JP2003248285A - Heat-developable silver salt photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-developable silver salt photographic sensitive material having high sensitivity, low fog, good storage stability, and excellent silver tone. <P>SOLUTION: The heat-developable silver salt photographic sensitive material contains at least one selected from a compound which is cleaved under light to generate an organic acid; a compound which is cleaved under light to generate a sulfonic acid, a sulfinic acid, a carboxylic acid or phosphoric acid; a compound of formula (1); a compound of formula (2); a compound of formula (3); a compound of formula (4); a compound (5); a compound of formula (6); a polymer having a repeating unit of formula (7); a copolymer containing repeating units of the formula (7) and formula (8); a compound which newly generates an acid under an acid; a compound of formula (10); a compound of formula (11); a compound of formula (12); and a compound of formula (13). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable silver salt photographic light-sensitive material, and more particularly to a heat-developable silver salt photographic light-sensitive material having good storage stability and excellent silver tone.

[0002]

2. Description of the Related Art A heat-developable silver salt photographic light-sensitive material (hereinafter, also referred to as "heat-developable photographic light-sensitive material" or "thermosensitive material") for forming a photographic image of a silver halide photographic light-sensitive material by a heat development processing method , U.S. Pat. Nos. 3,152,904, 3,457,075, and D.M. Morgan
n) and B. “Thermal Systems Produced by Heat (Thermally Proc) by Shelly
"Essed Silver Systems" (Imaging Processes and Materials (Im
aging Processes and Mater
als) Neblette, 8th edition; Sturge (St
urge), V.I. Wallworth
h), A. Edited by Shepp, page 2, 196
9 years).

In such a photothermographic material, a reducible silver source (such as an organic silver salt), a catalytically active amount of a photocatalyst (such as silver halide), and a reducing agent are usually contained in an (organic) binder matrix. It is contained in the state of being dispersed in.

The heat-developable photographic light-sensitive material is stable at room temperature, but when exposed to a high temperature (for example, 80 ° C. or higher) after exposure, it is between a reducible silver source (which functions as an oxidizing agent) and a reducing agent. To produce silver through the redox reaction of. 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 is imaged. However, when this image is irradiated with light such as fluorescent light and natural light, the redox reaction of the remaining reducible silver source, the catalytically active amount of the photocatalyst, and the reducing agent gradually causes silver to gradually disappear in the unexposed area. And a black image is formed, which causes image deterioration (fogging).

An antifoggant for controlling the fog of this image is optionally used in the thermosensitive 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 thermally 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 (US Pat. Nos. 3,874,946, 4,452,885 and 4,546,075). 4,756,999, 5,340,712, European Patent 605,981A1.
No. 622, 666A1 and 631, 176A1
Japanese Patent Publication No. 54-165, Japanese Patent Laid-Open No. 59-90842.
No. 61-129642 and No. 62-129845.
No. 6-202268, 6-208193.
No. 6, No. 6-340611, No. 7-2781, No. 7-
5621). However, the compounds described above have problems that the effect of preventing fog is low and that the color tone of silver is deteriorated. Also, those with high anti-fogging effect,
There was a problem such as a decrease in sensitivity, and there was a need for improvement. Further, there is a problem that fog in the unexposed area rises when exposed and developed after aged under the conditions of forced deterioration of humidification and heating in the form of laminated thermosensitive material. Was desired to be developed.

As a method for solving these problems, JP-A-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 and the like describe polyhalogen compounds in which the above-mentioned drawbacks are improved. However, in particular, when these compounds are applied to a heat-developable photographic light-sensitive material for medical laser imagers, the storage stability, antifoggant effect and silver tone are not satisfactory, and improvement has been desired.

On the other hand, a non-silver salt photothermographic material using a compound capable of cleaving with light to generate an acid is disclosed in, for example, JP-A-11-1.
80048, 11-181031, JP 2000
-71612, 2000-118147, 20
No. 00-141906, No. 2000-144004,
2000-280632 and 2000-28192
No. 0, 2000-284475, 2000-29
6679, 2000-343836, 2000
-343837, 2001-47747, 20
No. 01-88444, 2001-88445, etc., but the effect of preventing fogging by generating an acid is not intended.

Further, as a compound that proliferates an acid by the action of an acid, K. Ichimura: Chem. Let
t. 551 (1995) and JP-A-8-248561 describe a compound that produces an organic acid by decomposition with an acid catalyst. The compound is referred to as a substance that causes a structural change by the action of a photo-acid generator and an acid. Acid-reactive polymer compositions used in combination are described. However, in this document, a so-called photoresist is intended due to a structural change of solubilizing or insolubilizing in a polar solvent or an aqueous alkali solution by the action of an acid generated by a photo-acid generator, and it is intended to improve storage stability. Not a thing.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is thermal development which has high sensitivity, low fog, good storage stability, and excellent silver tone. It is to provide a silver salt photographic light-sensitive material.

[0011]

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

1) A heat-developable silver salt photographic light-sensitive material containing at least one compound which is cleaved by light to generate an organic acid.

2) A heat-developable silver salt photographic light-sensitive material containing at least one compound which is cleaved by light to generate sulfonic acid, sulfinic acid, carboxylic acid and phosphoric acid.

3) A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the general formula (1).

4) A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the general formula (2).

5) A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the general formula (3) "Chemical Formula 3".

6) A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the general formula (4).

7) Cleavage by light, HSbF ₆ , HP
A heat-developable silver salt photographic light-sensitive material containing at least one compound (5) which generates F ₆ , HAsF ₆ or HBF ₄ .

8) A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the general formula (6).

9) A heat-developable silver salt photographic light-sensitive material containing a polymer having at least one repeating unit "Chemical Formula 6" represented by the general formula (7).

10) A heat-developable silver salt photographic light-sensitive material containing at least one copolymer having at least one repeating unit represented by the general formula (7) and at least one repeating unit represented by the general formula (8). material.

11) A heat-developable silver salt photographic light-sensitive material containing at least one compound capable of newly generating an acid by an acid.

12) A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the general formula (10).

13) A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the general formula (11).

14) A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the general formula (12).

15) A heat-developable silver salt photographic light-sensitive material containing at least one compound of the chemical formula 11 represented by the general formula (13).

16) 1) to 1 containing an organic acid silver salt, a binder, a photosensitive silver halide and a reducing agent on a support.
The heat-developable silver salt photographic light-sensitive material according to any one of 5).

17) A heat-developable silver salt photographic light-sensitive material having a support having a light-sensitive layer and a surface protective layer, which is cleaved by light,
A heat-developable silver salt photographic light-sensitive material, wherein the surface protective layer contains at least one compound capable of generating an organic acid.

18) A heat-developable silver salt photographic light-sensitive material having a support having a light-sensitive layer and a surface protective layer, which is cleaved by light,
A heat-developable silver salt photographic light-sensitive material, wherein the surface protective layer contains at least one compound (5) which generates HSbF ₆ , HPF ₆ , HAsF ₆ , and HBF ₄ .

19) A heat-developable silver salt photographic light-sensitive material having a photosensitive layer and a surface protective layer on a support, wherein the surface protective layer contains at least one compound which newly generates an acid by an acid. 18) The heat-developable silver salt photographic light-sensitive material described in 18).

20) The heat-developable silver salt photographic light-sensitive material according to 17), wherein the surface protective layer contains at least one compound represented by the general formulas (1) to (4) and (6).

21) A polymer having at least one repeating unit represented by the general formula (7), or a polymer having at least one repeating unit represented by the general formula (7) and the general formula (8). The heat-developable silver salt photographic light-sensitive material according to 17), wherein the surface protective layer contains at least one polymer.

22) The heat-developable silver salt photographic light-sensitive material as described in 20) or 21), wherein the surface protective layer contains at least one compound represented by the general formulas (10) to (13).

23) The heat-developable silver salt photographic light-sensitive material according to any one of 1) to 22), which contains at least one compound having a halogen radical-releasing group.

The present invention will be described in detail below. The heat-developable silver salt photographic light-sensitive material of the present invention is a material for forming a photographic image by a heat-development processing method from a silver halide photographic light-sensitive material having a silver source such as silver halide or organic acid silver. It is essentially different from the photothermographic material containing no.

The organic acid in the present invention is a general term for all organic compounds having acidity. As an example of a compound that is cleaved by light to generate sulfonic acid, sulfinic acid, carboxylic acid, and phosphoric acid, "Organic Materials for Imaging", 187 to 198, edited by Organic Electronics Material Research Group (Bunshin Publishing), is published.
Page (1993) shows various examples (as nonionic compounds,
Sulfonic acid, sulfone compound generating sulfinic acid,
Carbonyl compounds that generate carboxylic acids, phosphorus compounds that generate phosphoric acid, etc.) are described. In the present invention, any of these can be used, but from the viewpoint of image storability, an acid generator that generates sulfonic acid, sulfinic acid, carboxylic acid and phosphoric acid is particularly preferable. In addition, various sensitizers (J. Pol.
ymer. Sci. , 16: 2441 (1978)
Etc., etc.) can also be added.

The compound capable of generating a sulfonic acid, a sulfinic acid, a carboxylic acid, or a phosphoric acid by being cleaved by light is only required to partially contain the structure of the compound described in the above literature, and a plurality of acid releasing sites exist in one compound. You may have. Further, it may be a polymer introduced into the main chain or a side chain, and the polymer may be blended with a homopolymer, a copolymer, or another general-purpose polymer.

Next, the compounds represented by the general formulas (1) to (4), the compound (5), the general formulas (6) to (8) and the general formulas (10) to (13) of the present invention are represented. The compound will be described.

In the general formula (1), R ₁₁ , R ₁₂ , and R ₁₃
Examples of the substituent represented by R ₁₄ and R ₁₄ include various ones and are not particularly limited.
Aryl, anilino, acylamino, sulfonamide,
Alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino , Alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxyl and mercapto groups, and spiro compound residues, bridged hydrocarbon compound residues, sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl,
Examples thereof include carbamoyl, acyl, acyloxy, oxycarbonyl, carboxyl, cyano, nitro, halogen-substituted alkoxy, halogen-substituted aryloxy, pyrrolyl, tetrazolyl, and other groups, and halogen atoms.

The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched. A phenyl group is preferred as the aryl group.

The acylamino group is an alkylcarbonylamino group or an arylcarbonylamino group; the sulfonamide group is an alkylsulfonylamino group or an arylsulfonylamino group; the alkyl component of the alkylthio group or the arylthio group, and the aryl component is the above alkyl group. , And an aryl group.

The alkenyl group has 2 to 23 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5
The alkenyl group may be linear or branched. The cycloalkenyl group has 3 to 12 carbon atoms,
Especially, those of 5 to 7 are preferable.

The ureido group is an alkylureido group,
Aryl ureido group; Sulfamoylamino group is alkylsulfamoylamino group, arylsulfamoylamino group; Heterocyclic group is preferably 5 to 7-membered, specifically 2-furyl, 2-thienyl , 2-pyrimidinyl, 2-benzothiazolyl, etc .; preferred saturated heterocycles are 5 to 7-membered, specifically, tetrahydropyranyl, tetrahydrothiopyranyl, etc .; heterocyclic oxy groups are 5 to 7-membered heterocycles. Those having a ring are preferable,
For example, 3,4,5,6-tetrahydropyranyl-2-oxy, 1-phenyltetrazole-5-oxy and the like; the heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group,
For example, 2-pyridylthio, 2-benzothiazolylthio,
2,4-diphenoxy-1,3,5-triazole-6
-Thio, etc .; siloxy groups as trimethylsiloxy, triethylsiloxy, dimethylbutylsiloxy, etc .; imide groups as succinimide, 3-heptadecyl succinimide, phthalimide, glutarimide, etc .; spiro compound residues as spiro [3. 3] heptan-1-yl, etc .; as a bridged hydrocarbon compound residue, bicyclo [2.2.1]
Heptan-1-yl, tricyclo [3.3.1.
1 ^3.7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like.

The sulfonyl group is an alkylsulfonyl group, an arylsulfonyl group, a halogen-substituted alkylsulfonyl group, a halogen-substituted arylsulfonyl group, etc .; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .;
An alkylsulfonyloxy group, an arylsulfonyloxy group, etc .; as a sulfamoyl group, an N, N-dialkylsulfamoyl group, an N, N-diaryl sulfamoyl group, an N-alkyl-N-arylsulfamoyl group, etc .;
Examples of the phosphoryl group include an alkoxyphosphoryl group, an aryloxyphosphoryl group, an alkylphosphoryl group, an arylphosphoryl group and the like; a carbamoyl group includes N, N
-Dialkylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group and the like; acyl group as an alkylcarbonyl group, arylcarbonyl group and the like; acyloxy group as an alkylcarbonyloxy group and the like; oxy The carbonyl group is an alkoxycarbonyl group, an aryloxycarbonyl group or the like; the halogen-substituted alkoxy group is an α-halogen-substituted alkoxy group or the like; the halogen-substituted aryloxy group is a tetrafluoroaryloxy group, a pentafluoroaryloxy group or the like; Examples of the pyrrolyl group include 1-pyrrolyl; and examples of the tetrazolyl group include 1-tetrazolyl.

In addition to the above substituents, trifluoromethyl,
Heptafluoro-i-propyl, nonylfluoro-t-
Each group such as butyl, a tetrafluoroaryl group, a pentafluoroaryl group and the like are also preferably used. Furthermore,
These substituents may be substituted with other substituents.

The substituent represented by R _{11 to} R ₁₄ is preferably an alkyl group or an aryl group.

In the general formula (2), R ₂₁ , R ₂₂ , R ₂₃
And the substituent represented by R ₂₄ is R _{11 in the} general formula (1).
To R _{14 have the same} meanings as those described above, and an alkyl group and an aryl group are preferable.

In the general formula (3), R ₃₁ , R ₃₂ and R
_The substituent represented by ₃₃ is R _{11 to} R _{14 in the} general formula (1).
Synonymous with those described above, preferably an alkyl group,
Of the cycloalkyl group, aryl group, heterocyclic group and saturated heterocyclic group, a cycloalkyl group is particularly preferable. R
₃₂ and R ₃₃ may combine with each other to form a ring structure.

In the general formula (4), R ₄₁ , R ₄₂ and R ₄₃
And the substituent represented by R ₄₄ is R _{11 in the} general formula (1).
To R _{14 have the same} meanings as those described above, and an alkyl group and an aryl group are preferable.

HSbF ₆ , HPF ₆ and HAs are cleaved by light.
Examples of the compound (5) generating F ₆ and HBF ₄ include aryliodonium salts, aryldiazonium salts, triarylsulfonium salts, benzylsulfonium salts, and benzylphosphonium salts. As for these photo-acid generators, various sensitizers and the like described in the examples can be added for the purpose of widening the photosensitive area.

In the general formula (6), G is alkylene.
Group, cycloalkylene group, arylene group, 2 or more substituted
Represents a substituted heterocyclic group or a composite group thereof,
In this case, each group is —O—, —N— (tertiary), —SO₂
It may be further connected by-. In addition, these groups are
Substitution with a substituent having the same meaning as described in formula (1)
May be done. L₆The linking group represented by
(R₆) C (R₆)-, -Ph (R₆)_p-, -O-, -S
-, -N (R₆)-, -N- (tertiary), -CO-, -C
OO-, -CON (R₆)-, -OCO-, -COS
-, -CSO-, -CSS-, -CS-, -SO-,-
SO₂-, -SO₃-, -SO₂N (R₆)-, -N
(R₆) SO₂N (R₆)-, -N (R₆) SO₂-, -N
(R₆) CO-, -N (R ₆) COO-, -N (R₆) C
OS-, -N (R₆) CSO-, -N (R₆) CSS-,
-N (R₆) CON (R₆)-, -N (R₆) CSN
(R₆)-, -N (R₆) SO₂-, -CON (R₆)-,
-CON (R₆) CO-, -CON (R₆) SO₂-,-
SO₂N (R₆) Represents CO-. Multiple of these substituents
They may be combined to form a composite group. p represents an integer of 0 to 4
And R₆Represents a hydrogen atom or a substituent. This substituent is
It has the same meaning as described in the general formula (1) and is preferably water.
Elemental atom, alkyl group, aryl group, particularly preferred
Is a hydrogen atom. Multiple R₆Are the same or different
Good.

In the general formula (7), R ₇₁ , R ₇₂ , R ₇₃
And the substituent represented by R ₇₄ is R _{11 of the} general formula (1).
To R _{14 have the same} meanings as those described for R ₁₄ , and preferably an alkyl group. The linking group represented by L ₇ has the same meaning as the linking group described for L ₆ in the general formula (6), and preferably —COO—, —OCO—, —CONH—, —NHCO.
−

In the general formula (8), R ₈₁ , R ₈₂ ,
The substituents represented by R ₈₃ , R _84, and R ₈₅ have the same meanings as those described for R _{11 to} R ₁₄ in the general formula (1), and preferably an alkyl group or an aryl group. Also, R ₈₁ ,
R ₈₂ , R ₈₃ , R ₈₄ and R ₈₅ may combine with each other to form a condensed ring. The linking group represented by L ₈ is L _{6 in the} general formula (6).
It has the same meaning as the linking group described in 1. and preferably -COO.
-, -OCO-, -CONH-, -NHCO-, and a phenylene group.

The compound which generates a new acid by an acid is a compound which is substituted with a residue of a relatively strong acid and which causes an elimination reaction relatively easily to generate an acid. Therefore, an acid-catalyzed reaction can significantly activate this elimination reaction, which is stable in the absence of acid, but can easily generate an acid by a thermochemical reaction in the presence of acid. Becomes By combining an acid multiplying agent having such properties with a photoacid generator, a photoreactive composition having a dramatically improved photosensitivity has become possible.

It decomposes by an acid-catalyzed reaction to generate an acid (YOH in the general formula) again. One or more acids are increased in one reaction, and the reaction proceeds acceleratingly as the reaction progresses.
Since the generated acid itself induces self-decomposition, the strength of the acid generated here is 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less. Acids weaker than this cannot cause autolysis.

Examples of such an acid include dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid and triphenylphosphonic acid.

In the general formula (10), R ₉₁ includes an alkyl group (having a substituent, preferably having 1 to 60 carbon atoms. For example, methyl, ethyl, i-propyl, t-butyl, trifluoromethyl, Ethoxymethyl etc.) or aryl group (including those having a substituent, having 6 to 6 carbon atoms)
0 is preferred. For example, phenyl, naphthyl, 4-chlorophenyl, 2-methoxyphenyl, 4-nitrophenyl, 3-methanesulfonylphenyl, etc., and R ₉₂ is an alkyl group (preferred examples are the same as those described for R ₉₁ ).
R ₉₃ represents a secondary or tertiary alkyl group having a hydrogen atom at the β-position (including those having a substituent and having 3 to 3 carbon atoms).
60 is preferred. For example, t-butyl, cyclohexyl,
Tetrahydropyranyl tetrahydrofuranyl, 4,5-
Dihydro-2-methylfuran-5-yl, 2-cyclohexenyl, etc., and Y is an acid represented by YOH (YOH
The pKa of is preferably 3 or less. For example, it represents a residue of p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, polyvinylbenzenesulfonic acid, p-nitrobenzoic acid, etc.).

In the general formula (11), B ₁ , B ₂ , B ₃
And B ₆ each represents a hydrogen atom, an alkyl group (preferred examples are the same as those described for the R ₉₁₎ or aryl group (preferred examples are the same as those described for the R ₉₁₎ represent, B ₄
And B ₅ are each an alkyl group (preferred examples are the same as those described for R ₉₁ ), an aryl group (preferred examples are the same as those described for R ₉₁ ), or a silyl group (trimethylsilyl, triethylsilyl, t-butyldimethyl, Phenyldimethylsilyl, etc., and B ₄ and B ₅ may combine with each other to form a ring, and when forming a ring, they must form a 5- to 10-membered ring together with —O—C—X—. Is preferred, and particularly preferred is the case of forming a 5- or 6-membered ring.

Y represents an acid residue represented by YOH,
Preferred examples are the same as those mentioned above.

In the general formula (12), D ₁ , D ₂ and D
₃ is a hydrogen atom, an alkyl group (preferred examples are the same as those described for R ₉₁ ) or an aryl group (preferred example is R
Same as those described in ₉₁ ), and D ₁ and D ₂ may form a ring. Y represents a residue of an acid represented by YOH (preferred examples are the same as those mentioned above).

In the general formula (13), E represents an alkyl group (preferred examples are the same as those described for R ₉₁ ) or an aryl group (preferred examples are the same as those described for R ₉₁ ), and Y is YOH. Represents a residue of the acid represented (preferred examples are the same as those mentioned above).

The compounds represented by the general formulas (1) to (4) of the present invention are described in, for example, Can. J. Chem. , 66 volumes, 5
17-527, 2860-2869 (1988),
Synth. Commun. , 20 volumes, 925-932
Pp. (1990), 25, 3471-34478 (1
995), 27, 1455-1464 (199).
7), ibid. 28, pp. 1785-1792 (1998),
J. Chem. Sect. B, Volume 36, 1069-10
70 (1997), 38, 297-301 (1
999), Tetrahedron, 50, 1048.
3-10490 (1994), Tetrahedro
n Lett. 33, pp. 1495-1498 (19
92), vol. 36, p. 3849-3850 (199
5), Chem. Lett. , Volume 9, 1705-170
P. 8 (1994), J. Chem. Soc. Perki
n Trans. 1, pp. 189-193 (1973),
J. Chem. Soc. Perkin Trans.
1, 5, 783-786 (1997), J. Am. Or
g. Chem. 50, 5148-5151 (198
5), ibid. 53, 4223-4227 (1988), ibid. 57, 697-701 (1992), J. Am. Org.
Chem. USSR (Engl. Transl.), 1
7, pp. 1991-1992 (1981), Syn. L
ett. 27-28 (1997), J. Am. Ch
em. Soc. , 82, 3982-3988 (19
60), J. Chem. Soc. C, 2020-202
P. 5 (1966), J. Chem. Soc. , 1231
~ 1235 (1956), J. Med. Chem. C
him. Ther. , 23, 31-38 (198
8), Chem. Pherm. Bull. , Volume 31, 2
329-2348 (1983), 32, 130-.
151 (1984), J. Am. Med. Chem. Che
m. 41, 2308-2318 (1998), M.
acromolecules, vol. 21, p. 2001 (1
988), Polym. Bull. 26, 297 (1991), Synthesis, 490-496 (1993), Syn. Lett. , 894-896 (1998), Pol. J. Chem. , Volume 53, 26
05 to 2613 (1979) and the like.

HSbF ₆ , HPF ₆ and HAs are cleaved by light.
The compound (5) generating F ₆ and HBF ₄ is Photog.
r. Sci. Eng. , 18, 387 (197
4), J. Am. Chem. Soc. , 119, 18
76-1883 (1997), J. Photopol
ym. Sci. Technol. , Vol. 5, p. 247 (1
992), Makromol. Chem. Rapid
Commun. , Vol. 13, p. 203 (1992), Ma.
kromol. Chem. Rapid Commu
n. 14: 203 (1993), J. Photo
polym. Sci. Technol. Vol. 6, p. 67 (1993), Development in Poly.
mer Photochemistry, Chapter
r1, Ed. by N.N. S. Allen: Applie
d Science Publishers (198
It can be synthesized by the method described in 1) or the like.

A compound represented by the general formula (6) of the present invention,
Representative synthesis examples of polymers having at least one repeating unit represented by the general formula (7), and polymers containing at least one repeating unit represented by the general formula (7) and the general formula (8) Indicates.

Synthesis Example 1 (Synthesis of Exemplified Compound 6-6)

[0066]

[Chemical 12]

5.0 g (14.2 mmo) of amine (A)
1.71 ml (21.3 mmol) of pyridine was added to a solution of 1) dissolved in 40 ml of ethyl acetate, and the mixture was stirred at room temperature. To this solution, 1.54 g (7.8 mmol) of diacid chloride (B) dissolved in 10 ml of ethyl acetate was added dropwise, and the reaction was continued at room temperature for 2 hours after the completion of the addition.

After completion of the reaction, 30 ml of water was added, neutralized with dilute hydrochloric acid, and washed with water. After liquid separation, the obtained organic layer was concentrated under reduced pressure, and the residue was recrystallized from ethyl acetate / n-hexane. As a result, 4.9 g of Exemplified Compound 6-6 was obtained. The structure was identified by mass spectrum and 1H-NMR.

Synthesis Example 2 (Synthesis of Exemplified Compounds 7-8)

[0070]

[Chemical 13]

Vinyl monomer (C) 5.0 g (11.9
mmol) and AIBN (azo-i-butyronitrile)
0.2 g of degassed THF (tetrahydrofuran) 2
It was dissolved in 0 ml and heated and refluxed for 8 hours. After completion of polymerization
The solution was cooled to room temperature and stirred vigorously with methanol 60
Dropped into 0 ml. After collecting the precipitated solids by filtration, 6
After heating and drying at 0 ° C. for 3 hours and measuring the molecular weight by GPC, 4.2 g of polymer 7-8 having a number average molecular weight of 7900 was obtained.

Synthesis Example 3 (Copolymer of Exemplified Compounds 7-8 and 8-5)

[0073]

[Chemical 14]

5.0 g of vinyl monomer (C) (11.9
mmol), 1.19 g of MMA (methyl methacrylate)
(11.9 mmol) and 0.39 g of AIBN were dissolved in 40 ml of degassed THF, and heated and refluxed for 8 hours.
After completion of the polymerization, the solution was cooled to room temperature and added dropwise to 1200 ml of vigorously stirred methanol. The precipitated solid content was collected by filtration, heated and dried at 60 ° C. for 3 hours, and the molecular weight was measured by GPC. As a result, 5.3 g of a polymer having a number average molecular weight of 9400 was obtained. From 1H-NMR, the unit ratio of 7-8 and 8-5 was 52:48.

The compounds represented by the general formulas (10) to (13) of the present invention can be synthesized according to the method described in JP-A-8-248561.

In the following, the compounds represented by the general formulas (1) to (4), the compound (5) which is cleaved by light to generate HSbF ₆ , HPF ₆ , HAsF ₆ or HBF ₄ , and the general formula (6) Representative specific examples of the compounds represented by the formulas, the polymers containing at least one of the repeating units represented by the formulas (7) and (8), and the compounds represented by the formulas (10) to (13). Examples are shown, but the present invention is not limited thereto.

[0077]

[Chemical 15]

[0078]

[Chemical 16]

[0079]

[Chemical 17]

[0080]

[Chemical 18]

[0081]

[Chemical 19]

[0082]

[Chemical 20]

[0083]

[Chemical 21]

[0084]

[Chemical formula 22]

[0085]

[Chemical formula 23]

[0086]

[Chemical formula 24]

[0087]

[Chemical 25]

[0088]

[Chemical formula 26]

[0089]

[Chemical 27]

[0090]

[Chemical 28]

[0091]

[Chemical 29]

[0092]

[Chemical 30]

[0093]

[Chemical 31]

[0094]

[Chemical 32]

[0095]

[Chemical 33]

[0096]

[Chemical 34]

[0097]

[Chemical 35]

[0098]

[Chemical 36]

[0099]

[Chemical 37]

[0100]

[Chemical 38]

[0101]

[Chemical Formula 39]

[0102]

[Chemical 40]

[0103]

[Chemical 41]

[0104]

[Chemical 42]

[0105]

[Chemical 43]

[0106]

[Chemical 44]

[0107]

[Chemical formula 45]

[0108]

[Chemical formula 46]

[0109]

[Chemical 47]

[0110]

[Chemical 48]

[0111]

[Chemical 49]

[0112]

[Chemical 50]

[0113]

[Chemical 51]

[0114]

[Chemical 52]

[0115]

[Chemical 53]

[0116]

[Chemical 54]

[0117]

[Chemical 55]

[0118]

[Chemical 56]

[0119]

[Chemical 57]

[0120]

[Chemical 58]

[0121]

[Chemical 59]

[0122]

[Chemical 60]

[0123]

[Chemical formula 61]

[0124]

[Chemical formula 62]

Here, the copolymer having at least one repeating unit represented by the general formula (7), the general formula (7) or the general formula (8) of the present invention will be described.

The copolymer of the present invention may contain the repeating unit represented by the general formula (8). For example (meta)
Acrylic acid, a (meth) acrylic acid derivative, a vinyl ether derivative, a vinyl thioether derivative, styrene, a styrene derivative, a compound having a saturated cyclic heterocycle and a polymerizable unsaturated bond, and the like can be mentioned. Preferred are (meth) acrylic acid derivatives and styrene derivatives, and particularly preferred are methacrylic acid derivatives.

In the copolymer of the general formula (7) and the general formula (8) of the present invention, the preferred range of the continuous unit represented by the general formula (7) is 5 to 95%, particularly preferably 20. ~ 80%.

The mass average molecular weight of the copolymers of the general formula (7), the general formula (7) and the general formula (8) is preferably 500 to 1,000,000, particularly preferably 1,000 to It is 100,000.

The polymerization method of the copolymer represented by the general formula (7), the general formula (7) and the general formula (8) is not limited, and examples thereof include a radical polymerization method and an ionic polymerization method. preferable. Examples of the polymerization initiator of the radical polymerization method include azo compounds and peroxides,
Azobis-i-butyronitrile (AIBN), azobis-i-butyric acid ester derivative, dibenzoyl peroxide and the like are preferable.

The polymerization solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene and chlorobenzene, halogenated hydrocarbons such as dichloroethane and chloroform, ethers such as diethyl ether, tetrahydrofuran and dioxane, and amides such as dimethylformamide. Examples thereof include solvents such as solvents, alcohols such as methanol and propanol, ester solvents such as ethyl acetate, and ketone solvents such as acetone. Depending on the selection of the solvent, it is possible to carry out solution polymerization in which the polymerization is carried out in a homogeneous system, or precipitation polymerization in which the produced polymer is precipitated.

Next, the photothermographic material of the present invention will be described. The organic silver salt used in the heat-sensitive material of the present 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, particularly a long chain (having 10 carbon atoms). -30, preferably 15-25) aliphatic carboxylic acids and nitrogen-containing heterocyclic silver salts are preferred. Organic or inorganic silver complexes having a total stability constant of the ligand for silver ions of 4.0 to 10.0 are also useful in the present invention.

Examples of suitable silver salts include Research Disclosure (hereinafter also simply referred to as RD) 17029 and 2
9963 and the following can be mentioned.

Silver salts of organic acids (silver salts such as gallic acid, oxalic acid, behenic acid, arachidic acid, stearic acid, palmitic acid and lauric acid); silver carboxyalkyl thiourea salts (1- (3-carboxypropyl) thio Urea, 1- (3
-Carboxypropyl) -3,3-dimethylthiourea and other silver salts); a silver complex of a polymer reaction product of an aldehyde and a hydroxy-substituted aromatic carboxylic acid [aldehydes (formaldehyde, acetaldehyde, butyraldehyde, etc.) and hydroxy-substituted acids (Salicylic acid, benzoic acid,
Silver complex of polymer reaction product with 3,5-dihydroxybenzoic acid, 5,5-thiodisalicylic acid, etc.]; Silver salt or complex of thiones [3- (2-carboxyethyl) -4-
Hydroxymethyl-4-thiazolin-2-thione, silver salt or complex such as 3-carboxymethyl-4-thiazoline-2-thione]; imidazole, pyrazole, urazole, 1,2,4-thiazole and 1H-tetrazole, Complexes or salts of silver with a nitrogen acid selected from 3-amino-5-benzylthio-1,2,4-triazole and benzotriazole; silver salts such as saccharin, 5-chlorosalicylaldoxime; and silver of mercaptides. Salt etc.
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.
Forward mixing method, reverse mixing method, simultaneous mixing method, JP-A-9-1276
The controlled double jet method described in No. 43 is preferably used. For example, alkali metal salts (sodium hydroxide, potassium hydroxide, etc.) in organic acids
After preparing the organic acid alkali metal salt soap (sodium behenate, sodium arachidate, etc.),
By the controlled double jet method, the soap and silver nitrate are added to prepare crystals of an organic silver salt. At that time, photosensitive silver halide grains described below (hereinafter, simply referred to as silver halide grains) may be mixed.

The silver halide grain in the invention functions as an optical sensor. 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, 0.1 μm or less, more preferably 0.01 to 0.1 μm, and particularly preferably 0. 0.02 to 0.08 μm. The grain size (grain size) referred to here is the length of the ridge of a silver halide grain when the silver halide grain is a cubic or octahedral so-called normal crystal. If the crystals are not normal crystals, for example, spherical,
In the case of rod-shaped or tabular grains, it means the diameter of a sphere assuming a sphere equivalent to the volume of a silver halide grain.

The silver halide grains are preferably monodisperse. The term "monodispersion" as used herein means particles having a monodispersity of 40% or less, more preferably 30% or less, and particularly preferably 0.1 to 20%, which is calculated by the following formula.

Monodispersity = (standard deviation of grain size / average value of grain size) × 100 In the present invention, silver halide grains preferably have a mean grain size of 0.1 μm or less and are monodisperse grains, Within this range, the granularity of the image also improves.

The shape of the silver halide grains is not particularly limited, but it is preferable that the ratio of Miller index [100] planes is high, and the number is 5 with respect to all the silver halide grains.
It is preferably 0% or more, more preferably 70% or more, and particularly preferably 80% or more. The ratio of Miller index [100] planes is determined by T.W. Tani J. Imagin
g Sci. 29, page 165 (1985).

Another preferable silver halide grain shape is a tabular grain. The tabular grains referred to herein are those in which r / h (aspect ratio) is 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 the tabular grains is preferably 0.1 μm or less, more preferably 0.01 to 0.08 μm.
These tabular grains can be easily obtained by the method described in US Pat. Nos. 5,264,337, 5,314,798 and 5,320,958. By using such tabular grains, the sharpness of the image can be further improved.

The halogen composition of the silver halide grains is not particularly limited and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and silver iodide.

The photographic emulsions used in the present invention are described in P. Gl
afkides: Chimieet Physiqu
e Photographique (Paul Mon)
tel, 1967), G.I. F. By Duffin:
Photographic Emulsion Chem
istry (published by The Focal Press, 19
66), V.I. L. By Zelikman et al:
Making and Coating Photog
radical Emulsion (TheFocal
It can be prepared using the method described in Press, 1964) and the like.

In order to improve the reciprocity law failure characteristic and adjust the gradation, the silver halide used in the present invention has the sixth element of the periodic table.
It is preferable to contain an ion of a metal belonging to Group 10 to 10 or a complex ion. The above metals include W, Fe,
Co, Ni, Cu, Ru, Rh, Pd, Re, Os, I
r, Pt and Au are preferred.

The silver halide grains can be removed (desalted) of unnecessary salts by a method known in the art such as a noodle method and a flocculation method, but the desalting is not performed. Alternatively, either may be used.

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

In order to prevent devitrification of the light-sensitive material, the total amount of silver halide and organic silver salt is 0.5-0.5 in terms of silver amount.
It is preferably 2.2 g / m ² . By setting the amount of silver in this range, a high contrast image can be obtained.
Further, the ratio of the amount of silver halide to the total amount of silver is 5 by mass.
0% or less, preferably 25% or less, more preferably 0.
1 to 15%.

Examples of the reducing agent used in the heat-developable photographic light-sensitive material include generally known reducing agents. Examples thereof include phenols, polyphenols having two or more phenol groups, naphthols, bisnaphthols, and two. Polyhydroxybenzenes having the above hydroxyl groups, polyhydroxynaphthalenes having two or more hydroxyl groups, ascorbic acids, 3-pyrazolidones, pyrazolin-5-ones, pyrazolines, phenylenediamines, hydroxylamines, hydroquinone mono Ethers, hydrooxamic acids, hydrazides, amidoximes, N
-Hydroxyureas and the like, more specifically, U.S. Pat. Nos. 3,615,533, 3,679,426, 3,672,904, 3,751,252, and 3,782. 949, 3,801,321, 3,794,488, 3,893,863, 3,887,376, 3,770,448, 3,819,382. , 3,773,512, 3,839,048, 3,887,378, 4,009,039, 4,021,240, British Patent 1,486,148, Belgian Patent 786,08
No. 6, JP-A Nos. 50-36143 and 50-36110.
No. 50-116023, No. 50-99719,
50-140113, 51-51933, 5
1-23721, 52-84727, Japanese Patent Publication No. 51
No. 35851 and the like can specifically include reducing agents and the like, which can be appropriately selected and used from the above known reducing agents. The most efficient selection method is to actually produce a thermosensitive 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 a silver salt of an aliphatic carboxylic acid 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 Two or more phenol groups substituted with an alkyl group (methyl, ethyl, propyl, t-butyl, cyclohexyl, etc.) or an acyl group (acetyl, propionyl, etc.) in at least one of the positions adjacent to the hydroxy-substituted position of the phenol group Polyphenols linked by alkylene groups or sulfur are preferred. Specifically, 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, etc. U.S. Pat. No. 3,589,903
No. 4,021,249, British Patent 1,486,1
48, JP-A-51-51933, and JP-A-50-3611.
No. 0, No. 50-116023, No. 52-84727.
No. 3, Japanese Patent Publication No. 51-35727 and the like, bisnaphthols described in US Pat. No. 3,672,904, for example, 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, further US Pat. No. 3,801,3
21. Sulfonamide phenols or sulfonamide naphthols, such as 4-benzenesulfonamide phenol, 2-benzenesulfonamide phenol, 2,6-dichloro-4-benzenesulfonamide phenol, 4-benzenesulfone. Examples thereof include amide naphthol.

The appropriate amount of the reducing agent used in the heat-developable photographic light-sensitive material of the present invention is not uniform depending on the type of the organic silver salt used, the reducing agent and other additives, but generally, the organic silver salt is used. 0.05 to 10 moles per mole, preferably 0.1
A range of up to 3 moles 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.

As the compound having a halogen radical-releasing group, which is preferably used in the heat-developable photographic light-sensitive material, there can be mentioned generally known compounds, which are disclosed in JP-A-9-16016.
4, No. 9-244178, No. 9-258367,
9-265150, 9-281640, 9-
319022, 10-171063, JP-A-200200
0-284402, 2000-284406, 2000-284410, 2000-284412.
Compounds listed in the above publications can be used. The halogen-releasing group is a group capable of releasing a halogen radical upon heating or light irradiation, and can be represented by, for example, the following general formula (9).

[0150]

[Chemical formula 63]

In the formula, X ₁ and X ₂ each represent a halogen atom, which may be the same or different, and are a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom,
A bromine atom and an iodine atom, more preferably a chlorine atom,
A bromine atom, particularly preferably a bromine atom.

X ₃ represents a hydrogen atom, a halogen atom or a substituent, and as the substituent, R _{11 to} R _{14 in the} general formula (1) can be used.
It has the same meaning as described above, preferably a halogen atom, and particularly preferably a bromine atom.

L represents a linking group, and as the linking group, --SO
_2- , -CO-, -NHCO-, -OCO-, -N
(R) SO ₂ — and the like can be mentioned, and R represents a substituent. The substituent has the same meaning as described for R _{11 to} R ₁₄ in the general formula (1).

As the skeleton of the compound, alkyl, aryl and the like can be used, but a compound having a halogen radical releasing group having an alkyl skeleton is preferable. Moreover, a plurality of halogen radical-releasing groups may be present in one compound. Further, it may be a polymer containing a halogen radical-releasing group, and the polymer may be blended with a homopolymer, a copolymer or another general-purpose polymer.

Typical examples of the compound having a halogen radical-releasing group represented by formula (9) are shown below, but the invention is not limited thereto.

[0156]

[Chemical 64]

[0157]

[Chemical 65]

[0158]

[Chemical formula 66]

[0159]

[Chemical formula 67]

[0160]

[Chemical 68]

[0161]

[Chemical 69]

[0162]

[Chemical 70]

[0163]

[Chemical 71]

[0164]

[Chemical 72]

[0165]

[Chemical formula 73]

Compounds having a halogen radical-releasing group used in heat-developable photographic light-sensitive materials and those represented by the general formula (1) to
Suitable amounts of the compound represented by (4), the compound (5) and the compounds represented by the general formulas (6) to (13) are uniform depending on the type of organic silver salt or polyhalomethane compound used and other additives. However, it is 0.0 per 1 m ^{2 of} light-sensitive material.
1 mg to 10 g is preferable, and further 10 mg to 0.1 g
Is preferred. Further, within this range, two or more of the above polyhalomethane compounds may be used in combination.

These compounds are dissolved in a suitable organic solvent such as alcohols (methanol, ethanol, propanol, fluoroalcohol, etc.), ketones (acetone, methylethylketone, etc.), dimethylformamide, dimethylsulfoxide, methylcellosolve, etc. Can be used. It can also be incorporated by the well-known emulsion dispersion method. For example, dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate and other high-boiling organic solvent and an auxiliary solvent such as ethyl acetate and cyclohexanone are dissolved and mechanically emulsified to prepare an emulsified dispersion. Can be added to the constituent layers. Further, a method known as a solid dispersion method, for example, a compound having a halogen-releasing group of the present invention and a compound represented by the general formulas (1) to (4), a compound (5) and a general formula (6) to ( The powder of the compound represented by 13) 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.

Compounds represented by the general formulas (1) to (4),
The compound (5) and the compounds represented by the general formulas (6) to (13) can be added to any layer, but the general formula (1) to
(4), the compound (5), the compound that generates an acid by light represented by the general formulas (6) to (8), and the general formula (10) to
The compound which newly generates an acid by the acid represented by (13) may be added in a different layer or in the same layer, or two or more kinds of these compounds may be used in combination.

Suitable binders for the photothermographic material are transparent or translucent, generally colorless natural polymer synthetic resins, polymers and copolymers, and other film forming media such as gelatin, gum arabic, and polyvinyl alcohol. Hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, polyvinylpyrrolidone, casein, starch, polyacrylic acid, polymethylmethacrylic acid, polyvinyl chloride, polymethacrylic acid, copoly (styrene-maleic anhydride), copoly (styrene-acrylonitrile) , Copoly (styrene-butadiene), polyvinyl acetals (polyvinyl formal, ribovinyl butyral, etc.), polyesters, polyurethanes, phenoxy resin, polyvinylidene chloride, polyepo Sid, polycarbonates, polyvinyl acetate, cellulose esters, and polyamides.

The binder may be hydrophilic or hydrophobic, but in order to reduce fog after the heat development treatment,
It is preferable to use a hydrophobic transparent binder. Examples of preferable binders include 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 photosensitive material and prevent scratches, it is preferable to coat a non-photosensitive layer on the outer side of the photosensitive 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 to 8 g / m ^2.
Is. 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 to be placed on the surface of the photosensitive material is the amount of the matting agent on the surface of the photosensitive layer in order to prevent scratching of the image after the heat development treatment. 0.5 to 30 mass% based on all binders
It is preferable to contain. Further, when a non-photosensitive layer is provided on the opposite side of the photosensitive layer with the support interposed, it is necessary for at least one layer on the non-photosensitive layer side to contain a matting agent in order to prevent slipping and fingerprint adhesion. Preferably, the amount of matting agent is
It is preferable to add 0.5 to 40% by mass of the total binder in the non-photosensitive layer. 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.

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

Various surfactants can be used as a coating aid in the photothermographic material. Among them, a fluorine-based surfactant is particularly preferably used for the purpose of improving charging characteristics and preventing 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 heat-developable photographic light-sensitive material has a mercapto compound, a disulfide compound, in order to suppress or accelerate development and control development intensity, to improve spectral sensitization efficiency, or to improve storage stability before and after development processing. Inhibitors such as thione compounds can be included.

The photothermographic material may further contain a surfactant, an antioxidant, a stabilizer, a plasticizer, an ultraviolet absorber, a coating aid and the like. As these additives and the above-mentioned other additives, RD17029 (June 1978,
The compounds described on pages 9 to 15) can be preferably used. These 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 (polyethylene terephthalate, polycarbonate, polyimide, nylon, cellulose triacetate, in order to obtain a predetermined optical density after development and to prevent the image from being deformed after development. Polyethylene naphthalate etc.) is preferable.

Among them, preferable supports include polyethylene terephthalate (PET) and plastic (SPS) containing a styrene polymer having a syndiotactic structure. The thickness of the support is 50 to
The thickness is about 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. The heat treatment of the support means a temperature higher than the glass transition point of the support by 30 ° C. or more, preferably 35 after the support is formed into a film and before the photosensitive layer is coated.
It means heating at a temperature higher than 0 ° C, more preferably at a temperature higher than 40 ° C.

To improve the charging property, a conductive compound such as a metal oxide and / or a conductive polymer may be included in the constituent layer. 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 heat-developable photographic light-sensitive material is described in, for example, JP-A-6-61.
3-159841, 60-140335, 63
-231437, 63-259651, 63-
304242, 63-15245, U.S. Pat.
639,414, 4,740,455, 4,7
41,966, 4,751,175, 4,83
The sensitizing dyes described in 5,096 and the like can be used. Specific examples of useful sensitizing dyes include, for example, RD17643IV-A.
Paragraph (December 1978, page 23) and Paragraph 18431X (August 1979, page 437).

In the present invention, particularly, a sensitizing dye having a spectral sensitivity adapted to the spectral characteristics of various scanner light sources can be advantageously selected. For example, A) for an argon laser light source, JP-A-60-162247, JP-A-2-48653, and US Pat. No. 2,161,331.
, West German Patent No. 936,071, Japanese Patent Application No. 3-18953
Japanese Patent Application Laid-Open No. 50-624, for the simple merocyanines and B) helium-neon laser light source described in JP-A No.
No. 25, No. 54-18726, No. 59-102229.
Cyanine dyes described in Japanese Patent Application No. 6-1032
For merocyanines, C) LED light source and red semiconductor laser described in No. 72, Japanese Patent Publication No. 48-42172.
No. 51-9609, No. 55-39818, and the thiacarbocyanines described in JP-A Nos. 62-284343 and 2-105135, and D) infrared semiconductor laser light source. Tricarbocyanines described in JP-A-59-191032 and JP-A-60-80841, JP-A-59-192242 and JP-A-3-6724.
Dicarbocyanines containing a 4-quinoline nucleus described in the general formula (IIIa) and general formula (IIIb) of No. 2 are advantageously selected.

These sensitizing dyes may be used alone or in combination thereof. In the combination of sensitizing dyes, the sensitizing dyes often used for the purpose of supersensitization may be used together with the sensitizing dyes. The silver halide emulsion may contain a dye which does not itself have a spectral sensitizing effect, or a substance which does not substantially absorb visible light and exhibits supersensitization.

Exposure of the photothermographic material of the present invention is
r laser (488 nm), He-Ne laser (63
3 nm), 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. Lasers are preferred.

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

The heat-developable photographic light-sensitive material of the present invention may be developed by any method, but one of the features is that the light-sensitive material exposed imagewise is heated and heat-treated at 80 to 250 ° C. And preferably 100 to 140 ° C.
Is. The developing time is preferably 1 to 180 seconds, and 1
0 to 90 seconds is more preferable.

[0190]

The present invention is described in detail below with reference to examples, but the present invention is not limited to these. Unless otherwise specified, “%” in the examples means “mass%”.

Example 1 (Preparation of Substrate 1 with Subbing) Commercially available biaxially stretched and heat-fixed, blue with a thickness of 175 μm and an optical density of 0.170 (measured by Konica Densitometer PDA-65). Both sides of the colored PET film were subjected to a corona discharge treatment of 8 W / m ² · min, and one side was coated with the following subbing coating solution a-1 and dried to a dry film thickness of 0.8 μm. Pulling layer A-
No. 1 and the undercoating coating solution b-1 described below was applied to the surface on the opposite side so as to have a dry film thickness of 0.8 μm and dried to form a subbing layer
-1 was set.

<Undercoating Coating Liquid a-1> Copolymer latex liquid of butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyethyl acrylate (30/20/25/25% ratio) (solid content 30%) 270 g Compound C-1 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water to 1 liter <Undercoating coating solution b-1> Butyl acrylate / styrene / glycidyl acrylate (40/20 / 40% ratio) copolymer latex liquid (solid content 30%) 270 g Compound C-1 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Water to 1 liter Subsequent undercoat layer 8 on the surface of A-1 and the undercoat layer B-1
A corona discharge of W / m ² · min was applied, and the following undercoating upper layer coating liquid a-2 was applied as the undercoating upper layer A-2 to a dry film thickness of 0.1 μm on the undercoating layer A-1. Further, on the undercoat layer B-1, the following undercoat upper layer coating solution b-2 was dried to a film thickness of 0.8 μm.
Was coated as an undercoating upper layer B-2 having an antistatic function.

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

[0194]

[Chemical 74]

[0195]

[Chemical 75]

(Back side coating) While stirring 830 g of methyl ethyl ketone (MEK), 84.2 g of cellulose acetate butyrate (manufactured by Eastman Chemical Co .: CAB381-20) and polyester resin (Bostic: VitelPE2200B).
4.5 g was added and dissolved. Next, lysate, 0.30
g of infrared dye-1 was added, and further 43.2 g of methanol was added.
Fluorine activator dissolved in (Asahi Glass Co., Ltd .: Surflon KH
40) 4.5 g and 2.3 g of a fluorine-based activator (manufactured by Dainippon Ink and Chemicals, Inc .: Megafag F120K) were added and sufficiently stirred until they were dissolved. Finally, silica dispersed in MEK at a concentration of 1% by a dissolver type homogenizer (W.
R. Grace: Syloid 64X6000) 75g
Was added and stirred to prepare a coating liquid for the back surface side.

[0197]

[Chemical 76]

The back surface coating liquid thus prepared was
Coating and drying were performed with an extrusion coater so that the dry film thickness was 3.5 μm. Drying temperature 100 ℃, dew point temperature 10
It was dried for 5 minutes using a dry air of ℃ to obtain a subbing support 1 having been subbed.

(Preparation of Photosensitive Silver Halide Emulsion A) A solution having the following composition was used.

A1 Phenylcarbamoylated gelatin 88.3 g Activator A (10% methanol aqueous solution) 10 ml Potassium bromide 0.32 g Finish with water to 5429 ml B1 0.67 mol / L silver nitrate aqueous solution 2635 ml C1 potassium bromide 51.55 g iodide Potassium 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 Potassium bromide aqueous solution Silver potential below Controlled amount F1 Potassium hydroxide 0.71 g Finish with water to 20 ml G1 56% aqueous acetic acid solution 18.0 ml H1 anhydrous sodium carbonate 1.72 g Finish with water to 151 ml A: HO (CH ₂ CH ₂ O) _n (CH (CH _{3 ) CH 2 O) 17 (CH} 2 C _{2 O) m H (m +} n = 5~7) JP-B-58-58288, using a mixing and stirring machine shown in Nos. 58-58289, solution to a solution (A1) (B
1/4 amount of 1) and the total amount of the solution (C1) were added at a temperature of 45 ° C., p
4 minutes 4 by simultaneous mixing method while controlling Ag 8.09.
It took 5 seconds to add and perform nucleation. After 1 minute, the total amount of solution (F1) was added. During this period, the pAg was adjusted appropriately using the solution (E1). After 6 minutes, 3/4 amount of the solution (B1) and the whole amount of the solution (D1) were heated at a temperature of 4
While controlling at 5 ° C. and pAg of 8.09, the mixture was added by the simultaneous mixing method over 14 minutes and 15 seconds. After stirring for 5 minutes, 4
The temperature was lowered to 0 ° 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. Settling part 1500m
The supernatant liquid was removed, leaving 1 l, and 10 liters of water was further added. After stirring, the silver halide emulsion was allowed to settle. After removing the supernatant liquid, leaving 1500 ml of the sedimented portion, the solution (H1) was added, the temperature was raised to 60 ° C., and the mixture was further stirred for 120 minutes. Finally, the pH was adjusted to 5.8 and water was added so that the amount of silver was 1161 g per mol of silver to obtain a photosensitive silver halide emulsion A. This emulsion has an average grain size of 0.058 μm, a grain size variation coefficient of 12%, and
[0] Monodispersed cubic silver iodobromide grains having a surface ratio of 92%.

(Chemical Sensitization of Silver Halide Emulsion A) Next,
To the above emulsion A, 240 ml of sulfur sensitizer S-5 (0.5% methanol solution) was added, and further gold sensitizer Au-5 corresponding to 1/20 mol of the sulfur sensitizer was added. Chemical sensitization was performed by stirring for 120 minutes.

[0202]

[Chemical 77]

(Preparation of powdered organic silver salt A) In 4720 ml of pure water, behenic acid 130.8 g and arachidic acid 67.7.
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 mol / L sodium hydroxide aqueous solution was added, and concentrated nitric acid 6.9 m
After adding l, it was cooled to 55 ° C. to obtain a fatty acid sodium solution. While maintaining the temperature of this fatty acid sodium 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, a 1 mol / L silver nitrate aqueous solution 702.
6 ml 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 centrifugally dehydration was carried out until the electric conductivity of the drainage became 2 μS / cm, and then the obtained cake-like organic silver salt was washed with a flash dryer flash jet dryer ( (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 dryer inlet 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 (manufactured by Monsanto: Butvar B-
79) 14.57 g was dissolved in 1457 g of MEK, and VM
A-GETZMANN: Dissolver DISPERM
Preliminary Dispersion A was prepared by gradually adding 500 g of powdered organic silver salt A while stirring with AT CA-40M type and thoroughly mixing.

(Preparation of Photosensitive Emulsion Dispersion Liquid 1) Pre-dispersion liquid A was mixed with zirconia beads having a diameter of 0.5 mm (Toray: Treceram) so that the residence time in the mill was 1.5 minutes by using a pump. ) Filled with 80% of the internal volume of the media type disperser DISPERMAT SL-C12EX type (VM
A-GETZMANN), and the peripheral speed of the mill is 8 m /
Photosensitive Emulsion Dispersion Liquid 1 was prepared by dispersing in s.

(Preparation of stabilizer liquid) 1.0 g of stabilizer-
1. 0.31 g of potassium acetate to methanol 4.97 g
To prepare a stabilizer solution.

[0208]

[Chemical 78]

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

[0210]

[Chemical 79]

(Preparation of Additive Solution a) 27.98 g of Developer-1, 1.54 g of 4-methylphthalic acid and 0.48 g
Infrared Dye-1 was dissolved in 110 g of MEK to obtain an additive liquid a.

[0212]

[Chemical 80]

(Preparation of Additive Solution b) Compound-1 was added to 4.5 ×
10 ⁻³ mol, 3.43 g of phthalazine and 15 × 10 ⁻³ mol of the compound of the general formula (1) of the present invention were added to MEK (40.9 g).
To be added liquid b.

[0214]

[Chemical 81]

(Preparation of Coating Solution for Photosensitive Layer) In an inert gas atmosphere (nitrogen 97%), 50 g of the above-mentioned photosensitive emulsion dispersion 1 and 15.11 g of MEK were kept at 21 ° C. with stirring to prevent an antifoggant. 1 (10% methanol solution) 39
0 μl was added and stirred for 1 hour. Further, 494 μl of calcium bromide (10% methanol solution) was added and stirred for 20 minutes. Then, 167 ml of stabilizer solution was added to
After stirring for 1 minute, 1.32 g of the infrared sensitizing dye solution was added and stirred for 1 hour. Then, the temperature was lowered to 13 ° C., and the mixture was further stirred for 30 minutes. While keeping the temperature at 13 ° C, polyvinyl butyral (Butvar B-79: supra) 1
After adding 3.31 g and stirring for 30 minutes, 1.084 g of tetrachlorophthalic acid (9.4% MEK solution) was added and stirred for 15 minutes. While further stirring, 12.4
3 g of additive liquid a, 1.6 ml of Desmodur N33
00 / Mobey's aliphatic isocyanate (10%
MEK solution), 4.27 g of Additive Solution b was sequentially added and stirred to obtain a photosensitive layer coating solution.

[0216]

[Chemical formula 82]

(Preparation of Matting Agent Dispersion) Cellulose Acetate Butyrate (Eastman Chemical)
Company: CAB171-15) 7.5 g MEK42.5
g of calcium carbonate (Specia)
Light Minerals: Super-Pfl
ex200) (5 g) was added and dispersed by a dissolver type homogenizer at 8000 rpm for 30 minutes to prepare a matting agent dispersion liquid.

(Preparation of coating liquid for surface protective layer) MEK865
While stirring g, 96 g of cellulose acetate butyrate (CAB171-15: described above) and polymethylmethacrylic acid (Rohm & Haas Co .: Paraloid A-2
4.5 g of 1), 1.5 g of a vinyl sulfone compound (VS-1), 1.0 g of benztriazole, and 1.0 g of a fluorine-based activator (Surflon KH40, Asahi Glass Co., Ltd.) were added and dissolved. Next, 30 g of the above-mentioned matting agent dispersion liquid was added and stirred to prepare a surface protective layer coating liquid.

VS-1: (CH ₂ = CHSO ₂ CH ₂ ) ₂ C
HOH (Coating on photosensitive layer surface side) The photosensitive layer coating liquid and the surface protective layer coating liquid were simultaneously applied in multilayers on the undercoated support 1 using an extrusion coater to prepare a photosensitive material. The coating is 1.9 on the photosensitive layer.
g / m ² , and the surface protective layer was dried to a thickness of 2.5 μm. Then, drying was carried out for 10 minutes using a drying air having a drying temperature of 75 ° C. and a dew point temperature of 10 ° C. to obtain heat-developable photographic material samples (1-A to 1-R).

(Image formation) From the emulsion surface side of the light-sensitive material prepared as described above, a wavelength of 800 to 820 was obtained by high frequency superposition.
Exposure by laser scanning was performed by an exposure device using a semiconductor laser having a multi-nm longitudinal multimode as an exposure source. At this time, an image was formed with the exposure surface of the light-sensitive material and the exposure laser beam at an angle of 75 degrees (note that compared to the case where the angle was 90 degrees, there was less unevenness and unexpectedly good sharpness, etc.). An image was obtained).

Then, heat development was carried out at 110 ° C. for 15 seconds using an automatic developing machine having a heat drum so that the protective layer of the photosensitive material was in contact with the drum surface. At that time, exposure and development were performed in a room conditioned at 23 ° C. and 50% RH (relative humidity).

(Sensitometry) The storability of the obtained image was evaluated by measuring the density. The measurement result is
Photosensitive material sample 1-A evaluated by sensitivity (reciprocal of exposure ratio giving 1.0 higher density than unexposed portion) and fog
The sensitivity is shown as a relative value with 100 as the sensitivity.

<Raw storability> After putting three coated samples in a closed container whose inside was kept at 25 ° C and 55% RH, 50 ° C
For 7 days (forced aging). The second sample and the sample for comparison with time (stored in a light-shielding container at room temperature) were subjected to the same treatment as in the above sensitometry evaluation, and the density of the fog portion was measured. An increase of 1 in fog was determined and evaluated as raw storability.

Increase in fog 1 = (fog after forced aging)-
(Fog over time for comparison) << Image storability >> Two samples that have been subjected to the same treatment as the raw storability evaluation are stored at 45 ° C. and 55% RH for 7 days in the dark.
The other sheet was exposed to natural light at 45 ° C. and 55% RH for 7 days, and then the density of the fog portion of both was measured, and the increase 2 of 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) << Silver tone >> For evaluation of silver tone, the density after development was 1.
A sample which was exposed and developed to have a density of 1 ± 0.05 was prepared. This sample has a color temperature of 7700 Kelvin and an illuminance of 1160.
Irradiation was carried out for 10 hours with a light source stand of 0 lux, and the color tone of silver was evaluated according to the following criteria. In terms of quality assurance, there are no problems with a rank of 4 or higher.

[0226] 5: Pure black tone with no yellow tint 4: Not pure black, but almost no yellow 3: Partially slightly yellowish 2: A slight yellow color is felt on the entire surface 1: At first glance, you can feel yellow color The results are summarized in Table 1.

[0227]

[Table 1]

From Table 1, it can be seen that the samples of the present invention have sufficient sensitivity, low fog, good raw storage stability of the photographic material, good image storability and good silver color tone.

Example 2 A method similar to that of Example 1 except that the compound of the general formula (1) of the present invention was changed to the compound of the general formula (2) in (Preparation of additive liquid b). A photosensitive material sample was prepared according to the above, and evaluated in the same manner as in Example 1. The results are shown in Table 2.

[0230]

[Table 2]

Even when the compound of the general formula (2) of the present invention was used, excellent results were obtained in raw storage stability, image storability and silver tone.

Example 3 A method similar to that in Example 1 except that the compound of the general formula (1) of the present invention was changed to the compound of the general formula (3) in (Preparation of additive liquid b). A photosensitive material sample was prepared according to the above, and evaluated in the same manner as in Example 1. The results are shown in Table 3.

[0233]

[Table 3]

Even when the compound of the general formula (3) of the present invention was used, excellent results were obtained in raw storage stability, image storability and silver tone.

Example 4 A method similar to that of Example 1 except that the compound of the general formula (1) of the present invention was changed to the compound of the general formula (4) in (Preparation of additive liquid b). A photosensitive material sample was prepared according to the above, and evaluated in the same manner as in Example 1. The results are shown in Table 4.

[0236]

[Table 4]

Even when the compound of the general formula (4) of the present invention was used, excellent results were obtained in raw storage stability, image storability and silver tone.

Example 5 In Example 1 (Preparation of additive liquid b), the compound of the general formula (1) of the present invention was changed to the compound (5) and the dissolving solvent was changed to methanol, except that A photosensitive material sample was prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 5.

[0239]

[Table 5]

Even when the compound (5) of the present invention was used, excellent results were obtained in raw storage stability, image storability and silver tone.

Example 6 A method similar to that in Example 1 except that the compound of the general formula (1) of the present invention was changed to the compound of the general formula (6) in (Preparation of additive liquid b). A photosensitive material sample was prepared according to the above, and evaluated in the same manner as in Example 1. The results are shown in Table 6.

[0242]

[Table 6]

Even when the compound of the general formula (6) of the present invention was used, excellent results were obtained in raw storage stability, image storability and silver tone.

Example 7 In Example 1 (Preparation of Additive Solution b), the compound of the general formula (1) of the present invention was replaced by a compound of the general formula (7), a compound of the general formula (7) and a general formula (8). A photosensitive material sample was prepared in the same manner as in Example 1 except that the copolymer was used, and evaluated in the same manner as in Example 1. The results are shown in Table 7.

[0245]

[Table 7]

From Table 7, even when the compound of the general formula (7) or the copolymer of the general formula (7) and the general formula (8) of the present invention is used, raw storage stability, image storability and silver tone are improved. Excellent results have been obtained.

Example 8 In Example 1, the compound of the general formula (1) of the present invention was
It was added at the time of 5 × 10 ⁻³ mol (preparation of additive liquid b), but instead of it, compounds of the general formulas (1) to (4) and (6) of the present invention, compound (5), general formula (7) A polymer having at least one repeating unit represented by the formula (1) and a copolymer having at least one repeating unit represented by the general formulas (7) and (8) in the same mole (surface protection layer coating liquid). A photosensitive material sample was prepared in the same manner as in Example 1 except that it was added, and evaluated in the same manner as in Example 1. The results are shown in Tables 8 and 9.

[0248]

[Table 8]

[0249]

[Table 9]

From the table, it is understood that the sample of the present invention has sufficient sensitivity, low fog, and good raw storage stability, image storability and silver tone of the light-sensitive material.

Example 9 In Example 1 (Preparation of additive liquid b), general formulas (1) to (4), compounds (5) and general formula (6) to
15 × 10 ⁻³ mol of the compound of (8) and the compound of the general formula (1
Photosensitive material samples were prepared in the same manner as in Example 1 except that 45 × 10 ⁻³ mol of the compounds 0) to (13) were added, and evaluated in the same manner. The results are shown in Table 10.

[0252]

[Table 10]

From the table, it is understood that the samples of the present invention have sufficient sensitivity, low fog, and good raw storage stability, image storability and silver tone of the light-sensitive material.

Example 10 In the <coating liquid for surface protective layer> of Example 8, the general formulas (1) to (4), the compound (5) and the general formula (6) to the present invention were used.
15 × 10 ⁻³ mol of the compound of (8) and the compound of the general formula (1
Photosensitive material samples were prepared in the same manner as in Example 8 except that 45 × 10 ⁻³ mol of the compounds 0) to (13) were added, and evaluated in the same manner as in Example 8. The results are shown in Table 11.

[0255]

[Table 11]

From the table, it is understood that the sample of the present invention has sufficient sensitivity, low fog, and good raw storage stability, image storability and silver tone of the light-sensitive material.

Example 11 (Preparation of Subbed Substrate 2) In the subbed Substrate 1 produced in Example 1, a commercially available biaxially stretched support having a thickness of 175 μm and an optical density of 0. 170 (manufactured by Konica: measured value by densitometer PDA-65) was replaced with a blue-colored PET film, and a commercially available biaxially stretched and heat-fixed PET film having a thickness of 100 μm was used, and Example 1 was used. Similarly, an undercoated support 2 was prepared.

(Preparation of Photosensitive Silver Halide Emulsion B) Water 9
After dissolving 7.5 g of inert gelatin and 10 mg of potassium bromide in 00 ml and adjusting the temperature to 35 ° C. and pH to 3.0, 370 ml of an aqueous solution containing 74 g of silver nitrate and an odor of (98/2) molar ratio. 370 ml of an aqueous solution containing potassium iodide, potassium iodide and rhodium chloride in an amount of 1 × 10 ⁻⁴ mol per mol of silver was added over 10 minutes by the controlled double jet method while keeping pAg at 7.7. Then 4-hydroxy-6-methyl-1,3,
0.3 g of 3a, 7-tetrazaindene was added, the pH was adjusted to 5.0 with sodium hydroxide, the average particle size was 0.06 μm, the variation coefficient of the projected diameter area was 8%, [10
0] Cubic silver iodobromide grains having an area ratio of 87% were obtained.

This emulsion was coagulated and sedimented by using a gelatin coagulant and desalted, and then phenoxyethanol.
1 g was added to adjust the pH to 5.9 and pAg to 7.5 to prepare a silver halide emulsion B.

(Preparation of Silver Behenate Dispersion) JP-A-9-1
A silver behenate dispersion was prepared according to the method described in Example 1 of 27643.

(Preparation of Sodium Behenate Solution) 340
34 g of behenic acid was dissolved in 65 ml of i-propanol at 65 ° C. Next, a 0.25 mol / L sodium hydroxide aqueous solution was added with stirring to adjust the pH to 8.7. At this time, about 400 ml of sodium hydroxide aqueous solution was required. Next, this sodium behenate aqueous solution was concentrated under reduced pressure to prepare a 8.9% -concentration sodium behenate solution.

(Preparation of silver behenate dispersion) In 750 ml of distilled water, 30 g of ossein gelatin was dissolved.
2.94 mol / L silver nitrate solution was added to adjust the silver potential to 40
It was set to 0 mV. Using the controlled double jet method, the sodium behenate solution 3 was added at 78 ° C.
74 ml was added at a speed of 44.6 ml / min, and at the same time, an aqueous silver nitrate solution of 2.94 mol / L was added at a silver potential of 40.
It was added to 0 mV. The amounts of sodium behenate and silver nitrate used at the time of addition were 0.092 mol,
It was 0.101 mol. After the addition was completed, the mixture was stirred for another 30 minutes, and water-soluble salts were removed by ultrafiltration to obtain a silver behenate dispersion.

(Preparation of Photosensitive Emulsion) To the above silver behenate dispersion, 0.01 mol of the above photosensitive silver halide emulsion B was added, and further, with stirring, a solution of polyvinyl acetate in butyl acetate (1.2%). After 100 g was gradually added to form a floc in the dispersion, water was removed, and two more washings and water removal were performed, and then 2.5% polyvinyl acetate (average molecular weight 3000) (acetic acid) was used as a binder. Butyl / i
-1/2 mixture of propyl alcohol) 60 g of the solution was added with stirring, and then polyvinyl butyral (average molecular weight 4000) and i-propyl alcohol were added as a binder to the gel-like mixture of silver behenate and silver halide. Dispersion was performed to obtain a photosensitive emulsion.

(Preparation of Photothermographic Material) The photothermographic material was prepared by successively coating the following layers on the undercoated support 2.

(Back side coating) A backing layer coating solution having the following composition was coated on the undercoating upper layer B-2 of the undercoated support 2 so that the wet film thickness was 80 μm. The drying was performed at 75 ° C. for 5 minutes.

<Backing Layer Coating Liquid> Polyvinyl butyral (10% i-propanol solution) 150 ml Infrared Dye-1 70 mg (Coating on the photosensitive layer side) A photosensitive layer coating liquid having the following composition was coated with a silver amount of 2.0 g. / M ² , and polyvinyl butyral as a binder was applied in an amount of 3.2 g / m ² . Further, a coating solution for the surface protective layer having the following composition is wet to a thickness of 100 μm.
Was coated on the photosensitive layer.

<Photosensitive Layer Coating Liquid> Photosensitive emulsion Amount that gives 3 g / m ² as silver amount Sensitizing dye-1 (0.1% DMF solution) 2 mg Compound-1 (2% of 3 × 10 ⁻³ mol) MEK solution) 3 ml Phtharazone (color tone agent) 360 mg Compounds of the general formulas (1) to (4), compounds (5) and general formulas (6) to (8) (20% DMF solution) of the present invention 10 ml Developer-1 (10% MEK solution) 13 ml 3-Hydroxy-2-p-toluyl acrylonitrile (1% methanol / DMF = 4/1 solution) 2 ml <Surface protection layer coating solution> MEK 175 ml i-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 Average particle size 1% relative to monodisperse silica binders μm (the sensitometric) thermal current-sensitive material samples prepared in the above 6
It was exposed to xenon flash light with an emission time of 10 ⁻³ seconds through an interference filter having a peak at 33 nm. After that, heat development treatment was performed at 115 ° C. for 15 seconds using a heat drum, and the fog value at that time was measured. Also, the concentration is 3.0
The reciprocal of the exposure dose that gives the value was taken as the sensitivity, and the sensitivity was expressed as the relative sensitivity with the sensitivity of Sample 6-A as 100. Also, the slope of the straight line connecting the points of density 0.1 and density 1.5 on the characteristic curve is shown as the gradation (γ _0.1-1.5 ) representing the breakage of the leg.

The raw storability, image storability and silver tone were evaluated according to the evaluation criteria of Example 1. The results are summarized in Tables 12 and 13.

[0269]

[Table 12]

[0270]

[Table 13]

From the table, it can be seen that the samples of the present invention have sufficient sensitivity, high gamma and good tonality, low fog, raw storage stability of the photographic material, image storability and silver tone. I know there is.

Example 12 In Example 11, general formulas (1) to (4) of the present invention,
The compound (5) and the compounds represented by the general formulas (6) to (8) were added to the <photosensitive layer coating solution> after being dissolved in DMF. The present invention was added to 175 ml of MEK used for preparing the <surface protective layer coating solution>. A light-sensitive material sample was prepared in the same manner as in Example 11 except that 10 × 10 ⁻³ mol of the above compound was dissolved and added to <coating liquid for surface protective layer>, and evaluated in the same manner as in Example 11. The results are shown in Table 14.

[0273]

[Table 14]

From Table 14, it is understood that the samples of the present invention have sufficient sensitivity, low fog, good raw storage stability of the photographic material, good image storability and good silver color tone.

Example 13 The procedure of Example 11 was repeated except that the compounds of the general formulas (10) to (13) of the present invention were further added in the <photosensitive layer coating solution> of Example 11 in an amount of 15 × 10 ^-3 mol. A photosensitive material sample was prepared by the same method and evaluated in the same manner as in Example 11. The results are shown in Table 15.

[0276]

[Table 15]

From the table, the samples of the present invention have sufficient sensitivity, high gamma and good tonality, low fog and good raw storage stability, image storability and silver tone of the light-sensitive material. It turns out that

Example 14 In Example 11, general formulas (1) to (4) of the present invention,
The compound (5) and the compounds represented by the general formulas (6) to (8) were added to the <photosensitive layer coating solution> after being dissolved in DMF. The present invention was added to 175 ml of MEK used for preparing the <surface protective layer coating solution>. Of the general formulas (1) to (4), the compound (5) and the compounds of the general formulas (6) to (8) (10 × 10 ⁻³ mol), and the compound of the general formulas (10) to (13) of the present invention. A photosensitive material sample was prepared in the same manner as in Example 11 except that x10 ^-3 mol was dissolved and added to the <surface protective layer coating solution>, and evaluated in the same manner as in Example 11. The results are shown in Table 16.

[0279]

[Table 16]

From the table, it can be seen that the samples of the present invention have sufficient sensitivity, high gamma and good tonality, low fog, and good raw storage stability, image storability and silver tone of the light-sensitive material. I know there is.

[0281]

According to the present invention, the sensitivity is high and the fog is low,
It is possible to provide a heat-developable silver salt photographic light-sensitive material having good storage stability and an excellent silver tone. The light-sensitive material is useful for a laser imager without causing fog increase even after the development process.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H123 AB00 AB03 AB23 AB25 BA00                       BA14 BB00 BB27 CB00 CB03

Claims (23)

[Claims] 1. A heat-developable silver salt photographic light-sensitive material comprising at least one compound capable of being cleaved by light to generate an organic acid. 2. A heat-developable silver salt photographic light-sensitive material containing at least one compound capable of generating a sulfonic acid, a sulfinic acid, a carboxylic acid and a phosphoric acid when cleaved by light. 3. A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the following general formula (1). [Chemical 1] [In the formula, R ₁₁ and R ₁₂ each represent a substituent, and R ₁₃ and R ₁₄ each represent a hydrogen atom or a substituent. p is 0 or 1
Represents the integer. ] 4. A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the following general formula (2). [Chemical 2] [In the formula, R ₂₁ represents a substituent, and R ₂₂ , R ₂₃ and R ₂₄ each represent a hydrogen atom or a substituent. q represents an integer of 0 to 5. When q is 2 or more, a plurality of R _22's may be the same or different, and may combine with each other to form a ring structure. ] 5. A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the following general formula (3). [Chemical 3] [Wherein R ₃₁ , R _32, and R ₃₃ each represent a substituent,
₃₂ and R ₃₃ may combine with each other to form a ring structure. ] 6. A heat-developable silver salt photographic light-sensitive material comprising at least one compound represented by the following general formula (4). [Chemical 4] [In the formula, each of R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ represents a hydrogen atom or a substituent. r represents an integer of 0 or 1, and s and t each represent an integer of 0 to 5. When s or t is 2 or more, a plurality of R ₄₁ or R ₄₂ may be the same or different, and
They may be bonded to each other to form a ring structure. ] 7. HSbF ₆ , HPF ₆ , which is cleaved by light,
A heat-developable silver salt photographic light-sensitive material containing at least one compound (5) which generates HAsF ₆ or HBF ₄ . 8. A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the following general formula (6). [Chemical 5] [In the formula, G represents an alkylene group, a cycloalkylene group, an arylene group, a heterocyclic group substituted with 2 or more substituents, or a composite group thereof. L ₆ represents a divalent linking group, and Z ₆ represents a compound represented by any of the general formulas (1) to (4) or a residue of the compound (5). k represents an integer of 0 or 1, and l represents an integer of 2 to 4. ] 9. A heat developable silver salt photographic light-sensitive material comprising a polymer having at least one repeating unit represented by the following general formula (7). [Chemical 6] [In the formula, each of R ₇₁ , R _72, and R ₇₃ represents a hydrogen atom or a substituent. L ₇ represents a linking group, and Z ₇ represents the general formula (1) to
It represents the compound represented by (4) and the residue of the compound (5). A ₇ represents an oxygen atom, a sulfur atom or —NR ₇₄ —,
R ₇₄ represents a hydrogen atom or a substituent. m represents an integer of 0 or 1. ] 10. A heat-developable silver salt photograph containing at least one copolymer having at least one repeating unit represented by the general formula (7) and at least one repeating unit represented by the following general formula (8). Photosensitive material. [Chemical 7] [In the formula, R ₈₁ , R ₈₂ , R _83, and R ₈₄ each represent a hydrogen atom or a substituent. L ₈ represents a linking group. A ₈ is an oxygen atom,
It represents a sulfur atom or —NR ₈₅ —, and R ₈₅ represents a hydrogen atom or a substituent. n and o each represent an integer of 0 or 1. ] 11. A heat-developable silver salt photographic light-sensitive material containing at least one compound which newly generates an acid by an acid. 12. A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the following general formula (10). [Chemical 8] [In the formula, R ₉₁ represents an alkyl group or an aryl group, and R ₉₂
Represents an alkyl group, and R ₉₃ has a hydrogen atom at the β-position.
Represents a primary or tertiary alkyl group, and Y represents a residue of an acid represented by YOH. ] 13. A heat-developable silver salt photographic light-sensitive material comprising at least one compound represented by the following general formula (11). [Chemical 9] [Wherein B ₁ , B ₂ , B ₃ and B ₆ each represent a hydrogen atom, an alkyl group or an aryl group, B ₄ and B ₅ each represent an alkyl group, an aryl group or a silyl group, and B ₄ and B ₅ may form a ring, and X represents an oxygen atom or a sulfur atom. Y
Represents a residue of an acid represented by YOH. ] 14. A heat-developable silver salt photographic light-sensitive material containing at least one compound represented by the following general formula (12). [Chemical 10] [In the formula, each of D ₁ , D ₂ and D ₃ represents a hydrogen atom, an alkyl group or an aryl group, and D ₁ and D ₂ may form a ring. Y represents an acid residue represented by YOH. ] 15. A heat-developable silver salt photographic light-sensitive material comprising at least one compound represented by the following general formula (13). [Chemical 11] [In the formula, E represents an alkyl group or an aryl group. Y is Y
Represents an acid residue represented by OH. ] 16. An organic acid silver salt, a binder, and
The heat-developable silver salt photographic light-sensitive material according to any one of claims 1 to 15, which contains a photosensitive silver halide and a reducing agent. 17. A heat-developable silver salt photographic light-sensitive material having a photosensitive layer and a surface protective layer on a support, which is cleaved by light,
A heat-developable silver salt photographic light-sensitive material, characterized in that the surface protective layer contains at least one kind of compound generating an organic acid. 18. A heat-developable silver salt photographic light-sensitive material having a light-sensitive layer and a surface protective layer on a support, which is cleaved by light,
A heat-developable silver salt photographic light-sensitive material, wherein the surface protective layer contains at least one compound (5) which generates HSbF ₆ , HPF ₆ , HAsF ₆ , and HBF ₄ . 19. A heat-developable silver salt photographic light-sensitive material having a photosensitive layer and a surface protective layer on a support, characterized in that the surface protective layer contains at least one compound capable of newly generating an acid by an acid. The heat-developable silver salt photographic light-sensitive material according to claim 17 or 18. 20. The general formulas (1) to (4) and (6)
The heat-developable silver salt photographic light-sensitive material according to claim 17, wherein the surface protective layer contains at least one compound represented by: 21. A polymer having at least one repeating unit represented by the general formula (7), or the general formula (7).
18. The heat-developable silver salt photographic light-sensitive material according to claim 17, wherein the surface protective layer contains at least one copolymer having at least one repeating unit represented by the general formula (8). . 22. The heat-developable silver salt photographic light-sensitive material according to claim 20, wherein the surface protective layer contains at least one of the compounds represented by the general formulas (10) to (13). . 23. The heat-developable silver salt photographic light-sensitive material according to claim 1, which contains at least one compound having a halogen radical-releasing group.