JPH09258367A - Novel polyhalomethane compound and photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the storage stability of the photosensitive material and that of an image without deteriorating sensitivity and color ones by incorporating a specified polyhalomethane compound. SOLUTION: This photosensitive material contains the polyhalo-methane compound represented by the formula in which Q is an aryl group: each of Z1 and Z2 is a halogen atom; Y is -C(=O)-, -SO-, or -SO2 -; (k) is 0 or 1; W is an electron withdrawing group; (m) is an integer of 2-7; and A is an H atom or an electron withdrawing group. This compound can be added either to a photosensitive layer or a nonphotosensitive layer, but preferably, to photosensitive layer. It is added in an amount of 1×10<-4> -1mol/mol of silver halide, preferably, 1×10<-3> -3×10<-1> mol/mol of silver halide, but it varies as the case may be, and it is preferred to add it by dissolving it in an organic solvent in all the case.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polyhalomethane compound and a photosensitive material, and more specifically,
Providing a highly active antifoggant with high manufacturing suitability,
The present invention relates to a photothermographic material, and particularly to a technique for improving the storability of a photographic material and the storability of an image without deteriorating the sensitivity or deteriorating the color tone.

[0002]

2. Description of the Related Art Polyhalomethane compounds are photopolymerization initiators,
It is used for applications such as silver halide photographic light-sensitive materials. As a conventionally known polyhalomethane compound, Japanese Patent Publication No.
4-165, U.S. Pat. Nos. 3,874,946 and 475.
6999, European Patents 605981A and 6311
76A1 and the like. The specific compound examples are shown below.

[0003]

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On the other hand, a photothermographic material for forming a photographic image using the photothermographic method is disclosed in, for example, US Pat. No. 3,152.
904, 3457075, and D. Morgan and B. Shely
By "The Silver System Heat Treated (Thermally
Processed Silver Systems) "(Imaging Process
es and Materials, Neblette 8th Edition, Sturge, V. Walw
orth, edited by A. Shepp, p. 2, 1969).

In such a photothermographic material, a reducible silver salt (eg organic silver salt), a catalytically active amount of a 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 it is exposed to high temperatures (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 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. A toning agent for controlling the silver tone of this silver image is optionally used in the light-sensitive material. Fogging is likely to occur in such an image forming system.

Mercury ions are known as the most effective antifoggant as a conventional antifogging technique. The use of mercury compounds as antifoggants in light-sensitive materials is disclosed, for example, in US Pat. No. 3,589,903. However, the use of mercury compounds is not preferable from an environmental point of view, and polyhalomethane compounds as described above have been developed as non-mercury antifoggants.

[0007] However, these known compounds have a problem that the antifogging effect is low and the color tone of silver is deteriorated. Further, those having a high fog-preventing effect have problems such as a decrease in sensitivity, and thus improvement is required. Furthermore, when considering the production of these polyhalogen compounds, it has been found that conventionally known compounds having a high antifoggant effect have low yields upon synthesis.
That is, without causing deterioration of sensitivity and deterioration of silver tone,
There has been a demand for the development of a polyhalogen compound which has a higher fog-inhibiting ability as a fog-inhibiting agent and is also suitable for production.

[0008]

The object of the present invention is to provide a fog inhibitor with high production suitability and higher activity, and to a photothermographic material, which can be used for preserving a light-sensitive material without deteriorating sensitivity or color tone. And the image storability. Another object of the present invention is to provide a novel polyhalomethane compound useful for photopolymerization initiators, silver halide photographic light-sensitive materials and the like.

[0009]

The above object has been achieved by the following means. (1) A silver halide light-sensitive material containing a polyhalomethane compound represented by the general formula (I). General formula (I)

[0010]

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(In the formula, Q represents an aryl group. Z ₁ and Z ₂ each represent a halogen atom. Y represents --C (═O).
-, - SO- or -SO ₂ - represents a. k represents 0 or 1. W represents an electron-withdrawing group, and m represents an integer of 1 to 7. A represents a hydrogen atom or an electron-withdrawing group. )

(2) (a) reducible silver salt, (b) reducing agent, (c) photocatalyst, (d) binder and (e) (1)
A photothermographic material containing the polyhalomethane compound represented by the general formula (I) described in 1.

(3) The photothermographic material according to (2), which is for infrared laser exposure.

(4) A polyhalomethane compound represented by the general formula (Ia). General formula (Ia)

[0015]

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(In the formula, Q represents an aryl group. Z ₁ and Z ₂ each represent a halogen atom. Y represents —C (═O).
-, - SO- or -SO ₂ - represents a. X represents a halogen atom. n represents an integer of 3 to 5. A represents a hydrogen atom or an electron-withdrawing group. )

(5) In the general formula (Ia), Q is a phenyl group, Y is --SO _2- , n is 3, and A is a halogen atom (4). ). The polyhalomethane compound described in (1).

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The general formula (I) will be described in detail. The aryl group represented by Q is preferably an aryl group having 6 to 30 carbon atoms, and more preferably 6 to 20 carbon atoms.
A monocyclic or condensed ring aryl group such as a phenyl group,
A naphthyl group can be mentioned, and a phenyl group is particularly preferable.

The aryl group represented by Q is W,-(Y) _k
It may have a substituent in addition to —CA (Z ₁ ) (Z ₂ ), and as the substituent, for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly It preferably has 1 to 8 carbon atoms, for example, methyl, ethyl,
iso-propyl, tert-butyl, n-octyl,
Examples include n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. ), 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 acyloxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 1 carbon atoms).
6, particularly preferably having 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, and particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino). (Preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms,
Particularly preferably, it has 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 carbon atoms).
To 12 and examples thereof include phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfonylamino and benzenesulfonylamino). 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 methylthio and ethylthio. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 12 carbon atoms, and examples thereof include phenylthio), and a ureido group (preferably having 1 carbon atom). ~
20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, ureide, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms,
For example, diethylphosphoramide, phenylphosphoramide and the like can be mentioned. ), A hydroxy group, a mercapto group, a hydroxamic acid group, a sulfino group, a hydrazino group, a heterocyclic group (for example, imidazolyl, pyridyl, furyl, piperidyl, morpholino, etc.) 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 alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group,
A sulfonylamino group, a ureido group, a phosphoric acid amide group, a sulfinyl group, a hydroxy group, a heterocyclic group, more preferably an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an acylamino group, an alkoxycarbonylamino group. , An aryloxycarbonylamino group, a sulfonylamino group, a ureido group, a phosphoric acid amide group, and a heterocyclic group, and more preferably an alkyl group, an alkenyl group, an aryl group, an acylamino group, a sulfonylamino group, a ureido group, a phosphoric acid amide. And a heterocyclic group, and particularly preferably an alkyl group and an aryl group.

The electron-withdrawing group represented by W is preferably a substituent having a σp value of 0.01 or more and 1.0 or less,
The substituent is more preferably 0.05 or more and 1.0 or less, and further preferably 0.1 or more and 1.0 or less. Regarding Hammett's substituent constant, see Journal of Medicinal
Chemistry, 1973, Vol.16, No11, 1207-1216, etc. can be referred to. Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp 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) .54)), a cyano group (σp value: 0.5.
66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl (σp value: 0.72)), aliphatic / aryl or heterocyclic acyl group (for example, Acetyl (σp value: 0.
50), benzoyl (σp value: 0.43)), alkynyl group (eg, C≡CH (0.23)), aliphatic / aryl or heterocyclic alkoxycarbonyl group (eg,
Methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σp value: 0.44)), carbamoyl group (σp value: 0.36), sulfamoyl group (σp value:
0.57), and the like.

W is preferably a halogen atom, a trihalomethyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group or a sulfamoyl group, more preferably a halogen atom, a trihalomethyl group, an acyl group or an alkoxycarbonyl. Group, an aryloxycarbonyl group, more preferably a halogen atom and a trihalomethyl group, and particularly preferably a halogen atom.

The halogen atoms represented by Z ₁ and Z ₂ may be the same or different from each other and are a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom, Chlorine atom and bromine atom are more preferable, and bromine atom is particularly preferable.

Y is -C (= O)-, -SO-, -SO ₂
- represents preferably -SO ₂ - is. k represents 0 or 1, and preferably k is 1. A preferred combination of Y and k is when Y is —SO ₂ — and k is 1.

The electron withdrawing group represented by A is preferably a substituent having a σp value of 0.01 or more, more preferably 0.1 or more. For the Hammett's substituent constant, see Journal of Medicinal Chemistry, 1
973, Vol.16, No11, 1207-1216, etc. can be referred to. Examples of the electron-withdrawing group include a halogen atom (fluorine atom (σp 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: 0.54)), cyano group (σp value: 0.66), nitro group (σp 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 (σp value: 0.50), benzoyl (σp value: 0.43)), alkynyl group (for example, C≡CH) (0.23)), aliphatic / aryl or heterocyclic alkoxycarbonyl group (for example, methoxycarbonyl (σp value: 0.45), phenoxycarbonyl (σp value: 0.44)), carbamoyl group (σp value:
0.36), sulfamoyl group (σp value: 0.57),
And the like.

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 alkoxycarbonyl group. Group, carbamoyl group, and sulfamoyl group, and 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.

Of the compounds represented by the general formula (I), the compounds represented by the general formula (Ia) are preferable. General formula (Ia)

[0028]

[Chemical 6]

In the formula, Q represents an aryl group. Z ₁ and Z
Each ₂ represents a halogen atom. Y is -C (= O)
-, - SO- or -SO ₂ - represents a. X represents a halogen atom, and n represents an integer of 3 to 5. A represents a hydrogen atom or an electron-withdrawing group. Specific examples and preferred ranges of each group are the same as those in formula (I).

Of the compounds represented by the general formula (I), more preferred are the compounds represented by the general formula (Ib). General formula (Ib)

[0031]

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In the formula, Z ₁ and Z ₂ each represent a halogen atom. X represents a halogen atom, and n represents an integer of 3 to 5. A represents a hydrogen atom or an electron-withdrawing group. Specific examples and preferred ranges of each group are the same as those in formula (I).

Of the compounds represented by the general formula (I), the compounds represented by the general formula (Ic) are more preferred. General formula (I-c)

[0034]

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(In the formula, X represents a halogen atom, and n is 3
Represents an integer of from 5 to 5. )

The halogen atoms represented by X are the same or
Fluorine atom, chlorine atom, bromine atom and iodine atom which may be different from each other, preferably chlorine atom, bromine atom and iodine atom, more preferably chlorine atom and bromine atom, particularly preferably chlorine atom is there. n is 3
It represents ~ 5, and is preferably 3.

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

[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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The compound represented by formula (I) of the present invention, Y = -SO -, - SO 2 - in the case, by combining the aryl mercaptan from (1) an aryl halide derivative,
(2) After conversion into a mercaptoacetic acid derivative, the compound can be synthesized by (3) oxidizing and brominating the mercaptoacetic acid derivative. (A commercially available mercaptan can be used to synthesize from (2).)

As a method for synthesizing aryl mercaptans, New Experimental Chemistry Course (Maruzen) 14-III, Chapter 8-8-1,
ORGANIC FUNCTIONAL GROUP PREPARATIONS (Sandler,
Karo, ACADEMIC PRESS New York and Rondon) I-Ch
apt.18 or THE CHEMISTRY OF FUNCTIONAL GROU
PS (Patai, JONE WILLY & SONS) "The Chemistry of
Various methods are known, as described in the thiol group "Chapt 4.".

Conversion to a mercaptoacetic acid derivative is carried out by converting the corresponding mercaptoheterocyclic compound to chloroacetic acid under basic conditions.
Alternatively, it can be synthesized by reacting with a salt of chloroacetic acid.

Regarding the oxidation and halogenation of the mercaptoacetic acid derivative, for example, as described in US Pat. No. 3,874,946, European Patent Publication No. 60598, etc., a hypomerous acid or a salt thereof is added to a basic aqueous solution of the mercaptoacetic acid derivative, Alternatively, oxidation / halogenation can be carried out simultaneously by adding / reacting the salt. Further, the mercaptoacetic acid derivative can be synthesized by converting the mercaptoacetic acid derivative into a sulfoxide or a sulfonylacetic acid derivative in advance using an oxidizing agent such as hydrogen peroxide and then halogenating the same.

When Y = -C (= O)-, (1) a carbonyl compound is synthesized from an aryl halide derivative,
(2) It can be synthesized by halogenating a carbonyl compound. (A commercially available carbonyl compound can also be used to synthesize from (2).) It is also possible to synthesize from halogenation including halogenation of the aromatic ring of the acetophenone derivative. Regarding the conversion to carbonyl compounds, new experimental chemistry course (Maruzen)
Various methods as described in 14-II, Chapter 4, 4-1 and 4-2 can be used. For halogenation, the method described in New Experimental Chemistry Course (Maruzen) 14-I, Chapter 2, etc. can be used.

When m = 0, the compound can be synthesized by halogenating a halogen-substituted methyl group such as toluene or xylene. As the halogenation method, the method described in New Experimental Chemistry Course (Maruzen) 14-I, Chapter 2, etc. can be used as in the above.

The compound represented by the general formula (I) of the present invention can be added in either the photosensitive layer or the non-photosensitive 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 from 10 ^-4 mol to 1 mol /
It is advisable to add Ag, preferably 10 ⁻³ mol to 0.3 mol / Ag. It is preferable that any compound be dissolved in an organic solvent and added.

The heat-developable light-sensitive 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 infrared laser exposure wavelength is 750 nm or more, more preferably 8
It is preferable that the thickness is 00 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 spectral sensitizing dyes may be used.

The photothermographic material of the present invention forms a photographic image using a photothermographic processing method. As such a photothermographic material, as described above, for example, US Pat.
52904, 3457075, and D. Morgan and B. Sh
ely "The Silver System Heat Treated (Thermal
ly Processed Silver Systems) ”(ImagingProces
ses and Materials, Neblette 8th Edition, Sturge, V.Wa
Lworth, edited by A. 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, such as a reducible silver salt (eg organic silver salt) and a photocatalyst having a catalytically active amount (eg light-sensitive). It is preferably a photothermographic material containing a photosensitive silver halide and / or a photosensitive silver halide-forming component) and a reducing agent in a state of being normally dispersed in an (organic) binder matrix. Further, it is preferable to contain a toning agent for controlling the color tone of silver. The photothermographic material of the present invention is stable at room temperature, but is developed by being heated to a high temperature (for example, 80 ° C. or higher) after exposure. 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.

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. There may be a plurality of photosensitive layers, and a high-sensitivity layer /
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 and the like materials; for example, aluminum, copper, magnesium and zinc. Metal sheaths or thin films; glass or chrome alloys,
Glass coated with metals such as steel, silver, gold, platinum; poly (alkylmethacrylates), (eg poly (methylmethacrylate)), poly (esters)
(Eg, poly (ethylene terephthalate)), poly (vinyl acetals), poly (amides) (eg,
There are synthetic polymeric materials such as nylon) and cellulose esters (eg, cellulose nitrate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate). For the photothermographic material of the present invention, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid and the like may be used.

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 provided with known auxiliaries such as vinylidene chloride, acrylic acid monomers (eg acrylonitrile or methyl acrylate) and unsaturated dicarboxylic acids (eg itaconic acid, acrylic acid), carboxymethylcellulose, copolymers of poly (acrylamide) and terpolymers. Polymers; and similar polymeric materials may additionally be coated.

Suitable binders are transparent or translucent,
Generally colorless, natural polymers synthetic resins, polymers and copolymers, and other film-forming media such as: gelatin, gum arabic, poly (vinyl alcohol), hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, poly (vinyl). Pyrrolidone), casein, starch, poly (acrylic acid), poly (methyl methacrylate), poly (vinyl chloride), poly (methacrylic acid), copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile), copoly (styrene) -Butadiene), poly (vinyl acetal) s (eg poly (vinyl formal) and poly (vinyl butyral)), poly (esters),
There are poly (urethane) s, phenoxy resins, poly (vinylidene chloride), poly (epoxides), poly (carbonates), poly (vinyl acetate) s, cellulose esters, poly (amides). The binder may be coated from water or an organic solvent or 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 quinazolines (for example, succinimide, 3-phenyl-2-pyrazolin-5-one, 1-phenylurazole, quinazoline and 2,4-thiazolidinedione); naphthalimides ( For example, N-hydroxy-1,8-naphthalimide); cobalt complex (for example, hexamine trifluoroacetate of cobalt), mercaptans (for example, 3-mercapto-1,2,4-triazole); N
-(Aminomethyl) aryldicarbonoxyimides (eg N- (dimethylaminomethyl) phthalimide); Blocked pyrazoles, isothiuronium derivatives and certain photobleaching combinations (eg N, N '). -Hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8-
(Combination of (3,6-dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole); merocyanine dye (for example, 3-ethyl-5-((3-ethyl -2-benzothiazolinyliden
e) -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-phthalazinone); phthalazone; a combination of phthalazinone and a sulfinic acid derivative (eg, 6-chlorophthalazinone + sodium benzenesulfinate) Or 8-methylphthalazinone + sodium p-toluenesulfinate); a combination of phthalazine + phthalic acid; phthalazine (including a phthalazine adduct) and maleic acid, and phthalic acid, 2,3-
Combination with at least one compound selected from naphthalenedicarboxylic acid or o-phenylene acid derivatives and their anhydrides (eg phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride); quinazo Lysinediones, benzoxazines, naltoxazine derivatives; benzoxazine-2,4-diones (eg 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric-triazines (eg
2,4-dihydroxypyrimidine), and tetrazapentalene derivatives (eg, 3,6-dimercapto-1,4)
-Diphenyl-1H, 4H-2,3a, 5,6a-tetrazapentalene). As a preferable color tone agent,

[0059]

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And more preferably phthalazine. The reducing agent may contain so-called photographic developers such as phenidone, hydroquinones, catechol and the like, but hindered phenol is preferable. A color light-sensitive material as disclosed in U.S. Pat. No. 4,460,681 is also conceivable in the realization of the present invention.

Examples of suitable reducing agents are described in US Pat. No. 3,770.
448, 3773512, 3593863, and Research Disclosure 17029 and 2
9963 and include the following: aminohydroxycycloalkenone compounds (eg, 2-hydroxy-piperidino-2-cyclohexenone); aminoreductones esters (eg, piperidines) as precursors for developers. Nohexose reductone monoacetate); N-hydroxyurea derivative (eg, 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 acid (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, aryl carboxylic acid aryl hydrazides and ascorbic acid); polyhydroxybenzene and hydroxylamine combinations, reductones and / or hydrazines; hydroxy acids; azines and sulfones Combination with amidophenols; α-cyanophenylacetic acid derivative; bis-β-naphthol and 1,3-
Combinations of dihydroxybenzene derivatives; 5-pyrazolones; sulfonamide phenol reducing agents; 2-phenylindane-1,3-diones; chromanes; 1,4-dihydropyridines (eg 2,6-dimethoxy-3 , 5-dicarboethoxy-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); UV-sensitive ascorbic acid derivatives and 3-pyrazolidones. A preferred reducing agent is a hindered phenol of general formula (A):

[0062]

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Where; R ₄ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (for example, —C ₄ H ₉ , 2, 2
4,4-trimethylpentyl), and R ₅ and R _{6 each} represent an alkyl group having 1 to 5 carbon atoms (eg, 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. The silver halide may be prepared by conversion of the silver soap part by reaction with halogen ions, may be preformed and added at the generation of soap, and combinations of these methods are 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 in which 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 found in Research Disclosure No. 1
7029 and 29963, and include: salts of organic acids (eg, gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkyl thiourea salts ( For example, 1
-(3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.);
Silver complexes of polymer reaction products of aldehydes with hydroxy-substituted aromatic carboxylic acids (eg aldehydes (formaldehyde, acetaldehyde, butyraldehyde), hydroxy-substituted acids (eg salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), a silver salt or complex of thioene (for example, 3
-(2-Carboxyethyl) -4-hydroxymethyl-
4-thiazoline-2-thioene, and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1. , 2,4-triazole, and a complex or salt of a nitric acid selected from benzotriazole with silver; 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 amount of 3 g / m ² or less.
It is more preferably 2 g / m ² or less.

The photothermographic material of the present invention includes, for example, JP-A-63-159841, JP-A-60-140335,
No. 63-23147, No. 63-259651, No. 6
3-394242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455 and 4741.
The sensitizing dyes described in Nos. 966, 475117 and 4835096 can be used. General formula (I) of the present invention
The compound represented by can be used in ordinary silver halide light-sensitive materials. For silver halide light-sensitive materials,
Any material may be used as long as it has a photosensitive silver halide emulsion layer on a support.

The present invention is described below based on examples, but the present invention is not limited to these.

[0068]

【Example】

Example 1 <Synthesis example> Synthesis of compound I-5 (a) Synthesis of 2,4,5-trichloro-phenylthioacetic acid 2,4,5-Trichloro-phenylmercaptan 21.
4 g (0.1 mol) and 11.7 g of chloroacetic acid (0.12
Mol) was ice-cooled while being stirred and suspended in 200 ml of ethanol, and the temperature in the system was reduced to 10 ° C. or lower. To the suspension, 3 g of sodium hydroxide (content: 93%) (5.2 g, 0.12 mol) was added.
A solution dissolved in 0 ml of water was added dropwise so that the temperature of the suspension did not exceed 10 ° C. After the dropwise addition, stirring and cooling were continued for 15 minutes, and then sodium hydroxide (content: 93%) was added.
A solution prepared by dissolving 2 g (0.12 mol) in 30 ml of water was added dropwise. After removing the ice-water bath and returning the reaction solution to room temperature, 5
The mixture was heated to 0 ° C. and reacted for 2 hours. 800 ml of water in the reaction solution
After the insoluble matter is filtered off, concentrated hydrochloric acid is added to the filtrate to adjust the pH to ˜3, and the precipitate is collected by filtration, washed with water and dried to give the desired mercaptoacetic acid derivative (20. g (0.074 mol) was obtained. Yield 74%

(B) Synthesis of Compound I-5 35 g of sodium hydroxide (0.81 mol, 93% content) was dissolved in 500 ml of water and cooled to 10 ° C. or lower with an ice / methanol refrigerant. 22 ml of bromine under stirring and cooling
(0.43 mol) was added dropwise. Separately, 13.6 g of 2,4,5-trichloro-phenylthioacetic acid (0.05 mol)
l) and 4.6 g of sodium bicarbonate (0.055 mol
l) was dissolved in 300 ml of water to prepare a solution, which was added dropwise to the bromine solution while maintaining the temperature at 10 ° C or lower. After completion of the dropwise addition, the cooling was stopped, the mixture was heated from room temperature to 30 ° C., reacted for 2 hours, and then left overnight, whereby an intended product was deposited. The target compound I is obtained by separating the precipitate by filtration, thoroughly washing it with water, drying it, and recrystallizing it with ethanol.
-5 (15.1 g, 0.03 mol) was obtained. Yield 60.
7% melting point 169-170 ° C

The synthetic yields of the above-mentioned known polyhalomethane compounds for the above are shown below from the description of the corresponding patent. Comparative compound d Yield: 41% European Patent 631176A1 (2-quinoline) 〃 c Yield: 19.4% European Patent 605981A1 (thiadiazole)

It can be seen that the yield of the compound I-5 of the present invention is higher than that of the comparative compounds c and d. Next, the photographic performance of the photothermographic material using the compound of the present invention and that of the comparative compound were compared.

Example 2 << Preparation of Photosensitive Emulsion A >> Solution (1) Stearic acid 135 g Behenic acid 635 g Distilled water 13 liters 85 ° C. mixed for 15 minutes Solution (2) NaOH 89 g Distilled water 1500 ml Solution (3) Concentrated HNO ₃ 21ml distilled water 50ml solution (4) AgNO ₃ 365 g distilled water 2500ml solution (5) polyvinyl butyral 86g ethyl acetate 4300ml solution (6) polyvinyl butyral 290g isopropanol 3580ml solution (7) N-bromosuccinimide 9.7g acetone 700ml

While the solution (1) was kept warm at 85 ° C., the solution (2) was added over 5 minutes with vigorous stirring, and then the solution (3) was added over 25 minutes. After stirring for 20 minutes as it is, the temperature is lowered to 35 ° C. Solution (4) was added over 5 minutes at 35 ° C. with more vigorous stirring, and 90%
Continue stirring for a minute. Then, the solution (5) was added, the stirring was stopped and the mixture was left to stand, the aqueous layer was removed together with the salt contained therein to obtain an oil layer, and the solvent (6) was added after removing the trace water by desolvation. After stirring vigorously at 0 ° C., solution (7) was added over 20 minutes and stirred for 105 minutes to obtain photosensitive emulsion A.

The following layers were sequentially formed on a biaxially stretched 175 μ-thick polyethylene terephthalate support (without an undercoat layer) which was colored in blue with a color tone adjusting dye (d). Drying was performed at 75 ° C. for 5 minutes each.

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<Back surface coating> ○ Antihalation layer (wet thickness 80 micron) Polyvinyl butyral (10% isopropanol solution) 150 ml Antihalation dye (a) (0.2% DMF solution) 70 ml

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<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 Phtharazone (4.5% DMF solution) 8 ml Reducing agent-1 (10% acetone solution) 13 ml Compounds described in Table 1.

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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 half-sized pieces, and a laser diode of 830 nm was cut from the vertical surface to 13
Exposed with a tilted beam. After that, heat development treatment was performed using a heat drum at 120 ° 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 by a relative value. The results are shown in Table 1.

Evaluation of storability After three coated samples were placed in a closed container whose inside was kept at 55% at 25 ° C., the sample was aged at 50 ° C. for 7 days (forced aging). The second sample of these and the sample for comparison aged (stored in a light-shielding container at room temperature) were subjected to the same treatment as that used for evaluation of photographic properties, and the density of the fog portion was measured. (Increase in fog) = (fog during forced aging) − (fog during comparative aging)

Table 1 shows the results.

[0085]

[Table 1]

From Table 1, it can be seen that the samples of the present invention have sufficient sensitivity and low fog. Further, it can be seen that the storage stability of the light-sensitive material is also good.

Example 3 << Preparation of silver halide grains A >> 16 g of phthalated gelatin and 30 mg of potassium bromide were dissolved in 700 ml of water, and the pH was adjusted to 5.0 at 35 ° C.
159 ml of an aqueous solution containing 6 g and an aqueous solution containing potassium bromide and potassium iodide (92/8) were added by the control double jet method over 10 minutes while keeping the pAg at 7.7. Then, an aqueous solution 47 containing 55.4 g of silver nitrate
An aqueous solution containing 6 ml and potassium bromide was added over 30 minutes while keeping the pAg at 7.7, and the pH was lowered to cause aggregation and sedimentation for desalting, and then 0.1 g of phenoxyethanol was added to adjust the pH to 7.9 and pAg 8.2. Adjusted silver iodobromide grains A (core 8 mol%, average 2 mol%, 0.05 μ cube, projected diameter area variation coefficient 8%, (100) plane ratio 88
%) Was completed.

The temperature of the silver halide grains A was raised to 60 ° C., sodium thiosulfate, selenium compound II-1, tellurium compound a-1, chloroauric acid and potassium thiocyanate were added.
After ripening for 0 minute, it was rapidly cooled to 35 ° C. to terminate the chemical sensitization to prepare silver halide grains. The added amount was as follows. Sodium thiosulfate 8.5 × 10 ^-5 mol / silver mol Selenium compound S-1 1.1 × 10 ^-5 mol / silver mol Tellurium compound T-1 1.5 × 10 ^-5 mol / silver mol Chloroauric acid 3 0.5 × 10 ^-6 mol / silver mol Potassium thiocyanate 2.7 × 10 ^-4 mol / silver mol

[0089]

[Chemical 21]

<< Preparation of Organic Fatty Acid Silver Emulsion B >> 300 m of water
10.6 g of behenic acid was added to 1 l and dissolved by heating at 90 ° C.,
31.1m of 1N sodium hydroxide with sufficient stirring
1 was added and left as it was for 1 hour. Thereafter, the mixture was cooled to 30 ° C., 7.0 ml of 1N phosphoric acid was added, and 0.01 g of N-bromosuccinimide was added with sufficient stirring.
Was added. Thereafter, silver halide grains A 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 silver nitrate aqueous solution was continuously added over 2 minutes, and the mixture was left stirring for 1 hour.

While stirring, 37 g of a 1.2 wt% butyl acetate solution of polyvinyl acetate was gradually added to this aqueous mixture to form flocs of the dispersion. After that, the water was removed, and the water was washed twice more. (Washing water conductivity 30μ
S · cm) Next, polyvinyl butyral (molecular weight 300
2.5 cc of 2-butanone solution of 0) (20 cc) was added and stirred at a sufficient speed for 10 minutes. Next, 40 g of 2-butanone and 6.0 g of polyvinyl butyral (molecular weight 4000) were added to the following compounds and stirred at a sufficient speed for 1 hour to complete the preparation of the organic fatty acid silver emulsion B.

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<< Preparation of Emulsion Coating Solution >> The following chemicals were added to the organic fatty acid silver prepared as described above to prepare an emulsion coating solution. (Hereinafter, added amount per mol of silver) Isocyanate (N3300 manufactured by Desmodur Co., Ltd.) 2.6 g Sensitizing dye-2 0.01 mmol Sensitizing dye-3 0.01 mmol 2-Mercapto-5-methylbenzimidazole 7.65 mmol p-chloro Benzoylbenzoic acid 53 mmol Reducing agent-1 0.27 mmol Tetrachlorophthalic anhydride 10.8 mmol Coating aid-1 0.001 mmol Compound

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<< Preparation of Surface Protective Layer Coating Solution >> A surface protective layer coating solution was prepared as follows. Cellulose acetate butyrate 7.5 g 2-butanone 80 g Methanol 10 g Phthalazine 71.5 mmol 4-Methylphthalic acid 0.3 g Tetrachlorophthalic acid 0.07 g Coating aid-1 0.01 g

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<< Preparation of Backing Layer Coating Liquid >> A backing layer coating liquid was prepared as follows. Polyvinyl butyral (10% 2-butanone solution) 30 ml Cellulose acetate butyrate 30 ml (10% ethyl acetate solution) Antihalation dye (b) 0.05 g Antihalation dye (c) 0.06 g Color control dye (d) 0. 1 g Color tone adjusting dye (e) 0.002 g Silica matting agent (Cyroid 162) 0.1 g Isocyanate (N3300 manufactured by Desmodur) 0.8 g Acetic acid ethyl ester 140 ml Coating aid-1 0.1 g

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The backing layer coating solution prepared as described above was applied to a biaxially stretched blue-colored polyethylene terephthalate film having a thickness of 175 μm and an absorbance at 810 nm higher than 1.2 polyethylene terephthalate.

<Preparation of Coating Sample> The prepared coating solution was coated on the opposite surface coated with the backing layer of polyethylene terephthalate so that the coated silver amount was 2.0 g / m ² and dried. After that, the coating solution for the surface protective layer was applied such that the cellulose acetate butyrate was 2.5 g / m ² . Thus, the coated sample was prepared.

<< Evaluation of Photographic Performance >> Cesitometry After processing the photothermographic material prepared above into a half-cut size, an FCR7000 manufactured by Fuji Photo Film Co., Ltd. was modified to perform imagewise exposure using a semiconductor laser of 810 nm. did. The angle between the exposed surface of the coated sample and the exposure laser beam is 80 de
g. Moreover, the output of the laser is 150 mW,
However, high frequency superimposition was performed and output was performed in vertical multi-mode. The heat development is performed by uniformly heating with a heat drum at 120 ° C.
Two types were performed: x15 seconds and 125 ° C x15 seconds. Then, the fog value at that time was measured. Further, when the maximum concentration of sample No. 1 in Table 2 was set to 100, the maximum concentration of each sample was evaluated by a relative value. Table 2 shows the results.

Evaluation of storability As in Example 1, three coated samples were put in a closed container whose inside was kept at 55% at 25 ° C., and then stored at 50 ° C. for 7 days (forced storage). The second sample of these and the sample for comparison aged (stored in a light-shielding container at room temperature) were subjected to the same treatment as that used for evaluation of photographic properties, and the density of the fog portion was measured. (Increase in fog) = (fog during forced aging) − (fog during comparative aging)

Table 2 shows the results.

[0104]

[Table 2]

It can be seen from Table 2 that the sample of the present invention has sufficient sensitivity and low fog as in Example 1.
Further, it can be seen that the storage stability of the light-sensitive material is also good.

[0106]

INDUSTRIAL APPLICABILITY The polyhalomethane compound of the present invention has a high synthetic yield, is preferable in production, and has a fog-inhibiting effect equivalent to or higher than that of a known polyhalomethane compound. Further, the light-sensitive material of the present invention has high sensitivity and low fog. Further, the storage stability of the photographic material is good.

Claims (5)

[Claims] 1. A silver halide light-sensitive material containing a polyhalomethane compound represented by formula (I). General formula (I) (In the formula, Q represents an aryl group. Z ₁ and Z ₂ each represent a halogen atom. Y represents —C (═O) — or —SO—.
Or -SO ₂ - represents a. k represents 0 or 1. W represents an electron-withdrawing group, and m represents an integer of 1 to 7. A represents a hydrogen atom or an electron-withdrawing group. ) 2. (a) a reducible silver salt, (b) a reducing agent,
A photothermographic material comprising (c) a photocatalyst, (d) a binder, and (e) a polyhalomethane compound represented by the general formula (I) according to claim 1. 3. The photothermographic material according to claim 2, which is for infrared laser exposure. 4. A polyhalomethane compound represented by the general formula (Ia). General formula (Ia): (In the formula, Q represents an aryl group. Z ₁ and Z ₂ each represent a halogen atom. Y represents —C (═O) — or —SO—.
Or -SO ₂ - represents a. X represents a halogen atom, and n
Represents an integer of 3 to 7. A represents a hydrogen atom or an electron-withdrawing group. ) 5. In the general formula (Ia), Q is a phenyl group, Y is —SO ₂ —, n is 3, and A is
Is a halogen atom, The polyhalomethane compound of Claim 4 characterized by the above-mentioned.