JP2000265077A - Recording material containing new squarylium compound, silver halide photographic photosensitive material, heat- development photosensitive material, heat-development image formation method, heat-sensitive recording material, heat-sensitive recording image formation method, infrared-absorbing composition, and new squarylium compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a material which gives images exhibiting a high sharpness and a low color turbidity by incorporating a new squarylium compound into the same. SOLUTION: A squarylium compound represented by formula I, II or III is incroporated as a colorant for thermal conversion. In the formulas, at least one of A1 and A2 is a 5- or 6-membered N-containing heterocyclic aromatic ring; at least one of R3 and R4 is a 6-membered N-containing heterocyclic aromatic ring represented by formula IV; at least one of R5 and R6 is an (iso)quinoline ring; R1 and R2 are each H, -OR4 or -NR5R6; R4 is H or a group replaceable by O; R5 and R6 are each H or a group replaceable by N; a ring containing both R1 and R2 may be formed; R5 and R6 may combine with each other to form a 5- or 6-membered ring; Z1 to Z6 are each C or N provided that at least one of them is C and that at least one of C-atoms represented by Z1 to Z6 is bonded to a squarylium carbon of formula II; R3 is a group capable of being bonded to atoms forming a 6-membered N- containing heterocyclic aromatic group; and n1 is 0-4. An example of the squarylium compound is represented by formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording material containing a novel squarylium compound, a silver halide photographic light-sensitive material, a heat-developable light-sensitive material, a heat-developable image forming method, a heat-sensitive recording material, a heat-sensitive recording image forming method, and infrared absorption Compositions and novel squarylium compounds.

[0002]

2. Description of the Related Art Naphthalene squarylium dyes using naphthalene derivatives as raw materials have been disclosed in J. Am. Chem. Soc.
Commun. , 452-454 (1993) and the like.
ocz. Chem. , 44, 691 (1970), but no squarylium dye from a benzene fused ring compound of a 6-membered nitrogen-containing heteroaromatic ring such as quinoline or isoquinoline is known.

Many recording materials using a phenylsquarylium dye or a naphthalene squarylium dye have been proposed, but a recording material using a compound in which a 5- or 6-membered nitrogen-containing heteroaromatic ring is directly bonded to a squarylium ring is proposed. Was unknown, and its properties were unknown.

On the other hand, various compounds are known as dyes for preventing halation and irradiation of silver halide photographic materials (including heat-developable materials). Particularly, for a recording material sensitized to an infrared wavelength, for example, a silver halide photographic light-sensitive material (including a heat-developable light-sensitive material) as a recording material for recording with the output of a near-infrared laser, the infrared region of the spectrum is used. Absorbing antihalation and antiirradiation dyes are needed. U.S. Pat. No. 5,380,635 uses dihydroperimidine dyes,
There is a problem that sharpness is poor when a laser of 0 nm is used. 350-450nm when used as a printing material
Was found to have a large absorption. Also, Japanese Patent Application Laid-Open No. 10-01 / 1998
No. 6410 uses a dihydroperimidine squarylium dye as a dye for photothermal conversion, but it has been found that there is a problem in the residual ratio of the dye.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a recording material, a silver halide photographic light-sensitive material, a heat-developable light-sensitive material, a heat-developable image forming method, and a novel squarylium compound containing a novel squarylium compound as a dye. And a method for forming a thermal recording image using the thermal recording material, and an infrared absorbing composition containing the novel squarylium compound as a dye. A squarylium compound is provided.

[0006]

The above objects of the present invention have been attained by the following constitutions.

[0007] 1. A recording material comprising a squarylium compound represented by the following general formula (1), (2) or (3).

[0008]

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[In the general formula (1), at least one of A ¹ and A ² represents a 5- or 6-membered nitrogen-containing heteroaromatic ring. ]

[0010]

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[In the general formula (2), at least one of A ³ and A ⁴ represents a 6-membered nitrogen-containing heteroaromatic ring represented by the following general formula (2 ′).

[0012]

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(In the general formula (2 ′), R ¹ and R ^{2 each} represent a hydrogen atom, —OR ⁴ or —NR ⁵ R ⁶ , and R ⁴ represents a group that can be substituted with a hydrogen atom or an oxygen atom. represents, R ^5, R ⁶ represents a group capable of substituting for a hydrogen atom or a nitrogen atom. in addition, may be ring containing R ¹ and R ² in the same ring is formed, R ⁵ and R
⁶ may combine with each other to form a 5- or 6-membered ring. Z ^{1 to} Z ⁶ each represent a carbon atom or a nitrogen atom, and any one of Z ^{1 to} Z ⁶ is a nitrogen atom, and at least one other is a carbon atom, represented by Z ^{1 to} Z ⁶ At least one of the carbon atoms is bonded to squarylium carbon of the general formula (2). R ³ represents a substituent capable of bonding to an atom forming a 6-membered nitrogen-containing heteroaromatic ring represented by the general formula (2 ′), and n1 represents an integer of 0 to 4. )]

[0014]

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[In the general formula (3), at least one of A ⁵ and A ⁶ represents a quinoline ring or an isoquinoline ring. ] 2. A silver halide photographic material comprising a squarylium compound represented by the above general formula (1).

3. A silver halide photographic material comprising a squarylium compound represented by the general formula (2).

4. A silver halide photographic material comprising a squarylium compound represented by the above general formula (3).

5. A photothermographic material comprising a squarylium compound represented by formula (1), (2) or (3).

A method for forming a heat-developable image, which comprises exposing the heat-developable photosensitive material according to 6.5 using an infrared laser beam.

[7] FIG. A heat-sensitive recording material comprising a squarylium compound represented by the general formula (1), (2) or (3).

8.7. A method for forming a thermosensitive recording image, which comprises exposing the thermosensitive recording material described in 8.7 using an infrared laser beam.

9. An infrared absorbing composition comprising a squarylium compound represented by the general formula (1), (2) or (3).

10. A squarylium compound represented by the general formula (1).

11. A squarylium compound represented by the general formula (2).

12. A squarylium compound represented by the general formula (3).

13. A compound represented by the following general formula (4).

[0027]

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[In the formula, Z ^{7 to} Z ⁹ each represent a carbon atom or a nitrogen atom, and one of Z ^{7 to} Z ⁹ is a nitrogen atom, and the other two are carbon atoms. Z ¹⁰ represents an oxygen atom or NR ⁷ , and Z ¹¹ represents an oxygen atom or NR ¹⁰ . R ⁷ to R ¹⁰ are each a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group or an aralkyl group, R ⁷ and R ^8, R ⁸ and R ⁹ or R ⁹ and R ¹⁰ are bonded to each other 5 Alternatively, a 6-membered ring may be formed. R ¹¹ represents a substituent capable of bonding to a quinoline ring or an isoquinoline ring;
2 represents an integer of 0 to 4; Hereinafter, the present invention will be described in detail.

The squarylium compound represented by the general formula (1), (2) or (3) will be described.

In the formula (1), at least one of A ¹ and A ² is a 5- or 6-membered nitrogen-containing heteroaromatic ring (for example, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxazole ring, a thiazole ring). , A triazole ring,
Oxadiazole ring, thiadiazole ring, indole ring, benzimidazole ring, benzothiazole ring, purine ring, pyridine ring, pyrazine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, isoquinoline ring, purine ring, cinnoline ring, quinoxaline Ring, acridine ring), and A ³ and A ⁴ in the general formula (2).
Is more preferably a 6-membered nitrogen-containing heteroaromatic ring represented by the general formula (2 ′), and particularly preferably a quinoline ring or isoquinoline ring structure.

The general formula (2 ') in the general formula (2)
In, Z ¹ to Z ⁶ each represents a carbon atom or a nitrogen atom, one of Z ¹ to Z ⁶ is a nitrogen atom, a remainder of at least one carbon atom, in Z ¹ to Z ⁶ At least one of the carbon atoms represented is bonded to squarylium carbon of the general formula (2).

R ¹ and R ² represent a hydrogen atom, —OR ⁴ or —
Represents NR ⁵ R ⁶ . Further, a ring containing R ¹ and R ² in the same ring may be formed. R ⁴ represents a substituent capable of substitution on a hydrogen atom or an oxygen atom, it represents an R ^5, R ⁶ are each a group capable of substituting for a hydrogen atom or a nitrogen atom, capable of substituting the oxygen atoms represented by R ⁴ Specific examples of the group and the substituent that can be substituted on the nitrogen atom represented by R ⁵ and R ⁶ include a halogen atom (including a chlorine atom, a bromine atom, an iodine atom, a fluorine atom, and preferably a bromine atom), and an alkyl group. (Preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms,
Particularly preferably, it has 1 to 8 carbon atoms, for example, methyl, trifluoromethyl, ethyl, iso-propyl, ter
t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), 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, for example, vinyl, allyl,
2-butenyl, 3-pentenyl and the like. ),
An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, and particularly preferably having 2 to 8 carbon atoms, such as propargyl and 3-pentynyl); Number 6 to 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 carbon atoms
-12, for example, phenyl, p-methylphenyl,
Naphthyl and the like. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, and dibenzylamino. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, and pivaloyl).
An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms;
More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl. ), An aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms, such as phenyloxycarbonyl, etc.), and an acylamino group (preferably). Has 2 to 20 carbon atoms,
More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino and benzoylamino. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino).
An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms, such as phenyloxycarbonylamino, etc.), and a sulfonylamino group ( It preferably has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino and the like.), A sulfamoyl group (preferably carbon number) It has 0 to 20, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl and the like.), Carbamoyl group (preferably carbon number) 1 to 20, more preferably 1 to 16, particularly preferably 1 to 2, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like; an alkylsulfonyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms). 12, for example, methylsulfonyl, ethylsulfonyl, etc.) and an arylsulfonyl group (preferably having 6 to 6 carbon atoms).
20, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylsulfonyl. ), A sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, such as methanesulfinyl and benzenesulfinyl), and a ureido group (preferably). Has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms,
For example, ureide, methylureide, phenylureide and the like can be mentioned. ), A hydroxyl group, a heterocyclic group (eg, triazolyl, imidazolyl, pyridyl, furyl,
Piperidyl, morpholino and the like. ). These substituents may be further substituted.

R ⁵ is preferably a hydrogen atom.
R ⁴ and R ⁶ are an alkyl group, an alkenyl group, an alkynyl group,
It is preferably an aryl group or a heterocyclic group. Particularly preferred is an alkyl group.

When a ring containing R ¹ and R ² in the same ring is formed, the ring is preferably a 6-membered ring or more, and particularly preferably a 6-membered ring.

R ³ represents a substituent capable of bonding to an atom forming a 6-membered nitrogen-containing heteroaromatic ring represented by the general formula (2 ′) in the general formula (2), and specifically, an alkyl group (Preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl group (preferably having 2 to 2 carbon atoms).
20, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms, such as propargyl and 3-pentynyl), and an aryl group (preferably). Has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 30 carbon atoms.
12, for example, phenyl, p-methylphenyl, naphthyl and the like. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, and dibenzylamino. ), An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, particularly preferably having 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, and butoxy), and aryloxy. A group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 12 carbon atoms, such as phenyloxy and 2-naphthyloxy), and an acyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms
2, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl and the like.), Aryloxycarbonyl Groups (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms, such as phenyloxycarbonyl, etc.), and acyloxy groups (preferably having 2 to 2 carbon atoms). 20, more preferably 2 carbon atoms
-16, particularly preferably 2-10 carbon atoms, such as acetoxy and benzoyloxy. ),
Acylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms)
And include, for example, acetylamino, benzoylamino and the like. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 1 carbon atoms)
6, particularly preferably having 2 to 12 carbon atoms, such as methoxycarbonylamino. ), An aryloxycarbonylamino group (preferably having 7 to 2 carbon atoms)
0, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino. ), A sulfonylamino 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, methanesulfonylamino, benzenesulfonylamino and the like. ), A sulfamoyl group (preferably having a carbon number of 0 to 20, more preferably a carbon number of 0 to 16, and particularly preferably a carbon number of 0 to 12, and examples thereof include sulfamoyl, methylsulfamoyl, and dimethylsulfamoyl. ), Carbamoyl group (preferably having 1 to carbon atoms)
20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, 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 having 1 to 12 carbon atoms, such as methylthio and ethylthio, etc.), and an arylthio group (preferably carbon Number 6 to 20, more preferably carbon number 6
To 16, particularly preferably 6 to 12 carbon atoms, such as phenylthio. ), A sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably 1 carbon atom)
To 16, particularly preferably 1 to 12 carbon atoms, for example, methanesulfinyl, benzenesulfinyl and the like. ), Ureido group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include ureide, methylureide, and phenylureide. ), A phosphoric amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 carbon atom)
To 16, particularly preferably 1 to 12 carbon atoms, for example, diethylphosphoramide, phenylphosphoramide and the like. ), Hydroxy, mercapto, halogen, (eg, fluorine, chlorine, bromine, iodine), cyano, sulfo, carboxyl, nitro, hydroxamic acid, sulfino, hydrazino,
Heterocyclic groups (eg imidazolyl, pyridyl, furyl,
Piperidyl, morpholino and the like. ). These substituents may be further substituted.

N1 represents an integer of 0 to 4, preferably 0 or 1, and particularly preferably 0.

The bonding position of the squarin ring is usually ortho or para to R ¹ or R ² .

In the general formula (3), at least one of A ⁵ and A ⁶ represents a quinoline ring or an isoquinoline ring.

The compound represented by formula (4) will be described.

In the general formula (4), Z ^{7 to} Z ⁹ each represent a carbon atom or a nitrogen atom, one of Z ^{7 to} Z ⁹ is a nitrogen atom, and the other two are carbon atoms. is there. Z ¹⁰ represents an oxygen atom or NR ⁷ , and Z ¹¹ represents an oxygen atom or NR ¹⁰ . n2 represents an integer of 0 to 4,
It is preferably 0 or 1, and particularly preferably 0.

[0041] R ¹¹ represents an linkable substituents quinoline ring or an isoquinoline ring, examples given for R ³ in the general formula in formula (2) specifically (2 ') is preferably also R ^11.

The alkyl group represented by R ^{7 to} R ¹⁰ is an alkyl group having 1 to 20, more preferably 1 to 12 carbon atoms (eg, methyl, ethyl, propyl, butyl, hexyl, undecyl). In addition, halogen atoms (F, C
l, Br), alkoxycarbonyl (eg, methoxycarbonyl, ethoxycarbonyl), hydroxy, alkoxy (eg, methoxy, ethoxy, phenoxy, isobutoxy), sulfo (which may be a salt), carboxyl (which may be a salt) or acyloxy (for example, Acetyloxy, butyryloxy, hexyloxy, benzoyloxy) and the like.

Examples of the cycloalkyl group represented by R ^{7 to} R ¹⁰ include cyclopentyl and cyclohexyl.

The aralkyl group represented by R ^{7 to} R ¹⁰ is 7
Aralkyl groups having from 12 to 12 carbon atoms are preferred (eg, benzyl, phenylethyl) and substituents (eg,
Methyl, methoxy, and chloro atoms).

Examples of the heterocyclic group represented by R ^{7 to} R ¹⁰ include thienyl, furyl, pyrrolyl, pyrazolyl, pyridyl, indolyl and the like.

R ⁷ and R ¹⁰ are preferably hydrogen atoms.

R ⁷ and R ⁸ , R ⁸ and R ⁹ or R ⁹ and R ¹⁰ may combine with each other to form a cyclopentane or cyclohexane ring.

Specific examples of the squarylium compound (dye) represented by the general formula (1), (2) or (3) of the present invention are shown below, but the present invention is not limited to these.

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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Specific examples of the compound represented by formula (4) of the present invention are shown below, but the present invention is not limited thereto.

[0057]

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[0058]

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The recording material of the present invention can be used for a silver halide photosensitive material such as a color negative film, a color reversal film, a color paper, a printing film, a medical x-ray film, a medical laser imager output, and a printing. In addition to photothermographic materials for image setter output, etc., recording with near-infrared light, especially recording materials using semiconductor lasers, printing plates for printing, direct printing plates, and optical recording materials such as photoresist materials and optical disks , An electrophotographic recording material, an ink jet recording material, a heat-sensitive recording material and the like.

The compounds of the present invention include filter dyes such as band-pass filters, optical filters, and heat-absorbing filters, inks for invisible printing, infrared absorbing paints for preventing laser light reflection, toners for electrophotography, and toners for promoting heat fixation. Infrared absorbing composition and halogenation for electrophotographic photoreceptors, sensitizers for photopolymerization or photocrosslinking, optical recording materials such as optical disks, inkjet inks, thermal transfer dyes, photothermal conversion dyes, optical sensors, etc. It can be used for silver photosensitive materials.

When the compound of the present invention is used in a silver halide light-sensitive material, the spectral sensitizer, silver halide emulsion and the like used in the silver halide light-sensitive material are described in JP-A-6-206.
No. 43,583 can be referred to.

When the compound of the present invention is used for detecting the position of a silver halide photographic light-sensitive material, JP-A-09-9
No. 6891 can be used as a reference.

Further, when the compound of the present invention is used for a heat-sensitive recording material, JP-A-10-114151 and JP-A-1
The method described in No. 0-16410 can be referred to.

When the compound of the present invention is used as a filter, ink or paint, JP-A-64-69686 describes
U.S. Pat.

The photothermographic material of the present invention forms a photographic image using a photothermographic processing method. Photothermographic materials for forming a photographic image by using a heat development processing method are described in, for example, U.S. Pat. Morgan and B.A. Sherry (She
ly) "Silver systems treated by heat (Th
thermally Processed Silver
Systems) "(Imaging Processes
And Materials (Imaging Procedures)
ses and Materials) Neblet
te 8th edition, Sturge, V.E. Walworth, A .; Shep (She
pp) Compilation, page 2, 1969).

The dye of the present invention is preferably dissolved in an organic solvent and added. The dye is 0.1-1000mg / m
² , preferably 1 to 200 mg / m ² . When using a binder, 0.1 to the binder
It is 60% by weight, preferably 0.2 to 30% by weight, more preferably 0.5 to 10% by weight.

The photothermographic material of the present invention preferably has a photosensitive layer containing an organic silver salt, a binder and photosensitive silver halide on a support. The dye of the present invention is preferably contained in the photosensitive layer.

The backing layer of the photosensitive material according to the present invention refers to a layer provided on the side opposite to the photosensitive layer with respect to the support, and the dye of the present invention is contained in the backing layer. Is preferred.

The support applicable to the photothermographic material of the present invention includes, for example, materials such as paper, polyethylene-coated paper, polypropylene-coated paper, parchment, and cloth;
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 or platinum; polyalkyl methacrylates (eg, polymethyl methacrylate), polyesters (eg, polyethylene terephthalate), polyvinyl acetal, polyamides (eg, nylon), cellulose esters (Eg, cellulose nitrate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate) and the like.

The photothermographic material of the present invention may contain, for example, a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, and a coating aid.

In the present invention, the organic silver salt is a reducible silver source, and a silver salt of an organic acid and a heteroorganic acid containing a reducible silver ion source, especially a long chain (10 to 3 carbon atoms).
0, preferably 15 to 25) aliphatic carboxylic acids and nitrogen-containing heterocycles are preferred. Organic or inorganic silver salt complexes whose ligands have a total stability constant for silver ions of 4 to 10 are also useful. An example of a suitable silver salt is Research Di.
Nos. 17029 and 29996, and includes: salts of organic acids (eg, salts of gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid, lauric acid, etc.); silver carboxyalkylthioureas Salts (for example, 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea, etc.); silver complexes of a polymer reaction product of an aldehyde and a hydroxy-substituted aromatic carboxylic acid ( Aldehydes such as formaldehyde, acetaldehyde, butyraldehyde, hydroxy-substituted acids such as salicylic acid, benzoic acid, 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), silver salts or complexes of thioenes (for example, 3 -(2-carboxyethyl) -4-hydroxymethyl-4-thiazoline 2-thioene and 3-carboxymethyl-4-thiazoline-2-thioene), imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,4- Complexes or salts of silver and a nitrogen acid selected from triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. The preferred silver source is silver behenate. The organic silver salt is preferably 3 g / m 2 in terms of silver amount.
It is contained in ² or less. More preferably, it is 2 g / m ² or less.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver, and includes a normal mixing method, a reverse mixing method, a simultaneous mixing method, and a method described in JP-A-9-12764.
A controlled double jet method as described in No. 3 is preferably used.

The silver halide grains in the present invention function as an optical sensor. In order to suppress white turbidity after image formation and to obtain good image quality, it is preferable that the average particle size is small.
0 μm or less, more preferably 0.03 to 0.15 μm,
Particularly, the thickness is preferably from 0.03 to 0.11 μm. The term "grain size" as used herein refers to the length of a ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. If the crystal is not normal, for example, spherical,
In the case of rod-shaped or tabular grains, it refers to the diameter of a sphere equivalent to the volume of silver halide grains.

The shape of the silver halide grains is not particularly limited, but the proportion occupied by the Miller index [100] plane is preferably high, and this proportion is 50% or more, more preferably 7%.
It is preferably at least 0%, particularly preferably at least 80%. The ratio of the [100] plane of the Miller index is determined by the T.V. method using the dependence of the adsorption of the sensitizing dye on the [111] plane and the [100] plane. Tani, J .; Imaging Sci. , 29,
165 (1985).

The halogen composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide. The photographic emulsion used in the present invention is P.I. Chimie et by Glafkids
Physique Photographique
(Paul Montel, 1967);
F. Photographic Em by Duffin
ulsion Chemistry (The Foca
l Press, 1966); L. Zelik
Making and Coa by man et al
ting Photographic Emulsio
n (published by The Focal Press, 1964)
Can be prepared using the methods described in US Pat. That is, any of an acidic method, a neutral method, an ammonia method, and the like may be used, and a method of reacting a soluble silver salt with a soluble halide may be any of a one-sided mixing method, a simultaneous mixing method, a combination thereof, and the like. Good. The silver halide may be added to the image-forming layer by any method, wherein the silver halide is arranged close to a reducible silver source. Further, the silver halide may be prepared by converting a part or all of silver in the organic acid silver by the reaction between the organic acid silver and the halogen ion, to the silver halide, or the silver halide may be prepared in advance. It may be prepared and added to a solution for preparing the organic silver salt, or a combination of these methods is possible, but the latter is preferred. Generally, silver halide is preferably contained in an amount of 0.75 to 30% by weight based on the organic silver salt.

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

These metal ions can be introduced into silver halide in the form of a metal complex or a metal complex ion. As these metal complexes or metal complex ions, hexacoordinate metal complexes represented by the following general formula are preferable.

In the formula [ML ₆ ] ^m , M is a transition metal selected from elements of Groups 6 to 11 of the periodic table, L is a ligand, and m is 0,-, 2-, 3- or 4-
Represents Specific examples of the ligand represented by L include halides (fluoride, chloride, bromide and iodide), cyanide, cyanate, thiocyanate, selenocyanate, tellurocyanate, azide and aquo. Ligand, nitrosyl, thionitrosyl and the like, preferably aquo, nitrosyl and thionitrosyl. If an aquo ligand is present, it preferably occupies one or two of the ligands. L may be the same or different.

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

Specific examples of transition metal complex ions are shown below, but the present invention is not limited to these.

[0081] 1: [RhCl _6] ^3- 2: [RuCl _6] ^3- 3: [ReCl _6] ^3- 4: [RuBr _6] ^3- 5: [OsCl _6] ^3- 6: [IrCl _6] ^{4 -} 7: [CrCl _6] ^4- 8: [Ru (NO) Cl _5] ^2- 9: [RuBr ₄ (H ₂ O)] ^2- 10: _{[Ru (NO) (H 2 O} ) Cl 4 ] ^- 11: [RhCl ₅ (H ₂ O)] ^2- 12: [Re (NO) Cl _5] ^2- 13: [Re (NO) (CN) _5] ^2- 14: [Re (NO) Cl (CN) _4] ^2- 15: [Rh (NO) ₂ Cl _4] ^- 16: _{[Rh (NO) (H 2 O} ) Cl 4 ] ^- 17: [Ru (NO) (CN) _5] ^2- 18: [Fe (CN) ₆ ] ^3-19 : [Rh (NS) Cl ₅ ] ^2-20 : [Os (NO) Cl ₅ ] ^2-21 : [Cr (NO) Cl ₅ ] ^2-22 : [Re (NO) Cl _5] ^- 23: [Os (N ) _Cl 4 (TeCN)] ^2- 24: [Ru (NS) Cl _5] ^2- 25: _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 26: [Os (NS) Cl (SCN) 4 ] ^{2 -} 27: [Ir (NO) Cl _5] ^2- 28: [Ir (NS) Cl _5] ^2- these metal ions, metal complexes or metal complex ions may be one type, the same kind of metal or different metals May be used in combination of two or more. The content of these metal ions, metal complexes or metal complex ions, generally is suitably 1 × 10 ^-9 ~1 × 10 ^-2 mol per mol of silver halide, preferably 1 × 10 ^{- It is 8} to 1 × 10 ^-4 mol.

The compounds providing these metals are preferably added during silver halide grain formation and incorporated into silver halide grains. Preparation of silver halide grains, that is, nucleation, growth, physical ripening, and chemical ripening are carried out. Although it may be added at any stage before and after sensitization, it is particularly preferable to add at the stage of nucleation, growth and physical ripening, more preferably at the stage of nucleation and growth, and most preferably. It is added at the stage of nucleation.

In the addition, it may be added in several portions, may be added uniformly in the silver halide grains, or may be added to silver halide grains.
-306236, 3-167545, 4-76
No. 534, No. 6-110146, No. 5-273683
As described in Japanese Patent Application Laid-Open No. H11-157, etc., the particles can be contained in the particles with a distribution. Preferably, a distribution can be provided inside the particles.

These metal compounds can be added by dissolving them in water or a suitable organic solvent (eg, alcohols, ethers, glycols, ketones, esters, amides). A method in which an aqueous solution of a powder or an aqueous solution in which a metal compound and sodium chloride and potassium chloride are dissolved together is added to a water-soluble silver salt solution or a water-soluble halide solution during grain formation, or a silver salt solution and a halide solution Are mixed at the same time,
A method of preparing silver halide grains by a method of simultaneous mixing of three liquids, adding a required amount of an aqueous solution of a metal compound into a reaction vessel during grain formation, or adding a third solution at the same time. There is a method in which another silver halide grain doped with a metal ion or complex ion is added and dissolved. In particular, a method of adding an aqueous solution of a powder of a metal compound or an aqueous solution in which a metal compound is dissolved together with sodium chloride and potassium chloride to a water-soluble halide solution is preferable.

When adding to the particle surface, a necessary amount of an aqueous solution of a metal compound can be charged into the reaction vessel immediately after the formation of the particles, during or during the physical ripening, or at the end of the ripening, or during the chemical ripening.

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

Aminohydroxycycloalkenones (eg, 2-hydroxypiperidino-2-cyclohexenone); aminoreductones (r
eductones) esters (eg, piperidinohexose reductone monoacetate); N-hydroxyurea derivatives (eg, Np-methylphenyl-N-hydroxyurea); hydrazones of aldehydes or ketones (eg, anthracene aldehyde phenylhydrazone); Furamidophenols; Phosphoramidoanilines; Polyhydroxybenzenes (eg, hydroquinone, t-butyl-hydroquinone, isopropylhydroquinone and (2,5-dihydroxy-phenyl) methylsulfone); Sulfhydroxamic acids (eg, benzenesulfuric acid) Hydroxamic acid); sulfonamidoanilines (for example, 4- (N-methanesulfonamido) aniline);
-Tetrazolylthiohydroquinones (e.g., 2-methyl-5- (1-phenyl-5-tetrazolylthio) hydroquinone); tetrahydroquinoxalines (e.g., 1,
2,3,4-tetrahydroquinoxaline); amideoxins; azines (for example, a combination of an aliphatic carboxylic acid arylhydrazide and ascorbic acid); a combination of polyhydroxybenzene and hydroxylamine;
Reductone and / or hydrazine; hydroxanoic acids;
Combinations of azines and sulfonamidophenols;
α-cyanophenylacetic acid derivatives; combinations of bis-β-naphthol and 1,3-dihydroxybenzene derivatives;
5-pyrazolones; sulfonamide phenol reducing agents;
2-phenylindane-1,3-dione and the like; chroman;
1,4-dihydropyridines (for example, 2,6-dimethoxy-3,5-dicarbethoxy-1,4-dihydropyridine); bisphenols (for example, bis (2-hydroxy-3-t-butyl-5-methylphenyl) Methane, bis (6-hydroxy-m-tri) mesitol (mesi
tol), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,5-ethylidene-bis (2-
t-butyl-6-methyl) phenol), ultraviolet-sensitive ascorbic acid derivatives and 3-pyrazolidones. Among them, particularly preferred reducing agents are hindered phenols.
Examples of the hindered phenols include compounds represented by the following general formula (A).

[0088]

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In the formula, R represents a hydrogen atom or a group having 1 to 1 carbon atoms.
Represents an alkyl group of 10 (for example, butyl, 2,4,4-trimethylpentyl), and R ′ and R ″ have 1 to 1 carbon atoms.
5 alkyl groups (eg, methyl, ethyl, t-butyl)
Represents

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

[0091]

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[0092]

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

Binders suitable for the photothermographic material of the present invention are transparent or translucent and generally colorless, and include natural polymer synthetic resins, polymers and copolymers, and other film-forming media such as gelatin, gum arabic and polyvinyl alcohol. , Hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate,
Polyvinylpyrrolidone, casein, starch, polyacrylic acid, polymethyl methacrylate, polyvinyl chloride, polymethacrylic acid, styrene-maleic anhydride copolymer,
Styrene-acrylonitrile copolymer, styrene-butadiene copolymer, polyvinyl acetal (eg, polyvinyl formal and polyvinyl butyral), polyesters, polyurethanes, phenoxy resin, polyvinylidene chloride, polyepoxides, polycarbonates,
There are polyvinyl acetate, cellulose esters and polyamides. It may be hydrophilic or non-hydrophilic.

In the present invention, the binder amount of the photosensitive layer is preferably from 1.5 to 6 g / m ² . More preferably, it is 1.7 to 5 g / m ² . If it is less than 1.5 g / m ² , the density of the unexposed portion will increase significantly and may not be usable.

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

The material of the matting agent used in the present invention may be either an organic substance or an inorganic substance. For example, inorganic substances include silica described in Swiss Patent No. 330,158, glass powder described in French Patent No. 1,296,995, etc., and alkaline earth described in British Patent No. 1,173,181 and the like. Metals or carbonates such as cadmium and zinc can be used as the matting agent. Examples of organic substances include starch described in U.S. Pat. No. 2,322,037, starch derivatives described in Belgian Patent No. 625,451 and British Patent No. 981,198, and JP-B-44-3643. Polyvinyl alcohol, Swiss Patent No. 330,15
Organic matting agents such as polystyrene or polymethacrylate described in No. 8, polyacrylonitrile described in U.S. Pat. No. 3,079,257, and polycarbonate described in U.S. Pat. No. 3,022,169 can be used. it can.

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

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

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

(Standard deviation of particle size) / (average value of particle size) × 100 The matting agent according to the present invention can be contained in any constituent layer, but in order to achieve the object of the present invention, , Preferably a constituent layer other than the photosensitive layer, and more preferably an outermost layer as viewed from the support.

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

When the photothermographic material of the present invention is a photothermographic material for output of an image setter for printing,
The hydrazine compound is preferably contained in the light-sensitive material.

The preferred hydrazine compound used in the present invention includes Research Disclosure
Item 23516 (November 1983, p. 34)
6) and the references cited therein, as well as U.S. Pat.
080,207, 4,269,929, 4,2
No. 76,364, No. 4,278,748, No. 4,38
5,108, 4,459,347, 4,47
Nos. 8,928, 4,560,638, 4,68
6,167, 4,912,016 and 4,98
8,604, 4,994,365 and 5,04
1,355, 5,104,769, British Patent 2,011,391B, European Patent 217,310
Nos. 301,799, 356,898, JP-A-60-179834, JP-A-61-170733, and 6
1-270744, 62-178246, 62
-270948, 63-29751, 63-3
No. 2538, No. 63-104047, No. 63-121
No. 838, No. 63-129337, No. 63-2237
No. 44, No. 63-234244, No. 63-23424
No. 5, 63-234246, 63-294552
No. 63-306438, No. 64-10233,
JP-A-1-90439, JP-A-1-100530, JP-A-1
No. -105941, No. 1-105943, No. 1-27
Nos. 6128, 1-280747, 1-228354
8, No. 1-283549, No. 1-285940,
2-2541, 2-77057, 2-139
No. 538, No. 2-196234, No. 2-196235
No. 2-198440, No. 2-198441, No. 2-198442, No. 2-220042, No. 2-2
No. 21953, No. 2-221954, No. 2-2853
No. 42, No. 2-285343, No. 2-289843
Nos. 2-302750, 2-304550, 3-37642, 3-54549, 3-125
No. 134, No. 3-184039, No. 3-240036
No. 3-240037, No. 3-259240, No. 3-280038, No. 3-282536, No. 4-5
No. 1143, No. 4-56842, No. 4-84134
No. 2-230233, No. 4-96053, No. 4
-216544, 5-45761, 5-457
No. 62, No. 5-45763, No. 5-45764, No. 5-45765, No. 6-289524, No. 9-16
No. 0164 and the like.

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

In the present invention, the amount of the hydrazine compound to be added is from 1 × 10 ^-6 mol to 1 × 10 ⁶ mol / mol of silver.
^-1 mol is preferable, and the range of 1 × 10 ⁻⁵ mol to 5 × 10 ⁻² mol is particularly preferable.

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

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

The photothermographic material of the present invention is stable at room temperature, but is developed by heating to a high temperature (for example, 80 to 140 ° C.) after exposure. Heating generates silver through an oxidation-reduction reaction between an organic silver salt (functioning as an oxidizing agent) and a reducing agent. This oxidation-reduction reaction is accelerated by the catalytic action of the latent image generated on the silver halide upon exposure. The silver formed by the reaction of the organic silver salt in the exposed areas provides a black image, which contrasts with the unexposed areas, resulting in the formation of an image. This reaction process proceeds without supplying a processing liquid such as water from the outside.

The photothermographic material of the present invention has at least one photosensitive layer on a support. Although only a photosensitive layer may be formed on the support, it is preferable to form at least one non-photosensitive layer on the photosensitive layer. The photosensitive layer may be composed of a plurality of layers, and the sensitivity may be changed to a high-sensitivity layer / low-sensitivity layer or a low-sensitivity layer / high-sensitivity layer for adjusting the gradation.
Various additives may be added to any of the photosensitive layer, the non-photosensitive layer, and other forming layers.

In 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.

The photothermographic material of the present invention preferably contains a toning agent. Examples of suitable toning agents include Rese
Arch Disclosure No. 17029, which includes:

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 (e.g., N-hydroxy-1,8-naphthalimide); cobalt complexes (e.g., hexamine trifluoroacetate of cobalt); mercaptans (e.g., 3-mercapto-1,2,4-triazole); -(Aminomethyl) aryldicarboximides (e.g. N-
(Dimethylaminomethyl) phthalimide); blocked pyrazoles, isothiuronium
Rnium derivative and a combination of certain photobleaches (eg, N, N'-hexamethylene (1-carbamoyl-3,5-dimethylpyrazole), 1,8- (3,6
-Dioxaoctane) bis (isothiuronium trifluoroacetate) and 2- (tribromomethylsulfonyl) benzothiazole in combination; merocyanine dyes (e.g., 3-ethyl-5-((3-ethyl-2-benzothia) Zolinylidene (benzothiazolinylidene)-
1-methylethylidene) -2-thio-2,4-oxazolidinedione); phthalazinone, a phthalazinone derivative or a metal salt of these derivatives (eg, 4- (1-naphthyl) phthalazinone, 6-chlorophthalazinone, 5,7-
Dimethyloxyphthalazinone and 2,3-dihydro-
1,4-phthalazinedione); a combination of phthalazinone and a sulfinic acid derivative (eg, 6-chlorophthalazinone + sodium benzenesulfinate or 8-methylphthalazinone + sodium p-trisulfonate); a combination of phthalazine + phthalic acid; Phthalazine (including adducts of phthalazine) and maleic anhydride, and phthalic acid,
Combination with at least one compound selected from 2,3-naphthalenedicarboxylic acid or o-phenylene acid derivatives and anhydrides thereof (for example, phthalic acid, 4-methylphthalic acid, 4-nitrophthalic acid and tetrachlorophthalic anhydride) Quinazolinediones, benzoxazines, naloxazine derivatives; benzoxazine-2,4-diones (eg, 1,3-benzoxazine-2,4-dione); pyrimidines and asymmetric triazines (eg, 2,4- Dihydroxypyrimidine) and tetrazapentalene derivatives (eg, 3,6-dimercapto-1,4-
Diphenyl-1H, 4H-2,3a, 5,6a-tetrazapentalen). Preferred toning agents are phthalazone or phthalazine.

The photothermographic materials of the present invention include, for example, JP-A-63-159841, JP-A-60-140335, JP-A-63-231437, JP-A-63-259651, and JP-A-6-259561.
3-304242, 63-15245, U.S. Pat. Nos. 4,639,414, 4,740,455, 4,741,966, 4,751,175, and 4,835. No. 096 can be used. Useful sensitizing dyes for use in the present invention include, for example, Re
search Disclosure Item176
Item 43IV-A (p.23, December 1978), Item
m1831X (August 1978, p. 437).

In particular, sensitizing dyes having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) For an argon laser light source,
JP-A-60-162247, JP-A-2-48653
No. 2,161,331, West German Patent 93
No. 6,071 and Japanese Patent Application Nos. 3-189532 and B) For helium-neon laser light sources, see JP-A-50-62425 and JP-A-50-62425.
For the trinuclear cyanine dyes described in JP-A Nos. 18726 and 59-102229, the merocyanines described in Japanese Patent Application No. 6-103272, C) LED light sources and red semiconductor lasers, see JP-B-48-42172. No. 51-9
Nos. 609 and 55-39818, JP-A-62-284.
Thiacarbocyanines described in JP-A-343-343 and JP-A-2-105135, and D) Infrared semiconductor laser light sources are described in JP-A-59-190332 and JP-A-60-808.
No. 41, tricarbocyanines described in
For example, dicarbocyanines containing a 4-quinoline nucleus described in formulas (IIIa) and (IIIb) of JP-A-192242 and JP-A-3-67242 are advantageously selected.

Further, the wavelength of the infrared laser light source is 750 n
m or more, more preferably 800 nm or more,
In order to cope with the laser in such a wavelength range, Japanese Patent Application Laid-Open Nos. 4-182439, 5-341432, 6-52387, and 3-10931, and U.S. Pat. No. 5,441,866. Sensitizing dyes described in JP-A-7-13295 and the like are preferably used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

Exposure of the photothermographic material of the present invention is performed using an infrared semiconductor laser (780 nm, 810 nm, 830 nm).
Are preferred.

[0118]

Hereinafter, the present invention will be described with reference to examples.
Embodiments of the present invention are not limited to this.

Example 1 << Synthesis of Exemplified Compound of the Present Invention >> Synthesis of Exemplified Compound 4-2 and Exemplified Compound 1-2 Synthetic Route

[0120]

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(Synthesis of Exemplified Compound 4-2) Hetero
cycles, 26 (4), 1029-1036 (19
87) Into 6.3 g of 4,5-quinolinediamine obtained by the method described in 87) and 20 ml of ethyl alcohol, 8.1 g of 5-undecanone was added and refluxed for 9 hours. Further, 15 g of 5-undecanone was added, and the mixture was refluxed for 3 hours. The reaction product was concentrated and purified by column chromatography to obtain 2.0 g of Exemplified Compound 4-2 as a brown solid. It was confirmed to be Exemplified Compound 4-2 from the NMR spectrum and the mass spectrum.

(Synthesis of Exemplified Compound 1-2) 2.0 g of Exemplified Compound 4-2 (used as an intermediate) obtained above, 3,4
0.4 g of dihydroxy-3-cyclobutene-1,2-dione, 30 ml of n-butanol and 30 m of toluene
1 was reacted at an external temperature of 140 ° C. for 3 hours while removing generated water. The reaction product was concentrated and purified by column chromatography to give Exemplified Compound 1-2 as a pale green solid.
4 g were obtained. From NMR spectrum and mass spectrum, it was confirmed to be Exemplified Compound 1-2.

Other compounds can be synthesized in the same manner.

Example 2 << Preparation and Evaluation of Photothermographic Material >> (Preparation of Silver Halide Particles A) 7.5 g of gelatin and 10 mg of potassium bromide were dissolved in 900 ml of pure water, and the temperature was 35 ° C. and the pH was 3 After adjusting the pH to 7.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (96/4) were maintained at pAg 7.7 by a controlled double jet method for 10 minutes. Was added. Thereafter, 4-hydroxy-6-methyl-1,
0.3 g of 3,3a, 7-tetrazaindene was added and Na was added.
Adjust the pH to 5 with OH and average particle size 0.06μ
m, coefficient of variation of projected diameter area 8%, {100} surface ratio 8
6% of cubic silver iodobromide grains were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, and after desalting, 0.1 g of phenoxyethanol was added to adjust the pH to 5.9 and the pAg to 7.5. Thereafter, sensitizing dye-1 and sensitizing dye-2 were added in an amount of 5 × 10 ^-5 mol per mol of silver halide. Thereafter, the temperature was raised to 60 ° C., 2 mg of sodium thiosulfate was added, the mixture was aged for 100 minutes, and then cooled to 38 ° C. to complete the chemical sensitization to obtain silver halide grains A.

[0125]

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(Preparation of Organic Fatty Acid Silver Emulsion A) 300 m of water
10.6 g of behenic acid is added to the mixture and heated and melted at 90 ° C.
11.1% sodium hydroxide 31.1m with sufficient stirring
was added and left as it was for 1 hour. Thereafter, the mixture was cooled to 30 ° C., 7.0 g of 1N phosphoric acid was added, and 0.01 g of N-bromosuccinimide was added with sufficient stirring.
Was added. Thereafter, the silver halide grains A prepared in advance as described above were used in an amount of 10 mol% as silver based on behenic acid.
While stirring at a temperature of 40 ° C. so that Further, 25 ml of a 1N aqueous solution of silver nitrate was continuously added over 2 minutes, and the mixture was allowed to stand for 1 hour with stirring.

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

(Composition of photosensitive layer) 1.75 g (in silver) of organic fatty acid silver emulsion A / m ² pyridinium hydrobromide perbromide 1.5 × 10 ^-4 mol / m ² Calcium bromide 1.8 × 10 ^-4 mol / M ² 2,4-dichlorobenzoic acid 1.5 × 10 ⁻³ mol / m ² sensitizing dye-1 2.1 × 10 ⁻⁶ mol / m ² sensitizing dye-2 2.1 × 10 ⁻⁶ mol / M ² 2-mercaptobenzimidazole 3.2 × 10 ⁻³ mol / m ² 2-tribromomethylsulfonylpyridine 6.0 × 10 ⁻⁴ mol / m ² Dye of the present invention, comparative dye 1 (see Table 1) Description) As a solvent of 5.0 × 10 ⁻⁵ mol / m ² , methyl ethyl ketone, acetone, and methanol were appropriately used.

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

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

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

Cellulose acetate 4 g / m ² Dye of the present invention, comparative dye 1 (described in Table 1) 5.0 × 10 ⁻⁵ mol / m ² Polymethyl methacrylate (particle size: 10 μm) 0.02 g / m ² Was applied to a biaxially stretched polyethylene terephthalate film having a thickness of 175 μm and dried to obtain a coated sample.

The photothermographic material prepared as described above was processed into a half-cut size, and a 810 nm laser diode was exposed to a beam inclined by 13 ° from the vertical plane. Thereafter, heat development was performed at 120 ° C. for 15 seconds using a heat drum.

<< Evaluation Method >>"Evaluation of Sharpness" The MTF value of each developed sample at 10 lines / mm was measured. Table 1 shows relative values when the MTF value of 101 is 100.

"Visual evaluation of color turbidity" Subjective evaluation was performed using 10 monitors. 3 levels that are practically acceptable
The score of all the evaluators was evaluated assuming that the point and the level of allowable margin were 1 point and the level that was not practically used was 0 point.

[0136]

[Table 1]

[0137]

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Table 1 shows that the sample of the present invention had good sharpness and little color turbidity.

Example 3 << Preparation and evaluation of photothermographic material >> [Preparation of subbed photographic support] <Preparation of PET subbed photographic support> Thickness of commercially available biaxially stretched heat fixed A corona discharge treatment of 8 w / m ² · min is applied to both sides of a 100 μm PET film, and the following undercoating coating solution a-1 is applied to one side to a dry film thickness of 0.8 μm and dried. An undercoating coating solution b-1 was applied to the opposite surface so as to have a dry film thickness of 0.8 μm and dried to obtain an undercoating layer B-1.

<< Undercoat Coating Solution a-1 >> Butyl acrylate (30% by weight) t-butyl acrylate (20% by weight) Styrene (25% by weight) Copolymer latex liquid of 2-hydroxyethyl acrylate (25% by weight) (Solid content 30%) 270 g (C-1) 0.6 g hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish to 1 liter with water << Subtraction coating solution b-1 >> Butyl acrylate (40 weight %) Styrene (20% by weight) Glycidyl acrylate (40% by weight) copolymer latex liquid (solid content: 30%) 270 g (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 8g Finished to 1 liter with water Then, on the upper surface of the undercoat layer A-1 and the undercoat layer B-1,
A corona discharge of 8 w / m ² · min. Was performed, and the following lower coating liquid a-2 was coated on the lower coating layer A-1 with a dry film thickness of 0.1 μm.
As the undercoat layer A-2, the undercoat layer B-1 is coated on the undercoat layer B-1 with the following undercoat layer coating solution b-2 so as to have a dry film thickness of 0.8 μm. Coated as B-2.

<< Coating Solution for Undercoating Upper Layer a-2 >> Weight of 0.4 g / m ² of Gelatin (C-1) 0.2 g (C-2) 0.2 g (C-3) 0.1 g Silica particles ( (Average particle size: 3 μm) 0.1 g Finished to 1 liter with water << Lower coating solution for upper layer b-2 >> (C-4) 60 g Latex liquid containing (C-5) as a component (solid content: 20%) 80 g Ammonium sulfate 0 0.5 g (C-6) 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finish to 1 liter with water

[0142]

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[0143]

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(Preparation of Silver Halide Emulsion B) 900 m of water
7.5 g of inert gelatin and 10 ml of potassium bromide
mg, and adjusted to a temperature of 35 ° C. and a pH of 3.0, and then 370 ml of an aqueous solution containing 74 g of silver nitrate (98/98).
An aqueous solution containing potassium bromide and potassium iodide in the molar ratio of 2) and rhodium chloride were added over 10 minutes by a controlled double jet method while maintaining a pAg of 7.7 at 1 × 10 ⁻⁴ mol per mol of silver. . Thereafter, 0.3 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added, the pH was adjusted to 5 with NaOH, the average particle size was 0.06 μm, and the variation coefficient of the projected diameter area was 8
%, And a [100] face ratio of 87% were obtained. This emulsion was subjected to coagulation sedimentation using a gelatin coagulant, desalting treatment, and then 0.1 g of phenoxyethanol was added.
5.9, pAg 7.5, and adjusted to silver halide emulsion B
I got

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

(Preparation of Sodium Behenate Solution B) 34
34 g of behenic acid was dissolved in 0 ml of isopropanol at 65 ° C. Next, while stirring, a 0.25N aqueous sodium hydroxide solution was added so as to have a pH of 8.7. At this time, about 400 ml of the sodium hydroxide aqueous solution was required. Next, the sodium behenate aqueous solution was concentrated under reduced pressure to prepare a sodium behenate solution B having a sodium behenate concentration of 8.9% by weight.

(Preparation of Silver Behenate Dispersion B) 750 ml
2.94M silver nitrate solution was added to a solution of 30 g of ossein gelatin dissolved in distilled water to adjust the silver potential to 400 mV. The sodium behenate solution B37 was added thereto at a temperature of 78 ° C. using a controlled double jet method.
4 ml was added at a speed of 44.6 ml / min, and simultaneously a 2.94 M silver nitrate aqueous solution was added so that the silver potential became 400 mV. The amounts of sodium behenate and silver nitrate used at the time of addition were 0.092 mol and 0.101 mol, respectively. After the addition was completed, the mixture was further stirred for 30 minutes, and the water-soluble salts were removed by ultrafiltration. This is designated as silver behenate dispersion B.

(Preparation of Photosensitive Emulsion B) To this silver behenate dispersion B, 0.01 mol of the silver halide emulsion B was added.
100 g of an n-butyl acetate solution of polyvinyl acetate (1.2 wt%) was gradually added with stirring to form a floc of the dispersion, and then water was removed, followed by two additional water washes and water removal. Then, a mixed solution 6 of butyl acetate / isopropyl alcohol = 1: 2 containing 2.5 wt% of polyvinyl butyral (average molecular weight 3000) as a binder 6
After adding 0 g with stirring, polyvinyl butyral (average molecular weight: 4000) and isopropyl alcohol were added and dispersed as a binder to the thus obtained mixture of behenic acid and silver halide. This is designated as photosensitive emulsion B.

The following layers were sequentially formed on a support to prepare a photothermographic material sample. The drying was 75 ° C,
Performed in 5 minutes.

Coating on Back Side A liquid having the following composition was applied to a wet thickness of 80 μm.

Polyvinyl butyral (10% isopropanol solution) 150 ml Dye of the present invention, comparative dye (described in Table 2) 70 mg Photosensitive layer side coating Photosensitive layer 1: A solution having the following composition was coated at a silver amount of 2.0 g /
m ² , polyvinyl butyral as a binder.
It was applied so as to be ² g / m ² .

Photosensitive Emulsion B Amount of 3 g / m ² in terms of silver sensitizing dye-1 (0.1% DMF solution) 1 mg sensitizing dye-2 (0.1% DMF solution) 1 mg pyridinium bromide perbromide ( 2 ml acetone solution) 0.3 ml 2-tribromomethylsulfonylpyridine (2% acetone solution) 3 ml phthalazine (4.5% DMF solution) 8 ml developer-1 (exemplary compound A-4 of general formula (A)) 13 ml Hardening agent H (1% methanol / DMF = 4: 1 solution) 2 ml Dye of the present invention, comparative dye (described in Table 2) (2% acetone solution) 0.1 ml

[0153]

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Surface protective layer: A solution having the following composition was wetted to a thickness of 1
It was applied on each photosensitive layer so as to have a thickness of 00 μm.

Acetone 175 ml 2-propanol 40 ml methanol 15 ml cellulose acetate 8.0 g phthalazine 1.0 g 4-methylphthalic acid 0.72 g tetrachlorophthalic acid 0.22 g tetrachlorophthalic anhydride 0.5 g monodisperse having an average particle size of 4 μm 1% (W / W) with respect to silica binder << Evaluation Method >>"Evaluation of Sensitometry" The photothermographic material prepared above was processed into a half-cut size, and a 810 nm laser diode was inclined by 13 ° from a vertical plane. The beam was exposed. Thereafter, heat development was performed at 120 ° C. for 15 seconds using a heat drum.

[Evaluation of Sharpness] 10 samples /
mm was measured and the sample No. was measured. Table 2 shows the relative values when the MTF value of 201 is 100.

"Visual evaluation of color turbidity" Subjective evaluation was performed using 10 monitors. 3 levels that are practically acceptable
The score of all the evaluators was evaluated assuming that the point and the level of allowable margin were 1 point and the level that was not practically used was 0 point.

[0158]

[Table 2]

Table 2 shows that the sample of the present invention had good sharpness and little color turbidity.

Example 4 << Preparation and Evaluation of Silver Halide Color Photographic Material >> (Preparation of Emulsion EM-P1) While controlling an aqueous solution containing ossein gelatin at 40 ° C., an aqueous solution containing ammonia and silver nitrate and an odor An aqueous solution containing potassium iodide and sodium chloride (KBr: NaCl = 95: 5 in molar ratio) was simultaneously added by a control double jet method to give a particle size of 0.1.
A 30 μm cubic silver chlorobromide core emulsion was obtained. At that time, the pH and pAg were controlled so that a cube was obtained as the particle shape.

An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 40: 60 in molar ratio) were simultaneously added to the obtained core emulsion by a control double jet method. Thus, a shell was formed until the average particle size became 0.42 μm.
At that time, the pH and pAg were controlled so that a cube was obtained as the particle shape.

After washing with water to remove water-soluble salts, gelatin was added to obtain an emulsion EM-P1. The width of the distribution of the emulsion EM-P1 was 8%.

(Preparation of Emulsion EM-P2) While controlling the aqueous solution containing ossein gelatin at 40 ° C., an aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (KBr: NaCl = 95: 5 by molar ratio). ) Was added simultaneously by the control double jet method to obtain a cubic silver chlorobromide core emulsion having a particle size of 0.18 μm. At this time, p is set so that a cube is obtained as the particle shape.
H and pAg were controlled.

An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 40: 60 in molar ratio) were simultaneously added to the obtained core emulsion by a control double jet method. Thus, a shell was formed until the average particle size became 0.25 μm.
At that time, the pH and pAg were controlled so that a cube was obtained as the particle shape.

After washing with water to remove water-soluble salts, gelatin was added to obtain an emulsion EM-P2. The width of the distribution of the emulsion EM-P2 was 8%.

(Preparation of Blue-Sensitive Silver Halide Emulsion) A sensitizing dye BS-1 was added to the emulsion EM-P1 for optimal color sensitization, and then 600 mg of a stabilizer ST-1 was added per mol of silver. A blue-sensitive emulsion Em-B1 was obtained.

(Preparation of Green-Sensitive Silver Halide Emulsion) A green-sensitive emulsion Em was prepared in the same manner as the blue-sensitive emulsion Em-B1 except that the sensitizing dye GS-1 was added to the emulsion EM-P2 for optimal color sensitization. -G1 was obtained.

(Preparation of Red-Sensitive Silver Halide Emulsion) Emulsion E
Red-sensitive emulsion Em-R1 was obtained in the same manner as blue-sensitive emulsion Em-B1, except that sensitizing dyes RS-1 and RS-2 were added to MP-P2 to optimize the color sensitization.

ST-1: 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene

[0170]

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(Preparation of Infrared-sensitive Silver Halide Emulsion) An infrared-sensitive silver halide emulsion was prepared in the same manner as in the blue-sensitive emulsion Em-B1, except that the sensitizing dye IRS-1 was added to the emulsion EM-P1 to optimize the color. Emulsion Em-IR was obtained.

[0172]

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The resulting Em-IR and Em-B1,
Em-G1 and Em-R1 emulsions were used, and high-density polyethylene was applied on the back surface and anatase-type titanium oxide was applied on the front surface.
A multilayer color photosensitive material sample 301 was prepared by coating each layer having the following constitution on a paper pulp reflective support having a thickness of 110 μm, on which a molten polyethylene containing a dispersed content of the content of weight% was laminated. In addition, H-
1, H-2 was added. Surfactants SU-1, SU-2, and SU-3 were added as coating aids and dispersion aids.

Twelfth layer (protective layer) Coating amount (g / m ² ) Gelatin 1.60 Silica matting agent 0.01 Eleventh layer (Ultraviolet absorbing layer) Gelatin 1.60 Ultraviolet absorbing agent (UV-1) 35 UV absorber (UV-2) 0.12 UV absorber (UV-3) 0.60 10th layer (blue photosensitive layer) Gelatin 1.10 Blue photosensitive emulsion (Em-B1) 0.36 Yellow coupler ( Y-1) 0.34 Fog inhibitor (AF-2, AF-3 equimolar) 0.0004 Stain inhibitor (HQ-1) 0.004 High boiling organic solvent (SO-1) 0.27 9th layer (Intermediate layer) Gelatin 0.94 Stain inhibitor (HQ-2, HQ-3 etc. by weight) 0.02 High boiling organic solvent (SO-2) 0.05 Anti-irradiation dye (AI-3) 0.03 8 layers (yellow filter layer) Tin 0.45 Yellow colloidal silver 0.11 Stain inhibitor (HQ-1) 0.03 High boiling organic solvent (SO-2) 0.008 Polyvinylpyrrolidone 0.04 7th layer (intermediate layer) Gelatin 0.45 Stain Inhibitor (HQ-2) 0.014 Stain inhibitor (HQ-3) 0.014 High boiling organic solvent (SO-2) 0.006 6th layer (green photosensitive layer) Gelatin 1.25 green photosensitive emulsion ( Em-G1) 0.32 Magenta coupler (M-1) 0.22 Yellow coupler (Y-2) 0.05 Stain inhibitor (HQ-1) 0.035 Fog inhibitor (AF-2, AF-3, etc.) Mol) 0.00036 High boiling organic solvent (SO-1) 0.33 Fifth layer (intermediate layer) Gelatin 0.80 Stain inhibitor (HQ-2) 0.03 Stain inhibitor (HQ-3) 0.01 High Boiling point organic solvent (SO-2) 0.007 Anti-irradiation dye (AI-1) 0.04 Fourth layer (red-sensitive layer) Gelatin 0.90 Red-sensitive emulsion (Em-R1) 0.27 Cyan coupler ( EC-1) 0.27 Stain inhibitor (HQ-1) 0.02 Fog inhibitor (AF-2, AF-3 equimolar) 0.0002 High boiling organic solvent (SO-1) 0.14 Third layer (Intermediate layer) Gelatin 0.80 Stain inhibitor (HQ-2) 0.03 Stain inhibitor (HQ-3) 0.01 High boiling organic solvent (SO-2) 0.01 Second layer (infrared photosensitive layer) Gelatin 1.25 Infrared-sensitive silver chlorobromide emulsion (Em-IR) 1.00 Yellow coupler (Y-1) 0.50 Magenta coupler (M-1) 0.20 Cyan coupler (EC-1) 35 Stain inhibitor (HQ-1 ) 0.04 High boiling point solvent (SO-1) 2.00 Fog inhibitor (AF-1, AF-2, AF-3 equimolar) 0.005 First layer (antihalation layer) Gelatin 1.20 Irradiation Inhibitory dye (AI-2) 0.055 13th layer (back layer) Gelatin 7.50 Silica matting agent 0.65 The structure of each compound is shown below.

SU-1: sodium sulfosuccinate di (2-ethylhexyl) ester SU-2: sulfosuccinate di (2,2,3,3,4,4,
5,5-octafluoropentyl) ester sodium SU-3: sodium tri-i-propylnaphthalenesulfonate H-1: 2,4-dichloro-6-hydroxy-S-triazine sodium H-2: tetrakis (vinyl) Sulfonylmethyl) methane SO-1: trioctylphosphine oxide SO-2: di-i-decyl phthalate HQ-1: 2,5-di-t-butylhydroquinone HQ-2: 2,5-di (1,1- Dimethyl-4-hexyloxycarbonylbutyl) hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone, 2,5-di-sec-tetradecylhydroquinone and 2-sec-dodecyl-5-sec-tetradecylhydroquinone (Weight ratio 1: 1: 2) AF-1: 4-hydroxy-6- Chill-l, 3,3
a, 7-Tetrazaindene AF-2: 1- (3-acetamidophenyl) -5-mercaptotetrazole AF-3: N-benzyladenine

[0176]

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[0177]

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Further, Sample 3 was prepared in the same manner as Sample 301 except that the dye shown in Table 3 was added to the first layer of Sample 301.
Nos. 02 to 304 were produced.

The obtained samples 301 to 304 were exposed to light under the following exposure condition -11 by bringing a cyan plate of a halftone original into close contact with the sample. Next, the magenta plate was brought into close contact with the sample and exposed under the following exposure conditions-12. Next, the yellow plate was brought into close contact with the sample and exposed under the following exposure conditions-13. Further, the black plate was brought into close contact with the sample and exposed under the following exposure conditions -14. As the halftone dot original, an original prepared by a screen method consisting of halftone dots of 300 lines per inch was used. In addition, 1 inch when the dot area ratio is 40%
The number of ch ² per dot was 90 × 10 ³ cells.

<Exposure Condition-11> When each photosensitive material sample was exposed to white light through a red filter (Ratten No. 26) and an ND filter, the density of the ND filter was adjusted to minimize the red density after the development processing. Exposure is performed for 0.5 seconds with a minimum exposure amount.

<Exposure Condition-12> When each photosensitive material sample was exposed to white light through a green filter (Watten No. 58) and an ND filter, the density of the ND filter was adjusted so that the green density after development processing was minimized. Exposure is performed for 0.5 seconds with a minimum exposure amount.

<Exposure Condition-13> When each light-sensitive material sample was exposed to white light through a blue filter (Ratten No. 47B) and an ND filter, the density of the ND filter was adjusted to minimize the blue density after the development processing. Exposure is performed for 0.5 seconds with a minimum exposure amount.

<Exposure condition-14> When each photosensitive material sample is exposed to white light through an infrared transmission filter and an ND filter, the density of the ND filter is adjusted to minimize the black density after development processing. Exposure is performed for 0.5 seconds at an exposure amount.

Incidentally, a fluorescent lamp for daylight was used as a light source under the exposure conditions-11 to 13, and a xenon lamp was used as a light source under the exposure condition-14.

Each of the exposed samples was processed under the following processing conditions-1.
To obtain a dye image consisting of halftone dots. However, in the fogging exposure, the entire surface of the photosensitive material was uniformly exposed through a layer of the developing solution having a thickness of 3 mm while being immersed in the developing solution.

<Processing condition-1> Processing step Temperature Time Immersion (developer) 37 ° C for 12 seconds Fog exposure -12 seconds Current image 37 ° C for 95 seconds Bleaching and fixing 35 ° C for 45 seconds Stabilizing treatment 25-30 ° C for 90 seconds Drying 60-85 ° C 40 seconds Color developer composition Benzyl alcohol 15.0 ml Ceric sulfate 0.015 g Ethylene glycol 8.0 ml Potassium sulfite 2.5 g Potassium bromide 0.6 g Sodium chloride 0.2 g Potassium carbonate 25.0 g ST-1 0.1 g Hydroxylamine sulfate 5.0 g Sodium diethylenetriaminepentaacetate 2.0 g 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline / 3/2 sulfuric acid / 1 Water salt 4.5 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Water Potassium oxide 2.0 g Diethylene glycol 15.0 ml Water is added to make the total volume 1 liter, and the pH is adjusted to 10.15.

Composition of bleach-fixing solution Ferric ammonium diethylenetriaminepentaacetate 90.0 g Diethylenetriaminepentaacetic acid 3.0 g Ammonium thiosulfate (70% aqueous solution) 180.0 ml Ammonium sulfite (40% aqueous solution) 27.5 ml 3-mercapto-1,2 , 4-triazole 0.15 g Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to make the total volume 1 liter.

Stabilizing solution composition o-phenylphenol 0.3 g potassium sulfite (50% aqueous solution) 12.0 ml ethylene glycol 10.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.5 g bismuth chloride 0.2 g zinc sulfate 7-hydrate 0.7 g Ammonium hydroxide (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g Add water The total volume is made up to 1 liter and adjusted to pH 7.5 with ammonium hydroxide or sulfuric acid. In addition, the stabilization process was a countercurrent system having a two-tank configuration.

The number of halftone dots of 40% is 90 × 10 ³ / in
in the halftone original ch ^2, the obtained image in the new liquid processing, the halftone dot quality points are 40% was visually evaluated by a loupe observation was scored dot quality 5 point scale. However, the dot quality is relatively scored with 5 being the best and 1 being the worst.
Table 3 shows the results.

[0190]

[Table 3]

From the above, it can be seen that the use of the dye of the present invention improves the dot quality.

Example 5 << Preparation and Evaluation of Thermosensitive Recording Material >> The following compounds were dissolved in methyl ethyl ketone to prepare a colored composition solution, applied to a 100 μm thick polyethylene terephthalate film, and dried to produce a colored transparent sheet. . Polyvinyl butyral is manufactured by Monsanto Butvar TMB7
6 was used.

<Preparation of Sample> Polyvinyl butyral 0.85 g / m ² Leuco dye (1) 1 mmol / m ² Acid (1) 3 mmol / m ² Dye (described in Table 4) 0.13 mg / m ²

[0194]

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<Exposure Conditions for Image Forming> Spect
ra Diode Labs No. SDL-2430
(Wavelength range: 800 to 830 nm), and
The output was set to 00 mW, and used as an image writing laser. Using this laser, a beam diameter of 160 μm, a laser scanning speed of 0.5 m / sec (center of scanning), a sample feeding speed of 15 mm / sec, and a scanning pitch of 8 lines / mm
, And the above-mentioned sample was exposed so that an image of 22 mm × 9 mm was obtained. At this time, the laser energy density on the sample was 10 mJ / mm ² . Further, the energy density was changed as shown in Table 4 by changing the laser scanning speed and the laser output.

<Evaluation of Dye Residual Rate at Laser Scanning Center (Image Area)> The minimum density (Dmin) at the laser scanning center (image area) was determined by Macbeth blue light or green light density measurement. The residual ratio of the dye was evaluated from the ratio. Table 4 shows the obtained results.

[0197]

[Table 4]

[0198]

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From Table 4, it was found that the dye of the present invention has a low residual dye ratio.

Example 6 << Preparation and Evaluation of Infrared Absorbing Composition (Filter) >>
10 g of the dye described in Table 5 was weighed, 11.5 g of tricresyl phosphate, a high-boiling organic solvent, was added, and 24 ml of chloroform was further added to dissolve the solution. weight%
It was emulsified and dispersed in an aqueous gelatin solution. A 10% by weight aqueous solution of gelatin was added to the total amount of the emulsified dispersion so as to be the following amount, and coated on a triacetylcellulose film support provided with an undercoat layer. A 10% by weight aqueous gelatin solution was added to 1 g of sodium dichloro-6-hydroxy-s-triazine so as to have the following amount, followed by coating. Samples 501 to 503 were prepared.

[0201] (1) filter layer Table 5 Dye 0.2 g / m ² tricresyl according to phosphate 1.0 g / m ² Gelatin 3.8 g / m ² (protective layer) 2,4-dichloro-6- Sodium hydroxy-s-triazine 0.1 g / m ² Gelatin 1.8 g / m ² Each sample was then divided into two parts, one of which was 60 ° C. and 70% relative humidity.
%, And the other was left under irradiation of a fluorescent lamp at 20,000 lux for 2 days, and then the concentration was measured. For each concentration, the residual ratio of the dye was determined by percentage with respect to the concentration before performing the fading test. Table 5 shows the results.

[0202]

[Table 5]

Table 5 shows that the compounds of the present invention are stable as dyes for filters.

[0204]

According to the present invention, a recording material containing a novel squarylium compound as a dye, a silver halide photographic light-sensitive material, a photothermographic material, a heat-developable image forming method, and the novel squarylium compound as a heat conversion dye A thermal recording material containing the same, a thermal recording image forming method using the thermal recording material, and an infrared absorbing composition containing the novel squarylium compound as a dye could be provided. Further, the novel squarylium compound could be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 215/14 C07D 215/42 2H111 215/40 217/02 2H123 215/42 217/12 4C031 217/02 217 / 16 4C034 217/12 239/74 4C065 217/16 471/04 113 4C072 239/74 471/06 4C204 471/04 113 471/10 102 4H056 471/06 471/16 471/10 102 491/06 471/16 498/06 491/06 519/00 498/06 311 519/00 C09K 3/00 105 311 G02B 5/22 C09K 3/00 105 G03C 1/498 G02B 5/22 1/83 G03C 1/498 G03G 5/06 384 1/83 B41M 5/18 Q G03G 5/06 384 R 101C 5/26 Y 101K F term (reference) 2H023 AA00 FD01 2H026 AA07 AA24 BB02 BB21 BB37 DD01 DD46 DD53 FF01 F F22 2H048 CA04 CA12 2H068 AA19 BA35 2H086 BA56 2H111 AA01 AA27 BA39 BA74 EA03 EA12 EA22 EA25 EA43 FB42 2H123 AB00 AB03 AB23 AB25 BA00 BA42 BA64 BB00 BB02 BB20 CA00 CA05 CA22 CB00 A03 A01 A03 A03 A01 A03 A06 A01 A03 BB11 BB15 CC01 CC03 CC09 DD02 DD03 EE02 EE03 HH01 HH04 JJ06 KK01 KK02 KK08 KK09 LL09 PP01 QQ02 4C072 AA02 BB02 CC02 CC11 EE06 FF07 GG01 HH01 HH05 MM02 UU05 4C204 BB05 BB09 DB03 FB05 FB09 DB03 Name] Recording material containing novel squarylium compound, silver halide photographic material, photothermographic material, thermal development image forming method, thermal recording material, thermal recording image forming method, infrared absorbing composition, and novel squarylium compound

Claims (13)

[Claims] 1. The following general formula (1), (2) or (3)
A recording material comprising a squarylium compound represented by the formula: Embedded image [In the general formula (1), at least one of A ¹ and A ² is 5
Represents a 6- or 6-membered nitrogen-containing heteroaromatic ring. [Chemical formula 2] (In the general formula (2), at least one of A ³ and A ⁴ represents a 6-membered nitrogen-containing heteroaromatic ring represented by the following general formula (2 ′). (In the general formula (2 ′), R ¹ and R ² represent a hydrogen atom, —OR ⁴
Or —NR ⁵ R ⁶ , R ⁴ represents a group that can be substituted with a hydrogen atom or an oxygen atom, and R ⁵ and R ⁶ represent a group that can be substituted with a hydrogen atom or a nitrogen atom. Further, a ring containing R ¹ and R ² in the same ring may be formed, or R ⁵ and R ⁶ may be bonded to each other to form a 5- or 6-membered ring. Z ^{1 to} Z ⁶
Represents a carbon atom or a nitrogen atom, ^one of Z ^{1 to} Z ⁶ is a nitrogen atom, at least one of the remaining is a carbon atom, and at least one of the carbon atoms represented by Z ^{1 to} Z ⁶ One is bonded to squarylium carbon of the general formula (2). R ³ represents a substituent capable of bonding to an atom forming a 6-membered nitrogen-containing heteroaromatic ring represented by the general formula (2 ′), and n1 represents an integer of 0 to 4. )] [In the general formula (3), at least one of A ⁵ and A ⁶ represents a quinoline ring or an isoquinoline ring. ] 2. A silver halide photographic material comprising a squarylium compound represented by the general formula (1). 3. A silver halide photographic material comprising a squarylium compound represented by the general formula (2). 4. A silver halide photographic material comprising a squarylium compound represented by the general formula (3). 5. The above-mentioned general formula (1), (2) or (3)
A photothermographic material comprising a squarylium compound represented by the formula: 6. A heat-developable image forming method, comprising exposing the photothermographic material according to claim 5 with infrared laser light. 7. The general formula (1), (2) or (3)
A heat-sensitive recording material comprising a squarylium compound represented by the formula: 8. A heat-sensitive recording image forming method, comprising exposing the heat-sensitive recording material according to claim 7 to light using infrared laser light. 9. The general formula (1), (2) or (3)
An infrared absorbing composition comprising a squarylium compound represented by the formula: 10. A squarylium compound represented by the general formula (1). 11. A squarylium compound represented by the general formula (2). 12. A squarylium compound represented by the general formula (3). 13. A compound represented by the following general formula (4). Embedded image [In the formula, Z ^{7 to} Z ⁹ each represent a carbon atom or a nitrogen atom, and one of Z ^{7 to} Z ⁹ is a nitrogen atom, and the other two are carbon atoms. Z ¹⁰ is an oxygen atom or NR ⁷
And Z ¹¹ represents an oxygen atom or NR ¹⁰ . R ⁷ ~R
¹⁰ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a heterocyclic group or an aralkyl group, and R ⁷ and R ⁸ ,
R ⁸ and R ⁹ or R ⁹ and R ¹⁰ are bonded to each other to form 5 or 6
A member ring may be formed. R ¹¹ represents a substituent capable of binding to a quinoline ring or an isoquinoline ring, and n2 represents an integer of 0 to 4. ]