JPH1165056A - Photosensitive member for heat developing, processing member and photograph member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a good and sharp black-and-white picture having higher maximum photographic density and lower minimum photographic density obtainable in a short time, by causing at least one layer on a processing member to contain at least one kind of specific compound. SOLUTION: At least one layer on a processing member contains a compound, isoion 1,2,4-thiazolium-3-thiolate. For this compound, a compound expressed by an expression is preferable. In the expression, R<1> denotes a hydroxyl radical, an alkyl radical or the like having 1 to 16 (preferably 4 or less) carbon atoms substituted or non-substituted. R<2> denotes a hydrogen atom, an alkyl radical or the like having 1 to 16 (preferably 8 or less) carbon atoms substituted or non-substituted. R<3> denotes an alkyl radical, an alkenyl radical or the like having 1 to 16 (preferably 8 or less) carbon atoms substituted or non-substituted. The total number of carbon atoms included in the R<1> to R<3> is preferably 2 to 32, and especially preferably 4 to 8. Among others, a compound is especially preferable in which R<2> or R<3> is made up of two or more carbon atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive member, a processing member and a photographic member using a photothermographic material, and more particularly, to a black-and-white image having a high maximum density, a low minimum density and good image sharpness for a short time. And a photothermographic member, a processing member, and a photographic member.

[0002]

2. Description of the Related Art A photographic method using silver halide is superior to other photographic methods such as electrophotography and diazo photography in photographic characteristics such as sensitivity, gradation control and resolution, and thus has been the most widely used. Has been used for At present, image information has largely changed from black-and-white images to color images due to the large amount of information and ease of expression.
Black and white images are favorably used in medical fields.
Further, in the printing field, plate making materials for color images are also used as black and white images for each printing ink, and there is still a great demand mainly for industrial applications.

In recent years, the image forming method of a photosensitive material using silver halide has been changed from the conventional wet processing to an instant system incorporating a developing solution, and a dry thermal developing processing by heating or the like. A system that can obtain images has been developed from the viewpoint of environmental protection. Such photothermographic materials are described in “Basics of Photographic Engineering (Non-Silver Photography), Corona”, pages 242 to 25.
5 pages, JP-B-43-4921, JP-B-43-4924
No. etc. For example, as a product, in the case of black-and-white systems, 3M company's dry silver sensitive material has been released.

[0004] Like dry silver, silver halide,
In a mono-sheet photosensitive material comprising an organic silver salt and a reducing agent, unused silver halide and organic silver salt remain in the heat-developed image. Therefore, when exposed to intense light or stored for a long period of time, the remaining silver halide or organic silver salt is printed out and the white background is colored, and the contrast is lost. Further, since the reducing agent and the silver halide coexist in the same light-sensitive material, there is a disadvantage that the preservability of the light-sensitive material before processing is poor. A method of obtaining a black color image by dry processing is described in Research Disclosure Magazine (hereinafter abbreviated as RD), September, 1978, pp. 49-51 (RD17326). Since it is an unfixed type containing a silver salt in an image, it has the same drawbacks as described above.

In order to improve these drawbacks, a movable (diffusible) dye is formed or released imagewise by heating, and then the movable dye is converted to a dye-receiving substance by using various transfer solvents. For example, a method for forming a black-and-white image having improved image storability by transferring to a dye-fixing material containing a mordant, a heat-resistant organic polymer, or the like is disclosed in Japanese Patent Publication No. 3-7861.
No. 7, 3-45820. However, since these methods are methods of transferring after thermal development, the number of steps is large and the processing time is long.

Further, JP-A-3-260645 discloses that
Regarding a thermal development transfer type black-and-white image forming method using a coupling reaction, a method of transferring after development and a method of simultaneously performing development and transfer are disclosed. However, this method also requires a high temperature and a long time for processing because it does not have an effective development transfer accelerator.

Japanese Patent Application Laid-Open No. 62-129848 discloses that a black and white image can be formed with a transferred dye image by performing thermal development using a small amount of water. However, in order to obtain an image at a transmission density of 2 or more, preferably 3 or more, required for many black-and-white images in a short time by the dye transfer method, the thickness of the photosensitive material, particularly the amount of the binder, must be reduced as much as possible. It is necessary to increase the use amount of the donor compound. For this reason, there arises a problem that the film quality is reduced and the manufacturing cost is increased. In addition, there is a problem that applications are limited due to a decrease in sharpness due to transfer. Further, it is difficult to synthesize a black dye-donating compound, and it is also difficult to obtain a neutral gray color image by mixing yellow, magenta, and cyan dye-donating compounds.

Further, a method of forming a silver image by thermal development silver salt diffusion transfer using a silver halide photosensitive material is described in JP-A-62-283332 and JP-A-63-19805.
No. 0, No. 60-194448 and the like,
These methods also use a transferred silver image, and it is difficult to obtain an image having a transmission density of 2 or more, preferably 3 or more, and high sharpness in a short time, and an improvement has been required.

JP-A-8-179458 and JP-A-8-339
No. 065 and the like disclose an image forming method utilizing silver remaining on a photosensitive material by a heat-developed silver salt diffusion transfer method, and an image having high density and high sharpness can be obtained by this method. In order to apply the method to a photographic material for plate making, halftone dots were insufficiently cut, and a higher maximum density and a lower minimum density were required. When a washing step was not provided after heat development, the image storability after processing was insufficient.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has as its object the purpose of providing a high density, a low density, and an image with good sharpness. An object of the present invention is to provide a heat-developable photosensitive member, a processing member, and a photographic member capable of obtaining a black-and-white image in a short time. Another object of the present invention is to provide a heat-developable photosensitive member, a processing member, and a photographic member having good image storability even without a washing step.

[0011]

The object of the present invention is to provide at least one photosensitive silver halide emulsion layer on a support,
A photothermographic member containing a reducing agent (developing agent) in the emulsion layer or other hydrophilic colloid layer, and at least one layer containing physical development nuclei on a support, wherein the layer or other hydrophilic colloid layer A processing member containing a silver halide solvent (fixing agent) in the colloid layer is superposed after imagewise exposure or simultaneously with imagewise exposure, and thermally developed in the presence of water, whereby the photothermographic member and / or Alternatively, in forming a silver image on the processing member, it is achieved by including at least one mesoion 1,2,4-thiazolium-3-thiolate compound in at least one layer on the processing member or the photosensitive member. Was found.

Further, by incorporating a compound having at least one acetylene group into at least one of the processing member and the photosensitive member, at least one of the compounds has an even higher maximum density and a lower minimum density. Black and white images can be obtained.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive member referred to in the present invention is also called a silver halide photographic material or a silver halide photographic sheet. On the other hand, the processing member referred to in the present invention is also referred to as a processing material or a processing sheet. Further, the photosensitive member and the processing member are collectively referred to as a photographic member. As the meso-ion 1,2,4-thiazolium-3-thiolate compound used in the present invention, those represented by the following general formula (I) are preferable.

[0014]

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In the formula (I), R ¹ is a hydroxyl group or a substituted or unsubstituted alkyl group having ¹ to 16 (preferably 8 or less, more preferably 4 or less) carbon atoms (for example, methyl group, An ethyl group, a lauryl group, a 2-methoxyethyl group, an ethoxycarbonylmethyl group, etc., a substituted or unsubstituted alkenyl group having 1 to 16 (preferably 8 or less, more preferably 4 or less) carbon atoms (for example, Represents an allyl group, a 2-buten-1-yl group or the like, substituted or unsubstituted 1 to 16 (preferably 8
Hereinafter, a cycloalkyl group having 4 or less carbon atoms (preferably, for example, a cyclopentyl group or a cyclohexyl group) or a substituted or unsubstituted aryl having 1 to 16 (preferably 8 or less) carbon atoms. Groups (eg, phenyl, 4-methoxyphenyl,
3,4-dichlorophenyl group, 4-sulfamoylphenyl group, 4-lauroylamidophenyl group, etc., having 1 to 16 (preferably 8 or less, more preferably 4 or less) substituted or unsubstituted carbon atoms Heterocycle (for example, 2-pyridyl group, 1-octylpiperidine-4-
Yl group).

In the formula, R ² is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 16 (preferably 8 or less) carbon atoms (eg, methyl, isobutyl, tert.
A butyl group, a methylthiomethyl group, etc.), a substituted or unsubstituted cycloalkyl group having 1 to 16 (preferably 8 or less) carbon atoms (for example, a cyclopentyl group,
Cyclohexyl group), substituted or unsubstituted 1-1
Aryl groups having 6 (preferably 8 or less) carbon atoms (eg, phenyl group, 4-methoxyphenyl group, etc.), substituted or unsubstituted 1 to 16 (preferably 8
The following represents a heterocyclic ring having a carbon atom (for example, a 2-pyridyl group or the like).

In the formula, R ³ is a substituted or unsubstituted 1-16
(Preferably 8 or less) alkyl groups (e.g., methyl group, ethyl group, octyl group, octadecyl group, methoxyethyl group, etc.), and 1 to 16 (preferably 8 or less) substituted or unsubstituted alkyl groups. An alkenyl group having a carbon atom (such as an allyl group or 2-buten-1-yl group) or a substituted or unsubstituted cycloalkyl group having 1 to 16 (preferably 8 or less) carbon atoms (such as a cyclopentyl group or a cyclohexyl group); A substituted or unsubstituted aryl group having 1 to 16 (preferably 8 or less) carbon atoms (phenyl group, 4-ethoxycarbonyl group, 3-sulfamoylphenyl group, 4-methoxyphenyl group, etc.) ), Substituted or unsubstituted heterocycles having 1 to 16 (preferably 8 or less) carbon atoms (eg, 4-pyridyl It represents a group, etc.). Further, R ¹ and R ² and R ² and R ³ can be respectively bonded to form a 5- to 7-membered carbocyclic or heterocyclic ring.

The total number of carbon atoms contained in R ¹ , R ² and R ³ is preferably from 2 to 32, more preferably from 4 to 8. Among them, compounds in which R ² or R ³ comprises two or more carbon atoms are particularly preferred.

In the following, the mesoions 1, 2, 2,
Specific examples of the 4-4-thiazolium-3-thiolate compound will be given, but the scope of the present invention is not limited to these examples. Incidentally, R ^{1 to} R ³ in the table are each represented by the general formula (I)
Represents the substituent.

[0020]

[Table 1]

[0021]

[Table 2]

Of the exemplified compounds, I-2, I-3 and I-
4, I-5, I-8, I-12, I-13, I-14,
I-16, I-22 and I-26 are particularly preferred.

The use of the compound (I) of the present invention as a silver halide solvent for forming grains of a silver halide emulsion is described below.
The use of a fixing agent or a silver halide solvent in a photographic processing agent is disclosed in JP-A-60-163242.
01659, JP-A-2-44355, JP-A-62-2
JP-A-57-15161 discloses that an effect obtained by adding a silver halide solvent to a light-sensitive material and utilizing the action of a silver halide solvent can be obtained.
No. 0842, JP-A-60-21044, JP-A-62-204
217237, JP-A-60-87322, JP-A-6
For example, it is known in Japanese Patent Application No. 0-144737. However, the fact that the compound (I) of the present invention was used in the photographic member for heat development of the constitution of the present invention, and that the compound (I) exerts effects other than the silver halide solvent in the constitution,
It was not known at all.

The above-mentioned meso-ion 1,1 used in the present invention
The synthesis of 2,4-thiazolium-3-thiolate compounds generally involves (i) anhydro-acylation of 1,4-disubstituted thiosemicarbazide, (ii) 4-acyl-1,4
-Heating of di-substituted thiosemicarbazide, (iii) reaction of N-aminoamidine with thiophosgene, (iv) reaction of N-aminoamidine or N-thioacylhydrazine with isothiocyanic acid, (v) N-aminoamidine or N-thio. It can be synthesized by the reaction of acylhydrazine with carbon disulfide-dicyclohexylcarbodiimide, (vi) the reaction of mesoion 1,3,4-thiadiazole or the corresponding methiodide with a primary amine, and the like.

More specifically, the above-mentioned compounds used in the present invention can be synthesized by the methods described in the following literatures or the literatures cited in these literatures. W. B
akerand WD Ollis, Chem. Ind. (London), 910 (195
5), M. Ohta and H. Kato, in "Nonbenzenoid Aromatic
s "(JPSnyder, ed.), KT Potts, SK Roy, and
DP Jones, J. Org.Chem. 32, 2245 (1967), GF Du
ffin, JD Kendall, and HRJ Waddington, J. Ch
em. Soc., 3799 (1959), RL Hinmann and D. Fulton,
J. Amer. Chem. Soc. 80, 1895 (1958), WD Ollis and
CA Ramsden, Chem. Commun., 1222 (1971), WDO
llis and CA Ramsden, J. Chem. Soc., Perkin. Tra
ns.I, 633 (1974), R. Grayshey, M. Baumann, and R.
Hamprecht, Tetrahedron Lett., 2939 (1972).

The mesoions 1, 2, 4 used in the present invention
The -thiazolium-3-thiolate compound may be used in combination of two or more. Mesoion 1 of the present invention
The 2,4-thiazolium-3-thiolate compound is added to any of the silver halide emulsion layer, undercoat layer, protective layer, intermediate layer, filter layer and antihalation layer of the silver halide photographic material (photosensitive member). However, an undercoat layer, an intermediate layer, and an antihalation layer are particularly preferable. Further, the compound is an undercoat layer of a treatment sheet (treatment member),
It may be added to any layer such as a protective layer, an intermediate layer and a filter layer.

The mesoions 1, 2, 4 used in the present invention
In order to add the -thiazolium-3-thiolate compound to these layers, the compound may be used as it is in a coating solution for forming the layers, or a solvent that does not adversely affect the photographic material, for example, water, methanol, It can be added by dissolving it in an appropriate concentration in alcohols such as ethanol. Further, the compound may be dissolved in a high-boiling point solvent and / or a low-boiling point organic solvent and emulsified and dispersed in an aqueous solution. Also, JP-A-51-39853, 51
-59942, 54-32552, U.S. Pat.
It may be added to the polymer latex by the method described in 199,363 or the like and added. Mesoion 1 of the present invention
The 2,4-thiazolium-3-thiolate compound may be added at any time during the production process, but is generally preferably immediately before coating. The preferred addition amount of the mesoionic 1,2,4-thiazolium-3-thiolate compound of the present invention is from 10 ^-7 to 1 mol, more preferably from 10 ^-5 to 10 ^-2 mol, particularly preferably from 10 ^-4 to 1 mol per m ^2. 2x
10 ^-3 mol.

The compound having an acetylene group used in the present invention is preferably a compound represented by the following general formula (II).

[0029]

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In the formula (II), L is a mere bond or a divalent
Represents a linking group. n represents a positive number of 1 to 4. R when n = 1¹¹
Represents a hydrogen atom, a carboxyl group, an alkyl group,
A kill group, an alkenyl group, an alkynyl group, an aralkyl group,
Represents an aryl group or a heterocyclic group. n = 2, 3 or 4
When R¹¹Represents a divalent, trivalent or tetravalent residue. R ¹²
Represents a hydrogen atom, a carboxyl group, an alkyl group,
A kill group, an alkenyl group, an alkynyl group, an aralkyl group,
Aryloxycarbonyl group, alkoxycarbonyl
Represents a group, an aryl group, a heterocyclic group or a carbamoyl group.
When n = 2, 3 or 4, L and R¹²Each pair of
The alignment may be the same or different. However, L is simple
When n = 1, R¹¹And R¹²Are both hydrogen
Except when it is an atom.

Next, the compound of the formula (II) will be described in detail. The alkyl group of R ¹¹ and R ¹² may be linear or branched, and examples of the alkyl group include a butyl group, an isobutyl group, a hexyl group, a heptyl group, an octyl group, a dodecyl group, and a pentadecyl group. Examples of the substituent of the substituted alkyl group include an alkoxy group (for example, a methoxy group), an aryloxy group, an acyloxy group, a heterocyclic oxy group, a hydroxy group, a carboxyl group or a salt thereof, a formyl group, an acyl group, a substituted or Unsubstituted carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, mercapto group, alkylthio group, arylthio group, sulfino group or a salt thereof, sulfo group or a salt thereof, alkylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, substituted or Unsubstituted sulfamoyl group, alkoxysul Honyl group, aryloxysulfonyl group, acylamino group, substituted or unsubstituted ureido group, alkoxycarbonylamino group, acylamino group, substituted or unsubstituted ureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, nitro group, nitroso Group, cyano group, halogen atom, alkylsulfonylamino group, arylsulfonylamino group, substituted or unsubstituted amino group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, heterocyclic group, alkynyl group (for example, ethynyl group) And so on.
These substituents may be two or more.

Examples of the cycloalkyl group of R ¹¹ and R ¹² include a cyclopentyl group, a cyclohexyl group and a decahydronaphthyl group. Examples of the alkenyl group include a alkynyl group such as a propenyl group, an isopropenyl group and a styryl group. Examples include an ethynyl group and a phenylethynyl group, and examples of the aralkyl group include a benzyl group and a phenethyl group. These groups may have the substituents described for the alkyl group. Further, there may be two or more substituents.

Examples of the aryl group of R ¹¹ and R ¹² include a phenyl group and a naphthyl group. Examples of the substituent of the substituted aryl group include an alkyl group (eg, a methyl group and a dodecyl group) and an alkenyl group. , Aryl, cycloalkyl, aralkyl, alkynyl, cyano, nitro, nitroso, substituted or unsubstituted amino, acylamino, alkylsulfonylamino, arylsulfonylamino, substituted or unsubstituted sulfo Famoylamine group, hydroxyl group, alkoxy group, aryloxy group,
An alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxy group, an acyloxy group, a heterocyclic (5 to 6
Membered ring, among which nitrogen-containing heterocyclic ring is preferred), alkoxysulfonyl group, aryloxysulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkylthio group, arylthio group, mercapto group, formyl group, acyl group, alkylsulfonyl group, aryl Sulfonyl group, carboxylic acid group or salt thereof, sulfonic acid group or salt thereof, sulfino group or salt thereof, halogen atom (fluorine, bromine, chlorine, iodine), substituted or unsubstituted ureido group, carbamoyl group, sulfamoyl group, etc. is there. These substituents may be further substituted. Further, there may be two or more substituents as exemplified above.

The heterocyclic group represented by R ¹¹ and R ¹² is a 5-membered or 6-membered
Members, such as furyl, thienyl, benzothienyl, pyridyl, and quinolyl.
These heterocycles may have the same substituent as the above-mentioned substituted aryl group.

Examples of the aryloxycarbonyl group for R ¹² include a phenoxycarbonyl group and the like, and examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

The carbamoyl group for R ¹² is --CONH
_In addition to ₂ , carbamoyl groups substituted with the above-mentioned substituted or unsubstituted alkyl groups, aryl groups, and heterocyclic groups can be mentioned. When n is 2, 3 or 4, R ¹¹ represents a divalent, trivalent or tetravalent residue, and examples thereof include the aforementioned R ¹¹
Or a group in which one, two or three hydrogen atoms have been removed from the monovalent group of R ¹² . R when n = 2
¹¹ also includes -NH-.

L represents a simple bond or a divalent linking group (preferably a -O-CO- group or a -CONH- group). n is preferably 1 or 2. Among these, R ¹¹ and R
Compounds in which one of ¹² is a hydrogen atom and the other is a group other than a hydrogen atom are preferred. More preferably, R ¹¹ , R
^It is preferred that one of ¹² is a hydrogen atom and the other is a phenyl group or a substituted phenyl group. Particularly, a compound represented by the following general formula (II ') is preferable.

[0038]

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In the formula (II ′), m is 1 or 2. When m = 1, R ¹³ is an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group having 1 to 20 carbon atoms,
Represents an aralkyl group, an aryl group or a heterocyclic group, m = 2
Represents an alkylene group, an arylene group or a cycloalkylene group. Further, these substituents may be further substituted with another substituent.

[0040] below R ¹³ will be described in detail. When R ¹³ is an alkyl group, it may be linear or branched, and examples of the alkyl group include propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, Heptyl group, isoheptyl group, octyl group, nonyl group, decyl group, dodecyl group and pentadecyl group. Examples of the substituent of the substituted alkyl group include a cycloalkyl group, an alkenyl group, an alkynyl group,
Aryl group, aralkyl group, heterocyclic group, halogen atom (fluorine, bromine, chlorine, iodine), hydroxyl group, alkoxy group, aryloxy group, acyloxy group, heterocyclic oxy group, carboxyl group or salt thereof, formyl group, acyl group A substituted or unsubstituted carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a mercapto group, an alkylthio group, an arylthio group,
Sulfino group or salt thereof, sulfo group or salt thereof, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, substituted or unsubstituted sulfamoyl group, alkoxysulfonyl group, aryloxysulfonyl group, substituted or unsubstituted Amino group, acylamino group, substituted or unsubstituted ureido group, alkoxycarbonylamino group, aryloxycarbonylalkylsulfonylamino group, arylsulfonylamino group, substituted or unsubstituted sulfamoylamino group, nitro group, nitroso group, etc. is there.
Two or more of these groups may be present, and the substituents thereof may be further substituted.

Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group and a decahydronaphthyl group, and examples of the alkenyl group include a propenyl group, an isopropenyl group and a styryl group. These groups may have the substituents described for the alkyl group. Further, there may be two or more substituents.

Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the substituent of the substituted aryl group include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, A heterocyclic group (5 to 6-membered ring, among which a nitrogen-containing heterocyclic ring is preferable),
A halogen atom (fluorine, bromine, chlorine, iodine), a hydroxyl group, an alkoxy group, an aryloxy group, an acyloxy group, a heterocyclic oxy group, a carboxyl group or a salt thereof,
Formyl group, acyl group, substituted or unsubstituted carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, mercapto group, alkylthio group,
Arylthio group, sulfino group or salt thereof, arylsulfonyl group, substituted or unsubstituted sulfamoyl group, alkoxysulfonyl group, aryloxysulfonyl group, substituted or unsubstituted amino group, acylamino group, substituted or unsubstituted ureido group, alkoxy Carbonylamino group, aryloxycarbonylamino group,
Alkylsulfonylamino group, arylsulfonylamino group, substituted or unsubstituted sulfamoylamino group,
A nitro group and a nitroso group. These substituents may be further substituted. Further, there may be two or more substituents as exemplified above.

Examples of the aralkyl group include a benzyl group and a phenethyl group. These substituents may have one or more substituents described for the alkyl group or the aryl group, and the substituents may be further substituted.

The heterocyclic group is preferably a 5- or 6-membered heterocyclic group. Examples thereof include a furyl group, a thienyl group, a benzothienyl group, a pyridyl group and a quinoline group. These heterocyclic groups may have the same substituent as the above-mentioned substituted aryl group. Examples of the alkylene group include a methylene group, an ethylene group, a trimethylene group, and a propylene group, and examples of the arylene group include (o-, m-, p-).
Examples thereof include a phenylene group and a naphthylene group (e.g., 1,4-), and examples of the cycloalkylene group include a cycloalkylene group. The divalent residue may have one or more substituents described for the alkyl group and the aryl group, and the substituent may be further substituted.

Of these, compounds in which R ¹³ is an alkyl group having 3 or more carbon atoms or a cycloalkyl group are preferred. More preferred are compounds in which R ¹³ is an alkyl group having 3 to 10 carbon atoms or a cycloalkyl group. Further, m is particularly preferably 1.

Hereinafter, specific examples of the compound of the general formula (II) in the present invention will be shown.

[0047]

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[0048]

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The acetylene compound of the general formula (II) of the present invention can be easily obtained from a condensation reaction between 4-ethynylaniline and an acid chloride of a carboxylic acid as shown below.

[0050]

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The starting 4-ethynylaniline is HELV
It is synthesized by the method described in ETICA CHIMICA ACTA 54: 2066 (1971).

The compounds having an acetylene group used in the present invention may be used in combination of two or more kinds. The compound having an acetylene group of the present invention can be added to any of the silver halide emulsion layer, undercoat layer, protective layer, intermediate layer, filter layer and antihalation layer of a silver halide photographic material (photosensitive member). Although good, an undercoat layer, an intermediate layer, and an antihalation layer are particularly preferable. The compound having an acetylene group of the present invention may be used as an undercoat layer, a protective layer, an intermediate layer, a filter layer, etc. of a treated sheet (treated member).
It may be added to any layer.

In order to add the compound having an acetylene group used in the present invention to these layers, the compound may be added to the coating solution for forming the layers as it is or in a solvent which does not adversely affect the photographic material. For example, it can be dissolved in an appropriate concentration in water, alcohols such as methanol and ethanol, and the like and added. Further, the compound may be dissolved in a high-boiling point solvent and / or a low-boiling point organic solvent and emulsified and dispersed in an aqueous solution. Also, Japanese Patent Application Laid-Open No.
No. 9853, No. 51-59942, No. 54-3255
No. 2, U.S. Pat. No. 4,199,363, etc., may be incorporated into the polymer latex and added. The compound of the present invention having an acetylene group may be added at any time during the production process. The preferable addition amount of the compound having an acetylene group of the present invention is 10 per 1 m ^2.
-5 to 1 mol, more preferably 10 ^-4 to 10 ^-2 mol.

In the present invention, as the base and the base precursor, known compounds used in the development processing of the photothermographic material can be used. Examples of the base precursor include a salt of an organic acid and a base that are decarboxylated by heat, a compound that releases an amine by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement, and the like. Specific examples thereof are described in US Pat. Nos. 4,514,493 and 4,657,843.
No. 8 and Known Technique No. 5 (March 22, 1991, issued by Aztec Co., Ltd.), pp. 55-86. Also, EP 210,660, US Pat.
A combination of a basic metal compound which is hardly soluble in water and a compound capable of forming a complex with a metal ion constituting the basic metal compound (referred to as a complex-forming compound) as described in US Pat. When used, it is preferred that the basic metal compound which is hardly soluble in water is added to the photosensitive material and the complex forming compound is added to the processing layer of the processed image receiving member. The amount of the base or base precursor used is 0.1 to 20 g.
/ M ² , preferably 1 to 10 g / m ² .

In the present invention, it is preferable that, after dampening water is applied to the photothermographic member, the photothermographic member is superposed on a processing image receiving member provided with a processing layer, and is heated and developed. In particular, it is effective when a combination of the above-mentioned basic metal compound which is hardly soluble in water and a complex-forming compound is used as the base precursor.

As the binder for the treatment layer, a hydrophilic binder is preferably used. Examples thereof include the above-mentioned Research Disclosure and JP-A-64-13546.
Nos. (71) to (75). Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan and polyvinyl alcohol, Synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymer are exemplified. Also, U.S. Pat. No. 4,960,681, JP-A-62-2452.
No. 60 etc., ie, -COO
A homopolymer of a vinyl monomer having M or —SO ₃ M (M is a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers or other vinyl monomers (eg, sodium methacrylate, ammonium methacrylate, Sumitomo Chemical (Sumikagel L-5H manufactured by Co., Ltd.)
Is also used. These binders can be used in combination of two or more kinds. In particular, a combination of gelatin and the above binder is preferable.The gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin in which the content of calcium and the like is reduced according to various purposes. Is also preferred.
The amount of the binder is preferably 20 g or less per 1 m ² , and particularly preferably 10 g or less. It is useful to provide a protective layer on the processed image receiving member.

The photothermographic member containing silver halide preferably used in the present invention is described in JP-A-8-22.
No. 0686, a black-and-white silver image can be obtained, a color image can be obtained by coupling as described in the above-mentioned known examples, and an image-emitting type diffusible dye can be obtained. . When a black and white silver image is obtained, a silver halide having a silver chloride content of 80 mol% or more is used as the silver halide.
The processing layer preferably contains a physical development nucleus and a silver halide solvent.

The physical development nucleus is for reducing the soluble silver salt diffused from the light-sensitive material to convert it into physically developed silver and fixing it to the processing layer. Physical development nuclei include zinc, mercury,
Heavy metals such as lead, cadmium, iron, chromium, nickel, tin, cobalt, copper, ruthenium, or noble metals such as palladium, platinum, silver, gold, or sulfur thereof;
All known physical development nuclei such as colloidal particles of chalcogen compounds such as selenium and tellurium can be used. These physical development nuclei substances reduce the corresponding metal ions with a reducing agent such as ascorbic acid, sodium borohydride, hydroquinone, etc. to form a metal colloid dispersion,
Alternatively, it is obtained by mixing a soluble sulfide, selenide or telluride solution to form a colloidal dispersion of water-insoluble metal sulfide, metal selenide or metal telluride. These dispersions are preferably formed in a hydrophilic binder such as gelatin. A method for preparing colloidal silver particles is described in U.S. Pat. No. 2,688,601. If necessary, a desalting method for removing an excessive salt known in the method for preparing a silver halide emulsion may be performed. The size of these physical development nuclei is 2 to
Those having a particle size of 200 nm are preferably used. These physical development nuclei are usually added to the processing layer in an amount of 10 ^{−3 to} 100 mg /
m ² , preferably 10 ⁻² to 10 mg / m ² .

The physical development nucleus can be separately prepared and added to the coating solution. However, in the coating solution containing a hydrophilic binder, for example, silver nitrate and sodium sulfide, or
It may be prepared by reacting gold chloride with a reducing agent or the like. Silver, silver sulfide, palladium sulfide and the like are preferably used as physical development nuclei. When using physically developed silver transferred to the complexing agent sheet as an image, palladium sulfide, silver sulfide, etc.
It is preferably used because min is short and Dmax is high.

Known silver halide solvents can be used. For example, sodium thiosulfate, thiosulfates such as ammonium thiosulfate, sulfites such as sodium sulfite and sodium bisulfite, potassium thiocyanate,
Thiocyanates such as ammonium thiocyanate, 1,8-di-3,6-dithiaoctane, 2,2'-thiodiethanol, 6,9- described in JP-B-47-11386.
Dioxa-3,12-dithiatetradecane-1,14-
Thioether compounds such as diols;
Compounds having a 5- or 6-membered imide ring such as uracil and hydantoin described in JP-A No. 9458/1979.
The compound of the general formula (I) described in No. 4319 can be used. The compounds described in JP-A-8-69097 which can fix and stabilize silver halide can also be used as a silver halide solvent.

The above-mentioned silver halide solvents may be used in combination. Among the above compounds, compounds having a 5- or 6-membered imide ring, such as sulfites, uracil and hydantoin, are particularly preferred. In particular, uracil or hydantoin is preferably added as a potassium salt since the reduction in gloss during storage of the processed image receiving member can be improved.

The total silver halide solvent content in the processing layer is 0.01 to 50 mmol / m ² , preferably
0.1 to 30 mmol / m ² . More preferably, 1
２０20 mmol / m ² . The molar ratio is 1/20 to 20 times, preferably 1/10, relative to the amount of silver applied to the photosensitive member.
It is 10 times, more preferably 1/3 to 3 times. The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide, methylpropylglycol, or an alkali or acidic aqueous solution, or may be added to a coating solution after dispersing solid fine particles.

Further, by incorporating a polymer having a repeating unit of vinylimidazole and / or vinylpyrrolidone as a constituent component described in JP-A-8-179458 in the processing layer, the density of the silver image in the photosensitive member can be increased. It is possible.

Hereinafter, a photothermographic member mainly used for forming a color image, particularly for photographing will be described. The silver halide that can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide.

The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases may be used, and silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed.
As described in JP-A-743-743 and JP-A-4-223463, a method of mixing monodispersed emulsions and adjusting gradation is preferably used. Particle size is 0.1-2 μm, especially 0.2-1.5
μm is preferred. The crystal habit of silver halide grains is cubic, 8
Those having regular crystals such as tetrahedron, tetrahedron, those having irregular crystal system such as spherical, high aspect ratio plate-like, those having crystal defects such as twin plane, or those thereof Any of a composite system and other types may be used.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,
029 (1978), No. 17, 643 (1978)
No. 18,716 (197)
Nov. 1997), p. 648, ibid. No. 307, 105 (19
Nov. 89, pp. 863-865, JP-A-62-253.
No. 159, 64-13546, JP-A-2-2365
No. 46, No. 3-110555 and "Physics and Chemistry of Photography" by Grafkid, published by Paul Monte (P. Glafkide)
s, ChemieetPhisiquePhotographique, PaulMontel, 196
7) Duffin's "Photographic Emulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emulsion Chemistry,
FocalPress, 1966), "Production and Coating of Photographic Emulsion", by Zerikman et al., Focal Press (VLZelikman et a).
l., Making and Coating Photographic Emalusion, Foc
al Press 1964) and the like, any of which can be used.

In the process of preparing a photosensitive silver halide emulsion, it is preferable to carry out so-called desalting for removing excess salts. As a means for this, a Nudel washing method performed by gelling gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate), anionic surfactants, anionic polymers (eg, polystyrenesulfonic acid) Sodium) or a precipitation method using a gelatin derivative (for example, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.). The sedimentation method is preferably used.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium for various purposes. These compounds may be used alone or in combination of two or more. The amount of addition depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide. When it is contained, it may be uniformly contained in the particles, or may be localized inside or on the surface of the particles. Specifically, JP-A-2-236542, JP-A-1-116637, and JP-A-5-116637.
Emulsions described in 181246 and the like are preferably used.

In the step of forming the grains of the photosensitive silver halide emulsion, as a silver halide solvent, a rhodan salt, ammonia, a 4-substituted thiourea compound, an organic thioether derivative described in JP-B-47-11386, or JP-A-53-14.
Sulfur-containing compounds described in No. 4319 can be used.

Other conditions are described in the above-mentioned "Physics and chemistry of photography" by Grafkid, published by Paul Monte (P. Glaf).
kides, Chemie et Phisique Photographique, Paul Mon
tel, 1967), Duffin, "Photographic Emulsion Chemistry", Focal Press (GFDuffin, Photographic Emulsion Chemis)
try, FocalPress, 1966), "Production and coating of photographic emulsions" by Zerikman et al., Focal Press (VLZelikman et a).
l., Making and CoatingPhotographicEmulsion, FocalPr
ess, 1964). That is, any of an acidic method, a neutral method, and an ammonia method may be used, and a method of reacting a soluble silver salt and a soluble halide may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. In order to obtain a monodisperse emulsion, a simultaneous mixing method is preferably used. An inverse mixing method in which grains are formed in the presence of excess silver ions can also be used. As one type of the double jet method, a so-called controlled double jet method in which pAg in a liquid phase in which silver halide is formed is kept constant can be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition speed of the silver salt and the halogen salt to be added may be increased (JP-A-55-142329, JP-A-5-142329).
No. 5-158124, U.S. Pat. No. 3,650,757). Further, the stirring method of the reaction solution may be any known stirring method. The temperature and pH of the reaction solution during the formation of silver halide grains may be set in any manner depending on the purpose. The preferred pH range is 2.2-7.0, more preferably 2.5-6.0.

The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion of the present invention, a sulfur sensitization method, a selenium sensitization method, a chalcogen sensitization method such as a tellurium sensitization method, and gold, platinum, and the like, which are known for an emulsion for a normal photosensitive member, are used. A noble metal sensitization method and a reduction sensitization method using palladium or the like can be used alone or in combination (for example, see JP-A-3-110555).
No. 5-241267). These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45833, JP-A-62-40446
Can be used.

The pH at the time of chemical sensitization is preferably 5.3 to 1
0.5, more preferably 5.5 to 8.5, and pAg
Is preferably 6.0 to 10.5, more preferably 6.8.
９9.0. The coating amount of the photosensitive silver halide emulsion used in the present invention is 1 mg to 10 g / m ² in terms of silver.
Range.

In order to impart green, red, and infrared sensitivity to the photosensitive silver halide used in the present invention, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat.
617,257, JP-A-59-180550, 6
4-135546, JP-A-5-45828, 5-4
Sensitizing dyes described in US Pat.

These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is particularly used for the purpose of controlling the wavelength of supersensitization or spectral sensitization. Often used. Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615,641
And those described in JP-A-63-23145).

These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to US Pat. Nos. 4,183,756 and 4,225,666. It may be before or after formation. These sensitizing dyes and supersensitizers may be used as a solution of an organic solvent such as methanol, a dispersion such as gelatin, or a surfactant.
What is necessary is just to add in a liquid. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

The additives used in such a process and the known photographic additives that can be used in the present invention are described in the above-mentioned RD.
No. 17, 643, No. 18, 716 and No. 3
07, 105, and the corresponding portions are summarized in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, page 23-24, page 648, right column, pages 866-868 Color sensitizer ~ page 649, right column 4. Brightener page 24, page 648, right column, page 868 5. Fogging prevention 24 ~ 25, page 649, right column, page 868 ~ 870 Agents, stabilizers 6. Light absorber, 25 ~ Page 26 649 Right column Page 873 Filter ~ Page 650 Left column Dyes, UV absorbers

7. Dye image 25 page 650 left column page 872 stabilizer 8. Hardener 26 page 651 left column 874-875 9. Binder page 26 651 left column 873-874 10. Plasticizer, Page 27 650 Right column 876 Lubricant 11. Coating aid, 26 to 27 Page 650 Right column 875 to 876 Surfactant 12. Static 27 Page 650 Right column 876 to 877 Inhibitor 13. Matting agent 878-879

In the present invention, an organic metal salt can be used in combination with the photosensitive silver halide as an oxidizing agent. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. The acetylenes described in U.S. Pat. No. 4,775,613 are also useful. Two or more organic silver salts may be used in combination. The above-mentioned organic silver salt is used in an amount of 0.01 per mole of photosensitive silver halide.
10 to 10 mol, preferably 0.01 to 1 mol, can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is 0.05 to 10 g / m ^{2 in} terms of silver, preferably 0.1 to 0.1 g / m ² .
To 4 g / m ² are suitable. The kind and amount of the binder of the photosensitive member of the present invention are the same as those of the processed image receiving member.

In the present invention, when a color image is obtained by coupling, the photosensitive member contains a coupler. The coupler that can be used in the present invention may be a 4-equivalent coupler or a 2-equivalent coupler. Further, the diffusion-resistant group may form a polymer chain. A specific example of a coupler is THJames "The Th
eory of the Photographic Process, 4th edition, pages 291-334 and 354-361, JP-A-58-123533, 5
Nos. 8-149046, 58-14947, 59
-111148, 59-124399, 59-
174835, 59-231539, 59-2
No. 31540, No. 60-2950, No. 60-2951
Nos. 60-14242, 60-23474, 60-66249, 8-110608, and 8-1
No. 46552, 8-146578, and the like.

It is preferable to use the following couplers. Yellow coupler: a coupler represented by formulas (I) and (II) of EP502,424A; a coupler represented by formulas (1) and (2) of EP513,496A; a general formula of claim 1 of JP-A-5-307248. Coupler represented by (I); US5,066,576 column
1 couplers represented by general formula D on lines 45 and 55; couplers represented by general formula D in paragraph 0008 of JP-A-4-274425; couplers described in claim 1 on page 40 of EP498,38A1, EP447,969A1 A coupler represented by the formula (Y) on page 4; a coupler represented by the formulas (I) to (IV) on lines 36 and 58 in column 7 of US Pat. No. 4,476,219; a magenta coupler: JP-A-3-39737 and JP-A-3-39737. -43611,
Couplers described in JP-A-5-204106 and JP-A-4-3626. Cyan coupler: JP-A-4-208443, JP-A-4-43345 and JP-A-6-67385. Polymer coupler: JP-A-2-44345. US 4,366,237, GB2,125,
570, EP 96,570 and DE 3,234,533 are preferred.

The photosensitive member may contain the following functional coupler. Couplers for correcting unnecessary absorption of color-forming dyes include yellow colored cyan couplers described in EP 456,257A1, yellow colored magenta couplers described in the EP, magenta colored cyan couplers described in US Pat. (2), WO92 / 1
A colorless masking coupler of the formula (A) of claim 1 of claim 1575 (especially the exemplified compounds on pages 36-45).

The compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound:
Compounds represented by formulas (I) to (IV) described on page 11 of EP378,236A1 Compounds represented by formula (I) described on page 7 of EP436,938A2, formula (1) described in JP-A-5-307248 The compounds represented by the formulas (I) and (I) described on pages 5 and 6 of EP440,195A2
Compounds represented by (I) and (III), JP-A-6-59411
2. A compound represented by the formula (I) -ligand releasing compound according to claim 1 of the present invention, a compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478.

In the photosensitive member used in the present invention, an oxidant formed by silver development is coupled with the above-mentioned coupler to form a dye for the purpose of shortening a developing time, improving sensitivity, and improving image density. A preferred embodiment is one in which a color developing agent capable of developing is incorporated. In this case, U.S. Pat. No. 3,531,
No. 256, phenol or an active methylene coupler as a p-phenylenediamine developing agent;
No. 1,270, a combination of a p-aminophenol developing agent and an active methylene coupler can be used.
U.S. Pat. No. 4,021,240, JP-A-60-128
A combination of a sulfonamide phenol and a 4-equivalent coupler as described in JP-A No. 438 or the like is excellent in raw storage when incorporated in a photosensitive member, and is a preferable combination.

When a color developing agent is incorporated, a precursor of the color developing agent may be used. For example, US3
No. 342,597, indoaniline compounds, US
No. 3,342,599, Research Disclosure N
o. 14,850 and Nos. 15,159, Schiff base type compounds, aldol compounds, described in US Pat. No. 13,924, metal salt complexes described in US Pat. No. 3,719,492, and JP-A-53-135628. Urethane compounds can be mentioned.

Further, a sulfonamide phenol-based active compound described in JP-A-9-15806 and JP-A-8-28634 are disclosed.
The combination of a hydrazine-based drug and a coupler described in JP-A Nos. 0 and 8-234388 is also preferable for use in the photosensitive member of the present invention.

When a diffusion-resistant developing agent is used,
If necessary, an electron transfer agent and / or an electron transfer agent precursor can be used in combination to promote electron transfer between the diffusion-resistant developing agent and the developable silver halide. Particularly preferably, said US Pat.
No. 9,919 and EP-A-418,743 are used. In addition, a method of stably introducing the compound into the layer as described in JP-A-2-230143 and JP-A-2-235044 is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned developing agents or its precursors. It is desirable that the electron transfer agent or its precursor has a higher mobility than the diffusion-resistant developing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. An electron donor precursor as described in JP-A-3-160443 is also preferably used.

Further, various reducing agents can be used in the intermediate layer and the protective layer for various purposes such as preventing color mixing and improving color reproduction. Specifically, European Patent Publication Nos. 524,649 and 357,040, JP-A-4-249245, and 2-
No. 46450 and JP-A-63-186240 are preferably used. In addition, Japanese Patent Publication 3-63733
No., JP-A-1-150135, JP-A-2-46450,
Development inhibitor releasing reducing compounds as described in JP-A-2-64634, JP-A-3-43735, and EP-A-451,833 may also be used.

In addition, the following reducing agents may be incorporated in the light-sensitive material. Examples of the reducing agent used in the present invention include U.S. Pat. No. 4,500,626, columns 49-50, 4,839,272, 4,330,617, and 4,590,152. Nos. 5,017,454 and 5,139,919, JP-A-60-140,335, pages (17) to (18), JP-A-57-40245, and JP-A-56-1.
No. 38736, No. 59-178458, No. 59-53
Nos. 831, 59-182449 and 59-1824
No. 50, No. 60-119555, No. 60-12843
No. 6, No. 60-128439, No. 60-198540
No. 60-181742, No. 61-259253
No. 62-244444 and No. 62-131253
Nos. 62-131256 and 64-13546, pages (40) to (57), JP-A-1-120553, and EP 220,746A2, pages 78 to 96, and the like. And reducing agent precursors. Also, combinations of various reducing agents such as those disclosed in U.S. Pat. No. 3,039,869 can be used.

The developing agent or the reducing agent may be incorporated in the processed image receiving member, but is preferably incorporated in the photosensitive member. In the present invention, the total amount of the developing agent and the reducing agent is from 0.01 to 20 mol, particularly preferably from 0.1 to 10 mol, per mol of silver.

Next, the case where the diffusible dye is released in the form of an image will be described. In the present invention, a non-diffusible coloring material which emits a diffusible dye in correspondence with silver development or reversely is used. This type of compound can be represented by the following general formula [L1]. Formula (L1) ((Dye) m-Y) n-Z Dye represents a diffusible dye group, Y represents a simple linking group, and Z corresponds to a photosensitive silver salt having an image-like latent image. Release a diffusive (Dye) m-Y in a corresponding manner, and
1 itself represents a non-diffusible group,
m represents an integer of 1 to 5, n represents 1 or 2, m,
When both n are not 1, a plurality of Dyes may be the same or different.

Specific examples of the coloring material represented by the general formula [L1] include the following compounds 1 to 4.
The following (1) to (3) release diffusible dyes in reverse response to silver halide development, and (4) release diffusible dyes in response to silver halide development. Is what you do. (1) U.S. Pat. Nos. 3,134,764 and 3,362
Nos. 819, 3,597,200, 3,544,5
No. 45, No. 3, 482, 972, Tokuhei 3-68,3
No. 87, etc., a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide. (2) As described in U.S. Pat. No. 4,503,137, etc., non-diffusible compounds which release diffusible dyes in an alkaline environment but lose their ability when reacted with silver halide can also be used. . Examples include U.S. Pat.
Compounds which release a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat.
Compounds which release a diffusible dye by an intramolecular reversal reaction of an isoxazolone ring described in JP-A No. 354 or the like.

(3) US Patent No. 4,559,290, European Patent No. 220,746A2, US Patent No. 4,78
3,396, published technical report 87-6199,
As described in No. 13546, a non-diffusible compound which reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used.

For example, see US Pat. No. 4,139,
No. 389, No. 4,139,379, JP-A-59-18.
Compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in US Pat. Nos. 4,232,107
No., JP-A-59-101649, and JP-A-61-88257.
No. RD24,025 (1984) and the like, which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-142530. No. 4,343,8
Nos. 93 and 4,619,884, etc., compounds which release a diffusible dye by cleavage of a single bond after reduction, and electron acceptors described in U.S. Pat. No. 4,450,223 Examples include nitro compounds which release a diffusible dye later, and compounds which release a diffusible dye after electron acceptance described in US Pat. No. 4,609,610.

[0095] More preferred are EP 220,746 A2, JP 87-6199, US Pat. No. 4,783,396, and JP-A-63-2016.
No. 53, No. 63-201654, No. 64-13546
Compounds having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in JP-A No. 1-26842;
A compound having O ₂ -X (X is as defined above) and an electron-withdrawing group, a PO-X bond (X is as defined above) and an electron-withdrawing group in the molecule described in JP-A-63-271344; A C-X 'bond (X' has the same meaning as X or -SO) in one molecule described in JP-A-63-271341.
_2- )) and a compound having an electron-withdrawing group. Also, JP-A-1-161237 and JP-A-1-1613.
Compounds described in No. 42, in which a single bond is cleaved after reduction by a π bond conjugated to an electron accepting group to release a diffusible dye, can also be used.

Among these, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. Examples are EP 220,746 A2 or U.S. Pat.
Nos. 83,396 (1) to (3), (7) to (1)
(0), (12), (13), (15), (23)-(26), (31), (32), (3
5), (36), (40), (41), (44), (53)-(59), (64), (7
0), Compounds (11) to (11) described in Published Technical Report 87-6199.
(23), compounds described in JP-A-64-13546
(1) to (84).

(4) A compound (DRR compound) which is reducible to silver halide or an organic silver salt and releases a diffusible dye when the partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. Representative examples are U.S. Pat. Nos. 3,928,312 and 4,053,312.
Nos. 4,055,428 and 4,336,322
And JP-A-59-65839 and JP-A-59-69839.
No. 53-3819, No. 51-104343, R
D17,465, U.S. Pat. No. 3,725,062,
JP-A-3,728,113, JP-A-3,443,939, JP-A-58-11637, JP-A-57-179840,
It is described in U.S. Pat. No. 4,500,626.
Specific examples of the DRR compound include the aforementioned US Pat.
Compounds described in Columns 22 to 44 of U.S. Pat. No. 00,626 can be mentioned. Among them, compounds (1) to (3), (10) to (13), (16) ) To (19), (28) to (3
0), (33) to (35), (38) to (40), and (42) to (64) are preferred.
Compounds described in U.S. Pat. No. 4,639,408, columns 37 to 39 are also useful.

In a system in which a diffusible dye is released in the form of an image and is diffuse-transferred to a processed image receiving member, it is preferable to include a mordant in the processed layer. As the mordant, those known in the field of photography can be used. Specific examples thereof include U.S. Pat. No. 4,500,626, columns 58 to 59 and JP-A-61-8.
No. 8256, pages 32 to 41;
Nos. 2-244043 and 62-244036. Also, U.S. Pat.
A dye-accepting polymer compound as described in JP-A-63,079 may be used.

Hydrophobic additives such as coloring materials, couplers, color developing agents, and diffusion-resistant reducing agents are described in US Pat. No. 2,322,0.
It can be introduced into the layer of the photosensitive member by a known method such as the method described in No. 27. In this case, U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476, and 4,464. High-boiling organic solvents such as those described in 599,296, JP-B-3-62256, and the like can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C as needed. These dye-donating compounds, nondiffusible reducing agents, high-boiling organic solvents, etc.
More than one species can be used in combination.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the dye-providing compound used. Further, 1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less is suitable for 1 g of binder. Tokiko Sho 51-39,85
3, a dispersion method using a polymer described in JP-A-51-59,943, and a method of adding as a fine particle dispersion described in JP-A-62-30242, etc. can also be used.

In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used.
For example, JP-A-59-157636, pages (37) to (38),
The surfactants described in the above Research Disclosure can be used. Also, Japanese Patent Application Laid-Open
Phosphate ester type surfactants described in US Pat. Nos. 5,56,267 and 7,228,589 and West German Patent Application No. 1,932,299A can also be used. In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the photosensitive member. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51 to 52.

The photosensitive member for photographing includes at least three types of photosensitive layers having different spectral sensitivities and different hues of color materials. Each photosensitive layer may be divided into a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The three types of photosensitive layers are preferably layers sensitive to any one of blue light, green light, and red light. In this arrangement order, generally, a red-sensitive layer,
The order is a green photosensitive layer and a blue photosensitive layer. However, other arrangements may be used depending on the purpose. For example, an arrangement as described in column 162 of JP-A-7-152129 may be used.

In the present invention, the silver halide and the coloring material may be contained in the same layer, but they may be added separately in separate layers as long as they can react. For example, when a layer containing a coloring material which is originally colored is disposed below a layer containing silver halide, a decrease in sensitivity can be prevented. The relationship between the spectral sensitivity of each layer and the hue of the colorant is arbitrary, but if a cyan colorant is used for the red photosensitive layer, a magenta colorant is used for the green photosensitive layer, and a yellow colorant is used for the blue photosensitive layer, the conventional color Projection exposure can be performed directly on paper or the like.

In the light-sensitive member, various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer are provided between and above the silver halide emulsion layers. May be provided, and various auxiliary layers such as a back layer may be provided on the side opposite to the support. Specifically, the layer structure described in the above patent, the undercoat layer described in US Pat. No. 5,051,335,
Intermediate layer having a solid pigment as described in JP-A-167838 and JP-A-61-20943;
Intermediate layer having a reducing agent or a DIR compound as described in JP-A-5-34884 and JP-A-2-64634; U.S. Pat. Nos. 5,017,454 and 5,139,919; And an intermediate layer having an electron transfer agent as described in JP-A No. 4-249245, a protective layer having a reducing agent as described in JP-A-4-249245, or a layer obtained by combining these.

A heat solvent may be added to the photosensitive member for the purpose of promoting thermal development. Examples thereof include organic compounds having polarity as described in U.S. Pat. Nos. 3,347,675 and 3,667,959. Specifically, amide derivatives (such as benzamide),
Urea derivatives (methyl urea, ethylene urea, etc.), sulfonamide derivatives (JP-B-1-40974 and JP-B-4)
No. 13701), polyol compounds (such as sorbitol), and polyethylene glycols. When the thermal solvent is insoluble in water, it is preferably used as a solid dispersion. The layer to be added may be either a photosensitive layer or a non-photosensitive layer depending on the purpose. The addition amount of the thermal solvent is from 10% by weight of the binder of the layer to be added.
It is 500% by weight, preferably 20% to 300% by weight.

The photosensitive member and the processed image receiving member used in the present invention are preferably hardened with a hardener. Examples of hardeners include U.S. Pat. No. 4,678,739, column 41,
4,791,042, JP-A-59-116655
No. 62-245261, No. 61-18942,
Hardening agents described in JP-A-4-218044 are exemplified. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), N-
Methylol-based hardeners (such as dimethylol urea), boric acid, metaboric acid or polymer hardeners (JP-A-62-2
No. 34157). These hardeners are used in an amount of 0.001 per gram of hydrophilic binder.
To 1 g, preferably 0.005 to 0.5 g.

Various antifoggants or photographic stabilizers and precursors thereof can be used in the photosensitive member. Specific examples thereof include the aforementioned Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A-64-13564 (7) to (9). ), (57)-(71) and
(81) to (97), U.S. Patent Nos. 4,775,610, 4,626,500, 4,983,494, JP-A-62-174747 and JP-A-62-239148, No. 1-150135, No. 2-110557 and No. 2
178650, RD17,643 (1978) (24)-
Compounds described on page (25) and the like can be mentioned. These compounds are preferably used in an amount of 5 × 10 ^-6 to 1 × 10 ^-1 mol, more preferably 1 × 10 ^-5 to 1 × 10 ^-2 mol, per mol of silver.

For the photosensitive member and the processed image receiving member, various surfactants can be used for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic, development promotion and the like. Specific examples of the surfactant are known in the art, No. 5 (March 2, 1991)
2nd, Aztec Co., Ltd.), pp. 136-138, and JP-A Nos. 62-173463 and 62-183457.

The photosensitive member and the processed image receiving member may contain an organic fluoro compound for the purpose of improving the slipperiness, preventing static charge, and improving the releasability. Representative examples of the organic fluoro compound include fluorine surfactants described in JP-B-57-9053, columns 8 to 17, JP-A-61-20944, JP-A-62-135826, and fluorine oils. And a hydrophobic fluorine compound such as a solid fluorine compound resin such as an tetrafluoroethylene resin.

A matting agent can be used for the photosensitive member. As the matting agent, those similar to those used for the processed image receiving member are used. In the present invention, the support for the photosensitive member and the processed image receiving member is not particularly limited as long as it can withstand the processing temperature. In general, papers and synthetic polymers (films) described in "Basics of Photographic Engineering-Silver salt photography-" edited by The Photographic Society of Japan, pages 223 to 240, published by Corona Co., Ltd. (1979). And photographic supports. Specifically, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose)
Or those containing pigments such as titanium oxide in these films, synthetic paper made from polypropylene or the like, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated Paper (especially cast-coated paper) or the like is used. Further, a film obtained by depositing aluminum on a synthetic polymer film is also preferably used. Further, a support which is mainly a styrene polymer having a syndiotactic structure can also be preferably used.

A hydrophilic binder, a semiconductive metal oxide such as alumina sol and tin oxide, carbon black and other antistatic agents are coated on the surface of the support opposite to the side where the photosensitive element and the processing element are coated. May be. When using an aluminum vapor-deposited film, it is preferable to add a boron compound to the lowermost layer of the photosensitive member and the processed image receiving member.
Preferred boron compounds include borate esters.

In particular, JP-A-6-41281 and JP-A-6-4358, which are hard to curl as a support for a photosensitive member.
No. 1, 6-51426, 6-51437, 6
-51442, 6-82961, 6-8296
Nos. 0, 6-123937, 6-82959, 6-67346, 6-118561, and 5-21
625, JP-A-6-202277 and JP-A-6-1752
No. 82, No. 6-118561, No. 7-219129
And the supports described in JP-A-7-219144 can be preferably used. Further, Japanese Patent Application Laid-Open No.
No. 5, No. 5-40321, No. 6-35092, and JP-A-6-317875 are preferably used to record photographing information and the like using a support having a magnetic layer.

The photographic photosensitive member used in the present invention is processed in the same manner as a normal color negative, and can be directly mounted on a camera for photographing. Tokuhei 2-32615, Jitsuhei 3-39
It can also be preferably used for a film unit with a lens described in No. 784. The photosensitive member and / or the processed image receiving member may have a form having a conductive heating element layer as a heating means for heating and developing. In this case, the heat generating element described in JP-A-61-145544 can be used.

The heating temperature in the heat development step is about 50 ° C. to 2 ° C.
It is 50 ° C, but especially about 60 ° C to 180 ° C is useful. In a system using the release of a diffusible dye, the diffusion transfer step of the dye may be performed simultaneously with the thermal development, or may be performed after the completion of the thermal development step. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is particularly preferably at least 50 ° C. and about 10 ° C. lower than the temperature in the heat development step. In a system that uses the release of diffusible dyes, the movement of the dyes is caused only by heat,
The above-mentioned thermal solvent and other solvents may be used to promote dye transfer.

In the present invention, a method of performing development by heating in the presence of a small amount of fountain solution is useful. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of water or lower. Examples of the fountain solution used for accelerating development and / or diffusing and transferring the dye include water, a basic aqueous solution containing an inorganic alkali metal salt and an organic base (these bases include The low-boiling solvent or a mixed solution of the low-boiling solvent and water or the basic aqueous solution can be used. Further, a surfactant, an antifoggant, a compound forming a complex with a hardly soluble metal salt, a fungicide, and a bactericide may be contained in the solvent.

As the dampening water used in the steps of the thermal development and / or the diffusion transfer, any water can be used as long as it is generally used. Specifically, distilled water, tap water,
Well water, mineral water and the like can be used.
Further, in the heat developing apparatus using the photosensitive member and the image receiving element of the present invention, the water may be used up or may be circulated and used repeatedly. In the latter case, water containing components eluted from the member will be used. Also, JP-A-63-
No. 144354, No. 63-144355, No. 62-3
No. 8,460, JP-A-3-210555 and the like or water may be used.

In the present invention, the amount of fountain solution applied to the photosensitive member may be not more than the weight of water corresponding to the maximum swelling volume of the entire coating film of the photosensitive member and the processed image receiving member. As a method of applying the water, for example, JP-A-62-253159
(5) The method described in, for example, JP-A-63-85544 is preferably used. Further, the solvent can be used by being encapsulated in a microcapsule or incorporated in the photosensitive member or the dye fixing element or both in advance in the form of a hydrate. The temperature of the water to be applied may be 30 ° C. to 60 ° C. as described in JP-A-63-85544.

As a heating method in the developing and / or transferring step, a heated block or a plate is brought into contact, a hot plate, a hot presser, a hot roller, a hot drum, a halogen lamp heater, an infrared lamp and a far infrared lamp heater. For example, or by passing through a high-temperature atmosphere. A method of superposing a photosensitive member and a processed image receiving member is described in JP-A-62-253159 and JP-A-61-253159.
The method described on page 27 of 147244 can be applied.

In the heat development process of the present invention, any of various heat development devices can be used. For example, see JP-A-59-752.
No. 47, 59-1777547, 59-18135
No. 3, No. 60-18951, Shokai 62-25944
JP-A-6-130509, JP-A-6-95338,
Nos. 6-95267, 8-29955, 8-29
No. 954 and the like are preferably used. Examples of commercially available devices include Pictrostat 100 and Pictrostat 200 manufactured by Fuji Photo Film Co., Ltd.
Pictrostats 300 and 330, Pictrostat 50, Pictrostat Digital 400, Pictography 2000, Pictography 300
0 and the same pictography 4000 can be used.

In the present invention, no additional development stop processing is required after the development processing. However, a development stopping agent may be included in the processing image receiving member, and the development stopping agent may act simultaneously with the development. The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. More preferably, JP-A-62-253 is preferred.
No. 159, pages 31 to 32. Further, a combination described in JP-A-8-54705 or the like in which a zinc salt of mercaptocarboxylic acid is contained in a photosensitive element and a complex forming compound is contained in a processed image-receiving member is advantageous.

Similarly, a printout inhibitor of silver halide may be included in a processing sheet so that its function can be exhibited simultaneously with development. Examples of the printout inhibitor include a monohalogen compound described in JP-B-54-164, a trihalogen compound described in JP-A-53-46020, and a halogen described in JP-A-48-45228 bonded to an aliphatic carbon atom. And polyhalogen compounds represented by tetrabromoxylene described in JP-B-57-8454. Also, UK Patent No. 1,005,1
Development inhibitors such as 1-phenyl-5-mercaptotetrazole described in No. 44 are also effective. Also,
The viologen compounds described in JP-A-8-184936 are also effective. The use amount of the printout inhibitor is preferably 10 ^-4 to 1 mol / Ag1 mol, particularly preferably 10 ^-3 to 10 ^-1 mol / Ag1 mol.

[0122]

EXAMPLES Hereinafter, the effects of the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

Example 1 First, the production of a black-and-white photosensitive member (K101) will be described. The method for preparing the photosensitive silver halide emulsion (1) will be described. Solution (I) and solution (II) shown in Table 4 were added simultaneously over 9 minutes to a well-stirred aqueous solution of gelatin having the composition shown in Table 3 and then 3 minutes later, (III) ) Solution and (IV) solution were added simultaneously over 10 minutes.

[0124]

[Table 3]

[0125]

Embedded image

[0126]

[Table 4]

After washing with water and desalting (adjusted to pH 3.1 with sulfuric acid using the sedimentation agent (1)), 25 g of lime-processed gelatin was added to adjust pH 6.03 and pAg 7.6 by a conventional method. After that, preservative (1) was added, and the mixture was chemically sensitized at 60 ° C. The compounds used for chemical sensitization were added sequentially as shown in Table 3. The particle size is 0.22 μm on average side length,
This was a silver chlorobromide cubic emulsion having a standard deviation of 0.022 μm and a silver bromide content of 2.2 mol%. The yield of this emulsion was 704.
g.

[0128]

[Table 5]

[0129]

Embedded image

The preparation method of the silver bromide fine grain emulsion (2) shown in Table 5 will be described. The gelatin solution having the composition shown in Table 6 which was well stirred was cooled to 30 ° C., and Solution (I) and Solution (II) shown in Table 7 were added simultaneously over 3 minutes and 40 seconds. Thereafter, the solution (III) and the solution (IV) were simultaneously added over 2 minutes while controlling the flow rate of the solution (IV) so that the silver potential became 50 mV.

[0131]

[Table 6]

[0132]

[Table 7]

After washing with water and desalting (adjusted to pH 4.1 with phosphoric acid using a precipitant (2)) in a conventional manner, 22 g of lime-processed gelatin was added, and the pH was 6.1 and the pAg was 7.8.
Adjusted (by KBr). Preservative (2) was used as a preservative. It was a silver bromide cubic emulsion having a grain size of 0.05 μm. The yield is 630 g.

[0134]

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100 g of this emulsion (1) was added with sensitizing dye (3) 9
4.5 cc of a methanol solution containing 4,4'-
1.2 ml of a 1% methanol solution of bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] stilbene-2,2'-disulfonate was added, and mercapto compound (1) was added. % Aqueous solution (0.65 cc), water-soluble polymer (1) (1.7 g) was added, and butyl acrylate latex (1.9 g) was further added as a dispersion to prepare a coating solution for an emulsion layer.

[0136]

Embedded image

Next, a method for preparing a dispersion of the reducing agent 1,5-diphenyl-3-pyrazolidone will be described. 10 g of 1,5-diphenyl-3-pyrazolidone and 0.2 g of Demol made by Kao were added to 90 cc of 5.7% lime-processed gelatin.
Milling using glass beads with an average particle size of 0.75 mm
Dispersed for minutes. The glass beads were separated to obtain a gelatin dispersion of a reducing agent.

Next, a method for preparing a dispersion of zinc hydroxide will be described. Zinc hydroxide 1 with an average particle size of 0.2 μm
2.5 g, 1 g of carboxymethylcellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 cc of a 4% aqueous solution of gelatin, and dispersed in a mill for 30 minutes using glass beads having an average particle size of 0.75 mm. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

A dispersion of a leuco dye and a developer was prepared as shown in Table 8. The oil phase component heated and dissolved at about 60 ° C.
After adding to the aqueous phase component heated to 60 ° C and stirring and mixing,
After dispersion with a homogenizer for 10 minutes at 10,000 rpm, water was added to obtain a uniform dispersion.

[0140]

[Table 8]

[0141]

Embedded image

Using the above materials, a light-sensitive material K101 was prepared by applying the composition on a support according to the composition and the addition amount shown in Table 9.

[0143]

[Table 9]

[0144]

Embedded image

Next, as shown in Table 10, photosensitive materials K102 to 109 in which the compound of the present invention or a comparative compound was added to K101 were prepared in the same manner as K101.

[0146]

[Table 10]

[0147]

Embedded image

Example 2 The production of a processing member (R201) used for forming an image on a photosensitive material by processing in combination with a photosensitive member will be described. First, a method for producing an emulsified dispersion of the high-boiling organic solvent (A) will be described.

[0149]

Embedded image

[Preparation of Solution 1] 1000 g of gelatin powder
To 6465 ml of ion-exchanged water and 7% of preservative (A)
The solution is added to 12.5 ml of an aqueous solution and dissolved by heating at 65 to 70 ° C. [Preparation of Solution 2] 2000 g of high-boiling organic solvent (A), 200 g of high-boiling organic solvent (B), 25 g of surfactant (B)
And heated and stirred at 65-70 ° C. to make it uniform. [Preparation of Solution 3] 53 g of surfactant (C) was added to MEK40.
and heat to 65-70 ° C to dissolve.

[Emulsification] Solutions 2 and 3 are added to solution 1, and the mixture is stirred and emulsified by a mixer. Thereafter, the pressure emulsification treatment is performed twice. After emulsification, 300 ml of ion-exchanged water is added and stirred. Filter and store with nylon mesh 100.
As a result, an emulsified dispersion having an average particle size of 0.2 to 0.3 μm was obtained.

[0152]

Embedded image

Using the above emulsified dispersion and the raw materials shown in Table 11, the composition was applied to a support in accordance with the composition and the amount of addition shown in Table 11, thereby producing a treated member R201.

[0154]

[Table 11]

[0155]

Embedded image

[0156]

Embedded image

R2 was prepared in the same manner as in R201, except that the compound of the present invention or the comparative compound was added as shown in Table 12.
Nos. 02 to 217 were produced.

[0158]

[Table 12]

Example 3 The photosensitive member (K101) described in Example 1 was 590 mm wide.
It was cut to a length of 470 mm, and exposed by using a semiconductor laser having an output peak wavelength of 670 nm while changing the amount of light at a rate of 1/10000 ^second per 100 μm ^2. Separately, a roll of 635 mm wide and 76 m long Example 2 processed into
The image receiving member (R201) described in (1) was wound around a 3-inch diameter roll-shaped core (delivery side) so that the coating surface faced outward. Thereafter, the leading end of the processed image receiving member was partially wound around another winding core (winding side).

The processing image receiving member was set such that the film surface of the processing image receiving member was in contact with the outer surface of the curved heater during the feeding and winding. Next, the exposed photosensitive member is bonded to water kept at 50 ° C. for 3.2 seconds so that the film surface of the photosensitive member and the film surface of the processed image receiving member are evenly overlapped, and then the processed image receiving member and the photosensitive member are curved. While moving over the heater, the processing was performed by adjusting the speed and the heater temperature so that the photosensitive member was heated at 85 ° C. for 23 seconds until the photosensitive member was separated from the processed image receiving member. Next, the photosensitive member was separated from the processed image receiving member.

Thereafter, the photosensitive member was immersed in water for 2.5 seconds in a water washing step on-line, and then squeezed with a roller so that the amount of water on the photosensitive member became approximately 15 ml / m ² or less. Thereafter, the photosensitive member was dried by drying with hot air at 50 ° C. However, for the evaluation of the storage stability after the treatment, a sample from which the final washing step was omitted was used. Similarly, the photosensitive member K
Images were obtained using K102-109 instead of 101.

The characteristic curve of each sample was obtained by measuring the transmission ultraviolet density of the image using a Macbeth densitometer using a filter having a peak wavelength of 380 nm. See THJames “The Theory of the Photographic Pro
cess ", 4th edition. From the characteristic curve, the maximum density (Dmax), the minimum density (Dmin), and the gamma (the ratio of the density when a double exposure amount was given based on the density of 0.3) were determined. Also, the sample obtained by omitting the washing step is
After leaving it under constant temperature and humidity of 40 ° C and 80% for 4 weeks, Dmin
(UV) gain was obtained. Table 13 shows the results.

[0163]

[Table 13]

As can be seen from Table 13, Sample Nos. 303 to 305, which are the constitutions of the present invention, have a larger gamma value than Comparative Example 301 or 302 using an equimolar amount of the comparative compound, and have a good storage stability after processing. It can be seen that the change in Dmin is small and excellent. Furthermore, it can be seen that Sample No. 309, in which Compound (I) and Compound (II) are used in combination, has a lower Dmin and a higher Dmax, which is more desirable.

Example 4 A similar process was carried out using K101 described in Example 1 and R102 to 119 instead of R101 described in Example 2.
Was used to obtain an image. Table 14 shows the results.

[0166]

[Table 14]

As can be seen from Table 14, Sample Nos. 403 to 408 of the present invention have lower Dmin and lower Dmax than Comparative Example 401 or 402 using the comparative compound in an equimolar amount.
Is high, and the value of gamma is large.
It can be seen that the change in min is small and excellent. However, sample
When the amount of the compound added is small or too large as in Nos. 403 and 405, the effect of the present invention is small. Sample No. 415 using compound (I) and compound (II) in combination
418 show that the effects of the present invention are more pronounced.

Example 5 An image was obtained in the same manner by using the combination of the photosensitive member described in Example 1 and the processing member described in Example 2 as shown in Table 15. Table 15 shows the results.

[0169]

[Table 15]

As can be seen from Table 15, even when Compound (I) and Compound (II) were separately added to the photosensitive member and the processing member and used in combination, as in Sample Nos. 503 to 509,
It can be seen that the effects of the present invention are exhibited.

[0171]

According to the present invention, a meso-ion 1,2,4-thiazolium-3-thiolate compound is contained in a processing member or a photosensitive member for thermal development processing, so that the highest concentration is higher and the lowest concentration is lower. A good black-and-white image with good image sharpness can be obtained in a short time. Also,
Excellent image storability even without a washing step. Furthermore, by incorporating a compound having an acetylene group into one of the processing member and the photosensitive member, an excellent black-and-white image having a higher maximum density and a lower minimum density can be obtained.

Claims (4)

[Claims] A photothermographic member having at least one photosensitive silver halide emulsion layer on a support, wherein said emulsion layer or another hydrophilic colloid layer contains a reducing agent (developing agent); A processing member having at least one layer containing physical development nuclei on a support and containing a silver halide solvent (fixing agent) in this layer or another hydrophilic colloid layer, after or after imagewise exposure At least one layer on the photothermographic member and / or the processing member used in the method of forming a silver image on the processing member by thermally developing in the presence of water. Characterized in that it contains at least one kind of meso-ion 1,2,4-thiazolium-3-thiolate compound. 2. A photothermographic member having at least one photosensitive silver halide emulsion layer on a support, wherein said emulsion layer or another hydrophilic colloid layer contains a reducing agent (developing agent); A processing member having at least one layer containing physical development nuclei on a support and containing a silver halide solvent (fixing agent) in this layer or another hydrophilic colloid layer, after or after imagewise exposure At the same time, by superimposing and thermally developing in the presence of water, the photothermographic member used in the method of forming a silver image on the photothermographic member and / or the processing member, wherein at least In one layer, at least one meso-ion 1,2,4-thiazolium-3-
A photothermographic member containing a thiolate compound. 3. A photographic member comprising the processing member and the photosensitive member according to claim 1, wherein at least one layer on the processing member or the photosensitive member contains a compound having at least one acetylene group. Photo components. 4. A photographic member comprising the processing member and the photosensitive member according to claim 2, wherein at least one layer on the processing member or the photosensitive member contains a compound having at least one acetylene group. Photo components.