrally sensitized so as to have sensitivity in these wavelength ranges, that is, in the infrared range. Known infrared sensitizing dyes may be used.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only the photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. A filter layer may be formed on the same side or on the opposite side of the photosensitive layer in order to control the amount or wavelength distribution of light passing through the photosensitive layer, or the photosensitive layer may contain a dye or a pigment. The photosensitive layer may be composed of multiple layers, and the sensitivity is high for adjusting the gradation.
It may be a low sensitive layer or a low sensitive layer / high sensitive layer. Various additives may be added to any of the light-sensitive layer, non-light-sensitive layer, and other forming layers.

The support applicable to the photothermographic material of the present invention includes, for example, paper, polyethylene-coated paper, polypropylene-coated paper, parchment, cloth, etc .;
Sheets or films of metals such as aluminum, copper, magnesium, zinc; glass or chromium alloy, steel,
Glass coated with a metal such as silver, gold, platinum; poly (alkyl methacrylates) (eg, poly (methyl methacrylate)), poly (esters) (eg, poly (ethylene terephthalate)), poly (vinyl acetal) ), Poly (amides) (eg, nylon), and cellulose esters (eg, cellulose nitrate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate). The photothermographic material of the invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

Each binder layer (eg, synthetic polymer) together with the chemical agent in the photothermographic material of the present invention may form a self-supporting film. The support is made of known auxiliary materials, for example, vinylidene chloride, acrylic acid monomers (for example, acrylonitrile and methyl acrylate)
And copolymers and terpolymers of unsaturated dicarboxylic acids (eg, itaconic acid, acrylic acid), carboxymethylcellulose, poly (acrylamide); and similar polymeric materials.

Suitable binders are transparent or translucent, generally colorless, and include natural polymeric synthetic resins, polymers and copolymers, and other film-forming media such as:
Gelatin, gum arabic, poly (vinyl alcohol),
Hydroxyethyl cellulose, cellulose acetate,
Cellulose acetate butyrate, poly (vinylpyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylic acid), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (Styrene-acrylonitrile), copoly (styrene-butadiene), poly (vinyl acetal)
(Eg, poly (vinyl formal) and poly (vinyl butyral)), poly (esters), poly (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), There are poly (vinyl acetate), cellulose esters, and poly (amide) s. The binder may be coated from water or an organic solvent or an emulsion.

The addition of toning agents is highly desirable. Examples of suitable toning agents are disclosed in Research Report No. 17029,
There are the following: imides (eg, phthalimide);
Cyclic imides, pyrazolin-5-ones, and quinazolinones (eg, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline, and 2,4-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 (eg, N- (dimethylaminomethyl) phthalimide);
Blocked pyrazoles, isothiuronium (isot
hiuronium) derivatives and certain photobleaching combinations (eg, N, N'hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6-
A combination of dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole; a merocyanine dye (e.g., 3-ethyl-5-((3-ethyl-2-benzothia) Zolinylidene (benzothiazolinylidene) -1
-Methylethylidene) -2-thio-2,4-oxazolidinedione); phthalazinone, phthalazinone derivatives or metal salts of these derivatives (e.g.,
4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-dimethyloxyphthalazinone, and 2,3-dihydro-1,4-phthalazinedione); phthalazone; a combination of phthalazinone and a sulfinic acid derivative (For example, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-toluenesulfinate); a combination of phthalazine + phthalic acid; phthalazine (including an adduct of phthalazine) and maleic anhydride, And phthalic acid, 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and their anhydrides (eg phthalic acid, 4-methylphthalic acid, 4
-A combination with at least one compound selected from nitrophthalic acid and tetrachlorophthalic anhydride);
Quinazolinediones, benzoxazines, nartoxazine derivatives; benzoxazine-2,4-diones (eg 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg 2,4 −
Dihydroxypyrimidine), and a tetraazapentalene derivative (for example, 3,6-dimerocapto-1,4-diphenyl-1H, 4H-2,3a, 5,6a-tetraazapentalene. Preferred toning agents are:

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And more preferably phthalazine. The reducing agent may contain a so-called photographic developer, for example, phenidone, hydroquinones, catechol and the like, but hindered phenol is preferred. US Patent No. 4
A color light-sensitive material as disclosed in 460681 is also conceivable in the realization of the present invention.

Examples of suitable reducing agents are described in US Pat. No. 3,770.
Nos. 448, 3773512, 3959633, and Research Disclosure Nos. 17029 and 29.
963, and include: aminohydroxycycloalkenone compounds (eg, 2-hydroxy-piperidino-2-cyclohexenone); aminoreductones esters (eg, Piperidinohexose reductone monoacetate); N-hydroxyurea derivatives (for example, Np-
Methylphenyl-N-hydroxyurea); aldehyde or ketone hydrazones (eg, anthracene aldehyde phenylhydrazone); phosphoramidophenols; phosphoramidoanilines; polyhydroxybenzenes (eg, hydroquinone, t-butyl-hydroquinone) , Isopropylhydroquinone and (2,5-dihydroxy-phenyl) methyl sulfone); sulfhydroxamic acids (eg, benzenesulfhydroxamic acid); sulfonamide anilines (eg, 4- (N-
Methanesulfonamido) aniline); 2-tetrazolylthiohydroquinones (for example, 2-methyl-5- (1-
Phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,2,3,4-
Tetrahydroquinoxaline); amidooxins; azines (for example, aliphatic carboxylic acid aryl hydrazides and ascorbic acid); polyhydroxybenzene and hydroxylamine, reductone and / or hydrazine; hydroxanoic acids; azines and sulfones Combination of amidophenols; α-cyanophenylacetic acid derivative; bis-β-naphthol and 1,3-
5-pyrazolones; sulfonamidophenol reducing agents; 2-phenylindane-1,3-dione and the like; chromans; 1,4-dihydropyridines (e.g., 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, 4,4 -Ethylidene-bis (2
-T-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. A preferred reducing agent is a hindered phenol of general formula (A):

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Here; R is a hydrogen atom or 1 carbon atom.
To 10 alkyl groups (for example, -C _FourH₉, 2,4,4
-Trimethylpentyl);^FiveAnd R⁶Is carbon source
An alkyl group having 1 to 5 children (for example, methyl, ethyl, t
-Butyl).

Silver halide useful as a catalytically active amount of a photocatalyst is any photosensitive silver halide (eg, silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, chloroiodobromide). It may be silver or the like) but preferably contains iodide ions. The silver halide may be added to the imaging layer in any manner, with the silver halide being placed in close proximity to the reducible silver source. In general, it is preferred that the silver halide contains from 0.75 to 30% by weight, based on the reducible silver source. Silver halide may be prepared by conversion of the silver soap portion by reaction with a halide ion, may be preformed and added during the generation of the soap, or a combination of these methods is possible. The latter is preferred.

The reducible silver source can be any material containing a source of reducible silver ions. Silver salts of organic and heteroorganic acids, especially long chains (10-30, preferably 15-25
) Aliphatic carboxylic acids are preferred. Organic or inorganic silver salt complexes wherein the ligand has a total stability constant for silver ions of 4.0 to 10.0 are also useful. Examples of suitable silver salts are described in Research Disclosure No. 1702.
9 and 29996, and include the following:
Salts of organic acids (eg gallic acid, oxalic acid, behenic acid,
Stearic acid, palmitic acid, lauric acid, etc.); carboxyalkylthiourea salt of silver (for example, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea); aldehyde Silver complexes (e.g., aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids (e.g., salicylic acid, benzoic acid, 3,5-
Dihydroxybenzoic acid, 5,5-thiodisalicylic acid),
Silver salts or complexes of thioenes (eg, 3- (2-carboxyethyl) -4-hydroxymethyl-4-thiazoline-2-thioene and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole ,
Urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4-
Complexes or salts of silver and nitrogen acids selected from triazoles and benzotriazoles; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are stearic acid and silver behenate, with behenic acid being especially preferred. The reducible silver source preferably has a silver content of 3 g / m ² or less. More preferably, it is 2 g / m ² or less.

The photothermographic material of the present invention includes, for example, JP-A Nos. 63-159841, 60-140335, 63-231437, 63-259651 and 6-63.
Nos. 3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, and 4,419.
Sensitizing dyes described in JP-A Nos. 66, 4751175 and 48335096 can be used. General formula (I) of the present invention
The compound represented by can also be used for a normal silver halide light-sensitive material and a silver halide light-sensitive material having a hard gradation. Any silver halide light-sensitive material may be used as long as it has a light-sensitive silver halide emulsion layer on a support.

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【Example】

Example 1 Preparation of Photosensitive Emulsion A Solution Stearic acid 135 g Behenic acid 635 g Distilled water 13 liter Mixed at 15 minutes at 85 ° C. Solution NaOH 89 g Distilled water 1500 ml Solution concentrated HNO ₃ 21 ml Distilled water 50 ml Solution AgNO ₃ 365 g Distilled water 2500 ml Solution polyvinyl butyral 86 g Ethyl acetate 4300 ml solution Polyvinyl butyral 290 g Isopropanol 3580 ml solution N-Bromosuccinimide 9.7 g Acetone 700 ml

While vigorously stirring the solution while maintaining the temperature at 85 ° C., the solution was added over 5 minutes, and then the solution was added to 2
Add over 5 minutes. After stirring for 20 minutes as it is, 35
Cool down to ° C. Add the solution over 5 minutes with more vigorous stirring at 35 ° C. and continue stirring for 90 minutes.
Then, the solution was added, and the mixture was left without stirring, and the aqueous phase was removed together with the salt contained therein to obtain an oil phase, which was desolvated to remove traces of water, and then the solution was added and vigorously stirred at 50 ° C. Then, the solution was added over 20 minutes and stirred for 105 minutes to obtain a photosensitive emulsion A.

The following layers were sequentially formed on a biaxially stretched 175 μm thick polyethylene terephthalate support (without an undercoat layer) which was colored blue with Dye-A. Drying was performed at 75 ° C. for 5 minutes each.

<Back side coating> ○ Antihalation layer (wet thickness 80 micron) Polyvinyl butyral (10% isopropanol solution) 150 ml Dye-C (solvent DMF) 70 mg

<Photosensitive layer side coating> ○ Photosensitive layer (wet thickness 140 μm) Photosensitive emulsion A 73 g Sensitizing dye-1 (0.1% DMF solution) 2 ml Antifoggant-1 (0.01% methanol solution) ) 3 ml phthalazone (4.5% DMF solution) 8 ml reducing agent-1 (10% acetone solution) 13 ml compound

Surface protection layer (wet thickness 100 micron) 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 Thing 0.5g

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Cesitometry The photothermographic material prepared above was processed into a 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 treatment was carried out at 20 ° C. for 15 seconds and 125 ° C. for 15 seconds. Then, the fog value at that time was measured. Further, when the maximum concentration of Sample No. 1 in Table 1 was set to 100, the maximum concentration of each sample was evaluated as a relative value. The results are shown in Table 1. Evaluation of Sensitive Material Coated with Aged Liquid Sample The compounds listed in Table 1 in the photosensitive layer surface side coated sample were evaluated as 1
Add 0% methanol solution after aging for 5 hours,
The photothermographic material prepared in the same manner as above was processed, exposed and heat-developed in the same manner as above, and the fog value at that time was measured. (Aged Sample Fog) The results are shown in Table 1.

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[Table 1]

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From Table 1, it can be seen that the samples of the present invention have sufficient sensitivity and have low fog and are good. In addition, in the comparative compound, in the sensitive material prepared using the aged liquid sample,
It can be seen that the antifoggant effect is remarkably reduced, whereas such a problem does not occur when the compound of the present invention is used.

Example 2 Preparation of Photosensitive Emulsion B Solution Stearic acid 135 g Behenic acid 635 g Distilled water 13 liters 85 ° C. and mixed for 15 minutes Solution A CuB AgBrI (I = 4 mol%) prepared in advance 0.06 μ (as Ag) 0.22 mole) distilled water 1250ml solution NaOH 89 g distilled water 1500ml solution of concentrated HNO ₃ 19 ml of distilled water 50ml solution AgNO ₃ 365 g distilled water 2500ml solution polyvinylbutyral 86g ethyl acetate 4300ml solution polyvinylbutyral 290g isopropanol 3580ml

The solution A was added over 10 minutes with vigorous stirring while keeping the solution at 85 ° C., followed by the addition of the solution over 5 minutes, and then the solution over 25 minutes. After stirring for 20 minutes as it is, the temperature is lowered to 35 ° C. Add the solution over 5 minutes with more vigorous stirring at 35 ° C. and continue stirring for 90 minutes. Thereafter, the solution was added, the stirring was stopped and the mixture was left to stand, and the aqueous phase was extracted together with the salt contained therein to obtain an oil phase. After removing the traces of water by removing the solvent, the solution was added and the mixture was stirred vigorously at 50 ° C. Later, 10
Emulsion B was obtained by stirring for 5 minutes.

A test was conducted in the same manner as in Example 1 (however, the antihalation layer was provided below the photosensitive layer on the side of the photosensitive layer). The sample using the compound of the present invention had low fog as in Example 1.

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The light-sensitive material of the present invention has high sensitivity and low fog. It is also preferable because it is stable under the manufacturing conditions of the light-sensitive material and the fluctuation of photographic performance is small.

Claims (6)

[Claims] 1. A polyhalomethane compound represented by the general formula (I). General formula (I) Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇
Each represent a hydrogen atom or a substituent. However, R ₂ ~
At least one of R ₇ is a substituent represented by the following general formula (a). General formula (a) Y is -CO -, - SO- or -SO ₂ - represents a. X ₁ and X ₂ each represent a halogen atom. A represents a hydrogen atom or an electron-withdrawing group. ) 2. R ₁ is a hydrogen atom, and R ₄ , R ₅ , R
Any one of ₆ and R ₇ is a group represented by the general formula (a), Y is —SO ₂ —, and A is a halogen atom. Polyhalomethane compound. 3. The polyhalomethane compound according to claim 1 or 2, wherein R ₇ is a group represented by the general formula (a). 4. A light-sensitive material containing at least one polyhalomethane compound represented by the general formula (I) according to claim 1, 2, or 3. 5. A photothermographic material comprising at least one polyhalomethane compound represented by formula (I) according to claim 1, 2, or 3. 6. The photothermographic material according to claim 5, which is infrared-sensitized for infrared laser exposure.