JP2003050441A - Thermally developable photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermally developable photographic sensitive material having high sensitivity, low fog and good storage stability and excellent in silver tone and to provide an imaging method using the material. SOLUTION: The thermally developable photographic sensitive material contains a compound of formula (1-1) or (1-2).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material and an image forming method using the same.

[0002]

2. Description of the Related Art A heat-developable photographic light-sensitive material (hereinafter also referred to as a heat-developable light-sensitive material or a light-sensitive material) for forming a photographic image of a silver halide photographic light-sensitive material by a heat development processing method is disclosed in, for example, US Pat. No. 904, No. 3,45
7,075, and D.I. Morgan and B.M. "Thermal Processed Thermal System" by Shelly
d Silver Systems ”(Imaging Processes and Materials (Imagi
ng Processes and Material
s) Nablette 8th Edition, Sturg
e), V. Wallworth, A.S.
Edited by Shepp, p. 2, 1969).

In such a photothermographic material, a reducible silver source (eg organic silver salt), a catalytically active amount of photocatalyst (eg silver halide), and a reducing agent are dispersed in a usual (organic) binder matrix. It is contained in the state. The photothermographic material is stable at room temperature, but at a high temperature (for example,
When heated to 80 ° C. or higher), silver is produced through a redox reaction between a reducible silver source (which functions as an oxidizing agent) and the reducing agent. This redox reaction is promoted by the catalytic action of the latent image generated by exposure. The silver produced by the reaction of the organic silver salt in the exposed areas provides a black image, which is symmetrical to the unexposed areas and forms the image. An antifoggant for controlling the fog of the image is optionally used in the light-sensitive material. The most effective conventional fog prevention technique has been a method using a mercury compound as an antifoggant. The use of mercury compounds as antifoggants in light-sensitive materials is disclosed, for example, in US Pat. No. 3,589,903. However, mercury compounds are not environmentally preferable, and development of a non-mercury antifoggant has been desired.

Various polyhalogen compounds have been disclosed as non-mercury antifoggants (for example, US Pat. Nos. 3,874,946 and 4,452,88).
5, No. 4,546,075, No. 4,756,999
No. 5,340,712, European Patent No. 605,98.
1A1, 622,666A1, 631,176
A1, JP-B-54-165, JP-A-59-9084.
No. 2, JP-A-61-129642, JP-A-62-12
9845, JP-A-6-202268, JP-A-6-2
08193, JP-A-6-340611, JP-A-7-
2781, JP-A-7-5621). However, these described compounds have a low antifoggant effect,
There was a problem of deteriorating the color tone of silver. Further, those having a high fog-preventing effect have problems such as lowering of sensitivity and need to be improved. In addition, after stacking the photosensitive materials, after aging under forced conditions of humidification and heating,
When developed, there is a problem that fog in the unexposed area rises, and the development of an antifoggant without these problems has been desired.

As a method for solving these problems, Japanese Patent Laid-Open No. 9-
160164, 9-244178, 9-258.
No. 367, No. 9-265150, No. 9-281640
No. 9-319022, 10-171063,
JP-A-2000-284402, JP-A-2000-284
406, JP 2000-284410 A, JP 200 A
No. 0-284412 discloses polyhalogen compounds in which the above-mentioned drawbacks are improved. However,
In particular, when these compounds are applied to a photothermographic material for a medical laser imager or a photothermographic material for output of a printing imagesetter having an oscillation wavelength of 600 to 800 nm, which contains a contrast-increasing agent. However, the storage stability, antifoggant effect and silver tone are not satisfactory, and further improvement has been desired.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is heat development which has high sensitivity, low fog, good storage stability, and excellent silver tone. A photographic light-sensitive material and an image forming method using the same.

[0007]

The above object of the present invention can be achieved by the following constitutions.

1. The general formula (1-1) or (1-2)
A heat-developable photographic light-sensitive material containing a compound represented by:

2. A photothermographic material comprising a compound represented by the general formula (2).

3. 3. The photothermographic material according to the item 2, wherein the compound represented by the general formula (2) is a compound represented by the following general formula (2-1).

4. 4. The photothermographic material according to 2 or 3 above, wherein G ₃ and G ₄ of the compound represented by the general formula (2-1) are —CONH—.

5. 1. An organic silver salt, a binder and a photosensitive silver halide on a support,
The heat-developable photographic light-sensitive material as described in 2, 3, or 4.

6. 6. The photothermographic material according to 1, 2, 3, 4 or 5 above, which contains at least one selected from the group consisting of hydrazine derivatives and compounds represented by the general formula (3).

7. 7. An image forming method, which comprises exposing the heat-developable photographic light-sensitive material described in 1, 2, 3, 4, 5 or 6 using a laser light source and then developing at 80 to 250 ° C.

The present invention will be described in detail below. The compounds represented by formulas (1-1) and (1-2) of the present invention will be described.

In the general formula (1-1), the halogen atom represented by X ₁ and X ₂ is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom which may be the same or different from each other, preferably Chlorine atom, bromine atom, iodine atom, more preferably chlorine atom, bromine atom,
Particularly preferred is a bromine atom.

A ₁ represents a hydrogen atom, a halogen atom or a substituent, and examples of the substituent include an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an amino group, an acyl group, Examples thereof include an acyloxy group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfonyl group, an alkylsulfonyl group, a sulfinyl group, a cyano group and a heterocyclic group. A halogen atom is preferable, and a bromine atom is particularly preferable.

Y ₁ represents a linking group, and examples of the linking group include --SO _2- , --CO--, --NHCO--, --OOC.
—, —N (R ₅ ) SO ₂ —, and R ₅ represents a substituent. Examples of the substituent represented by R ₅ include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an acyloxy group, an alkylthio group, a carboxy group, an acylamino group, an acyl group and trifluoromethyl. Groups and the like.

Z represents an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group. These groups may further have a substituent, and as the substituent, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group,
Butyl group, pentyl group, iso-pentyl group, 2-ethyl-hexyl group, octyl group, decyl group, etc.), cycloalkyl group (eg, cyclohexyl group, cycloheptyl group, etc.), alkenyl group (eg, ethenyl-2- Propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, etc., cycloalkenyl group (for example, 1-cycloalkenyl group, 2-cycloalkenyl group) Etc.), alkynyl group (eg ethynyl group, 1-propynyl group etc.), alkoxy group (eg methoxy group, ethoxy group, propoxy group etc.), alkylcarbonyloxy group (eg acetyloxy group etc.), alkylthio group ( For example, methylthio group, trifluoromethylthio group, etc.), carboxy group, alkylcarbonylamido Group (eg, acetylamino group etc.), ureido group (eg, methylaminocarbonylamino group etc.), alkylsulfonylamino group (eg, methanesulfonylamino group etc.), alkylsulfonyl group (eg, methanesulfonyl group, trifluoromethanesulfonyl group) Groups, etc.), carbamoyl groups (eg, carbamoyl groups, N, N-dimethylcarbamoyl groups, N-morpholinocarbonyl groups, etc.), sulfamoyl groups (sulfamoyl groups, N, N-dimethylsulfamoyl groups, morpholinosulfamoyl groups, etc.) ), Trifluoromethyl group, hydroxy group, nitro group, cyano group, alkylsulfonamide group (for example, methanesulfonamide group, butanesulfonamide group, etc.), alkylamino group (for example, amino group,
N, N-dimethylamino group, N, N-diethylamino group, etc.), sulfo group, phosphono group, sulfite group, sulfino group, alkylsulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl group, ethanesulfonylaminocarbonyl group, etc.) ), Alkylcarbonylaminosulfonyl group (eg, acetamidosulfonyl group, methoxyacetamidosulfonyl group, etc.), alkynylaminocarbonyl group (eg, acetamidocarbonyl group, methoxyacetamidocarbonyl group, etc.), alkylsulfinylaminocarbonyl group (eg, methanesulfinylamino) Carbonyl group, ethanesulfinylaminocarbonyl group and the like). When there are two or more substituents, they may be the same or different. However, it does not have an aryl group or a heteroaryl group as a part of the substituent.

L ₁ represents a linking group, for example, an alkylene group (including an alkylidene group and a cyclo compound, preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 carbon atom). 10), an alkenylene group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms), an alkynylene group (preferably carbon). Number 2 to 30, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms), -O.
- group, -NR ₆ - group, -CO- group, -S- group, -SO-
Examples thereof include a group, a —SO ₂ — group, a group containing a phosphorus atom, and a group formed by combining these (the group represented by R ₆ may have a hydrogen atom or a substituent). Is an alkyl group).

The linking group represented by L ₁ may have a substituent, and examples thereof include the same substituents as Z described above. The linking group is preferably an alkylene group or -O.
A group, a —CONR— group, a —SO ₂ NR ₆ — group or a group formed by combining these, and L ₁
Is at least an -O- group, a -CONR- group or -SO ₂
Most preferably it contains one of the NR- groups.

W ₁ is a carboxy group or a salt thereof (Na,
K, ammonium salts, etc.), sulfo groups or salts thereof (N
a, K, ammonium salt, etc.), phosphate group or salt thereof (Na, K, ammonium salt etc.), hydroxyl group or salt thereof (Na, K, ammonium salt etc.), quaternary ammonium group (eg tetrabutylammonium, trimethyl) Benzylammonium) and a polyoxyethylene group. Preferred are a carboxy group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group or a salt thereof, and a polyoxyethylene group, and more preferred are a carboxy group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group or a salt thereof.

N represents 0 or 1. The general formula (1-
In 2), the halogen atom represented by X ₃ and X ₄ is
Fluorine atom, chlorine atom, bromine atom and iodine atom which may be the same or different from each other, preferably chlorine atom, bromine atom and iodine atom, more preferably chlorine atom and bromine atom, particularly preferably bromine Is an atom.

A ₂ represents a hydrogen atom, a halogen atom or a substituent, and examples of the substituent include an alkyl group, an aryl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an amino group, an acyl group, Examples thereof include an acyloxy group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfonyl group, an alkylsulfonyl group, a sulfinyl group, a cyano group and a heterocyclic group. A halogen atom is preferable, and a bromine atom is particularly preferable.

Y ₂ is --NHCO--, --OOC--, --N
(R ₁ ) SO ₂ — represents, and R ₁ represents a substituent. Examples of the substituent represented by R ₁ include those having the same meaning as the substituent represented by R ₅ in A ₁ of the general formula (1-1).

Q represents a divalent aryl group or a divalent heterocyclic group, and the divalent aryl group represented by Q is
It is preferably a monocyclic or condensed ring arylene group having 6 to 30 carbon atoms, more preferably a 6 to 20 monocyclic or condensed ring arylene group, and examples thereof include a phenylene group and a naphthylene group. Preferred is a phenylene group. The arylene group represented by Q may have a substituent, and the substituent may be any group as long as it does not adversely affect the photographic performance. For example, a halogen atom (fluorine atom, Chlorine atom, bromine atom, or iodine atom), alkyl group (including aralkyl group, cycloalkyl group, active methine group, etc.), alkenyl group, alkynyl group, aryl group, heterocyclic group (N-substituted nitrogen-containing heterocyclic ring) Group), a heterocyclic group containing a quaternized nitrogen atom (for example, a pyridinio group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a carboxy group or a salt thereof, an imino group, an N atom Substituted imino group, thiocarbonyl group, carbazoyl group, cyano group, thiocarbamoyl group, alkoxy group (ethyleneoxy group or Including a group containing repeated Ropiren'okishi group units), an aryloxy group, a heterocyclic oxy group, an acyloxy group, an (alkoxy or aryloxy) carbonyloxy group, carbamoyloxy group,
Sulfonyloxy group, acylamino group, sulfonamide group, ureido group, thioureido group, imide group, (alkoxy or aryloxy) carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, quaternary ammonio Group, (alkyl or aryl) sulfonylureido group, nitro group, (alkyl, aryl or heterocycle) thio group, acylthio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group,
Examples thereof include a sulfo group or a salt thereof, a sulfamoyl group, a phosphoryl group, a group containing a phosphoric acid amide or a phosphoric acid ester structure, and a silyl group. These substituents may be further substituted with these substituents. The substituent is particularly preferably an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a cyano group, a carboxy group or a salt thereof, a salt of a sulfo group, and a phosphoric acid group.

The divalent heterocyclic group represented by Q is
That is, the hetero ring of the hetero ring group is N, O or S
Is a 5- to 7-membered saturated or unsaturated heterocycle containing at least one atom of the above, and these may be a single ring or may form a condensed ring with another ring. Examples of the heterocycle include pyridine, pyrazine, pyrimidine,
Examples thereof include benzothiazole, benzimidazole, thiadiazole, quinoline, isoquinoline and triazole. These may have a substituent, for example, Q
The same group as the substituent for the divalent aryl group represented by

L ₂ represents a linking group, for example, an alkylene group (including an alkylidene group and a cyclo compound, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 carbon atoms). 10), an alkenylene group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms), an alkynylene group (preferably carbon). Number of 2 to 30, more preferably 2 to 20 carbons, particularly preferably 2 to 10 carbons), heterocyclic group (preferably 1 to 30 carbons, more preferably carbons) 1 to 20 and particularly preferably 1 carbon atom
It is -10. ), —O— group, —NR ₇ — group, —CO—
Group, -S- group, -SO- group, -SO ₂ - group, or a group containing a phosphorus atom, a group represented by R ₇ is the group, etc. (here formed by combining these hydrogen An atom or an alkyl group which may have a substituent or an aryl group which may have a substituent, but is preferably a hydrogen atom or an alkyl group). Preferably, it is an alkylene group, an —O— group, a —CONR ₇ — group, a —SO ₂ NR ₇ — group or a group formed by combining these, and L ₂ is at least an —O— group or a —CONR ₇ — group. Most preferably, it also contains one of the —SO ₂ NR ₇ — groups. These linking groups may have a substituent, and examples of the substituent include the same groups as the substituents for the divalent aryl group represented by Q.

W ₂ is a carboxy group or a salt thereof (Na,
K, ammonium salts, etc.), sulfo groups or salts thereof (N
a, K, ammonium salt, etc.), phosphate group or salt thereof (Na, K, ammonium salt etc.), hydroxyl group or salt thereof (Na, K, ammonium salt etc.), quaternary ammonium group (eg tetrabutylammonium, trimethyl) Benzylammonium) and a polyoxyethylene group. Preferred are a carboxy group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group or a salt thereof, and a polyoxyethylene group, and more preferred are a carboxy group or a salt thereof, a sulfo group or a salt thereof, a hydroxyl group or a salt thereof.

M represents 0 or 1. Hereinafter, the compound represented by the general formula (1-1) and the general formula (1-
Specific examples of the compound represented by 2) are shown below, but the present invention is not limited thereto. Compound represented by general formula (1-1)

[0031]

[Chemical 6]

Compound represented by formula (1-2)

[0033]

[Chemical 7]

[0034]

[Chemical 8]

Specific examples of the synthesis of the compound represented by the general formula (1-1) and the compound represented by the general formula (1-2) are shown below.

Synthesis Example 1-1. Synthesis of Exemplified Compound 1-1h 4.8 g of triethylamine, 40 ml of dichloromethane,
5.0 g of 2-amino-3-cyclohexyl-1-propanol hydrochloride was sequentially mixed, and a solution of 6.8 g of tribromoacetyl chloride in 10 ml of dichloromethane was added dropwise under cooling with ice water. After completion of the dropping, the mixture was stirred at room temperature for 3 hours, 100 ml of ethyl acetate was added, and the organic layer was mixed with 50 ml of 1 mol / L hydrochloric acid and saturated aqueous solution of sodium hydrogencarbonate 5
It was washed successively with 0 ml and 50 ml of saturated saline. The crystals were dried over magnesium sulfate, filtered, and concentrated under reduced pressure to obtain crude crystals. Recrystallization from ethanol gave the objective exemplified compound 1-1h (7.1 g).

Synthesis Example 1-2. Synthesis of Exemplified Compound 1-2b 5.0 g of triethylamine, 40 ml of dichloromethane,
5.0 g of 2-amino-3-hydroxypyridine was sequentially mixed, and tribromoacetyl chloride 1 was added under cooling with ice water.
A solution prepared by dissolving 4.3 g in 20 ml of dichloromethane was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 3 hours, 120 ml of ethyl acetate was added, and the organic layer was added with 1 mol / L hydrochloric acid of 50 m.
1, washed with 50 ml of a saturated aqueous solution of sodium hydrogen carbonate and 50 ml of a saturated saline solution in that order. The crystals were dried over magnesium sulfate, filtered, and concentrated under reduced pressure to obtain crude crystals. Example compound 1 of interest by recrystallization from ethanol
-2b (10.5 g) was obtained. It was confirmed from the ¹ H-NMR spectrum and MS spectrum that the compound was the desired exemplified compound 1-2b.

Other compounds represented by the above general formula (1-1) and compounds represented by the general formula (1-2) can be easily synthesized according to the above synthesis.

Next, the compound represented by the general formula (2) of the present invention will be described. In the general formula (2), X
_The halogen atoms represented by ₅ , X ₆ , X ₇ and X ₈ are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, which may be the same or different, and are preferably a chlorine atom, a bromine atom and an iodine atom. Is more preferable, a chlorine atom and a bromine atom are more preferable, and a bromine atom is particularly preferable.

B ₁ and B ₂ each independently represent a hydrogen atom, a halogen atom or a substituent, and the substituent is, for example,
Alkyl group, aryl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, amino group,
Examples thereof include an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, a sulfamoyl group, a carbamoyl group, an alkylthio group, a sulfonyl group, an alkylsulfonyl group, a sulfinyl group, a cyano group and a heterocyclic group.

P represents an integer of 1 or more and 3 or less. G₁as well as
G₂Represents a linking group, and examples of the linking group include —SO₂
-, -CO-, -NHCO-, -OOC-, -N
(R₈) SO₂-, And further via an alkyl group
A group selected from —S—, —NH—, —CO—, and —O—
It may combine with each other to form a linking group. R₈Represents a substituent
You R₈The substituent represented by the general formula (1-
1) A₁R in_FiveIs the same as the substituent represented by
Can be mentioned. G₁And G₂Can be the same or different
Yes. However, G₁And G₂Together-SO ₂If-p is 2
Or 3 is represented.

J is an alkylene group, a cycloalkylene group,
It represents an alkenylene group, an alkynylene group, or a p + 1-valent group derived from each of these groups. It is preferably an alkylene group having a total carbon number of 2 to 20, a cycloalkylene group, or a p + 1-valent group derived from each of these groups, and particularly preferably an alkylene group having a total carbon number of 2 to 10, a cycloalkylene group, or It is a p + 1 valent group derived from each of these groups. These groups may further have a substituent,
As the substituent, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, etc.), alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, i
so-pentyl group, 2-ethyl-hexyl group, octyl group, decyl group, etc.), cycloalkyl group (eg, cyclohexyl group, cycloheptyl group, etc.), alkenyl group (eg, ethenyl-2-propenyl group, 3-butenyl group) Base,
1-methyl-3-propenyl group, 3-pentenyl group, 1
-Methyl-3-butenyl group etc.), cycloalkenyl group (eg 1-cycloalkenyl group, 2-cycloalkenyl group etc.), alkynyl group (eg ethynyl group, 1-
Propynyl group etc.), alkoxy group (eg methoxy group, ethoxy group, propoxy group etc.), alkylcarbonyloxy group (eg acetyloxy group etc.), alkylthio group (eg methylthio group, trifluoromethylthio group etc.), carboxy Group, alkylcarbonylamino group (eg, acetylamino group, etc.), ureido group (eg, methylaminocarbonylamino group, etc.), alkylsulfonylamino group (eg, methanesulfonylamino group, etc.), alkylsulfonyl group (eg, methanesulfonyl group) Group, trifluoromethanesulfonyl group, etc.), carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, N-morpholinocarbonyl group, etc.), sulfamoyl group (sulfamoyl group, N, N-dimethylsulfamoyl group, N − Luforinosulfonylsulfamoyl group, etc.), trifluoromethyl group, hydroxy group, nitro group, cyano group, alkylsulfonamide group (eg, methanesulfonamide group, butanesulfonamide group, etc.), alkylamino group (eg, amino) Group, N, N-dimethylamino group, N, N-diethylamino group, etc.), sulfo group, phosphono group, sulfite group, sulfino group,
Alkylsulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl group, ethanesulfonylaminocarbonyl group, etc.), alkylcarbonylaminosulfonyl group (eg, acetamidosulfonyl group, methoxyacetamidosulfonyl group, etc.), alkylcarbonylaminocarbonyl group (eg, acetamide) Carbonyl group, methoxyacetamidocarbonyl group, etc.), alkylsulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl group, ethanesulfinylaminocarbonyl group, etc.) and the like. When there are two or more substituents, they may be the same or different. However, it does not have an aryl group or a heteroaryl group as a part of the substituent.

Next, the compound represented by formula (2-1) will be described. In the general formula (2-1),
The halogen atom represented by X ₉ , X ₁₀ , X ₁₁ and X ₁₂ is
Fluorine atom, chlorine atom, bromine atom and iodine atom which may be the same or different from each other, preferably chlorine atom, bromine atom and iodine atom, more preferably chlorine atom and bromine atom, particularly preferably bromine Is an atom.

B ₃ and B ₄ each independently represent a hydrogen atom, a halogen atom or a substituent, and the substituent has the same meaning as the substituent represented by B ₁ and B ₂ in the general formula (2). Is mentioned.

Q represents an integer of 1 or more and 3 or less. G ₃ and G ₄ represent a linking group, and examples of the linking group include those having the same meanings as the linking groups represented by G ₁ and G ₂ in the general formula (2).

J ₂ represents a q + 1 valent alkylene group, cycloalkylene group, alkenylene group or alkynylene group. Preferred are alkylene groups and cycloalkylene groups having 2 to 20 total carbon atoms, and particularly preferred is 2 total carbon atoms.
10 are alkylene groups and cycloalkylene groups. These groups may further have a substituent, and examples of the substituent include those having the same meaning as the substituent for J ₁ in the general formula (2).

Q ₁ and Q ₂ are each independently --C (CH ₃ ).
_{2 -, - CH 2 C (} CH 3) 2 -, - CH (CH 3) - or -CH ₂ CH (CH ₃₎ - represents a.

R and s represent 0 or 1. T ₁ and T ₂ each independently represent a divalent linking group, and as the divalent linking group, —COO—, —OCO—, —CONH— or —NH
CO- and the like can be mentioned.

Specific examples of the compound represented by the general formula (2) and the compound represented by the general formula (2-1) of the present invention are shown below, but the present invention is not limited thereto. . Compound represented by general formula (2)

[0050]

[Chemical 9]

[0051]

[Chemical 10]

[0052]

[Chemical 11]

[0053]

[Chemical 12]

[0054]

[Chemical 13]

Compound represented by formula (2-1)

[0056]

[Chemical 14]

Specific examples of the synthesis of the compound represented by the general formula (2) and the compound represented by the general formula (2-1) are shown below.

Synthesis Example 2-1. Synthesis of Exemplified Compound 2a 2,2-Dimethyl-1,3-propanediamine 3.1
g, toluene 100 ml, triethylamine 12.2 g
Were sequentially mixed, and a solution of 20.0 g of tribromoacetyl chloride dissolved in 10 ml of toluene was added dropwise under cooling with ice water. After completion of dropping, the mixture was stirred at room temperature for 1 hour, and then water 20
ml was added, the mixture was cooled with ice water, and the precipitated crystals were collected by filtration. After removing the aqueous layer of the filtrate, the organic layer was washed with 40 ml of water. The crystals were dried over magnesium sulfate, filtered, and concentrated under reduced pressure to obtain crude crystals. The target compound 2 was obtained by recrystallizing the above-obtained crystal together with 60 ml of acetonitrile.
a (14.8 g) was obtained. ¹ H-NMR spectrum, M
It was confirmed by the S spectrum that the compound was objective compound 2a.

Synthesis Example 2-2. Synthesis of Exemplified Compound 2-1k 0.18 g of trimethylolethane, 1.8 m of ethyl acetate
l, 1,8-diazabicyclo [5,4,0] undeca-
0.75 g of 7-ene was sequentially mixed, and under cooling with ice water, 2-methyl-2- (2,2,2-tribromoacetylamino).
A solution of 2.0 g of propionyl chloride dissolved in 4 ml of ethyl acetate was added dropwise. After dripping, cool with ice water 1
After stirring for 0 minutes, 30 ml of 1 mol / L hydrochloric acid was added.
After adding 30 ml of ethyl acetate and separating the organic layer, 30 ml of a saturated aqueous solution of sodium hydrogen carbonate and 30 m of a saturated saline solution.
The organic layer was washed successively with 1. The crystals were dried over magnesium sulfate, filtered, and concentrated under reduced pressure to obtain crude crystals. The desired compound 2-1k (1.2 g) was obtained by recrystallization from a mixed solvent of ethyl acetate and hexane. ¹ H-NMR
Exemplified Compound 2 of interest based on spectrum and MS spectrum
It was confirmed to be -1k.

Other compounds represented by the above general formula (2) and compounds represented by the general formula (2-1) can be easily synthesized in accordance with the above synthesis.

The addition layer of the compound represented by the general formula (1-1), the general formula (1-2), the general formula (2) or the general formula (2-1) contains a silver halide emulsion as a light-sensitive layer. Although it can be added in either a layer or a non-light-sensitive layer, it is preferably a light-sensitive layer and / or a layer adjacent to the light-sensitive layer. When the compound represented by the general formula (1-1), the general formula (1-2), the general formula (2) or the general formula (2-1) is added to the light-sensitive material, the addition amount is There is no particular limitation, but it is preferably about 10 ^{−4 to} 1.0 mol, and particularly preferably 10 ^{−3 to} 0.3 mol per mol of silver halide.

Next, the compound represented by formula (3) will be described. In the general formula (3), R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a substituent, and the substituent includes a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group. Group (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, iso-
Pentyl group, 2-ethyl-hexyl group, octyl group, decyl group, etc.), cycloalkyl group (eg, cyclohexyl group, cycloheptyl group, etc.), aryl group (eg, phenyl group, carboxyphenyl group, etc.) group, heterocycle Group (eg, imidazolyl group, thiazolyl group, benzoxazolyl group, pyridyl group, pyrrolyl group, indolyl group, pyrimidinyl group, etc.), alkenyl group (eg, ethenyl-2
-Propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, etc., cycloalkenyl group (for example, 1-cycloalkenyl group, 2-cycloalkenyl group) Groups, etc.), alkynyl groups (eg, ethynyl group, 1-propynyl group, etc.), alkoxy groups (eg, methoxy group, ethoxy group, propoxy group, etc.), acyloxy groups (eg, acetyloxy group, benzoyloxy group, etc.), Aryloxy group (eg, phenoxy group, p-tolyloxy group, etc.), heteroaryloxy group (eg, 2-pyridyloxy group, pyrrolyloxy group, etc.), alkylthio group (eg, methylthio group, trifluoromethylthio group, etc.), arylthio A group (for example, a phenylthio group, a 2-naphthylthio group, etc.),
Heteroarylthio groups (eg 3-thienylthio groups, 3
-Pyrrolylthio group etc.), aralkyl group (eg benzyl group, 3-chlorobenzyl group etc.), carboxy group, acylamino group (eg acetylamino group, benzoylamino group etc.), acyloxycarbonylamino group (eg acetyloxycarbonyl) Amino group, benzoyloxycarbonylamino group, etc.), ureido group (eg, methylaminocarbonylamino group, phenylaminocarbonylamino group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), acyl group (Eg, acetyl group, benzoyl group, etc.), sulfonyl group (eg, methanesulfonyl group, trifluoromethanesulfonyl group, etc.), carbamoyl group (eg, carbamoyl group, N, N-dimethylcarbamoyl group, N-morpholinoca) Boniru group), a sulfamoyl group (a sulfamoyl group, N, N- dimethylsulfamoyl group, N- morpholino sulfonyl group, etc.), a trifluoromethyl group, a hydroxy group, a styryl group, a nitro group,
Cyano group, sulfonamide group (for example, methanesulfonamide group, butanesulfonamide group, etc.), amino group (for example, amino group, N, N-dimethylamino group, N, N-diethylamino group, etc.), sulfo group, phosphono group , Sulfite group, sulfino group, sulfonylaminocarbonyl group (eg, methanesulfonylaminocarbonyl group, ethanesulfonylaminocarbonyl group, etc.), acylaminosulfonyl group (eg, acetamidosulfonyl group, methoxyacetamidosulfonyl group, etc.), alkylcarbonylamino Carbonyl group (eg, acetamidocarbonyl group, methoxyacetamidocarbonyl group, etc.), sulfinylaminocarbonyl group (eg, methanesulfinylaminocarbonyl group, ethanesulfinylaminocarbonyl group, etc.), etc. The recited, these substituents may be further substituted by these substituents. When there are two or more substituents, they may be the same or different.

D represents a substituent. As the substituent, the above R
Examples thereof include those having the same meanings as the substituents represented by 2, R3 and R4, and preferably an electron-withdrawing group. The electron-withdrawing group is a substituent having a Hammett's substituent constant σp value of 0.15 or more, more preferably 0.2 or more.
Regarding Hammett's substituent constant, Journalof
Medicinal Chemistry, 197
3, Vol. 16, No. 11, 1207-1216 can be referred to. Examples of the electron-withdrawing group include a halogen atom (chlorine atom (σp value: 0.23), bromine atom (σp value: 0.23), iodine atom (σp value:
0.18)), a trihalomethyl group (for example, tribromomethyl (σp value: 0.29), trichloromethyl (σp
Value: 0.33), trifluoromethyl (σp value: 0.5)
4) etc.), cyano group (σp value: 0.66), nitro group (σp value: 0.78), aliphatic / aryl or heterocyclic sulfonyl group (for example, methanesulfonyl group (σp)
Value: 0.72), etc., an aliphatic / aryl or heterocyclic acyl group (for example, an acetyl group (σp value: 0.50),
Benzoyl group (σp value: 0.43), etc., aliphatic / aryl or heterocyclic oxycarbonyl group (for example, methoxycarbonyl group (σp value: 0.45), phenoxycarbonyl group (σp value: 0.45), etc. ), Carbamoyl group (σp value: 0.36), sulfamoyl group (σp value:
0.57) and the like, and preferably a cyano group.

R ₂ and D, R ₂ and R ₃ , R ₃ and R _4, and R ₄ and D
May combine with each other to form a cyclic structure.

In the general formula (3), a compound in which R ₃ is an electron donating group and R ₄ is a hydrogen atom is preferable. In the present invention, the electron-donating group means a substituent having a negative Hammett's substituent constant σp, and examples of the electron-donating group include a hydroxy group (or a salt thereof), a mercapto group (or Salt), an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an amino group, an alkylamino group, an arylamino group, a heterocyclic amino group, and a negative value for σp. Heterocyclic groups or phenyl groups substituted with these electron donating groups are mentioned.

Specific examples of the compound represented by formula (3) are shown below, but the invention is not limited thereto. In addition, in these compounds, when a tautomer or a geometrical isomer exists, both of them are represented.

[0067]

[Chemical 15]

[0068]

[Chemical 16]

The hydrazine derivative used in the present invention is not limited, but a compound represented by the following general formula (4) is preferable.

[0070]

[Chemical 17]

In the formula, R ₃₆ , R ₃₇ and R ₃₈ each independently represent a substituted or unsubstituted aryl group or heteroaryl group, R ₃₉ represents a heterocyclic oxy group or a heterocyclic thio group, and D ₁ , D ₂ is a hydrogen atom, or one is a hydrogen atom and the other is an acyl group, a sulfonyl group or an oxalyl group.

In the general formula (4), R₃₆, R₃₇And R
₃₈Are each independently a substituted or unsubstituted aryl group or
It represents a heteroaryl group, but specifically as an aryl group
Is, for example, phenyl group, p-methylphenyl group, naphthyl group.
And the like. Specific as a heteroaryl group
Include, for example, triazole residues, imidazole residues,
Lysine residue, furan residue, thiophene residue, etc.
Be done. Also, R₃₆, R ₃₇And R₃₈Are arbitrary concatenations
You may couple | bond through a group. R₃₆, R₃₇And R ₃₈Is replaced
When it has a group, the substituent is the above-mentioned R.₁~ R₂₇Replacement of
A group can be mentioned. R₃₆, R₃₇And R₃₈As good as
More preferably, each is a substituted or unsubstituted phenyl group.
Yes, more preferably R₃₆, R₃₇And R₃₈Any of
It is an unsubstituted phenyl group.

R ₃₉ represents a heterocyclic oxy group or a heterocyclic thio group. Specific examples of the heterocyclic oxy group include a pyridyloxy group, a pyrimidyloxy group, an indolyloxy group, a benzothiazolyloxy group and a benzimidazolyl group. Examples thereof include an oxy group, a furyloxy group, a thienyloxy group, a pyrazolyloxy group, and an imidazolyloxy group. Specific examples of the heterocyclic thio group include a pyridylthio group, a pyrimidylthio group, an indolylthio group, a benzothiazolylthio group, a benzimidazolylthio group, a furylthio group, a thienylthio group, a pyrazolylthio group and an imidazolylthio group. R ₃₉ is preferably a pyridyloxy group,
It is a thienyloxy group.

D ₁ and D ₂ are both hydrogen atoms, or one is a hydrogen atom and the other is an acyl group (acetyl group, trifluoroacetyl group, benzoyl group, etc.), sulfonyl group (methanesulfonyl group, toluenesulfonyl group, etc.) Or represents an oxalyl group (such as an ethoxaryl group). Preferably D ₁ ,
This is the case where both D ₂ are hydrogen atoms.

Specific examples of the hydrazine derivative used in the present invention will be given below, but the present invention is not limited thereto.

[0076]

[Chemical 18]

[0077]

[Chemical 19]

[0078]

[Chemical 20]

As the hydrazine compound used in the present invention, the following compounds other than the above can be used.

Research Disclosure No. 23
516 (November 1983, p. 346) and references cited therein, as well as U.S. Pat. No. 4,080,207.
No. 4,169,929, 4,276,364
Nos. 4,278,748, 4,385,108
Issue No. 4,459,347 Issue No. 4,478,928
Nos. 4,560,638 and 4,686,167
No. 4,912,016, 4,988,604
Issue No. 4,994,365 Issue 5,041,355
No. 5,104,769, British Patent No. 2,011,
391B, European Patent Nos. 217,310 and 301,
799, 356, 898, JP-A-60-1797.
34, 61-170733, 61-27074.
No. 4, No. 62-178246, No. 62-270948.
No. 63, No. 63-29751, No. 63-32538, No. 63-104047, No. 63-121838, No. 6
3-129337, 63-223744, 63
-234244, 63-234245, 63-
234246, 63-294552, 63-3
06438, 64-10233 and JP-A-1-90.
No. 439, No. 1-100530, No. 1-105941
No. 1, No. 1-105943, No. 1-276128, No. 1-280747, No. 1-283548, No. 1-2.
83549, 1-285940, 2-2541.
No. 2, No. 2-77057, No. 2-139538, No. 2
-196234, 2-196235, 2-19
No. 8440, No. 2-198441, No. 2-19844
No. 2, No. 2-220042, No. 2-221953,
2-221954, 2-285342, 2-
285343, 2-289843, 2-302
No. 750, No. 2-304550, No. 3-37642
No. 3, No. 3-54549, No. 3-125134, No. 3
-184039, 3-240036, 3-24
No. 0037, No. 3-259240, No. 3-28003
No. 8, No. 3-228536, No. 4-51143, No. 4-56842, No. 4-84134, No. 2-230.
No. 233, No. 4-96053, No. 4-216544.
No. 5, No. 5-45761, No. 5-45762, No. 5-
No. 45763, No. 5-45764, No. 5-45765.
No. 6-289524, No. 9-160164, and the like.

In addition to these, the compounds represented by (Chemical formula 1) described in JP-B-6-77138, specifically, the compounds described on pages 3 and 4 of the publication. Compounds represented by formula (I) described in JP-B-6-93082, specifically, compounds 1 to 38 described on pages 8 to 18 of the publication; JP-A-6
General formula (4) and general formula (5) described in JP-A-230497.
And compounds represented by the general formula (6), specifically, Compounds 4-1 to 4-described on pages 25 and 26 of the same publication.
10, Compounds 5-1 to 5-4 described on pages 28 to 36
2, and Compounds 6-1 to 6-7 described on pages 39 and 40. Compounds represented by formulas (1) and (2) described in JP-A-6-289520, specifically, compounds 1-1) to 1-1 described on pages 5 to 7 of the publication.
7) and 2-1). The compounds represented by (Chemical Formula 2) and (Chemical Formula 3) described in JP-A-6-313936, specifically the compounds described on pages 6 to 19 of the same. JP 6-3
A compound represented by (Chemical Formula 1) described in No. 13951, specifically, the compounds described on pages 3 to 5 of the same publication. JP-A-7-
A compound represented by the general formula (I) described in 5610,
Specifically, the compounds I-1 to 1 described on pages 5 to 10 of the same publication are disclosed.
I-38. The general formula (I described in JP-A-7-77783)
Compounds represented by I), specifically, pages 10 to 2 of the same 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 publication.
The compounds H-1 to H-44 described on the page can be used.

The compound represented by the general formula (3) and the hydrazine derivative according to the present invention can be easily synthesized by a known method. There are also compounds that can be purchased directly from drug manufacturers.

The compound represented by the general formula (3) and the hydrazine derivative may be added as a light-sensitive layer containing a silver halide emulsion or a non-light-sensitive layer. Adjacent layers are preferred. When the compound represented by the general formula (3) and the hydrazine derivative are added to the light-sensitive material, the addition amount thereof is not particularly limited, but is generally about 1 per 1 mol of silver halide.
About 0 ^-6 mol to 10 ^-1 mol is preferable, and 10 ^-5 mol to 1
A range of 0 ^-2 mol is particularly preferred.

Compounds and hydrazine derivatives represented by the general formula (1-1), the general formula (1-2), the general formula (2), the general formula (2-1) and the general formula (3) according to the present invention. Can be dissolved in a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, etc. It can also be incorporated by the well-known emulsion dispersion method.
For example, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate is dissolved using a high boiling organic solvent such as or diethyl phthalate and an auxiliary solvent such as ethyl acetate or cyclohexanone, mechanically emulsified to produce an emulsion dispersion, It can be added to a desired constituent layer.

Further, a method known as a solid dispersion method, for example, the general formula (1-1) or the general formula (1-
2), general formula (2), general formula (2-1), general formula (3)
The powder of the compound represented by and the hydrazine derivative can be optionally added as an aqueous fine particle dispersion by using a dispersing means such as a ball mill, a colloid mill, or an ultrasonic disperser.

In the photothermographic material of the present invention, in addition to the above compounds, hydroxylamine compounds, alkanolamine compounds and ammonium phthalate compounds described in US Pat. No. 5,545,505 and US Pat. Fifty
Hydroxamic acid compounds described in No. 7, US Pat. No. 5,5
58,983, N-acyl-hydrazine compounds, and benzhydrol, diphenylphosphine, dialkylpiperidine, alkyl-β-ketoesters, and other hydrogen atom donor compounds described in US Pat. No. 5,937,449. It can be added. By including these compounds, the maximum density Dmax can be further improved in the image formed using the hydrazine derivative.

Next, the photothermographic material of the present invention will be described. The organic silver salt used in the photothermographic material of the invention is a reducible silver source, and is a silver salt of an organic acid or a heteroorganic acid containing a reducible silver ion source, and particularly long-chain (carbon atom) Number 10 to 30, preferably 15 to 2
The aliphatic carboxylic acid and nitrogen-containing heterocycle of 5) are preferable.
The ligand has a total stability constant of 4.0 to 4.0 for silver ions.
Organic or inorganic silver complexes having a value of 10.0 are also useful in the present invention. An example of a suitable silver salt is Research Disclosure (hereinafter, also simply referred to as RD) No. 1
7029 and 29963 and may include the following: Silver salts of organic acids (eg, silver such as gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid, lauric acid). Salt); silver carboxyalkyl thiourea salt (for example, silver salt such as 1- (3-carboxypropyl) thiourea, 1- (3-carboxypropyl) -3,3-dimethylthiourea); aldehyde and hydroxy-substituted aromatic Silver complexes of polymer reaction products with carboxylic acids (eg, aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.) and hydroxy-substituted acids (eg, salicylic acid, benzoic acid, 3,
5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid), a silver complex of a polymer reaction product); a silver salt or complex of thiones (for example, 3- (2-carboxyethyl)-
4-hydroxymethyl-4- (thiazolin-2-thione, and 3-carboxymethyl-4-thiazoline-2-
Thione) or other silver salt or complex); imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, 3-amino-5-benzylthio-1,2,2.
Examples thereof include complexes or salts of nitric acid and silver selected from 4-triazole and benzotriazole; silver salts such as saccharin and 5-chlorosalicylaldoxime; and silver salts of mercaptides. Preferred silver sources are silver behenate, silver arachidate, silver stearate and mixtures thereof.

The organic silver salt compound can be obtained by mixing a water-soluble silver compound and a compound which forms a complex with silver. The forward mixing method, the reverse mixing method, the simultaneous mixing method, and JP-A-9-12764.
The controlled double jet method described in No. 3 is preferably used. For example, after adding alkali metal salt (eg, sodium hydroxide, potassium hydroxide, etc.) to organic acid to make organic acid alkali metal salt soap (eg, sodium behenate, sodium arachidate), controlled double By the jet method, the soap and silver nitrate are added to prepare crystals of an organic silver salt. In that case, photosensitive silver halide grains described below (hereinafter, simply referred to as silver halide grains) may be mixed.

The silver halide grain in the present invention functions as an optical sensor. In the present invention,
In order to suppress white turbidity of the light-sensitive material after image formation and obtain good image quality, the average particle size is preferably small, the average particle size is preferably 0.1 μm or less, more preferably 0.01 μm to 0.1 μm, Particularly preferably 0.02
It is μm to 0.08 μm. The grain size (grain size) as used herein refers to the length of the ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. Also, in the case of non-normal crystals, for example, in the case of spherical, rod-shaped, or tabular grains, it means the diameter of a sphere assuming a sphere equivalent to the volume of silver halide grains. The silver halide grains are preferably monodisperse.
The monodispersion as used herein means that the monodispersity calculated by the following formula is 40% or less. More preferably, it is 30% or less,
Particularly preferably, the particles are 0.1% or more and 20% or less.

Monodispersity = {(standard deviation of grain size) / (average grain size)} × 100 In the present invention, silver halide grains have a mean grain size of 0.1.
It is preferable that the particle size is not more than μm and the particles are monodisperse particles, and if the particle size is within this range, the granularity of the image is also improved.

The shape of the silver halide grains is not particularly limited, but it is preferable that the ratio of Miller index [100] faces is high, and this ratio is 50% or more, and further 7%.
It is preferably 0% or more, and particularly preferably 80% or more. The ratio of Miller index [100] planes is determined by T.W. Tani J. Imaging Sci. 29
165 (1985).

Further, another preferable shape of the silver halide grain in the present invention is a tabular grain. The tabular grains referred to herein mean those having an aspect ratio = r / h of 3 or more when the square root of the projected area is rμm and the vertical thickness is hμm. Among them, the aspect ratio is preferably 3 to 50. The particle size of tabular grains is
It is preferably 0.1 μm or less, and further 0.01
μm to 0.08 μm is preferable. These tabular grains are described in US Pat. Nos. 5,264,337 and 5,314,79.
It can be easily obtained by the method described in No. 8, No. 5,320,958 and the like. In the present invention, the sharpness of the image can be further improved by using the tabular grains.

The halogen composition of the silver halide grains is not particularly limited, and silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide,
It may be either silver iodobromide or silver iodide. The photographic emulsion used in the present invention is described in P. By Glafkides Ch
imie et Physique Photogra
picture (Paul Montel, 1967)
Year), G. F. Duffin Photograph
ic Emulsion Chemistry (The
Focal Press, 1966), V.I. L.
By Zelikman et al Making an
d Coating Photographic Em
ulsion (published by The Focal Press, 1
964) and the like.

The silver halide used in the present invention contains an ion or a complex ion of a metal belonging to Groups 6 to 10 of the Periodic Table of the Elements in order to improve reciprocity law failure characteristics and adjust gradation. It is preferable. Examples of the above metals include W, Fe, Co, Ni, Cu, Ru, Rh, Pd,
Re, Os, Ir, Pt and Au are preferable.

The silver halide grains can be removed (desalted) of unnecessary salts by a method known in the art, such as a noodle method or a flocculation method. In the present invention, desalting is performed. It may or may not be performed.

The silver halide grains in the present invention are preferably chemically sensitized. Preferred chemical sensitization methods include a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, a noble metal sensitization method such as a gold compound, platinum, palladium, or an iridium compound, or reduction, which are well known in the art. A sensitizing method or the like can be used.

In the present invention, in order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is preferably 0.5 g or more and 2.2 g or less per 1 m ² in terms of silver amount. . By setting the amount of silver in this range, a high contrast image can be obtained. The ratio of the amount of silver halide to the total amount of silver is 50% or less, preferably 25% or less, and more preferably 0.1 to 15% by mass.

Examples of the reducing agent used in the photothermographic material of the present invention include generally known reducing agents such as phenols, polyphenols having two or more phenol groups, naphthols, and bisnaphthols. Two
Polyhydroxybenzenes having two or more hydroxyl groups, 2
Polyhydroxynaphthalene having at least one hydroxyl group,
Ascorbic acids, 3-pyrazolidones, pyrazoline-
5-ones, pyrazolines, phenylenediamines, hydroxylamines, hydroquinone monoethers,
There are hydrooxamic acids, hydrazides, amidoximes, N-hydroxyureas, and the like, and more specifically, for example, US Pat. Nos. 3,615,533 and 3,67.
9,426, 3,672,904, 3,7
No. 51,252, No. 3,782,949, No. 3,
801,321, 3,794,488, 3,893,863, 3,887,376, 3,770,448, 3,819,382,
No. 3,773,512, No. 3,839,048
No. 3, No. 3,887,378, No. 4,009,03
No. 9, No. 4,021,240, British Patent No. 1,48
No. 6,148, Belgian Patent No. 786,086, JP-A Nos. 50-36143, 50-36110, and 50.
-116023, 50-99719, 50-1
40113, 51-51933, 51-237.
21, No. 52-84727, Japanese Patent Publication No. 51-3585.
The reducing agent and the like specifically exemplified in No. 1 can be cited, and the present invention can be appropriately selected and used from the above known reducing agents. The most efficient selection method is to actually produce a photothermographic material containing a reducing agent and directly evaluate its photographic performance to confirm the suitability of the reducing agent.

Among the above reducing agents, when an aliphatic carboxylic acid silver salt is used as the organic silver salt, preferred reducing agents include polyphenols in which two or more phenol groups are linked by an alkylene group or sulfur, particularly An alkyl group (eg, methyl group, ethyl group, propyl group, t-butyl group, cyclohexyl group, etc.) or acyl group (eg, acetyl group, propionyl group, etc.) is present in at least one position adjacent to the hydroxy-substituted position of the phenol group. Polyphenols in which two or more of the substituted phenol groups are linked by an alkylene group or sulfur, such as 1,1-bis (2
-Hydroxy-3,5-dimethylphenyl) -3,5
5-trimethylhexane, 1,1-bis (2-hydroxy-3-t-butyl-5-methylphenyl) methane,
1,1-bis (2-hydroxy-3,5-di-t-butylphenyl) methane, (2-hydroxy-3-t-butyl-5-methylphenyl)-(2-hydroxy-5-methylphenyl) Methane, 6,6'-benzylidene-bis (2,4-di-t-butylphenol), 6,6'-benzylidene-bis (2-t-butyl-4-methylphenol), 6,6'-benzylidene- Bis (2,4-dimethylphenol), 1,1-bis (2-hydroxy-)
3,5-dimethylphenyl) -2-methylpropane,
1,1,5,5-tetrakis (2-hydroxy-3,5
-Dimethylphenyl) -2,4-ethylpentane, 2,
2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5)
-Di-t-butylphenyl) propane and the like, U.S. Pat. Nos. 3,589,903 and 4,021,249, British Patent 1,486,148, JP-A-51-5193.
No. 3, No. 50-36110, No. 50-116023
Nos. 52-84727 and JP-B-51-35727, US Pat.
72,904, bisnaphthols such as 2,2'-dihydroxy-1,1'-binaphthyl,
6,6'-dibromo-2,2'-dihydroxy-1,
1'-binaphthyl, 6,6'-dinitro-2,2'-dihydroxy-1,1'-binaphthyl, bis (2-hydroxy-1-naphthyl) methane, 4,4'-dimethoxy-
1,1'-dihydroxy-2,2'-binaphthyl and the like, and further sulfonamide phenols or sulfonamide naphthols such as those described in U.S. Pat. No. 3,801,321, such as 4-benzenesulfonamide phenol, 2-benzenesulfonamide phenol, 2,6
-Dichloro-4-benzenesulfonamidophenol,
4-benzenesulfonamide naphthol and the like can be mentioned.

The appropriate amount of the reducing agent used in the photothermographic material of the present invention varies depending on the type of the organic silver salt used, the reducing agent and other additives, but in general, the organic silver salt 1
0.05 to 10 moles per mole, preferably 0.1 to 3
A molar range is suitable. Further, within this range, two or more kinds of the above-mentioned reducing agents may be used in combination. In the present invention, it is preferable to add the reducing agent to the coating solution for the photosensitive layer immediately before coating so as to reduce variations in photographic performance due to stagnation time of the coating solution for the photosensitive layer.

Suitable binders for the photothermographic material of the present invention are transparent or translucent, generally colorless natural polymer synthetic resins and 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 methacrylic acid), 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 (ester) ), Li (urethanes), phenoxy resins, poly (vinylidene chloride), poly (epoxides),
Poly (carbonate) s, poly (vinyl acetate),
There are cellulose esters and poly (amides). The binder may be hydrophilic or hydrophobic, but in the present invention, it is preferable to use a hydrophobic transparent binder in order to reduce fog after the heat development treatment.
Preferred binders include, for example, polyvinyl butyral, cellulose acetate, cellulose acetate butyrate, polyester, polycarbonate, polyacrylic acid, polyurethane and the like. Among them, polyvinyl butyral, cellulose acetate, cellulose acetate butyrate and polyester are particularly preferably used.

In order to protect the surface of the light-sensitive material and prevent scratches, it is preferable to apply a non-light-sensitive layer outside the light-sensitive layer. The binder used in these non-photosensitive layers may be the same or different from the binder used in the photosensitive layers.

In the present invention, the binder amount in the photosensitive layer is preferably 1.5 to 10 g / m ² in order to increase the heat development rate. More preferably, 1.7-8 g / m
^{Is 2} . If it is less than 1.5 g / m ² , the density (D
min) is significantly increased, which may cause a practical problem.

In the present invention, it is preferable to add a matting agent to the photosensitive layer side, and the amount of the matting agent provided on the surface of the photosensitive material is the total amount on the photosensitive layer side in order to prevent the image from being scratched after the heat development treatment. 0.5 to 3 in mass ratio to binder
It is preferable to contain 0%. Further, when a non-photosensitive layer is provided on the side opposite to the photosensitive layer sandwiching the support, it is preferable that at least one layer on the non-photosensitive layer side contains a matting agent for the purpose of slipperiness and fingerprint adhesion prevention. , And the amount of the matting agent was 0.
It is preferable to contain 5 to 40%. The shape of the matting agent may be either a fixed shape or an amorphous shape, but a fixed shape is preferable, and a spherical shape is particularly preferable.

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. Further, in order to control the amount or wavelength distribution of light passing through the photosensitive layer, a filter dye layer may be formed on the same side as the photosensitive layer and / or an antihalation dye layer, a so-called backing layer may be formed on the opposite side, or The dye or pigment may be directly contained in the photosensitive layer.

These non-photosensitive layers may contain a polysiloxane compound, a wax or a slipping agent such as liquid paraffin, in addition to the above-mentioned binder and matting agent.

In the photothermographic material of the present invention, various surfactants can be used as coating aids. Among them, a fluorine-based surfactant is particularly preferably used in order to improve the charging property and prevent spot-like coating failure.

The photosensitive layer may be composed of a plurality of layers, or may be composed of a plurality of layers such as a high sensitivity layer / low sensitivity layer or a low sensitivity layer / high sensitivity layer for adjusting gradation.

Examples of suitable toning agents used in the present invention are:
It is disclosed in RD17029.

The photothermographic material of the present invention contains a mercapto compound for suppressing or accelerating the development to control the development intensity, for improving the spectral sensitization efficiency, or for improving the storage stability before and after the development processing. An inhibitor such as a disulfide compound or a thione compound may be contained.

Further, 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. As these additives and the above-mentioned other additives, RD17029 (1
June 978 p. The compounds described in 9 to 15) can be preferably used.

The above-mentioned various additives may be added to any of the photosensitive layer, the non-photosensitive layer and other forming layers.

The support used in the present invention is a plastic film (eg, polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate) in order to obtain a predetermined optical density after development and to prevent deformation of the image after development. , Polyethylene naphthalate) are preferred.

Among them, preferred supports include polyethylene terephthalate (hereinafter abbreviated as PET) and a plastic (hereinafter abbreviated as SPS) containing a styrene polymer having a syndiotactic structure. The thickness of the support is about 50 to 300 μm, preferably 70 to 180 μm.

It is also possible to use a heat-treated plastic support. The plastics to be adopted include the above-mentioned plastics. What is heat treatment of the support?
After the support is formed into a film, it is heated at a temperature higher than the glass transition point of the support by 30 ° C. or higher, preferably by 35 ° C. or higher, more preferably by 40 ° C. or higher, until the photosensitive layer is coated. It means to do.

In the present invention, a conductive compound such as a metal oxide and / or a conductive polymer may be contained in the constituent layer in order to improve the charging property. These may be contained in any layer, but are preferably an undercoat layer, a backing layer, a layer between the photosensitive layer and the undercoat layer, and the like.

The photothermographic material of the present invention includes, for example, JP-A Nos. 63-159841, 60-140335, 63-231437, 63-259651, and 6-59.
3-304242, 63-15245, U.S. Patents 4,639,414, 4,740,455, 4,741,966, 4,751,175, 4,835,096. The sensitizing dyes described in No. 1 can be used.

Specific examples of useful sensitizing dyes used in the present invention include, for example, RD17643IV-A (December 1978).
Month p. 23), Item 18431X (August 1979, p.
437) or cited therein.

In the present invention, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) with respect to an argon laser light source, JP-A-60-162247, JP-A-2-48653, and US Pat. No. 2,161,331.
, West German Patent No. 936,071, Japanese Patent Application No. 3-1895
No. 32, etc., and the B) helium-neon laser light source described in JP-A No. 50-62.
No. 425, No. 54-18726, No. 59-10222.
Trinuclear cyanine dyes described in No. 9 and the like, Japanese Patent Application No. 6-103
Japanese Patent Publication No. 48-42172 for the merocyanines described in No. 272, C) LED light source and red semiconductor laser.
JP-A-51-9609, JP-A-55-39818, JP-A-62-284343, JP-A-2-105135, and D) infrared semiconductor laser light sources. Sho 59-191032, No. 6
Tricarbocyanines described in 0-80841,
4-described in the general formula (IIIa) and the general formula (IIIb) of JP-A-59-192242 and JP-A-3-67242.
Dicarbocyanines containing a quinoline nucleus and the like are advantageously selected.

These sensitizing dyes may be used alone or in combination thereof. In the combination of sensitizing dyes, the sensitizing dyes are often used together with the sensitizing dyes often used for the purpose of supersensitization. A dye having no sensitizing action or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the silver halide emulsion.

Exposure of the photothermographic material of the present invention was carried out by Ar laser (488 nm) and He-Ne laser (633n).
m), a red semiconductor laser (670 nm), an infrared semiconductor laser (780 nm, 830 nm) or the like is one of the characteristics, and the wavelength of the laser light source is 700 to 1000 nm. Semiconductor lasers are preferred.

The photothermographic material of the present invention can be provided with a layer containing a dye as an antihalation layer. For Ar lasers, He-Ne lasers, and red semiconductor lasers, it is preferable to add a dye in the range of 400 nm to 750 nm so that the absorption at the exposure wavelength is at least 0.3 or more, preferably 0.8 or more.
For infrared semiconductor lasers, it is preferable to add a dye in the range of 750 nm to 1500 nm so that the absorption at the exposure wavelength is at least 0.3 or more, preferably 0.8 or more. The dyes may be used alone or in combination of several kinds. The dye can be added to the dye layer near the support on the same side as the photosensitive layer or to the dye layer on the opposite side to the photosensitive layer.

The photothermographic material of the present invention may be developed by any method. In the present invention, the photothermographic material exposed imagewise is heated to a temperature of 8
One of the characteristics is that the heat development treatment is carried out at 0 to 250 ° C, preferably 100 to 140 ° C. The developing time is preferably 1 to 180 seconds, more preferably 10 to 90 seconds.

[0124]

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

Example 1 [Preparation of undercoated photographic support] <Preparation of PET undercoated photographic support> Commercially available biaxially stretched and heat-fixed 175 μm thick optical density 0.170
8 W / m ^{2 on} both sides of the PET film colored in blue (measured with Konica Densitometer PDA-65)
・ Corona discharge treatment for minutes is applied, and one side of the following undercoating coating solution a-1 is applied to a dry film thickness of 0.8 μm and dried to form an undercoating layer A-1. The undercoating coating solution b-1 described below was applied to the surface so as to have a dry film thickness of 0.8 μm, and dried to form an undercoating layer B-1.

<< Undercoating Liquid a-1 >> Butyl acrylate (30% by mass) t-Butyl acrylate (20% by mass) Styrene (25% by mass) 2-Hydroxyethyl acrylate (25% by mass) Copolymer latex liquid (Solid content 30%) 270 g C-1 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water to 1 liter << Subbing coating liquid b-1 >> Butyl acrylate (40 mass%) Styrene (20% by mass) Copolymer latex liquid of glycidyl acrylate (40% by mass) (solid content 30%) 270 g C-1 0.6 g hexamethylene-1,6-bis (ethyleneurea) 0.8 g Water to 1 liter After finishing, 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 applied, and the following undercoating upper layer coating liquid a-2 was dried to a thickness of 0.1 μm on the undercoating layer A-1.
As the undercoating upper layer A-2, the following undercoating upper layer coating liquid b-2 is provided on the undercoating layer B-1 to have an antistatic function so that the dry film thickness becomes 0.8 μm. It was applied as B-2.

<< Undercoating Upper Layer Coating Liquid a-2 >> Gelatin 0.4 g / m ² Mass C-1 0.2 g C-2 0.2 g C-3 0.1 g Silica particles (average particle size 3 μm) 0 1g Finish with water to 1l << Undercoating upper layer coating liquid b-2 >> C-4 60g Latex liquid containing C-5 (solid content 20%) 80g Ammonium sulfate 0.5g C-6 12g Polyethylene glycol (weight average) Molecular weight 600) 6g Make up to 1l with water

[0128]

[Chemical 21]

[0129]

[Chemical formula 22]

<< Back surface side coating >> While stirring 830 g of methyl ethyl ketone (MEK), cellulose acetate butyrate (Eastman Chemical Co.,
CAB381-20) 84.2 g and polyester resin (Bostic, VitelPE2200B) 4.
5 g was added and dissolved. Next, add 0.3 to the dissolved liquid.
4.5 g of an F-type activator (Asahi Glass Co., Ltd., Surflon KH40) and F-type activator (Dainippon Ink and Co., Ltd., Megafag F120K) added with 0 g of infrared dye Dye-1, and further dissolved in 43.2 g of methanol. 2.3 g was added, and the mixture was sufficiently stirred until it was dissolved. Finally, silica dispersed in methyl ethyl ketone at a concentration of 1% by a dissolver type homogenizer (WR Grace, Syloid 6).
4 x 6000) was added and stirred to prepare a coating liquid for the back side.

[0131]

[Chemical formula 23]

The back surface coating liquid thus prepared was
It was applied by an extrusion coater and dried so that the dry film thickness was 3.5 μm. Drying temperature 100 ℃, dew point temperature 1
It was dried for 5 minutes using a drying air of 0 ° C.

<< Preparation of Photosensitive Silver Halide Emulsion A >> A1 Phenylcarbamoylated gelatin 88.3 g Compound (A) (10% aqueous methanol solution) 10 ml Potassium bromide 0.32 g Water to make 5429 ml B1 0.67 mol / L Aqueous silver nitrate solution 2635 ml C1 Potassium bromide 51.55 g Potassium iodide 1.47 g Finish with water to 660 ml D1 Potassium bromide 154.9 g Potassium iodide 4.41 g Iridium chloride (1% solution) 0.93 ml Finish with water to 1982 ml E1 0.4 mol / L aqueous solution of potassium bromide F1 potassium hydroxide 0.71 g Finish with water to 20 ml G1 56% acetic acid aqueous solution 18.0 ml H1 anhydrous sodium carbonate 1.72 g Finish with water to 151 ml Compound (A) : HO (CH ₂ C _{2 O) n - (CH (} CH 3) CH 2 O) 17 - (CH 2 CH 2 O) m H (m + n = 5~7) Japanese Patent Publication No. 58-58288, mixing and stirring machine shown in Nos. 58-58289 Solution (B1) to solution (A1) using
1/4 amount and the total amount of the solution (C1) at a temperature of 45 ° C. and pAg
While controlling at 8.09, the mixture was added for 4 minutes and 45 seconds by the simultaneous mixing method to perform nucleation. After 1 minute, the solution (F
The whole amount of 1) was added. During this time, adjust pAg (E1)
Was appropriately used. After 6 minutes, 3 of solution (B1)
/ 4 amount and the total amount of the solution (D1) at a temperature of 45 ° C. and pAg
While controlling to 8.09, 14 minutes 15 by simultaneous mixing method
Added over seconds. After stirring for 5 minutes, the temperature was lowered to 40 ° C., the entire amount of the solution (G1) was added, and the silver halide emulsion was precipitated. The supernatant was removed, leaving 2000 ml of the sedimented portion, 10 liters of water was added, and after stirring, the silver halide emulsion was sedimented again. Leaving 1500 ml of sedimentation part,
The supernatant liquid was removed, 10 liters of water was further added, and after stirring, the silver halide emulsion was precipitated. Settling part 1500
After removing the supernatant liquid while leaving ml, the solution (H1) was added, the temperature was raised to 60 ° C., and the mixture was further stirred for 120 minutes. Finally, adjust the pH to 5.8 and add 1 for 1 mol of silver.
Water was added so that the amount was 161 g to obtain a photosensitive silver halide emulsion A.

This emulsion has an average grain size of 0.058 μm.
m, variation coefficient of particle size 12%, [100] plane ratio 9
It was 2% of monodisperse cubic silver iodobromide grains.

Next, the sulfur sensitizer S-5 (0.5
% Methanol solution), and then a gold sensitizer Au-5 corresponding to 1/20 mol of this sensitizer is added at 55 ° C.
The mixture was stirred for 120 minutes for chemical sensitization.

[0136]

[Chemical formula 24]

<< Preparation of Powdered Organic Silver Salt A >> 130.8 g of behenic acid and 67.7 of arachidic acid were added to 4720 ml of pure water.
g, stearic acid 43.6 g, and palmitic acid 2.3 g were dissolved at 80 ° C. Next, 540.2 ml of a 1.5 M sodium hydroxide aqueous solution was added, 6.9 ml of concentrated nitric acid was added, and the mixture was cooled to 55 ° C. to obtain a fatty acid sodium solution. While maintaining the temperature of the sodium fatty acid solution at 55 ° C., 45.3 g of the above photosensitive silver halide emulsion A and 450 ml of pure water were added and stirred for 5 minutes.

Next, 12.6 mol / L silver nitrate solution 702.6 m
1 was added over 2 minutes and stirred for 10 minutes to obtain an organic silver salt dispersion. After that, the obtained organic silver salt dispersion was transferred to a water washing container, deionized water was added thereto, and the mixture was stirred and then allowed to stand to separate the organic silver salt dispersion by flotation to remove the water-soluble salts below. After that, washing with deionized water and drainage were repeated until the conductivity of the drainage reached 2 μS / cm, and centrifugal dehydration was carried out. Then, the cake-shaped organic silver salt obtained was washed with a flash dryer, flash jet dryer (stock). (Manufactured by Seishin Enterprise Co., Ltd.) was dried until the water content became 0.1% under the operating conditions of nitrogen gas atmosphere and hot air temperature at the entrance of the dryer to obtain dried organic silver salt A of organic silver salt.

An infrared moisture meter was used to measure the water content of the organic silver salt composition. << Preparation of Preliminary Dispersion A >> Polyvinyl butyral powder (M
Onsanto, Butvar B-79) 14.
57g was dissolved in 1457g of methyl ethyl ketone,
A-GETZMANN Dissolver DISPERMA
Powdered organic silver salt A5 while stirring with TCA-40M type
A preliminary dispersion liquid A was prepared by gradually adding 00 g and thoroughly mixing them.

<< Preparation of Photosensitive Emulsion Dispersion 1 >> Preliminary Dispersion A containing zirconia beads (Toray's Treceram) having a diameter of 0.5 mm so that the residence time in the mill was 1.5 minutes using a pump. Media type disperser D filled with 80% of product
ISPERMAT SL-C12EX type (VMA-GE
TZMANN) and dispersed at a mill peripheral speed of 8 m / s to prepare Photosensitive Emulsion Dispersion Liquid 1.

<< Preparation of Stabilizer Solution >> 1.0 g of stabilizer 1,
0.31 g of potassium acetate was dissolved in 4.97 g of methanol to prepare a stabilizer solution.

[0142]

[Chemical 25]

<< Preparation of infrared sensitizing dye solution A >> 19.2 mg
Sensitizing dye 1, 1.488 g of 2-chloro-benzoic acid,
Infrared sensitizing dye solution A was prepared by dissolving 2.779 g of stabilizer 2 and 365 mg of 5-methyl-2-mercaptobenzimidazole in 31.3 ml of MEK in the dark.

[0144]

[Chemical formula 26]

<< Preparation of Additive Liquid a >> 1,1 as a Developer
-Bis (2-hydroxy-3,5-dimethylphenyl)
27.98 g of 2-methylpropane and 1.54 g of 4
-Methylphthalic acid, 0.48 g of the above dye-1 with MEK
It was dissolved in 110 g to obtain an additive liquid a.

<< Preparation of Additive Liquid b >> The general formula (1-
1), the compound of the general formula (1-2), the compound of the general formula (2), the compound of the general formula (2-1) or the comparative compound (described in Table 1) for each 9 × 10 ⁻³ mol,
Addition liquid b is obtained by adding 3.43 g of phthalazine and 40.9 g of MEK and dissolving them.

<< Preparation of Coating Solution for Photosensitive Layer >> The photosensitive emulsion dispersion 1 was prepared under an inert gas atmosphere (97% nitrogen).
(50 g) and MEK 15.11 g with stirring 2
The temperature was kept at 1 ° C., 390 μl of antifoggant 1 (10% methanol solution) was added, and the mixture was stirred for 1 hour. Further, 494 μl of calcium bromide (10% methanol solution) was added and stirred for 20 minutes. Subsequently, 167 ml of the stabilizer solution was added and stirred for 10 minutes, and then 1.32 g of the infrared sensitizing dye solution was added and stirred for 1 hour. After that, increase the temperature to 13 ℃
The temperature was lowered to and stirred for 30 minutes. While keeping the temperature at 13 ℃, polyvinyl butyral (Monsanto B
After adding 13.31 g of utvar B-79) and stirring for 30 minutes, tetrachlorophthalic acid (9.4 mass% ME
K solution) (1.084 g) was added, and the mixture was stirred for 15 minutes. With further stirring, 12.43 g of the additive liquid a, 1.
6 ml Desmodur N3300 / Mobey aliphatic isocyanate (10% MEK solution) 4.2
A photosensitive layer coating solution was obtained by sequentially adding 7 g of Additive solution b and stirring.

[0148]

[Chemical 27]

<< Preparation of Matting Agent Dispersion >> Cellulose Acetate Butyrate (Eastman Chemical)
Company, 7.5 g of CAB171-15) to MEK42.5
g of calcium carbonate (Specia)
Light Minerals, Super-Pfle
x200) (5 g) was added, and the mixture was dispersed with a dissolver type homogenizer at 8000 rpm for 30 min to prepare a matting agent dispersion liquid.

<< Preparation of Coating Solution for Surface Protective Layer >> While stirring 865 g of MEK (methyl ethyl ketone), cellulose acetate butyrate (Eastman Chemical) was prepared.
Al, CAB171-15) 96 g, polymethylmethacrylic acid (Rohm & Haas, Paraloid A-21)
4.5 g, vinyl sulfone compound (VSC) 1.5
g, benztriazole (1.0 g) and an F-based activator (Asahi Glass Co., Ltd., Surflon KH40) (1.0 g) were added and dissolved. Next, 30 g of the above matting agent dispersion is added and stirred,
A coating solution for the surface protective layer was prepared.

[0151]

[Chemical 28]

<< Coating on Photosensitive Layer Surface Side >> A photosensitive material was prepared by simultaneously coating the photosensitive layer coating liquid and the surface protective layer coating liquid in layers using an extrusion coater. The coating of the photosensitive layer was 1.9 g / m ^{2 on} the photosensitive layer,
The surface protective layer was formed to have a dry film thickness of 2.5 μm. Then, it was dried for 10 minutes using a drying air having a drying temperature of 75 ° C. and a dew point temperature of 10 ° C. to obtain a coated sample (heat-developable photosensitive material).

<< Exposure and Development Processing >> From the emulsion side of the light-sensitive material prepared as described above, a wavelength of 800
The exposure was performed by laser scanning with an exposure device using a semiconductor laser having a vertical multimode of nm to 820 nm as an exposure source. At this time, an image was formed by setting the angle between the exposed surface of the photosensitive material and the exposure laser beam to 75 degrees. (Note that an image with less unevenness and unexpectedly good sharpness was obtained compared to the case where the angle was 90 degrees.) After that, the photosensitive material was protected using an automatic developing machine having a heat drum. The layer was heat-treated at 110 ° C. for 15 seconds so that the layer was in contact with the surface of the drum. At that time, exposure and development are 23 ° C. and 50% R
I went to a room where the humidity was adjusted to H. The obtained image was evaluated with a densitometer. The measurement results are evaluated by sensitivity (the reciprocal of the ratio of the exposure amount that gives a density 1.0 higher than that of the unexposed portion) and fog, and shown in Table 1 as a relative value with the sensitivity of the photosensitive material 1-1 being 100. It was

[Evaluation of Raw Preservability] Three coated samples were placed in a closed container whose inside was kept at 25 ° C. and relative humidity of 55%, and then stored at 50 ° C. for 7 days (forced storage). The second sample of these and the sample for comparative aging (stored in a light-shielding container at room temperature) were subjected to the same treatment as the above sensitometry evaluation, and the density of the fog portion was measured. An increase in fog of 1 was obtained and evaluated as raw preservation.

(Increase in fog 1) = (fog after forced aging)-(comparison fog after aging) "Evaluation of image storability" Two samples subjected to the same treatment as the sensitometric evaluation were 25 ° C, relative humidity 55%
Stored in the dark for 7 days, the other one at 25 ° C and relative humidity 55
After exposure to natural light for 7 days, the densities of the fog portions of both were measured, and the increase 2 in fog was determined by the following formula and evaluated as image storability.

(Increase in fog 2) = (fog when exposed to natural light)-(fog when stored in the dark) "Evaluation of silver tone" For evaluation of silver tone, the density after development was 1.1 ±. A sample which was exposed and developed to 0.05 was prepared. This sample had a color temperature of 7700 Kelvin and an illuminance of 11
Irradiation was performed for 10 hours with a light source stand of 600 lux, and the color tone of silver was evaluated according to the following criteria. The rank with no problem in quality assurance is 4 or higher.

Evaluation criteria 5: Pure black tone with no yellowness 4: Not pure black, but almost no yellowness 3: Partially slightly yellowish 2: A slight yellowishness is felt on the entire surface 1: At first glance, you can feel yellowishness Table 1 shows the above progress and results.

[0158]

[Table 1]

[0159]

[Chemical 29]

Table 1 shows that the samples of the present invention have sufficient sensitivity, low fog, stability in raw storage of the light-sensitive material (fog increase 1 is small and good), and image storability (increase of fog). It can be seen that the value of 2 is small and good), and the silver tone is also good.

Example 2 [Preparation of undercoated photographic support] <Preparation of PET undercoated photographic support> 8 W / m on both sides of a commercially available biaxially stretched and heat-fixed PET film having a thickness of 100 μm ^After applying a corona discharge treatment for ² minutes, one side of the undercoating coating solution a-1 below is applied to a dry film thickness of 0.8 μm and dried to form an undercoating layer A-1. The undercoating coating solution b-1 described below was applied to the surface of the above to a dry film thickness of 0.8 μm and dried to form an undercoating layer B-1.

[0162]   << Subbing coating solution a-1 >>   Butyl acrylate (30% by mass)     t-Butyl acrylate (20 mass%)     Styrene (25% by mass)     2-hydroxyethyl acrylate (25% by mass)     270 g of copolymer latex liquid (solid content 30%)   (C-1) 0.6 g   Hexamethylene-1,6-bis (ethylene urea) 0.8 g   Make up to 1 liter with water.

[0163]   <Subbing coating solution b-1>   Butyl acrylate (40% by mass)     Styrene (20 mass%)     Glycidyl acrylate (40% by mass)     270 g of copolymer latex liquid (solid content 30%)   (C-1) 0.6 g   Hexamethylene-1,6-bis (ethylene urea) 0.8 g   Make up to 1 liter with water.

Subsequently, the undercoat layer A-1 and the undercoat layer B-1
8 W / m ² · min of corona discharge is applied to the upper surface of the undercoat layer A-1, and the undercoating upper layer coating solution a-2 below is undercoated onto the undercoating layer A-1 to a dry film thickness of 0.1 μm. As the upper layer A-2, the undercoating upper layer coating liquid b-2 described below is applied to the undercoating upper layer B-1 having an antistatic function so that the dry film thickness becomes 0.8 μm.
Painted as 2.

<< Undercoating Upper Layer Coating Liquid a-2 >> Gelatin 0.4 g / m ² Mass (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 Make up to 1 liter with water.

[0166]   << Undercoating upper layer coating liquid b-2 >>   (C-4) 60g   Latex liquid containing (C-5) as a component (solid content 20%) 80 g   Ammonium sulfate 0.5g   (C-6) 12g   Polyethylene glycol (weight average molecular weight 600) 6g   Make up to 1 liter with water.

(Preparation of silver halide emulsion) 900 ml of water
7.5 g of inert gelatin and 10 m of potassium bromide
After dissolving g and adjusting the temperature to 35 ° C. and pH to 3.0,
370 ml of an aqueous solution containing 74 g of silver nitrate, an aqueous solution containing potassium bromide and potassium iodide in a molar ratio of (98/2) and 1 × 10 ⁻⁴ mol of rhodium chloride per mol of silver, pA
It was added over 10 minutes by the controlled double jet method while maintaining the g of 7.7. Then 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene 0.3
g and adjusting the pH to 5 with NaOH, the average particle size is 0.06 μm, the variation coefficient of the projected diameter area is 8%, [10
0] Cubic silver iodobromide grains having an area ratio of 87% were obtained. This emulsion was coagulated and sedimented using a gelatin coagulant, desalted, and added with 0.1 g of phenoxyethanol to give a pH of 5.9 and pA.
It was adjusted to g 7.5 to prepare a silver halide emulsion.

According to the method of Example 1 of JP-A-9-127643, a silver behenate dispersion was prepared by the following method.

Preparation of Sodium Behenate Solution To 340 ml of isopropanol was added 34 g of behenic acid to 65 parts.
Melted at ° C. Then, with stirring, a 0.25 mol / L sodium hydroxide aqueous solution was added so as to have a pH of 8.7.
At this time, about 400 ml of sodium hydroxide aqueous solution was required. Next, this sodium behenate aqueous solution is concentrated under reduced pressure so that the concentration of sodium behenate is 8.9% by mass.
A sodium behenate solution was prepared.

Preparation of silver behenate dispersion A 2.94 mol / L silver nitrate solution was added to a solution of 30 g of ossein gelatin dissolved in 750 ml of distilled water to adjust the silver potential to 400 mV. Using the controlled double jet method, 374 ml of the sodium behenate solution was added at a speed of 44.6 ml / min at the temperature of 78 ° C., and at the same time, a 2.94 mol / L silver nitrate aqueous solution was added at a silver potential of 4
It was added so that it might be 00 mV. The amounts of sodium behenate and silver nitrate used during addition were 0.092 mol,
It was 0.101 mol. After the addition was completed, the mixture was stirred for another 30 minutes and the water-soluble salts were removed by ultrafiltration to prepare a silver behenate dispersion.

Preparation of Photosensitive Emulsion The silver halide emulsion was added to this silver behenate dispersion in an amount of 0.0
Add 1 mol and, with further stirring, acetic acid n of polyvinyl acetate
-Slowly adding 100 g of butyl solution (1.2% by mass) to form flocs in the dispersion, removing water, washing with water twice and removing water, and then using polyvinyl butyral (average molecular weight as a binder). 3,000) was added with stirring 60 g of a 1: 2 mixed solution of 2.5% by mass butyl acetate and isopropyl alcohol, and then polyvinyl butyral as a binder was added to the resulting gel-like mixture of silver behenate and silver halide. (Average molecular weight 4,000) and isopropyl alcohol were added and dispersed to prepare a photosensitive emulsion.

The following layers were sequentially formed on the support to prepare a sample (photothermographic material). The drying is 75
The test was performed at 5 ° C for 5 minutes.

Back surface side coating: A liquid having the following composition was coated so as to have a wet thickness of 80 μm. Polyvinyl butyral (10% isopropanol solution) 150 ml Dye-1 70 mg Photosensitive layer side coated photosensitive layer: Liquid having the following composition was coated at a silver amount of 2.0 g /
m ² , polyvinyl butyral as a binder, 3.
It was applied so as to be ² g / m ² .

Photosensitive Emulsion Amount to be 3 g / m ² as silver amount Sensitizing dye 1 (0.1% DMF solution) 2 mg General formula (1-1), (1-2), (2) of the present invention, Compound of (2-1), comparative compound (described in Table 2) (2% methyl ethyl ketone solution) 3 ml Phtharazone (4.5% DMF solution) 8 ml Developer-1 (10% methyl ethyl ketone solution) 13 ml General formula (3) of the present invention 2) Compound and hydrazine derivative (described in Table 2) (1% methanol / DMF = 4: 1 solution) 2 ml

[0175]

[Chemical 30]

Surface protective layer: Wet a liquid having the following composition with a thickness of 1
It was coated on each photosensitive layer so as to have a thickness of 00 μm.

Methyl ethyl ketone 175 ml 2-propanol 40 ml Methanol 15 ml Cellulose acetate 8.0 g 4-Methylphthalic acid 0.72 g Tetrachlorophthalic acid 0.22 g Phthalazine 1.0 g Tetrachlorophthalic anhydride 0.5 g Monodisperse with an average particle size of 4 μm 1% by mass relative to silica binder “Evaluation of sensitometry” The sample (heat-developable photosensitive material) prepared above was exposed to xenon flash light with an emission time of 10 ⁻³ seconds through an interference filter having a peak at 633 nm. . After that, using a heat drum, 115 ° C, 15
Second heat development processing was performed. Then, the fog value at that time was measured. In addition, the reciprocal of the exposure amount giving a density of 3.0 was taken as the sensitivity, and the sample It is represented by relative sensitivity with the sensitivity of 2-1 being 100. Further, the slope of the straight line connecting the points of the densities of 0.1 and 1.5 on the characteristic curve is represented as the gradation (γ) representing the leg break.

[Evaluation of Raw Preservability] Three coated samples were placed in a closed container whose inside was kept at 25 ° C. and relative humidity of 55%, and then stored at 50 ° C. for 7 days (forced storage). The second sample of these and the sample for comparative aging (stored in a light-shielding container at room temperature) were subjected to the same treatment as the above sensitometry evaluation, and the density of the fog portion was measured. An increase in fog of 1 was obtained and evaluated as raw preservation.

(Increase in fog 1) = (fog after forced aging)-(fog after aging for comparison) "Evaluation of image storability" Two samples treated in the same manner as the evaluation of sensitometry 25 ° C, relative humidity 55%
Stored in the dark for 7 days, the other one at 25 ° C and relative humidity 55
After exposure to natural light for 7 days, the densities of the fog portions of both were measured, and the increase 2 in fog was determined by the following formula and evaluated as image storability.

(Increase in fog 2) = (fog when exposed to natural light)-(fog when stored in the dark) "Evaluation of silver tone" For evaluation of silver tone, the density after development was 1.5 ±. A sample which was exposed and developed to 0.05 was prepared. This sample had a color temperature of 7700 Kelvin and an illuminance of 11
Irradiation was performed for 10 hours with a light source stand of 600 lux, and the color tone of silver was evaluated according to the following criteria. The rank with no problem in quality assurance is 4 or higher.

Evaluation criteria 5: Pure black tone with no yellowness 4: Not pure black, but almost no yellowness 3: Partially slightly yellowish 2: A slight yellowishness is felt on the entire surface 1: At first glance, you can feel yellowishness Table 2 shows the above process and results.

[0182]

[Table 2]

From Table 2, the sample of the present invention has sufficient sensitivity, high gamma and good contrast, low fog, and good raw storage stability and image storage stability of the light-sensitive material. I understand.

[0184]

According to the present invention, the sensitivity is high and the fog is low,
It is possible to provide a heat-developable photographic light-sensitive material excellent in storage stability and excellent in silver tone, and an image forming method using the same. In particular, to provide a photothermographic material that does not cause fogging of developed samples over time, and a photothermographic material for a laser imager that has high sensitivity and low fog, and has good storage stability of the photosensitive material. It is possible to provide a material and a photothermographic material for imagesetter output film which has high contrast, high sensitivity, low fog, and good storage stability of the photosensitive material.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H123 AB00 AB01 AB03 AB23 AB25                       BB00 BB25 BB27 CA00 CA22                       CB00 CB03

Claims (7)

[Claims] 1. A photothermographic material which comprises a compound represented by the following general formula (1-1) or (1-2). [Chemical 1] (In the formula, X ₁ and X ₂ represent a halogen atom, A ₁ represents a hydrogen atom, a halogen atom or a substituent. Y ₁ represents a linking group, Z represents an alkyl group, a cycloalkyl group, an alkenyl group or an alkynyl group. L ₁ represents a linking group, W ₁ represents a carboxy group or a salt thereof, a sulfo group or a salt thereof, a phosphoric acid group or a salt thereof, a hydroxyl group or a salt thereof,
It represents a quaternary ammonium group or a polyoxyethylene group.
n represents 0 or 1. ) [Chemical 2] (In the formula, X ₃ and X ₄ represent a halogen atom, A ₂ represents a hydrogen atom, a halogen atom or a substituent. Y ₂ represents —NHC.
O -, - OOC- or -N (R ₁₎ SO ₂ - represents, R ₁
Represents a substituent. Q represents a divalent aryl group or a divalent heterocyclic group. L ₂ represents a linking group, and W ₂ represents a carboxy group or a salt thereof, a sulfo group or a salt thereof, a phosphoric acid group or a salt thereof, a hydroxyl group or a salt thereof, a quaternary ammonium group or a polyoxyethylene group. m represents 0 or 1. ) 2. A photothermographic material comprising a compound represented by the following general formula (2). [Chemical 3] (In the formula, X ₅ , X ₆ , X ₇ and X ₈ represent a halogen atom,
B ₁ and B ₂ each independently represent a hydrogen atom, a halogen atom or a substituent. p represents an integer of 1 or more and 3 or less, and J represents an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group or a p + 1-valent group derived from each of these groups. G ₁ and G ₂ represent a linking group. However, G ₁ and G ₂
When both are SO ₂ , p represents 2 or 3. ) 3. The compound represented by the general formula (2):
The photothermographic material according to claim 2, which is a compound represented by the following general formula (2-1). [Chemical 4] (In the formula, X ₉ , X ₁₀ , X ₁₁ and X ₁₂ represent a halogen atom, B ₃ and B ₄ each independently represent a hydrogen atom, a halogen atom or a substituent. Q represents an integer of 1 or more and 3 or less. Represent, J ₂
Is an alkylene group, a cycloalkylene group, an alkenylene group, an alkynylene group or q + 1 derived from each of these groups.
Represents a valence group. G ₃ and G ₄ represent a linking group. However, G ₃
And G ₄ are both SO ₂ , q represents 2 or 3. Q ₁
And Q ₂ are each independently -C (CH ₃ ) _2- , -CH ₂ C (C
_{H 3) 2 -, - CH} (CH 3) - or -CH ₂ CH (C
H ₃₎ - represents a. r and s represent 0 or 1, and T ₁ and T
_2's each independently represent a divalent linking group. ) 4. The photothermographic material according to claim 2, wherein G ₃ and G ₄ of the compound represented by the general formula (2-1) are —CONH—. 5. A support having an organic silver salt, a binder and a photosensitive silver halide on a support,
The heat-developable photographic light-sensitive material as described in 2, 3, or 4. 6. A hydrazine derivative and at least one compound selected from the compounds represented by the following general formula (3) are contained:
The heat-developable photographic light-sensitive material as described in 1. [Chemical 5] (In the formula, R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a substituent, and D represents a substituent. R ₂ and D, R ₂ and R ₃ ,
R ₃ and R ₄ and R ₄ and D may be bonded to each other to form a cyclic structure. ) 7. An image obtained by exposing the photothermographic material according to claim 1, 2, 3, 4, 5 or 6 using a laser light source and then developing at 80 to 250 ° C. Forming method.