JPH0934079A - Diffusion transfer type heat developable photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a diffusion transfer type heat-developable photosensitive material capable of obtaining a cyan dye image low in fog and sufficient in density and superior in color reproduction performance by incorporating a specified dye donor. SOLUTION: The photosensitive material contains on a support a hydrophilic binder, photosensitive silver halide, and a dye donor represented by the formula: A1 -(J1 )a -(X1 )b -Dye1 in which A1 is a 1,3-sulfur-nitrogen group to cause cleavage reaction in the presence of a silver ion or a soluble sliver complex at high temperature to release -(J1 )a -(X1 )b -Dye1 ; J1 is a divalent bonding group; X1 is a divalent bonding group selected from a -CO- group or the like; each of (a) and (b) is 0 or 1; and Dye1 is a group of formula I; R11 is a substituted straight or branched alkyl group; each of R12 and R13 is an alkyl or aryl group or the like; R14 is H atom or the like; one of Z11 and Z12 is N atom and the other is a group of formula II; R15 is H atom or the like; (p) is an integer of 0-4; (q) is an integer of 1-5; and one of R11 and R15 is a group represented by the formula: A1 -(J1 )a -(X1 )b -.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diffusion transfer type photothermographic material (hereinafter, also simply referred to as a photothermographic material), and more specifically to a diffusion which has improved cyan dye image transfer density and excellent color reproducibility. The present invention relates to a transfer type photothermographic material.

[0002]

2. Description of the Related Art A heat development process in which a development process is performed by heating is known, and a process for obtaining a monochrome image and a color image is known. Further, a so-called transfer type photothermographic material is also well known, which transfers an image obtained by heat development from the photosensitive material to the image receiving layer.

The photothermographic material usually has a binder, a photosensitive silver halide emulsion, a reducing agent and, if necessary, a dye-providing substance, an organic silver salt and various other photographic additives on a support. ing. In the transfer type photothermographic material, an image receiving layer capable of receiving silver or a dye is provided separately from the case where the photothermographic material has an image receiving layer capable of receiving silver or a dye. It may be used together with the image-receiving material that it has.

Among the heat-developable light-sensitive materials, a dye-donor substance that forms or releases a dye during heat development is usually used for obtaining a color image. Particularly, in the case of a color photothermographic material, from the viewpoints of image sharpness and dye image storability, a method of forming or releasing a diffusible dye from the dye-donor substance at the time of heat development and performing a diffusion transfer to a dye image-receiving material is proposed. It is preferably used. Various dye-donor substances used in such diffusion transfer thermal development have been known, and most of them are dye-donor substances of the type used in the wet diffusion transfer system (so-called instant photography). Is being diverted.

This dye-donor substance is roughly classified into a type that releases a diffusible dye corresponding to the development of silver halide and a type that releases a diffusible dye corresponding to the development of silver halide. . As one of the latter type, a reaction is made with silver ions constituting silver halide or organic silver remaining without being used during development or a soluble silver ion complex using these silver particles as a silver source substance. There are dye-donor substances that release diffusible dyes.

An example in which this type of dye-donor material is applied to a wet diffusion transfer system is, for example, US Pat. No. 4,362,806.
No. 3, No. 3,719,489, and No. 4,375,50
No. 7. An example applied to diffusion transfer type thermal development is described in, for example, JP-A-59-180548.

However, a problem with these dye-donor substances is that the developability is not sufficient because a sufficient dye concentration cannot be obtained. In particular, in the cyan dye image, this problem is prominently expressed, and under the present circumstances, immediate countermeasures are demanded.

Further, such a cyan dye image has a great problem in color reproduction. That is, it has unnecessary absorption, that is, asymmetrical absorption in the unnecessary wavelength region,
Due to this, the color reproducibility is considerably poor.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and a first object of the present invention is to provide a diffusion containing a cyan dye-donor which gives low fog and gives a sufficient maximum density. It is to provide a transfer type photothermographic material.

A second object of the present invention is to provide a diffusion transfer type photothermographic material containing a cyan dye-donating substance which is excellent in color reproducibility.

[0011]

The above object of the present invention has been attained by the following constitutions.

1) A diffusion transfer type photothermographic material characterized in that it contains a hydrophilic binder, a photosensitive silver halide and a dye-providing substance represented by the following general formula [I] on a support.

In the general formula [I] A _1- (J ₁ ) _a- (X ₁ ) _b -Dye ₁ formula, A ₁ undergoes a cleavage reaction at high temperature in the presence of a silver ion or a soluble silver complex to give-( _{J 1) a - (X 1} ) b -Dye
Represents a 1,3-sulfur-nitrogen compound group that releases ₁ . J ₁ represents a divalent linking group. X ₁ is -CO-, -COO-,-
_{CONH -, - SO 2 -,} - SO 2 NH -, - SO 3 -,
-NHCO -, - represents a or a divalent linking group selected from -O- - NHSO _2. a and b each represent 0 or 1,
Dye ₁ represents a group represented by the following general formula [II].

[0014]

[Chemical 7]

In the formula, R ₁₁ represents a branched or straight chain alkyl group having a substituent, R ₁₂ and R ₁₃ are each an alkyl group,
Represents a cycloalkyl group or an aryl group, R ₁₂ and R ₁₃
May combine with each other to form a ring structure. R ₁₄ represents a hydrogen atom, an alkyl group, an acylamino group or an alkoxy group. One of Z ₁₁ and Z ₁₂ is a nitrogen atom, and the other is

[0016]

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## EQU1 ## R ₁₅ represents a hydrogen atom or a substituent, p represents an integer of 0 to 4, and when p is 2 or more, R ₁₄ may be the same or different. q is 1
Represents an integer of 5, and when q is 2 or more, R ₁₅ may be the same or different. One of R ₁₁ and R ₁₅ A ₁ - represents a group represented by _{- (J 1) a - (} X 1) b.

2) A diffusion transfer type photothermographic material comprising a support, on which a hydrophilic binder, a photosensitive silver halide and a dye-donor represented by the following general formula [III] are contained.

In the general formula [III] A _2- (J ₂ ) _c- (X ₂ ) _d -Dye ₂ formula, A ₂ undergoes a cleavage reaction in the presence of a silver ion or a soluble silver complex at a high temperature to give-( _{J 2) c - (X 2} ) d -Dye
Represents a 1,3-sulfur-nitrogen compound group which releases ₂ . J ₂ represents a divalent linking group. X ₂ is -CO-, -COO-,-
_{CONH -, - SO 2 -,} - SO 2 NH -, - SO 3 -,
-NHCO -, - NHSO ₂ -0 represents a divalent linking group selected from -O-. c and d each represent 0 or 1,
Dye ₂ represents a group represented by the following general formula [IV].

[0020]

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In the formula, R ₂₁ represents a branched or straight chain alkyl group having a substituent, R ₂₂ and R ₂₃ are each an alkyl group,
Represents a cycloalkyl group or an aryl group, R ₂₂ and R ₂₃
May combine with each other to form a ring structure. R ₂₄ represents a hydrogen atom, an alkyl group, an acylamino group or an alkoxy group. One of Z ₂₁ and Z ₂₂ is a nitrogen atom, and the other is

[0022]

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Represents R ₂₅ represents a hydrogen atom or a substituent, s represents an integer of 0 to 4, and when s is 2 or more, R ₂₄ may be the same or different. t is 1
Represents an integer of 5, and when t is 2 or more, R _{25 s} may be the same or different. One of R ₂₁ and R ₂₅ A ₂ - represents a group represented by _{- (J 2) c - (} X 2) d.

3) A diffusion transfer type photothermographic material according to claim 1, wherein A ₁ in the general formula [I] is a thiazolidinyl residue represented by the following general formula [V].

[0025]

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In the formula, R _A1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group, and R _B1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, heterocyclic group, or - (J _{1) a} -
(X ₁ ) _b represents a group represented by Dye ₁ . R _C1 , R _D1 ,
R _E1 and R _F1 each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a carboxyl group, an acyl group, a sulfonyl group or a sulfo group.

4) A diffusion transfer type photothermographic material according to claim 2, wherein A ₂ in the general formula [III] is a thiazolidinyl residue represented by the following general formula [VI].

[0028]

[Chemical 12]

In the formula, R _A2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group, and R _B2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, heterocyclic group, or - (J _{2) c} -
(X ₂ ) _d represents a group represented by _d- Dye ₂ . R _C2 , R _D2 ,
R _E2 and R _F2 each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a carboxyl group, an acyl group, a sulfonyl group or a sulfo group.

Hereinafter, the present invention will be described in detail. In the general formula [I], A ₁ causes a cleavage reaction in the presence of a silver ion or a soluble silver complex at a high temperature to give — (J ₁ ) _a — (X
₁ ) represents a 1,3-sulfur-nitrogen compound group that releases _b- Dye ₁ . A preferred embodiment of A _{1 in} the present invention is a thiazolidinyl residue represented by the above general formula [V].

In the above general formula [V], the alkyl group represented by R _A1 is a linear or branched alkyl group such as methyl, ethyl, i-propyl, t-butyl, dodecyl and 1-hexylnonyl. Groups. In addition, examples of the cycloalkyl group include groups such as cyclopropyl, cyclohexyl, bicyclo [2.2.1] heptyl, and adamantyl. Examples of the aryl group include phenyl, 1-naphthyl, 9-
Examples include groups such as anthranil. Further, as the heterocyclic group, for example, 2-tetrahydrofuryl, 2-thienyl,
Groups such as 4-imidazolyl and 2-pyridyl are mentioned. In addition, examples of the acyl group include a carbonyl group (for example, an alkylcarbonyl group such as acetyl and trifluoroacetylpivaloyl, an arylcarbonyl such as benzoyl, pentafluorobenzoyl, and 3,5-di-t-butyl-4-hydroxybenzoyl). Group), an oxycarbonyl group (for example, an alkoxycarbonyl group such as methoxycarbonyl, cyclohexyloxycarbonyl, dodecyloxycarbonyl, etc.), phenoxycarbonyl, 2,4-di-t.
-Arylphenoxycarbonyl, aryloxycarbonyl groups such as 1-naphthyloxycarbonyl and 2-pyridyloxycarbonyl, 1-phenylpyrazolyl-5-
Heterocyclic oxycarbonyl groups such as oxycarbonyl) and carbamoyl groups (eg dimethylcarbamoyl, 4-
(2,4-di-t-amylphenoxy) butylaminocarbonyl and other alkylcarbamoyl groups, phenylcarbamoyl, 1-naphthylcarbamoyl and other arylcarbamoyl groups) and the like.

Examples of the sulfonyl group include a sulfonyl group (eg, an alkylsulfonyl group such as methanesulfonyl and trifluoromethanesulfonyl and an arylsulfonyl group such as p-toluenesulfonyl), a sulfamoyl group (eg, dimethylsulfamoyl, 4- ( 2,4-
And alkylsulfamoyl groups such as di-t-amylphenoxy) butylaminosulfonyl, arylsulfamoyl groups such as phenylsulfamoyl) and the like.

Each group represented by R _A1 in the above general formula [V] may further have a substituent, and examples of the substituent include the alkyl group represented by R _A1 and cycloalkyl. Group, an aryl group, a heterocyclic group, an acyl group, and a group having the same meaning as each sulfonyl group can be exemplified, and in addition, a halogen atom-substituted alkyl group (for example, a trifluoromethyl group), a halogen atom (for example, a chlorine atom, Bromine atom, etc.), cyano group, nitro group, alkenyl group (eg 2-
Propylene group, oleyl group, etc.), hydroxyl group, alkoxy group (eg, methoxy group, 2-ethoxyethoxy group, etc.), aryloxy group (eg, phenoxy group, 2,4)
-Di-t-amylphenoxy group, 4- (4-hydroxyphenylsulfonyl) phenoxy group, etc.), heterocyclic oxy group (for example, 4-pyridyloxy group, 2-hexahydropyranyloxy group, etc.), carbonyloxy group ( For example, alkylcarbonyloxy group such as acetyloxy group, trifluoroacetyloxy group, pivaloyloxy group, benzoyloxy group, aryloxy group such as pentafluorobenzoyloxy, etc., urethane group (eg, N, N-dimethylurethane group, etc.) Aryl urethane group such as urethane group, N-phenyl urethane group, N- (p-cyanophenyl) urethane group), sulfonyloxy group (for example, methanesulfonyloxy group, trifluoromethanesulfonyloxy group, dodecanesulfonyloxy group, etc., alkylsulfonyl) Oki Group, benzenesulfonyloxy group,
Arylsulfonyloxy group such as p-toluenesulfonyloxy group), amino group (eg, alkylamino group such as dimethylamino group, cyclohexylamino group, dodecylamino group, anilino group, arylamino such as pt-octylanilino group) Group), sulfonylamino group (for example, methanesulfonylamino group, heptafluoropropanesulfonylamino group, alkyldecylsulfonylamino group such as hexadecylsulfonylamino group, p-toluenesulfonyl group, arylsulfonylamino group such as pentafluorobenzenesulfonylamino group) ), A sulfamoylamino group (for example, an alkylsulfamoylamino group such as an N, N-dimethylsulfamoylamino group, an arylsulfamoylamino group such as an N-phenylsulfamoylamino group), an acylamino (E.g. acetylamino group, myristoyl alkylcarbonylamino group such as an amino group, arylcarbonylamino group such as benzoylamino group),
Alkoxycarbonyl group (for example, alkylcarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group,
Arylcarbonyl group such as phenoxycarbonyl group),
Ureido group (eg, alkylureido group such as N, N-dimethylaminoureido group, N-phenylureido, N-
(Arylureido group such as (p-cyanophenyl) ureido group), alkylthio group (for example, methylthio group, t-octylthio group, etc.), arylthio group (for example, phenylthio group) and heterocyclic thio group (for example, 1-phenyltetrazole-5-). Thio group, 5-methyl-1,3,4-oxadiazole-2-thio group, etc.) and the like. In the present invention, R _A1 is preferably an alkyl group or an aryl group.

R _B1 in the above general formula [V] represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, and the alkyl group, the cycloalkyl group, the aryl group and the hetero group represented by R _B1. Examples of the ring group include the same groups as the above R _A1 . Each group represented by R _B1 may have a substituent, and examples of the substituent include the substituents of the alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R _A1. And a group having the same meaning as the above-mentioned group. In the present invention, R _B1 is preferably a hydrogen atom.

In the above general formula [V], R _C1 , R _D1 ,
R _E1 and R _F1 each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a carboxyl group, an acyl group, a sulfonyl group or a sulfo group.

The alkyl group, aryl group, heterocyclic group, acyl group and sulfonyl group represented by R _C1 , R _D1 , R _E1 and R _F1 in the above general formula [V] are each represented by R _A1. And a group having the same meaning as the above group. Further, these groups may have a substituent, and examples of the substituent include the same groups as the groups mentioned as the substituents of the respective groups represented by R _A1 .

R _C1 , R _D1 , R in the above general formula [V]
_E1 and R _F1 are preferably a hydrogen atom, an alkyl group, an aryl group and an acyl group, more preferably a hydrogen atom and an alkyl group.

In the above general formula [I], J ₁ is a divalent linking group, for example, an alkylene group such as a 1,2-ethylene group or a 1,3-propylene group, a 1,4-phenylene group or 1, Examples thereof include an arylene group such as a 5-naphthylene group.

In the above general formula [I], X ₁ is --CO
-, - COO -, - CONH -, - SO 2 -, - SO 2 N
_{H -, - SO 3 -,} - NHCO -, - NHSO 2 - and -
It represents a divalent linking group selected from O-. X ₁ is preferably -CONH-, -SO ₂ NH-, -NHCO.
It is a divalent linking group selected from — and —NHSO ₂ —.

In the above general formula [I], a and b each represent 0 or 1, and a and b are preferably 1.

In the general formula [I], Dye ₁ represents a group represented by the above general formula [II]. In the general formula [II], R ₁₁ represents an alkyl group having a branched or substituted group, preferably having 2 to 8 carbon atoms, and examples of the linear alkyl group include ethyl group, propyl group, octyl group and the like. be able to. The branched alkyl group is iso
-Propyl group, t-butyl group, cyclohexyl group and the like can be mentioned. These alkyl groups may have a substituent, and examples of the substituent include the substituents of the alkyl group, cycloalkyl group, aryl group and heterocyclic group represented by R _A1 in the general formula [V]. And a group having the same meaning as the above-mentioned group.

In the general formula [II], the alkyl group, cycloalkyl group and aryl group represented by R ₁₂ and R ₁₃ have the same meanings as the respective groups represented by R _A1 in the general formula [V]. A group can be mentioned. Further, each group represented by R ₁₂ and R ₁₃ may have a substituent, and examples of the substituent include R _A1 in the general formula [V].
And a group having the same meaning as the group described as the substituent of the alkyl group, cycloalkyl group and aryl group represented by. A preferred substituent represented by R ₁₂ and R ₁₃ is an alkyl group.

In the general formula [II], examples of the alkyl group represented by R ₁₄ include groups having the same meanings as the alkyl group represented by R _A1 in the general formula [V].
Examples of the acylamino group or alkoxy group represented by R ₁₄ include groups synonymous with the respective groups represented by R _A1 in the general formula [V]. The acylamino group or alkoxy group represented by R ₁₄ may have a substituent, and examples of the substituent include a substituent of the alkyl group, cycloalkyl group and aryl group represented by R _A1 in the general formula [V]. A group having the same meaning as the group mentioned above can be mentioned. A preferred substituent represented by R ₁₄ is an alkyl group.

In the general formula [II], Z ₁₁ and Z ₁₂ are each a nitrogen atom or

[0045]

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When Z ₁₁ is -N =, Z ₁₂ is Chemical formula 13, and when Z ₁₁ is Chemical formula 13, Z ₁₂ is -N =.

In the general formula [II], R ₁₅ represents a hydrogen atom or a substituent, and the substituent is, for example, the general formula [V].
Examples thereof include the groups defined as the substituents of the alkyl group, cycloalkyl group and aryl group represented by R _A1 in R. Either R ₁₁ or R ₁₅ must have a group represented by A _1- (J ₁ ) _a- (X ₁ ) _b- .

In the general formula [II], p represents an integer of 0 to 4, preferably 1.

Among the dye-donor substances represented by the above general formula [I], those represented by the following general formula [VII] are preferable.

[0050]

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In the above general formula [VII], R _A1 ,
R _C1 , R _D1 , R _E1 and R _F1 represent the same groups as R _A1 , R _C1 , R _D1 , R _E1 and R _F1 in the general formula [V].

In the above general formula [VII], J ₁ and X ₁
Each represents a group having the same meaning as J ₁ and X ₁ in formula (I). Dye ₁ has the same meaning as the dye residue represented by the general formula [II].

Next, the dye-providing substance represented by the general formula [III] will be described. In the general formula [III], A ₂ is preferably a thiazolidinyl residue represented by the general formula [VI].
In the general formula [VI], R _A2 , R _B2 , R _C2 , R _D2 , R _E2
And R _F2 are R _A1 , R _B1 , R _C1 in the general formula [V],
The groups having the same meanings as R _D1 , R _E1 and R _F1 are shown, and the preferable groups are the same meanings.

In the general formula [III], J ₂ and X ₂ each represent a group having the same meaning as J ₁ and X ₁ in the general formula [I], and preferable groups include the same groups.

In the general formula [III], c and d each represent 0 or 1, and c and d are preferably 1.

In the general formula [III], Dye ₂ is represented by the general formula [IV]. In the general formula [IV], R ₂₁ represents a group having the same meaning as R _{11 in the} general formula [II], R _{22 in the} general formula [IV].
And R ₂₃ represent a group having the same meaning as R ₁₂ and R ₁₃ in the general formula [II], R _{24 in the} general formula [IV] represents a group having the same meaning as R _{14 in the} general formula [II], each of which is a preferred group. And the synonymous groups can be mentioned.

In the general formula [IV], Z ₂₁ and Z ₂₂ are each a nitrogen atom or

[0058]

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When Z ₂₁ is -N =, Z ₂₂ is chemical formula 15, and when Z ₂₁ is chemical formula 15, Z ₂₂ is -N =.

In the general formula [IV], R ₂₅ represents a hydrogen atom or a substituent, and the substituent is, for example, the general formula [V].
Examples thereof include the groups defined as the substituents of the alkyl group, cycloalkyl group and aryl group represented by R _A1 in R. Incidentally, either R ₂₁ or R ₂₅ always has a group represented by A _2- (J ₂ ) _c- (X ₂ ) _d- .

In the general formula [IV], s represents an integer of 0 to 4, preferably 1.

Among the dye-donor substances represented by the above general formula [III], those represented by the following general formula [VIII] are preferable.

[0063]

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In the above general formula [VIII], R _A2 ,
R _C2 , R _D2 , R _E2 and R _F2 represent the same groups as R _A2 , R _C2 , R _D2 , R _E2 and R _F2 in the general formula [VI].

In the above general formula [VIII], J ₂ and X ₂
Each represents a group having the same meaning as J ₂ and X ₂ in formula [III]. Dye ₂ has the same meaning as the dye residue represented by the general formula [IV].

Specific examples of the dye-donor substances represented by the general formulas [I] and [III] used in the present invention are shown below.
The present invention is not limited by these.

[0067]

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[0068]

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[0069]

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[0070]

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[0071]

[Chemical 21]

[0072]

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[0073]

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[0074]

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[0075]

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[0076]

[Chemical formula 26]

[0077]

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[0078]

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[0079]

[Chemical 29]

[0080]

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The dye-providing substance represented by the general formulas [I] and [III] of the present invention is obtained by, for example, previously synthesizing a dye moiety and a 1,3-sulfur-nitrogen compound group and binding them. Can be easily synthesized. Also, with the dye part,
The 3-sulfur-nitrogen compound group can be easily synthesized by a conventionally known method. For example, regarding the dye portion, U.S. Pat. Nos. 2,369,929 and 2,772,162.
Issue 2, Issue 2,895,826, Issue 3,758,308
No. 5, JP-A-55-163537, JP-B-63-108
No. 18, No. 63-30619, Japanese Patent Publication No. 3-18175
And EP 250,954, and the like. Further, regarding the 1,3-sulfur-nitrogen compound group, for example, US Pat.
8,783, 4,33,2950, 4,33
6,387, 4,355,169, and J. Am
er. Chem. Soc. (Journal of the American Chemical Society), 101, 4
It can be easily synthesized according to the method described on page 20 (1979).

Typical synthetic examples of the dye-donor compounds represented by formulas [I] and [III] of the present invention are shown below. The dye intermediate (a) used in this synthesis example
And (c) and the thiazolidine intermediate (b) (1,3-sulfur-nitrogen compound group) are each synthesized according to the description in the above-mentioned literature.

The synthesis examples of the dye-donor compound represented by the general formula [I] of the present invention are shown below.

Synthesis Example 1: Synthesis of Exemplified Compound I-1

[0085]

[Chemical 31]

2.87 g of the compound (a) was added to 29 m of pyridine.
A solution prepared by dissolving 3.33 g of the compound (b) in 35 ml of chloroform was added dropwise thereto in 10 minutes. After completion of dropping, the reaction was carried out at room temperature for 5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate, and ice water 10
The pH was adjusted to 2 or less by sequentially adding 0 ml and concentrated hydrochloric acid.
After separating the solution, the obtained ethyl acetate solution was washed once with tap water, neutralized with a 5% sodium carbonate solution, and then washed twice with tap water. The ethyl acetate solution was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue is purified by silica gel chromatography to obtain the target Exemplified Compound I-1 in 3.21.
g (58% yield).

The structure of the exemplified compound I-1 is shown by NMR, I
It was confirmed by R and mass spectrum. Further, other exemplified compounds were also synthesized according to the above-mentioned synthesis examples, starting from the corresponding starting materials.

The synthesis examples of the dye-donor compound represented by the general formula [III] of the present invention are shown below.

Synthesis Example 2: Synthesis of Exemplified Compound II-9

[0090]

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1.43 g of compound (C)
A solution prepared by dissolving 1.50 g of the compound (b) in 16 ml of chloroform was added dropwise thereto in 10 minutes. After completion of dropping, the reaction was carried out at room temperature for 5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was dissolved in ethyl acetate, then ice water 50
The pH was adjusted to 2 or less by sequentially adding ml and concentrated hydrochloric acid. After separating this solution, the obtained ethyl acetate solution was washed with tap water to give 1
After washing twice, it was neutralized with a 5% sodium carbonate solution, and then washed twice with tap water. The ethyl acetate solution was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure.
The obtained residue was purified by silica gel chromatography to obtain 1.65 g of the desired exemplary compound II-9 (yield 63%).

The structure of Exemplified Compound II-9 is NMR, I
It was confirmed by R and mass spectrum. Further, other exemplified compounds were also synthesized according to the above-mentioned synthesis examples, starting from the corresponding starting materials.

The dye-providing substance of the present invention is used alone or
Although more than one species may be used in combination, the amount used may vary widely depending on the type of dye-donor substance and the use of the photothermographic material, but it is generally 0.05 to 10 g, preferably 0.1 to 1 m ^{2 of the} photographic material. It is in the range of up to 5 g.

As a method for incorporating the dye-donor substance into the photographic constituent layer of the photothermographic material, a known high-boiling organic solvent such as dibutyl phthalate, dioctyl phthalate, tricresyl phosphate is used in a hydrophilic colloid solution. Known as a method of emulsifying and dispersing in water, a method of dissolving in an alkaline hydrophilic colloid aqueous solution and then neutralizing with an acid to disperse, or a method of mechanically wet pulverizing and dispersing into fine particle solids in the hydrophilic colloid aqueous solution. Can be appropriately selected and used. When used by dispersing fine particles, the average particle diameter is generally 0.05 to 10 μm,
The range is preferably 0.1 to 5 μm.

The diffusion transfer type photothermographic material of the present invention is disclosed in, for example, JP-A-2-293753 and JP-A-2-3081.
A dye-donor substance is contained in a microcapsule together with the polymerizable compound described in No. 62, etc., and this is heat-developed to cause a polymerization reaction of the polymerizable compound in an image-like or reverse image-like manner to form a microcapsule. It can also be applied to a photothermographic material of the type in which an image is formed by curing and changing the diffusivity of the dye-donor substance into the image-receiving layer.

As the photosensitive silver halide used in the diffusion transfer type photothermographic material of the present invention, conventionally known ones can be used, for example, silver chloride, silver bromide, silver iodobromide, chloroodor. Silver halide and silver chloroiodobromide can be used.

These silver halides have a uniform composition from the inside to the surface of the grain, a so-called core / shell type in which the composition is different between the inside and the surface, or a multi-layer structure in which the composition changes stepwise or continuously. The silver halide may be

Further, the silver halide may be either monodisperse with a relatively uniform grain size or polydisperse with a broad grain size distribution.

The shape of silver halide has a clear crystal habit such as a cube, a sphere, an octahedron, a dodecahedron and a tetrahedron.
Alternatively, the other one can be used. Also, for example, JP-A-58-111933 and JP-A-58-111934.
Issue, Research Disclosure (hereinafter referred to as RD)
No. 22534, having two parallel crystal faces, each of which has a larger area than the other crystal faces and has a diameter to thickness ratio of about 5 grains. One or more tabular silver halides can also be used.

Further, for example, US Pat. No. 2,592,250
Nos. 3,220,613 and 3,271,257
No. 3,317,322 and 3,511,622
Nos. 3,531,291 and 3,447,927
Nos. 3,761,266 and 3,703,584
Nos. 3,736,140 and 3,761,276
No., JP-A-50-8524, JP-A-50-38525,
The internal latent image type silver halide emulsions described in JP-A Nos. 52-15661 and 55-127549, whose grain surfaces are not previously fogged, can also be used.

The photosensitive silver halide can be added with a metal ion species such as iridium, gold, rhodium, iron and lead in the form of a suitable salt at any stage of grain formation. In this case, these metal ions are added per mol of silver,
It is generally added in the range of 10 ⁻⁷ to 10 ⁻⁵ mol.

The light-sensitive silver halide emulsion has a grain size of about 0.05 to 2 μm, preferably about 0.1 to 1.0.
μm. It is also possible to use silver halides having different average grain sizes in the same photosensitive layer for the purpose of gradation adjustment.

In the present invention, as a method for preparing a photosensitive silver halide, a photosensitive silver salt-forming component is allowed to coexist with an organic silver salt described below, and a part of the organic silver salt is converted into photosensitive silver halide. You can also let it.

The photosensitive silver halide emulsion can be chemically sensitized on the grain surface with a known sensitizer (eg, active gelatin, inorganic sulfur, sodium thiosulfate, thiourea dioxide, sodium chloroaurate). The chemical sensitization can be performed in the presence of a nitrogen-containing heterocyclic compound or a mercapto group-containing heterocyclic compound.

Further, the photosensitive silver halide can be appropriately subjected to spectral sensitization to blue, green, red and infrared light by a known spectral sensitizing dye. Typical sensitizing dyes are, for example, JP-A-59-180553, JP-A-60-140335 and JP-A-60-135335.
0-263937, 61-65232, 61-
No. 153635, No. 61-153631, No. 62-3
No. 2446, No. 63-61242, No. 63-1383.
43, JP-A-3-163440 and 4-31854.
And Nos. 4-34547 and 5-45833. Further, for example, JP-A-62-39846,
No. 62-86360, No. 62-89037, No. 62
As described in JP-A-147450 and JP-A-62-147451, two or more kinds of sensitizing dyes may be used in combination with a single silver halide.

The amount of the sensitizing dye used is 1
It is preferably 10 ⁻⁵ to 10 ⁻² mol per mol.
The sensitizing dye may be added in any step of preparing a silver halide emulsion, and specifically, during formation of silver halide grains, removal of soluble salts, before initiation of chemical sensitization, during chemical sensitization, or chemical sensitization. After the sensitization is completed.

These photosensitive silver halide and photosensitive silver salt-forming components are used in an amount of about 0.01 to 10 per 1 m ² of the photosensitive material.
g, preferably in the range of 0.05 to 1 g (per each photosensitive layer).

In the photothermographic material of the present invention, a known organic silver salt can be used, if desired, for the purpose of increasing sensitivity and improving developability.

The organic silver salt that can be used in the present invention is
For example, JP-A Nos. 53-4921 and 49-52626.
No. 52-141222, No. 53-36224,
No. 53-37626, No. 53-36224, No. 53
-37610, etc. and U.S. Pat. No. 3,330,633.
No. 3,794,496, No. 4,105,451 and the like, silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocyclic ring (for example, silver behenate, α- ( 1
-Phenyltetrazolethio) silver acetate, etc.) or JP-B-44-25582, 45-12700, 45
No. 18416, No. 45-22815, JP-A No. 52-
137321, 58-118638, 58-1
18639, U.S. Pat. No. 4,123,274 and the like, there are silver salts of compounds having an imino group. Further, acetylene silver described in JP-A-61-249044 can be used.

Of these, silver salts of compounds having an imino group are preferable, and silver salts of benzotriazole and its derivatives are particularly preferable. The amount of organic silver salt used is 1 m of light-sensitive material
0.005 g to 10 g per ² , preferably 0.01 to
The range is 5 g.

As the reducing agent used in the photothermographic material of the present invention, an appropriate reducing agent can be selected from those known in the conventional thermal development for photothermographic materials depending on the developing mechanism and the dye forming or releasing mechanism. . The reducing agent referred to here also includes a reducing agent precursor that releases the reducing agent during thermal development.

Examples of the reducing agent which can be used in the present invention include US Pat.
1,270, 3,764,328, 3,34
No. 2,599, No. 3,719,492, RD1214
No. 6, No. 15,108, No. 15,127, and JP-A Nos. 56-27132, 53-135628, 57.
-79035, etc., p-phenylenediamine type and p-aminophenol type developing agents, phosphoric acid amidophenol type developing agents, sulfonamideaniline type developing agents,
Hydrazone-based developing agents, phenols, sulfonamidephenols, polyhydroxybenzenes, naphthols, hydroxybisnaphthyls, methylenebisphenols, ascorbic acids, 1-aryl-3-pyrazolidones, hydrazones, and various reductions described above. There are drug precursors. Further, the dye-donor substance can also serve as the reducing agent.

Two or more reducing agents may be used in combination, and a combination of 1-aryl-3-pyrazolidone and a diffusion-resistant hydroquinone derivative is particularly preferable. The amount of the reducing agent used is 0.01 to 100 mmo per 1 m ² of the light-sensitive material.
Used in the l range.

Examples of the binder that can be used in the photothermographic material of the present invention include polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethacrylate, polyvinyl alcohol, polyvinyl pyrrolidone, gelatin, phthalated gelatin and other gelatin derivatives, and cellulose derivatives. , Proteins, starch, gum arabic and the like, and synthetic or natural polymer substances, and these can be used alone or in combination of two or more kinds.

Gelatin is particularly preferably used. As the gelatin, usual alkali-treated gelatin or acid-treated gelatin, or a gelatin derivative such as phenylcarbamoylated gelatin or phthalated gelatin is used, and two or more kinds of gelatin are used in combination. You can also It is also preferable to use the above-mentioned various gelatins in combination with a water-soluble polymer other than gelatin. The amount of the binder used is usually 0.1 to 50 g, and preferably 1 to ²⁰ g per 1 m ^{2 of the} support.

The binder is preferably hardened with a known photographic hardener. Examples of the hardener include vinyl sulfone-based, aldehyde-based, epoxy-based, N-methylol-based, halogen-substituted-s-triazine-based hardeners. Further, a polymer hardener may be used.

In addition to the above, various additives as shown below may be used in the photothermographic material of the present invention, if necessary.

In the present invention, the thermal solvent used for the purpose of accelerating the transfer of the dye and other purposes is a compound having a function of liquefying at the time of thermal development and promoting thermal development and thermal transfer of the dye, and is in a solid state at room temperature. Is preferred.

Examples of the thermal solvent that can be used in the present invention include US Pat. Nos. 3,347,675 and 3,66.
7,959, 3,438,766, 3,66
6,477, RD 17,643, JP-A-51-19
No. 525, No. 53-24829, No. 53-60223.
No. 58, No. 58-118640, No. 58-198038.
No. 59-229556, 59-68730,
59-84236, 60-191251, 6
0-232547, 60-60241, 61-
No. 52643, No. 62-78554, No. 62-421.
No. 53, No. 62-44737, No. 63-53548.
No. 63-161446, JP-A No. 1-224751.
No. 2, 2-863 and the like.

Of the above-mentioned thermal solvents, water-insoluble solid thermal solvents are particularly preferably used, and specific examples thereof include, for example, JP-A Nos. 62-136645 and 62-13954.
5, No. 63-53548, No. 63-161446
, JP-A Nos. 1-222451, 2-863 and 2
The compounds described in No. 120739, No. 2-123354 and the like can be mentioned.

The thermal solvent can be added to any layer such as a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, an image receiving layer of an image receiving material, and the addition amount thereof is usually 5 with respect to the binder. ~ 500 wt%, more preferably 10-200
% By weight.

Examples of the development accelerator that can be used in the present invention include those disclosed in JP-A-59-177550 and JP-A-59-177550.
111636, 59-124333, 61-7.
No. 2233, No. 61-236548, JP-A-1-15
The compounds described in JP 2454 are useful, and JP
The development accelerator releasing compounds described in JP-A-1-159642, JP-A-1-104645 and JP-A-1-110767 can also be used.

Examples of the antifoggants which can be used in the present invention include higher fatty acids described in US Pat. No. 3,645,739, N-halides described in JP-A-51-47419, US patents. 3,700,457 and JP-A-51-50725, JP-A-2-29754.
Nos. 8 and 2-282241, mercapto compound-releasing compounds, arylsulfonic acids described in JP-A-49-125016, oxidations described in British Patent 1,455,271 and JP-A-50-101019. Agent, 53-1
9825, sulfinic acids and thiosulfonic acids, 51-3223, thiouracils, 51
No. 26019, sulfur, No. 51-42529, No. 51-81124, and No. 55-93149, disulfides and polysulfides, No. 51-5743.
Rosin or diterpenes described in No. 5, 51-10
4338, a polymer acid having a carboxyl group or a sulfonic acid group, a thiazolithion described in U.S. Pat. No. 4,138,265, JP-A-54-51821 and JP-A-55-1521.
142331, U.S. Pat. No. 4,137,079, triazoles, JP-A-55-140883, thiosulfinic acid esters, JP-A-59-46641.
No. 59-57233, No. 59-57234, and di- or tri-halides described in JP-A-59-1116.
No. 36 thiol compound, No. 60-198540 and No. 60-227255 hydroquinone derivatives, and the like.

Other preferable antifoggants that can be used in the present invention are the antifoggants having a hydrophilic group described in JP-A-62-78554 and JP-A-62-12.
No. 1452, polymer antifoggant, JP-A-62-
The antifoggant having a ballast group described in No. 123456 can be mentioned.

Further, water-soluble halides (potassium bromide,
Potassium iodide, sodium chloride, etc.) can also be used for the purpose of preventing fog and other purposes. The antifoggant can be added to any layer of the photothermographic material and the dye image receiving material.

As the base precursor which can be used in the present invention, a compound (guanidine trichloroacetic acid or the like) which decarboxylates upon heating to release a basic compound, or an amine which is decomposed by an intramolecular nucleophilic substitution reaction to release amines. Compound,
And a basic precursor technology that releases a base by reacting a poorly soluble basic metal compound (such as zinc hydroxide) with a compound capable of forming a complex with a metal ion forming the same (such as picolinic acid). Specifically, for example, JP-A-56
-130745, 59-157637, 59-
No. 166943, No. 59-180537, No. 59-1
No. 74830, No. 59-195237, No. 62-10.
No. 8249, No. 62-174745, No. 62-187.
847, 63-97942, 63-96159.
And JP-A-1-68746.

As the silver ion scavenger which can be used in the present invention, physical development nuclei described in JP-A-63-163345, a diffusion resistant compound which forms a stable complex against silver ions, Further, there can be mentioned conventionally known silver ion scavengers for diffusion transfer such as compounds forming a poorly soluble silver salt.

Examples of the silver halide solvent that can be used in the present invention include compounds having the general formula described in JP-A-62-283335, page 3, upper left column, line 15 to page 11.

Examples of silver ion complexing agents which can be used in the present invention include bipyridines described in JP-A-63-309948.

The diffusion transfer type photothermographic material of the present invention comprises
In addition to the above, various known photographic additives can be used, for example, a water-soluble or hydrophobic filter dye,
Colloidal silver, fluorescent whitening agent, antistatic agent, surfactant (anionic, cationic, nonionic, fluorine-containing anion type, etc.), inorganic and organic matting agent, anti-fading agent, ultraviolet absorber, white background color adjustment Agents and the like can be contained. Regarding these, specifically, RD 17,029 and 2
9,963, JP-A-62-135825 and 64.
No. 13546 and the like.

These various additives include not only the photosensitive layer but also the intermediate layer, the undercoat layer, the protective layer or the backing layer.
It can be appropriately added to any constituent layer.

When the photothermographic material of the present invention comprises two or more photosensitive layers, an intermediate layer is preferably used between the two photosensitive layers for the purpose of preventing color mixture. The intermediate layer is generally composed of a hydrophilic binder such as gelatin, and the intermediate layer has a resistance to prevent interlayer migration of the reducing agent oxidant for the purpose of effectively preventing color mixing. A reducing agent such as a diffusible hydroquinone derivative or a silver ion scavenger for preventing the diffusion of silver ions can be added.

The support used in the diffusion transfer type photothermographic material of the present invention is preferably a transparent or opaque synthetic plastic film such as polyethylene terephthalate film or polyethylene naphthalate film, art paper,
Examples include cast coated paper, various coated papers such as baryta paper, polyethylene resin coated paper, and supports obtained by coating and curing the electron beam curable resin composition on these various supports.

The diffusion transfer type thermosensitive photosensitive material of the present invention is
(A) Photosensitive silver halide emulsion, (b) reducing agent, (c)
It contains a binder and (d) a dye-providing substance. These may be contained in a single photographic constituent layer, or may be added by dividing them into two or more layers. Specifically, the components (a), (b), and (c) are added to the same layer and (d) is added to a layer adjacent thereto, or (a), (c), ( d) is added to a single layer,
(B) can be added to another layer.

Further, the photosensitive layer having substantially the same color sensitivity can be composed of two or more photosensitive layers, and can be a low sensitivity layer and a high sensitivity layer, respectively.

When the diffusion transfer type photothermographic material of the present invention is used as a full-color recording material, it usually has three photosensitive layers having different color sensitivities, and each photosensitive layer has a different hue by heat development. Different dyes are formed or released.
In this case, in general, the yellow dye (Y) is used in the blue photosensitive layer (B), the magenta dye (M) is used in the green photosensitive layer (G), and the red photosensitive layer (R) is used. Is a cyan dye (C)
However, the present invention is not limited to this, and any combination is possible. Specifically, (BC) /
(GM) / (RY), (infrared photosensitivity-C) / (G-
A combination such as Y) / (RM) is also possible. Further, as described in JP-A-4-329541, it can be applied to a photothermographic material having two different color sensitivities in the infrared region and the third color sensitivities in the red region.

Further, as described in JP-A-60-162251, the present invention can be applied to a system of forming a black image using a diffusible dye.

The diffusion transfer type photothermographic material of the present invention comprises
In addition to the photosensitive layer, a non-photosensitive layer such as an undercoat layer, an intermediate layer, a protective layer, a filter layer, a backing layer and a peeling layer can be optionally provided.

When the diffusion transfer type photothermographic material of the present invention is of a dye transfer type, it is preferable to use an image receiving material having a dye image receiving layer. The image-receiving material is usually composed of a support and an image-receiving layer having a dye-receiving ability provided on the support, but the support itself can also serve as the image-receiving layer having a dye-receiving ability. The image receiving layer is roughly classified into a case in which the binder itself constituting the image receiving layer has a dye receiving ability and a case in which a mordant capable of receiving the dye is contained in the binder.

When the binder has a dye-accepting ability, a substance preferably used has a glass transition temperature of about 4
Polymers at 0 ° C. to about 250 ° C. are preferred, specifically
"Polymer Handbook Second Edition" by Joy Brand Wrap, edited by HI Inmargut, published by John Willie & Sons {Poly
mer Handbook 2nd. ed. , J. et al. Br
andrup, E .; H. Edited by Immergut, John
A synthetic polymer having a glass transition temperature of about 40 ° C. or higher described in Wiley & Sons} is useful and generally has a molecular weight of 2,000 to 200,
Those of about 000 are useful. These polymers may be used alone or in combination of two or more kinds, or may be a copolymerizable polymer having two or more kinds of repeating units,
Specific examples thereof include polyvinyl chloride, polyester, polycarbonate, polyvinylidene chloride and polyether.

In the present invention, an image receiving material in which the image receiving layer contains a mordant in a hydrophilic binder is also preferably used.

As the mordant, a polymer containing a tertiary amine or a quaternary ammonium salt is preferably used. For example, JP-A Nos. 48-75237 and 50-61228.
No. 50, No. 50-80132, No. 50-73440, No. 53-129034, No. 54-145529, No. 5
5-142339, 56-14610, 59
-219745, 62-30249 and 62-
Polymer mordanting agents having a quaternary ammonium group described in U.S. Pat. No. 34159, U.S. Pat. No. 3,249,393, polyvinylpyridine mordants described in JP-A-60-23851, U.S. Pat. No. 4,115,124. British Patent Nos. 2,056,101, 2,093,041, JP-A-59-55436, 60-238854, 6
0-39644, 60-60643, 60-1
18834, 60-122941, 60-23
No. 5,124, etc., a polyvinyl imidazole-based mordant, a mordant having a group having a mordant ability described in JP-A-47-3689, which is grafted, and JP-A-60-57.
836 combined use of a tertiary amine type mordanto and a quaternary ammonium type mordant, JP-A-63-1980.
51, and mordants having an image stabilizing group described in JP-A-2-32335.

As the binder used for holding these mordants, hydrophilic binders such as gelatin and polyvinyl alcohol are preferably used.

The image-receiving material used in the present invention may have a single image-receiving layer provided on a support, or may have a plurality of constituent layers coated thereon. All can be dye image-receiving layers, or only part of the constituent layers can be image-receiving layers.

When the image receiving material has a support separately from the image receiving layer, the support of the image receiving material may be either a transparent support or a reflective support. Specifically, polyethylene phthalate, polypropylene, and a support prepared by adding a white pigment such as barium sulfate or titanium dioxide to the support, art paper, cast coated paper, baryta paper, or a white support is contained on the paper support. Laminated paper coated with a thermoplastic resin (polyethylene or the like), cloth, glass, metal foil such as aluminum, or the like can be used.
Further, a support obtained by coating and curing an electron beam curable resin composition containing a pigment on the support, a reflective support having a second-class diffuse reflection property, and the like can also be used as the support of the image receiving material. .

When a paper support is used as a support for the diffusion transfer type photothermographic material and the image receiving material of the present invention, a support in which both sides of the paper support are coated with polyethylene is particularly preferable, and in this case, at least one of them is used. It is preferable that the polyethylene on the side of contains a titanium oxide.

It is preferable that the paper support coated with such polyethylene has excellent smoothness in terms of planarity, and the surface on the side coated with the dye image-receiving layer or the photosensitive layer is JIS-P-8.
Beck smoothness defined by 119 is preferably 50 seconds or more, preferably 100 seconds or more, and the surface of the support has a cutoff value of 0 from the cross-sectional curve measured according to JIS-B-0610. When measuring the maximum waviness of a filter with a standard length of 2.5 mm for a filtered waviness curve derived under the condition of 0.8 mm, it is preferable that the number of points where the maximum waviness is 4 μm or more is 4 or less at 100 arbitrary measurement points. , And the centerline average roughness Ra in that case is 3
It is preferably μm or less.

Further, the base paper for the polyethylene-coated paper is described in JP-A-4-321043, page 4, column 6, line 32 to page 5, column 8, column 2.
Those having the configuration and characteristics described in the eighth line are preferable.

The diffusion transfer type photothermographic material of the present invention comprises R
D15, 108, JP-A-57-198458, 5
It is also possible to use a so-called mono-sheet type photothermographic material in which a photosensitive layer and an image receiving layer are previously laminated on the same support, as described in 7-207250 and 61-80148.

Various known additives can be added to the image receiving material used in the invention.

Examples of such additives include stain inhibitors and ultraviolet absorbers (for example, JP-A-60-130735).
No. 61-153638, etc., benzophenone compounds, benzotriazole compounds, etc., fluorescent whitening agents (for example, diaminostilbene compounds described in JP-A-61-143752, JP-A-63). -14
7166) and image stabilizers (for example, JP-A-59-182785 and 61-159644).
No.), development accelerator, antifoggant (KB
r, NaCl, KI, benzotriazole derivatives and 1-
Nitrogen-containing heterocyclic compounds such as phenyl-5-mercaptotriazole derivatives), pH adjusters (acid and acid precursors, base precursors, etc.), thermal solvents, organic fluorine compounds,
Examples thereof include oil drops, surfactants, hardeners, polymer latices (for example, described in JP-A-61-156045), matting agents and various transition metal ions.

The diffusion transfer type photothermographic material and the image receiving material of the present invention may have a so-called back layer for curling balance and improving slipperiness. For the back layer, either a hydrophilic binder or a hydrophobic binder can be used, but it can be appropriately selected according to the application and constitution.

The diffusion transfer type photothermographic material of the present invention is exposed by a known exposure means suitable for the color sensitivity of the photosensitive material.

The exposure light source used in the present invention includes a tungsten lamp, a halogen lamp, a xenon lamp,
A mercury lamp, a CRT light source, a FO-CRT light source, a light emitting diode, a laser light source (for example, a gas laser, a dye laser, a YAG laser, a semiconductor laser, etc.) can be used alone or in combination. Also, a light source in which a semiconductor laser and an SHG element (second harmonic generation element) are combined can be used.

For the exposure time, one screen is exposed once, or
Or, it varies depending on the digital exposure for each pixel, but in the former case, it is usually 0.001 seconds to 10 seconds, and in the latter, it is performed in the range of 10 ^-8 to 10 ^-2 seconds per pixel. Be seen. In the case of digital exposure, one pixel may be exposed only once, or multiple exposure may be performed in which multiple exposures are performed. In the case of performing multiple exposure, it is also possible to shift the image area little by little each time.

The diffusion transfer type photothermographic material of the present invention is preferably 60 to 170 after imagewise exposure or at the same time as exposure.
C., more preferably 70 to 150.degree. C., and heat developed for 1 to 80 seconds, preferably 2 to 60 seconds to form a dye image. The transfer of the diffusible dye to the image-receiving material may be carried out simultaneously with the heat-development by bringing the image-receiving layer surface of the image-receiving material into close contact with the photosensitive layer side of the photosensitive material during the heat-development. After that, the image receiving material may be brought into close contact with the photosensitive material and heated to transfer the dye.

Further, the photosensitive material is preheated in the range of 50 to 150 ° C. before exposure, or as described in JP-A-60-143338 and JP-A-61-162041, the photosensitive material is immediately before development. And at least one of the image receiving material
It is also possible to preheat in the temperature range of 120 ° C.

Further, immediately before the heat development, a small amount of water may be supplied to the photosensitive material or the image receiving material, and then the both may be adhered together for heat development. In this case, the water may be mere water, or may be water containing an alkaline aqueous solution, a surfactant, or the hot solvent. The amount of supply of water is preferably within the range of the maximum swelling film thickness of the photosensitive material or the image receiving material to be supplied. The water may contain known antifungal agents, development accelerators or antifoggants, fluorescent whitening agents and the like.

When the diffusion transfer type photothermographic material of the present invention is thermally developed, known heating means can be applied,
For example, a method of contacting with a heated heat block or surface heater, a method of contacting with a heat roller or a thermal drum, a method of passing through an atmosphere maintained at a high temperature, a method of using a high frequency heating method, or a method of using a photosensitive material or an image receiving material. A known heat development method such as a method in which a heat generating conductive material such as a carbon black layer is provided on the back surface and Joule heat generated by energization is used can be applied.

The heating pattern at the time of heat development is not particularly limited, and it may be carried out at a constant temperature, at a high temperature in the early stage of development and at a low temperature in the latter half of the development, or vice versa, and further in 3 steps or more. Any method such as a method of changing the temperature region or a method of continuously changing the temperature can be used. In particular, as described in JP-A-63-250646, in the dye releasing method, silver development is carried out in advance at a low temperature so that silver development takes place preferentially prior to the dye releasing reaction, and silver development is carried out to some extent. Can also be developed by heating.

[0161]

【Example】

Example 1 <Preparation of Halogenated Emulsion> AgBrI particles having an average particle size of 0.14 μm (AgI composition 0.8 mol%) were added to an aqueous gelatin solution, and this emulsion was used as a core emulsion to prepare a silver nitrate emulsion and an aqueous potassium bromide solution. Was simultaneously added while controlling pAg to prepare a monodisperse cubic silver iodobromide emulsion A (average particle size 0.40 μm). In the process of grain formation, silver halide 1 is added when the grain size becomes 0.36 μm.
10 ⁻⁶ mol potassium iridium (IV) hexachloride per mol was added.

Using the same core emulsion, the addition time of the silver nitrate aqueous solution and the potassium bromide aqueous solution was extended to prepare a monodispersed cubic silver iodobromide emulsion B having an average grain size of 0.58 μm. The potassium iridium hexachloride has an average particle size of 0.
The above amount was added when it reached 54 μm.

After desalting according to a conventional method, pAg = 40 ° C.
The pH was adjusted to 6.5 and pH = 5.9. Then 3.5 mg (emulsion A) or 2.8 g per mol of silver halide
Sodium thiosulfate of (Emulsion B) was added, and the mixture was chemically ripened to an optimum point at 60 ° C., and the sensitizing dye and phenol formalin resin shown below were added at 0.6 per mol of silver halide.
g was added as a 3% methanol solution. After addition of the sensitizing dye, ripening was further carried out at 60 ° C. for 10 minutes, and then ST-1 (2-methyl-5-chloro-3-isothiazolone) was added as a stabilizer in an amount of 0.9 g per mol of silver halide to be chemically added. The sensitization was terminated to obtain three kinds of silver halide emulsions.

For the first infrared photosensitive layer For the second infrared photosensitive layer For the red photosensitive layer Emulsion B Emulsion A Emulsion A Emulsion A Sensitizing dye-1 Sensitizing dye-2 Sensitizing dye-3 Sensitizing dye Amount 10 mg / mol 8 mg / mol 10 mg / mol

[0165]

[Chemical 33]

<< Preparation of Photothermographic Material >> Thickness 100 μm
A positive type photothermographic material in which a layer having the following constitution is coated on the titanium dioxide-containing layer side of a paper support having polyethylene laminated on both sides thereof (the polyethylene layer on one side contains 10% by weight of titanium dioxide). 101 was created. here,
The addition amount of each material is shown as an amount per 1 m ^{2 of the} photothermographic material, and the photosensitive silver halide emulsion is shown in terms of silver.

First layer (first infrared-sensitive layer) First infrared-sensitive silver halide 0.08 g DIDP (diisodecyl phthalate) 0.33 g Dye-donor (2) 0.65 g Alkali-treated gelatin 0.23 g Phenylcarbamoylated gelatin 0.53 g Polyvinylpyrrolidone (PVP) 0.1 g Surfactant (SU-1) 0.09 g Surfactant (SU-2) 0.02 g Development inhibitor 0.006 g Second layer (first intermediate) Layer) Alkali-treated gelatin 0.27 g Phenylcarbamoylated gelatin 0.62 g PVP 0.13 g Reducing agent 0.40 g Surfactant (SU-1) 0.03 g Surfactant (SU-2) 0.008 g Zinc hydroxide 0 .3 g Hardener (1) 0.10 g Hardener (2) 0.08 g Third layer (red photosensitive layer) Red photosensitive silver halide 0.09 DIDP 0.37 g Dye-donor (1) 0.74 g Potassium bromide 0.0012 g Development inhibitor 0.006 g Alkali-treated gelatin 0.26 g Phenylcarbamoylated gelatin 0.61 g PVP 0.03 g Surfactant (SU-1) 0.12 g Surfactant (SU-2) 0.14 g.

Fourth layer (second intermediate layer) Alkali-treated gelatin 0.18 g Phenylcarbamoylated gelatin 0.42 g PVP 0.14 g Reducing agent 0.40 g Surfactant (SU-1) 0.03 g Surfactant (SU -2) 0.008 g Zinc hydroxide 0.35 g Hardener (1) 0.07 g Hardener (2) 0.02 g Fifth layer (second infrared photosensitive layer) Infrared photosensitive silver halide 04g DIDP 0.17g Dye-providing substance (3) 0.34g Development inhibitor 0.006g Alkali-treated gelatin 0.14g Phenylcarbamoylated gelatin 0.32g PVP 0.10g Surfactant (SU-1) 0.15g Surfactant Agent (SU-2) 0.033 g.

Sixth layer (lower layer of protective layer) Alkali-treated gelatin 0.18 g Phenylcarbamoylated gelatin 0.42 g Zinc hydroxide 0.35 g Reducing agent 0.40 g Matting agent (average particle size 5 μm) 0.002 g Surfactant ( SU-1) 0.002 g Surfactant (SU-2) 0.010 g Seventh layer (protective layer upper layer) Alkali-treated gelatin 0.16 g Phenylcarbamoylated gelatin 0.40 g PVP 0.06 g Surfactant (SU-1) ) 0.014g Surfactant (SU-2) 0.012g Hardener (1) 0.08g Hardener (2) 0.06g.

The hardeners (1) and (2) used for the second layer, the fourth layer and the seventh layer were added to the coating solution immediately before coating.

After coating, the photothermographic material was stored at 35 ° C. and a relative humidity of 30 to 60% for 3 days, and hardened to a desired degree of hardening.

The structural formulas of the additives used for preparing the photothermographic material are shown below.

[0173]

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[0174]

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Next, instead of the dye-donor material (2) of the first layer of Sample 101, 1 /
Sample 102 to which 3 moles of the dye-providing substance shown in Table 1 was added.
111 was created.

<Preparation of Dye Image Receiving Material> A paper support having a thickness of 200 μm and laminated on both sides with polyethylene (the polyethylene layer on one side contains 10% by weight of titanium dioxide) has the following structure on the titanium dioxide-containing layer side. Was applied to prepare a dye image receiving material. The addition amount of each material is shown as an amount per 1 m ² of the dye image receiving material.

First Layer Gelatin 1.0 g Surfactant (SU-1) 0.02 g Surfactant (SU-2) 0.01 g Dye mordant 2.8 g Liquid paraffin 0.2 g Benzylimino sodium diacetate 2.8 g Second layer Gelatin 0.4 g Surfactant (SU-1) 0.08 Surfactant (SU-2) 0.03 UV absorber-1 0.2 g UV absorber-2 0.1 g Diicidyl phthalate ( DIDP) 0.15 g Polyvinyl alcohol (PVP) 0.1 g Third layer Gelatin 0.5 g Polyvinyl alcohol 0.08 g Surfactant (SU-1) 0.09 g Hardener (1) 0.14 g.

The obtained roll-shaped dye image-receiving material has a temperature of 23 ° C.
It was stored for 3 days and cured to the desired dura degree. In addition,
The film surface pH of the image receiving material on the image receiving layer side was 10.1.

The additive used has the following structure:

[0180]

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<< Evaluation of Photothermographic Material >> Obtained Sample 1
Each of the photothermographic materials of Nos. 01 to 111 has 677 nm and 78
After exposing the entire amount of light corresponding to the maximum required light amount of the red photosensitive layer and the second infrared photosensitive layer using a 6 nm semiconductor laser, wedge exposure was performed using a 833 nm semiconductor laser. Here, the maximum required exposure is the exposure amount at which the transfer density of the image dye in the layer becomes minimum at a certain wavelength.

Then, the photothermographic material was immersed in water at 40 ° C. for 4 hours.
After dipping for 2 seconds, superimpose it on the image receiving material,
Heated for a second. After peeling off the image receiving material from the photosensitive material, the reflection density (PDA-65: manufactured by Konica Corporation) of the transferred image of the image receiving material was measured with blue, green and red light.

The exposure conditions are as follows.

Laser beam intensity on photosensitive material surface: mW (833 nm) Beam diameter: Main scanning direction 100 ± 10 nm: Sub-scanning direction 70 ± 10 nm From the obtained cyan wedge image, the reflection density was measured with red light, The values of Dmax and Dmin of each sample are shown in Table 1. The reflection density was measured with blue light and green light where the red density was 1.5. Table 1 also shows the obtained values (however, the density of fog is subtracted).

[0185]

[Table 1]

As is clear from Table 1, by incorporating the dye-providing material of the present invention into the photothermographic material, a cyan dye image having a low fog and a sufficient density can be obtained, and the color reproducibility is further improved. It turns out that it is also excellent.

[0187]

By incorporating the dye-providing material of the present invention into a photothermographic material, a cyan dye image having a low fog and a sufficient density can be obtained, and further, a color image having excellent color reproducibility can be obtained. A photothermographic material could be provided.

Claims (4)

[Claims] 1. A diffusion transfer type photothermographic material comprising a support, on which a hydrophilic binder, a photosensitive silver halide, and a dye-providing substance represented by the following general formula [I] are contained. Formula (I) _{A 1 - (J 1) a} - (X 1) b -Dye in _{1 set,} A ₁ undergoes a cleavage reaction at a high temperature in the presence of silver ions or a soluble silver complex, - (J _{1) a} - (X _{1) b} -Dye
Represents a 1,3-sulfur-nitrogen compound group that releases ₁ . J ₁ represents a divalent linking group. X ₁ is -CO-, -COO-,-
_{CONH -, - SO 2 -,} - SO 2 NH -, - SO 3 -,
-NHCO -, - represents a or a divalent linking group selected from -O- - NHSO _2. a and b each represent 0 or 1,
Dye ₁ represents a group represented by the following general formula [II]. Embedded image In the formula, R ₁₁ represents a branched or straight chain alkyl group having a substituent, R ₁₂ and R ₁₃ each represent an alkyl group, a cycloalkyl group or an aryl group, and R ₁₂ and R ₁₃ are bonded to each other to form a cyclic structure. May be formed. R ₁₄ represents a hydrogen atom, an alkyl group, an acylamino group or an alkoxy group.
One of Z ₁₁ and Z ₁₂ is a nitrogen atom, and the other is Represents R ₁₅ represents a hydrogen atom or a substituent, p is 0 to 4
When p is 2 or more, R ₁₄ may be the same or different. q represents an integer of 1 to 5, and when q is 2 or more, R ₁₅ may be the same or different. Either R ₁₁ or R ₁₅ is A ₁ −
It represents a group represented by _{- (J 1) a - (} X 1) b. 2. A diffusion transfer type photothermographic material comprising a support, on which a hydrophilic binder, a photosensitive silver halide and a dye-donor represented by the following general formula [III] are contained. Formula (III) _{A 2 - (J 2) c} - (X 2) d -Dye ₂ wherein, A ₂ undergoes a cleavage reaction at a high temperature in the presence of silver ions or a soluble silver complex, - (J _{2) c} - (X _{2) d} -Dye
Represents a 1,3-sulfur-nitrogen compound group which releases ₂ . J ₂ represents a divalent linking group. X ₂ is -CO-, -COO-,-
_{CONH -, - SO 2 -,} - SO 2 NH -, - SO 3 -,
-NHCO -, - represents a or a divalent linking group selected from -O- - NHSO _2. c and d each represent 0 or 1,
Dye ₂ represents a group represented by the following general formula [IV]. Embedded image In the formula, R ₂₁ represents a branched or straight chain alkyl group having a substituent, R ₂₂ and R ₂₃ each represent an alkyl group, a cycloalkyl group or an aryl group, and R ₂₂ and R ₂₃ are bonded to each other to form a cyclic structure. May be formed. R ₂₄ is a hydrogen atom,
It represents an alkyl group, an acylamino group or an alkoxy group.
One of Z ₂₁ and Z ₂₂ is a nitrogen atom, and the other is Represents R ₂₅ represents a hydrogen atom or a substituent, and s is 0 to 4
When R is ₂₄ or more, R ₂₄ may be the same or different. t represents an integer of 1 to 5, and when t is 2 or more, R ₂₅ may be the same or different. Either R ₂₁ or R ₂₅ is A ₂ −
It represents a group represented by _{- (J 2) c - (} X 2) d. 3. The diffusion transfer type photothermographic material according to claim 1, wherein A ₁ in the general formula [I] is a thiazolidinyl residue represented by the following general formula [V]. Embedded image In the formula, R _A1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group, and R _B1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group. or _{- (J 1) a - (} X 1) b -
It represents a group represented by Dye ₁ . R _C1 , R _D1 , R _E1 and R
_F1 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a carboxyl group, an acyl group, a sulfonyl group or a sulfo group. 4. The diffusion transfer type photothermographic material according to claim 2, wherein A ₂ in the general formula [III] is a thiazolidinyl residue represented by the following general formula [VI]. [Chemical 6] In the formula, R _A2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group, and R _B2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group. or _{- (J 2) c - (} X 2) d -
It represents a group represented by Dye ₂ . R _C2 , R _D2 , R _E2 and R
_F2 represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a carboxyl group, an acyl group, a sulfonyl group or a sulfo group.