JPH0862810A - Picture forming method - Google Patents

Abstract

PURPOSE: To obtain a sufficient activity when a picture is formed, a sufficient stability when the picture is preserved and a high picture stability when the picture is preserved by incorporating a specified compd. into one between a photosensitive element and an image receiving element and a specified metallic compd. into the other. CONSTITUTION: One or more kinds of compds. shown by formula I and >=1 kind of compd. shown by formula II are incorporated into one between a photosensitive element and an image receiving element, and >=1 kind of metallic compd. shown by formula III and hardly soluble in water is incorporated into the other. In the formula I, E is -S-, -O-, etc., C is carbon element, Z is an atom group necessary to form a heterocyclic ring with C and E, D<-> is a C substituent, -CO2 -, etc., and Bk is an alkali metal ion, etc. In the formula II, E and C are the same as in the formula I, Z is an atom group necessary to form a heterocyclic ring with C and E and has subsistent X and Y, X is -CN-, -CHNOH, etc., and Y is a substituents on the heterocyclic ring and is alkyl, aryl, etc. In the formula III, M is a metal other than alkali metals, and W is an oxide ion, hydroxyl ion, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method. Further, the present invention relates to an image forming method which utilizes two substantially neutral compounds during storage and utilizes the reaction of the two compounds to generate an alkali during image formation.

[0002]

2. Description of the Related Art In some processing for forming an image (so-called developing process), a dye is imagewise formed or released, and the dye is fixed by diffusion (transfer) (for example, in an image receiving element having a mordant). Many methods have been proposed as image forming methods for mordant).

In the method of forming an image by forming or releasing such a dye and diffusing (transferring), in order to promote the formation, release and diffusion (transferring) of the dye,
Some means (eg high heat, high pH, pressure, ultrasound,
Electromagnetic waves, etc.) are generally used. Among these promoting means, a combination of high heat and high pH, or a combination of high heat and pressure is generally used. In particular, the pH is advantageous for distinguishing the image forming condition of dye formation or release from the image forming condition before storage.

In a so-called image forming system which does not use a developing solution, as a means for distinguishing between pH during storage and pH during image formation, a base generation method by a reaction of two neutral compounds is disclosed in, for example, JP-A-60-169585. It has been proposed in the issue. This method is extremely effective in distinguishing between the time of image formation and the time of storage before that. However, it has been found that the image formed by this method contains a large amount of salts during its storage, so that a decrease in gloss which is considered to be associated with it is observed. Therefore, there has been a demand for means for solving these problems.

[0005]

An object of the present invention is to have sufficient activity during image formation, sufficient stability during storage before that, and excellent image stability during image storage after image formation. An object is to provide an image forming method.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method for forming an image using a photosensitive element and an image receiving element, wherein one of the photosensitive element and the image receiving element is represented by the general formula (1). Containing at least one kind of the compound and at least one kind of the compound represented by the general formula (2), and the other contains at least one kind of the water-insoluble metal compound represented by the general formula (3). Was achieved by the image forming method.

[0007]

[Chemical 4]

In the general formula (1), E is -S-, -O.
-, or -NR ¹ - (R ¹ represents a hydrogen atom, an alkyl group,
It represents a bond for forming a double bond between an aryl group or N and an atom adjacent to N. ), And is adjacent to C as shown above. C represents a carbon atom. Z represents an atomic group necessary for forming a heterocycle with C and E, and D
^- it does not have a substituent other than. D ^- represents a substituent of the C, -
CO ₂ ⁻ , —SO ₂ ²⁻ , or —SO ₃ ²⁻ is shown. Bk ⁺ represents an alkali metal ion, an alkaline earth metal ion, a substituted or unsubstituted guanidinium ion, an aminidium ion, or a quaternary ammonium ion.

[0009]

[Chemical 5]

In the general formula (2), E and C are the same as those in the general formula (1). Z represents an atomic group necessary for forming a heterocycle with C and E, and has substituents X and Y.
Have. X represents -CN, -CHNOH or a group represented by D ^- Bk ⁺ in the general formula (1). Y represents a substituent on the heterocycle and represents an alkyl group, an aryl group, a carboxyl group, an alkyloxycarbonyl group, a hydroxy group, an alkyloxy group, an aryloxy group, a halogen atom, a cyano group or an amidoxime group. n represents an integer of 1 to 4. However, when X is -CN or -CHNOH, n
Represents an integer of 0 to 4.

[0011]

[Chemical 6]

In the general formula (3), M represents a metal other than an alkali metal, W represents an oxide ion, a hydroxide ion,
Represents carbonate ion, silicate ion, borate ion or aluminate ion. p and m represent integers with which the atomic values of M and W can be balanced, respectively. Note that M _p
W _m may have water of crystallization and may form a double salt.

The present invention will be described in detail below. In the image forming method of the present invention, the chelating agent represented by the general formula (1) or (2) and the poorly water-soluble metal compound represented by the general formula (3) are added in the presence of water. The base obtained by the reaction is used. From the principle, a salt in which the group represented by Bk ⁺ in the general formula (1) and the general formula (2) is replaced with the group represented by W _m in the general formula (3) is formed in the image forming process. To generate.

The presence of the salt in the image-receiving element after image formation has various effects. For example, deterioration of gloss, influence of fastness to temperature, humidity and light, and influence on film strength, curl and the like which are considered to be accompanied by change of film quality. The relationship between these changes in performance and the above-mentioned salt is not clear, but the effect of the salt on inhibiting or promoting dyeing, mordant, etc. of the dye in the image-receiving element, or the presence of the salt causes The effect of increasing the equilibrium water content, the precipitation of the salt itself and the precipitation of other compounds due to the salting-out effect, the effect of promoting phase separation by the salt, or the effect of increasing the compatibility are considered.

It cannot be clearly explained that the above-mentioned change in performance is improved by using the compounds of the general formulas (1) to (3) of the present invention together. In the image forming method of the present invention, the chelating agent represented by the general formula (1) or (2) and the poorly water-soluble metal compound represented by the general formula (3) are added in the presence of water. The base obtained by the reaction is used. From the principle, a salt in which the group represented by Bk ⁺ in the general formula (1) and the general formula (2) is replaced with the group represented by W _m in the general formula (3) is formed in the image forming process. To generate. At this time, the complex salt according to the general formula (1) having a central metal derived from the general formula (3), the complex salt according to the general formula (2), and the complex salt having both the general formulas (1) and (2) as ligands are It is formed. These mixtures are believed to interfere with each other's crystallization. Further, it is considered that the solubility of the complex salt in water as a whole and the solubility of the membrane containing water are different. It is presumed that the membrane structure of the dye-fixing element itself may change due to these differences. It seems that it shows the above effects.

The compound of the general formula (1) will be described.
In the general formula (1), E is -S-, -O-, or-.
NR ¹ — (R ¹ represents a hydrogen atom, an alkyl group, an aryl group, or a bond for forming a double bond between N and an atom adjacent to N), and is represented by C as shown above. Adjacent. C represents a carbon atom. Z represents an atomic group necessary for forming a heterocycle with C and E and has no substituent other than D ⁻ . D ^- represents a substituent of C, -CO ₂ ^{-, -}
Indicates SO ₂ ²⁻ or —SO ₃ ²⁻ . Bk ⁺ represents an alkali metal ion, an alkaline earth metal ion, a substituted or unsubstituted guanidinium ion, an aminidium ion, or a quaternary ammonium ion.

As the above-mentioned heterocycle, a 5- or 6-membered heterocycle is preferable, and an aromatic heterocycle is particularly preferable. Examples of preferred heterocycles include pyridine ring, quinoline ring,
Examples thereof include a pyrazine ring, a thiophene ring and a furan ring.

Among the compounds represented by the general formula (1), the compounds represented by the following general formula (4) are particularly preferable.

[0019]

[Chemical 7]

In the general formula (4), Bk ⁺ has the same meaning as in the general formula (1). Further, D ⁻ has the same meaning as in the general formula (1). Preferred specific examples of the compound represented by formula (1) are shown below. However, the compound of the present invention is not limited to the following examples.

101 lithium picolinate 102 potassium picolinate 103 sodium picolinate 104 guanidinium picolinate 105 calcium dipicolinate 112 2 potassium pyridinesulfonate 113 2 sodium pyridinesulfonate 114 2 guanidinium pyridinesulfonate 122 2 potassium furanate 124 2 furan Guanidium carboxylate 132 2 Potassium thiophenecarboxylate 134 2 2 Guanidium thiophenecarboxylate 143 Sodium pyrazinecarboxylate 144 Guanidium pyrazinecarboxylate

The compound of the general formula (2) will be described.
In the general formula (2), E and C are the same as those in the general formula (1). Z represents a group of atoms necessary for forming a heterocycle with C and E, and has substituents X and Y. X
Is -CN, -CHNOH or D ^- Bk ⁺ in the general formula (1).
The group represented by is shown. Y represents a substituent on the heterocycle and represents an alkyl group, an aryl group, a carboxyl group, an alkyloxycarbonyl group, a hydroxy group, an alkyloxy group, an aryloxy group, a halogen atom, a cyano group or an amidoxime group. n represents an integer of 1 to 4. However, X
Is -CN or -CHNOH, n represents an integer of 0 to 4.

As the above-mentioned heterocycle, a 5- or 6-membered heterocycle is preferable, and an aromatic heterocycle is particularly preferable. Examples of preferred heterocycles include pyridine ring, quinoline ring,
Examples thereof include a pyrazine ring, a thiophene ring and a furan ring.

Among the compounds represented by the general formula (2), the compounds represented by the following general formula (5) are particularly preferable.

[0025]

Embedded image

In the above general formula (5), X has the same meaning as in the general formula (2). Y represents a substituent on the pyridine ring, and n has the same meaning as in formula (2). When n is 2 or more, Y may be the same or different, and may be bonded to each other to form a ring. Y
As preferred examples, -CO ₂ ^- Bk ⁺ (e.g. -CO _{2
K, -CO 2 Na, -CO 2} H · HN = C (NH 2) 2 , etc.),
-SO ₂ ^- Bk ⁺ (e.g. _{-SO 2 K, -SO 2 Na,} -S
O ₂ H · HN = C (NH ₂ ) ₂ etc.), —SO ₃ ⁻ Bk ⁺ (eg —SO ₃ K, —SO ₃ Na etc.), hydrogen atom, halogen atom (eg Cl, F, Br, I etc.) ), Cyano group, nitro group, hydroxyl group or substituted or unsubstituted alkyl group (eg, methyl, ethyl, propyl, isopropyl, butyl, carboxymethyl, etc.), cycloalkyl group (eg, cyclohexyl, etc.), aralkyl group (eg, benzyl, etc.) , Aryl group (eg phenyl etc.), alkenyl group (eg vinyl, allyl etc.), alkynyl group (eg ethynyl etc.), alkoxy group (eg methoxy, ethoxy, methoxyethoxy etc.), aryloxy group (eg phenoxy etc.), acylamino Groups (eg acetylamino, benzoylamino etc.), acyl groups (eg acetyl, benzoyl etc.) Amino group (e.g. methylamino,
Dimethylamino etc.), alkylthio group (eg methylthio etc.), arylthio group (eg phenylthio etc.), heterocyclic group (eg pyridine etc.), alkylsulfonyl group (eg methanesulfonyl etc.), arylsulfonyl group (eg benzenesulfonyl etc.), Alternatively, a carbamoyl group (eg, phenylcarbamoyl, diethylcarbamoyl, etc.) can be mentioned. In addition, examples of the ring when Y is bonded to each other to form a ring include a benzene ring and the like. Preferred examples of Bk ⁺ include Li ⁺ , Na ⁺ , K ⁺ ,
Cs ⁺ , N ⁺ (CH ₃ ) ₄ , H ₂ N ⁺ = C (NH ₂ ) ₂ , H ₂ N ⁺ = C
_{(N (CH 3) 2)} 2, H 2 N + = C (NHCH 3) NH 2,

[0027]

[Chemical 9]

(C ₂ H ₅ ) ₃ N ⁺ H and the like can be mentioned.

Preferred specific examples of the compound represented by the general formula (2) are shown below. However, the compound of the present invention is not limited to the following examples.

203 2-carboxy-3-hydroxypyridine sodium salt 204 2-carboxy-3-hydroxypyridine guanidinium salt 211 2,3-dicarboxypyridine lithium salt 212 2,3-dicarboxypyridine potassium salt 213 2,3- Dicarboxypyridine sodium salt 214 2,3-Dicarboxypyridine guanidinium salt 223 2,4-Dicarboxypyridine sodium salt 224 2,4-Dicarboxypyridine guanidinium salt 231 2,5-Dicarboxypyridine lithium salt 232 2,5- Dicarboxypyridine potassium salt 233 2,5-dicarboxypyridine sodium salt 234 2,5-dicarboxypyridine guanidinium salt 243 2,6-dicarboxypyridine sodium salt 252 3- Ethoxycarbonylpicolinic acid potassium salt 253 3-ethoxycarbonylpicolinic acid sodium salt 254 3-ethoxycarbonylpicolinic acid guanidinium salt 261 3-butoxycarbonylpicolinic acid lithium salt 262 3-butoxycarbonylpicolinic acid potassium salt 2643-butoxycarbonylpicolinic acid guanidinium Salt 274 3-isopropoxycarbonylpicolinic acid guanidinium salt 282 3-methoxypicolinic acid potassium salt 283 3-methoxypicolinic acid sodium salt 284 3-methoxypicolinic acid guanidinium salt 292 3-ethoxypicolinic acid potassium salt 293 3-ethoxypicolinic acid sodium salt Salt 294 3-ethoxypicolinic acid guanidinium salt 303 3-dimethylaminopicolinic acid sodium salt 314 - cyano picolinic acid guanidinium salt

322 5-methoxycarbonylpicolinic acid potassium salt 323 5-methoxycarbonylpicolinic acid sodium salt 324 5-methoxycarbonylpicolinic acid guanidinium salt 332 5-ethoxycarbonylpicolinic acid potassium salt 333 5-ethoxycarbonylpicolinic acid sodium salt 334 5 -Ethoxycarbonylpicolinic acid guanidinium salt 343 5-propoxycarbonylpicolinic acid sodium salt 344 5-propoxycarbonylpicolinic acid guanidinium salt 351 5-isopropoxycarbonylpicolinic acid lithium salt 352 5-isopropoxycarbonylpicolinic acid potassium salt 354 5-isopropoxy Carbonyl picolinic acid guanidinium salt 362 5-butoxy carbonyl picolinic acid potassium salt 363 5- Butoxycarbonylpicolinic acid sodium salt 364 5-Butoxycarbonylpicolinic acid guanidinium salt 373 5-Chloropicolinic acid sodium salt 382 5-Bromopicolinic acid potassium salt 392 5-Ethoxypicolinic acid potassium salt 393 5-Ethoxypicolinic acid sodium salt 394 5- Ethoxypicolinic acid Guanidium salt 401 5-Ethylpicolinic acid lithium salt 402 5-Ethylpicolinic acid potassium salt 403 5-Ethylpicolinic acid sodium salt 404 5-Ethylpicolinic acid guanidinium salt 413 5-Propylpicolinic acid sodium salt 414 5-Propylpicoline Acid Guanidium salt 421 5-Isopropylpicolinic acid lithium salt 422 5-Isopropylpicolinic acid potassium salt 431 5-Butylpicolinic acid lithium salt

432 5-Butylpicolinic acid potassium salt 433 5-Butylpicolinic acid sodium salt 434 5-Butylpicolinic acid guanidinium salt 442 5-isobutylpicolinic acid potassium salt 444 5-isobutylpicolinic acid guanidinium salt 452 5-t-butylpicolinic acid Potassium salt 453 5-t Butylpicolinic acid sodium salt 463 6-Ethylpicolinic acid sodium salt 464 6-Ethylpicolinic acid guanidinium salt 472 6-Aminopicolinic acid potassium salt 474 6-Aminopicolinic acid guanidinium salt 482 3,5-Diethylpicolinic acid Acid potassium salt 483 3,5-diethylpicolinic acid sodium salt 484 3,5-diethylpicolinic acid guanidinium salt 493 2,4,6-tricarboxypyridine sodium salt

[0033]

[Chemical 10]

The compound represented by formula (3) will be described.
In the general formula (3), M represents a metal other than an alkali metal, W represents an oxide ion, a hydroxide ion, a carbonate ion,
Represents silicate ion, borate ion or aluminate ion. p and m represent integers with which the atomic values of M and W can be balanced, respectively. Note that M _p W _m may have water of crystallization and may form a double salt.

Preferred metals for M are zinc, titanium,
Aluminum, silicon, calcium, cobalt, copper, nickel and manganese. Particularly preferred metals include those whose complexes with the compounds of the general formulas (1) and (2) used have no visible absorption. A particularly preferable metal is zinc.

A preferred combination of the compound of the general formula (1) and the compound of the general formula (2) is a combination of both compounds having the same heterocyclic skeleton. Therefore, a particularly preferred combination is a combination of the compound represented by the general formula (4) and the compound represented by the general formula (5). Compounds of general formula (1) and general formula (2)
The preferable ratio of the compound of formula (1) to the compound of formula (1) is
The compound of the general formula (2) is added in an amount of 0.005 to 2 based on mol.
The ratio is 00 mol.

The compounds represented by the general formulas (1) and (2) may be used in the same addition layer or may be added in different layers. The compounds of general formula (1) and general formula (2) may be used alone or in combination of two or more. The amount of the compound of the general formula (1) and the general formula (2) are each preferably a 0.15 to 150 mmol / m ^2, more preferably is 0.75 to 30 mmol / m ^2. The amount of the compound of the general formula (3) used is preferably 1 to 150 mmol / m ² , and more preferably 5 to 30 mmol / m ² .

The present invention can be used for all photographic image forming methods by the diffusion transfer method, but since it is particularly preferably used for the image forming method by thermal development, the thermal development system will be described. The heat-developable photosensitive element used in the present invention basically has a photosensitive silver halide emulsion and a binder on a support, and further, if necessary, an organic metal salt oxidizing agent and a dye-donating compound (described later). In some cases, the reducing agent may also serve as such). These components are often added to the same layer, but they may be added separately in different layers. For example, when a colored dye-donor compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. The reducing agent is preferably incorporated in the photothermographic element, but it may be supplied from the outside by, for example, a method of diffusing from a dye fixing element described later.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers having light sensitivity in different spectral regions is used. . For example, JP-A-59-180,550 and JP-A-64-13,546, 6
2-253,159, European Patent Publication No. 479,167.
No. 3 combination of blue-sensitive layer, green-sensitive layer and red-sensitive layer, green-sensitive layer, red-sensitive layer, infrared-sensitive layer combination, red-sensitive layer, infrared-sensitive layer (I), red There is a combination of the outer photosensitive layer (II). Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers as required, as described in JP-A-1-252954. The heat-developable photosensitive element includes various non-photosensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer and an antihalation layer between the silver halide emulsion layers and the uppermost layer and the lowermost layer. It may be provided, and various auxiliary layers such as a back layer can be provided on the opposite side of the support. Specifically, the layer structure as described in the above patent, US Pat. No. 5,051,33
An undercoat layer as described in JP-A No. 5-167838.
No. 6, intermediate layers having a solid pigment as described in JP-A-61-20943, JP-A-1-120553, 5-
Nos. 34,884 and 2-64,634, an intermediate layer containing a reducing agent or a DIR compound, US Pat.
17,454, 5,139,919, JP-A-2-
An intermediate layer having an electron transfer agent as described in JP-A No. 235,044, a protective layer having a reducing agent as described in JP-A-4-249,245, or a layer combining these may be provided. The support is preferably designed to have an antistatic function and a surface resistivity of 10 ¹² Ω · cm or less.

The silver halide emulsion that can be used in the present invention is
It 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 an optical fogging. Also,
It may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases, or silver halide having a different composition may be joined by epitaxial joining. The silver halide emulsion may be monodisperse or polydisperse, and the method of mixing the monodisperse emulsions and adjusting the gradation as described in JP-A-1-167,743 and 4-223,463 is preferably used. . The particle size is preferably 0.1 to 2 μm, particularly preferably 0.2 to 1.5 μm. The crystal habit of silver halide grains is one having a regular crystal such as a cube, octahedron, or tetrahedron, a sphere, an irregular crystal system such as a flat plate having a high aspect ratio, or a twin plane. Any of those having such a crystal defect, a composite system thereof or the like may be used. Specifically, US Pat. No. 4,500,626
No. 50, No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) No. 17,0.
29 (1978), No. 17, 643 (December 1978), pages 22-23, No. 18, 716 (1979).
Nov., pp. 648, No. 307, 105 (198).
Nov. 9, pp. 863-865, JP-A-62-253,
159, 64-13,546, JP-A-2-23.
No. 6,546, No. 3-110,555, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel (P. Glafkides, Chemie et Phisique Photographiqu.
e, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photo
graphic Emulsion Chemistry, Focal Press, 196
6), "Production and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VL Zelikman et al., Makin).
g and CoatingPhotographic Emulsion, Focal Press,
Any of the silver halide emulsions prepared by the method described in (1964) etc. can be used.

In the process of preparing the light-sensitive silver halide emulsion of the present invention, it is preferable to carry out so-called desalting to remove excess salt. As a means for this, a Nudel water washing method in which gelatin is gelled may be used, and inorganic salts (for example, sodium sulfate) composed of polyvalent anions, anionic surfactants, anionic polymers (for example, polystyrene sulfonic acid). The precipitation method using sodium) or a gelatin derivative (eg, aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may be used. 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 kinds. The addition amount 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 added to the particles, or may be localized inside or on the surface of the particles. Specifically, the emulsions described in JP-A-2-236542, JP-A-1-116637, JP-A-5-181246 and the like are preferably used.

In the step of forming grains of the light-sensitive silver halide emulsion of the present invention, rhodan salt, ammonia, 4-substituted thioether compound and JP-B No. 47-1 are used as a silver halide solvent.
The organic thioether derivatives described in 1,386 or the sulfur-containing compounds described in JP-A-53-144,319 can be used.

For other conditions, see Graphide, "Physics and Chemistry of Photography", published by Paul Montell (P.
Glafkides, Chemie et Phisique Photographique, Pau
Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Em
ulsion Chemistry, Focal Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikman et al., VL Zelikman et al., Making and Coating Phot.
See the description of ographic Emulsion, Focal Press, 1964), etc. That is, any of the acidic method, the neutral method, and the ammonia method may be used, and the method of reacting the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method,
Any of those combinations may be used. The double jet method is preferably used to obtain a monodisperse emulsion.
A back mixing method in which the grains are formed in the presence of excess silver ions can also be used. As one type of double jet method, the pAg in the liquid phase where silver halide is produced is kept constant,
The so-called controlled double jet method can also be used.

Further, in order to accelerate the grain growth, the addition concentration, the addition amount and the addition rate of the silver salt and the halogen salt to be added may be increased (JP-A-55-142,329 and JP-A-55-158). 124, U.S. Pat. No. 3,650,757). Further, the stirring method of the reaction liquid may be any known stirring method. Further, the temperature and pH of the reaction solution during the formation of silver halide grains may be set arbitrarily according to the purpose. The preferred pH range is 2.2 to 8.5, more preferably 2.5 to 7.5.

The photosensitive 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 chalcogen sensitizing method such as a sulfur sensitizing method, a selenium sensitizing method, a tellurium sensitizing method, or the like, which is known in emulsions for conventional light-sensitive materials, gold, platinum, A noble metal sensitization method using palladium or the like and a reduction sensitization method can be used alone or in combination (for example, JP-A-3-110,55).
No. 5, No. 5-241267, etc.). These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253,159). Further, an antifoggant described below can be added after the completion of the chemical sensitization. Specifically, JP-A-5-45,833, JP-A-62-40,
The method described in No. 446 can be used. The pH during chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5, and pAg is preferably 6.0 to 1.
It is 0.5, and more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide emulsion used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to provide the photosensitive silver halide used in the present invention with green-sensitive, red-sensitive and infrared-sensitive color sensitivity, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . Further, if necessary, the blue-sensitive emulsion may be spectrally sensitized in the blue region. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, US Pat.
617,257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization or wavelength adjustment of spectral sensitivity. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound that 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-63-23, 145). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after the nucleation of silver halide grains. Good. Further, these sensitizing dyes and supersensitizers may be added in a solution of an organic solvent such as methanol, a dispersion of gelatin or a solution of a surfactant. The addition amount is generally 10 ^-8 to 10 per mol of silver halide.
^-It is about ² mol.

Additives used in such steps and known photographic additives usable in the heat-developable photosensitive element and dye fixing element of the present invention are RDNo. 17,643 and No. 18,716 described above. And No. 307, 105 of the same, and the corresponding parts are summarized in the table below. Types of additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity enhancer page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer, to page 649, right column 4. 4. Optical brightener page 24 page 648 right column page 868 5. Antifoggants, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizers 6. Light absorber, page 25-26, page 649, right column, page 873, filter dye, page-650, left column, ultraviolet absorber 7. Dye image stabilizer, page 25, page 650, left column, page 872 8. Hardener, page 26, page 651, left column, pages 874-875 9. Binder page 26 page 651 left column page 873-874 10. Plasticizers, lubricants Page 27 Page 650 Right column Page 876 11. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surfactant 12. Statica page 27 page 650 right column 876 to 877 inhibitor 13. Matting agent pp. 878-879

A hydrophilic binder is preferably used as the binder of the constituent layers of the photothermographic element and the dye fixing element. Examples thereof include Research Disclosure mentioned above and pages (71) to (75) of JP-A-64-13,546.
The thing described in the page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, natural compounds such as starch, gum arabic, dextran, and polysaccharides such as pullulan and polyvinyl alcohol,
Examples thereof include synthetic polymer compounds such as polyvinylpyrrolidone and acrylamide polymers. Also, U.S. Pat. No. 4,96
No. 0,681, JP-A No. 62-245,260 and the like, a superabsorbent polymer, that is, -COOM or -SO
Homopolymers of vinyl monomers having ₃ M (M is a hydrogen atom or an alkali metal) or copolymers of these vinyl monomers or copolymers with other vinyl monomers (for example, sodium methacrylate, ammonium methacrylate,
Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd. is also used. These binders can be used in combination of two or more. A combination of gelatin and the above binder is particularly preferable. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin and so-called demineralized gelatin having a reduced content of calcium etc. according to various purposes, and it is also preferable to use them in combination.

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the above superabsorbent polymer. Also, apart from the present invention, the use of superabsorbent polymers in the dye fixing layer or its protective layer can prevent the dye from retransferring from the dye fixing element to another after transfer. In the present invention, the coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, and further 7 g to 0.5 g.
Is appropriate.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the light-sensitive silver halide emulsion. Among such organic metal salts, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in Nos. 00,626, columns 52 to 53. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more kinds of organic silver salts may be used in combination. The above organic silver salt is 0.01 mol per mol of photosensitive silver halide.
-10 mol, preferably 0.01-1 mol can be used in combination. Total coating amount of light-sensitive silver halide emulsion and the organic silver salt is 0.05 to 10 g / m ² in terms of silver, and preferably from 0.1-4 g / m ^2.

As the reducing agent used in the present invention, those known in the field of photothermographic elements can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property itself but exhibits reducing property by the action of a nucleophile or heat during the development process can also be used. Examples of reducing agents used in the present invention include US Pat. No. 4,500,626.
No. 49-50, No. 4,839,272, No. 4,
330,617, 4,590,152, 5,0
17,454, 5,139,919, JP-A-60
-140,335, pages (17)-(18), ibid. 57.
-40,245, 56-138,736, 59
-178,458, 59-53,831, 59
-182,449, 59-182,450, 6
0-119,555, 60-128,436, 60-128,439, 60-198,540,
No. 60-181, 742, No. 61-259, 253.
No. 62-201, 434, and No. 62-244, 04.
No. 4, 62-131, 253, 62-131, 62
No. 56, No. 63-10, 151, No. 64-13, 54
No. 6, pages (40) to (57), JP-A-1-120,5
No. 53, No. 2-32, 338, No. 2-35, 451
No. 2-234, 158, 3-160, 443
And EP-A-220,746, pages 78 to 96, and the like. Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

When a diffusion resistant reducing agent is used, an electron transfer agent and / or
Alternatively, electron transfer agent precursors can be used in combination. Particularly preferably, said US Pat. No. 5,139,
919, European Patent Publication No. 418,743, JP-A-1
Those described in Nos. -138,556 and 3-102,345 are used. Further, a method of stably introducing into a layer as described in JP-A-2-230,143 and JP-A-2-235,044 is preferably used. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agent or its precursor. It is desirable that the mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one that does not substantially move in the layer of the light-sensitive material among the reducing agents described above, and preferably hydroquinone, Sulfonamide phenols, sulfonamide naphthols, JP-A-53-
110827, U.S. Pat. Nos. 5,032,487, 5,026,634, and 4,839,272, and compounds described as electron donors, and a diffusion-resistant and reducing dye described later. Donor compounds and the like can be mentioned. Further, an electron donor precursor as described in JP-A-3-160,443 is also preferably used. Further, the reducing agent can be used in the intermediate layer and the protective layer for various purposes such as prevention of color mixture, improvement of color reproduction, improvement of white background, and prevention of silver transfer to dye fixing element. Specifically, European Patent Publication No. 52
4,649, 357,040, Japanese Patent Laid-Open No. 4-24
No. 9,245, No. 2-64,633, No. 2-46,4
No. 50 and the reducing agents described in JP-A No. 63-186,240 are preferably used. In addition, Japanese Examined Patent Publication No. 3-63,733,
JP-A-1-150,135, 2-110,557
Development inhibitor releasing reducing compounds such as those described in JP-A Nos. 2-64,634, 3-43,735 and EP-A-451,833 can also be used. In the present invention, the total amount of the reducing agent added is 0.01 to 20 mol per mol of silver,
It is particularly preferably 0.1 to 10 mol.

In the present invention, silver can be used as the image forming substance. In addition, when silver ions are reduced to silver under high temperature conditions, they may contain a compound that generates or releases a mobile dye corresponding to this reaction or vice versa, that is, contains a dye-donating compound. it can. Examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain.
Specific examples of color developing agents and couplers are described in T.W. H. James
Author "The Theory of the Photographic Process" 4th Edition, pages 291 to 334 and 354 to 361, RD-30
No. 7,105, page 871, JP-A-58-123,533.
No. 58-149,046, 58-149,04
No. 7, No. 59-111, 148, No. 59-124, 3
99, 59-174, 835, 59-231,
No. 539, No. 59-231, 540, No. 60-2, 9
50, 60-2, 951, 60-14, 242
No. 60, No. 60-233, 474, No. 60-66, 249, etc.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye in an image form. This type of compound can be represented by the following general formula [LI]. ((Dye) _m -Y) _n -Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image-like structure. A diffusivity of the compound represented by ((Dye) _m -Y) _n -Z corresponding to or opposite to the photosensitive silver salt having a latent image on the (dye) _m-
Y is released, and the released (Dye) _m −Y and ((Dy) _m −Y
e) _m- Y) _n- Z represents a group having a property of causing a difference in diffusibility, m represents an integer of 1 to 5, n represents 1 or 2, and m and n One of
If not, the plurality of Dyes may be the same or different. Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds. In addition, the following items (1) to (5) are for forming a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and is the diffusible dye image (positive dye image) corresponding to the development of silver halide ( To form a negative dye image).

US Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, 3,482,972 and Japanese Patent Publication No. 3-68. No. 387, etc., a dye developing agent in which a hydroquinone-based developing agent and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide. As described in U.S. Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can be used. . An example is U.S. Pat. No. 3,983.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 4,199,
Compounds that release a diffusible dye by the intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354 and the like.

US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,783.
No. 396, Open Technical Report 87-6, 199, JP-A-64-1
As described in No. 3,546, a non-diffusible compound that reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used. Examples thereof include U.S. Pat. Nos. 4,139,389 and 4,139,379.
No. 59-185,333, 57-84,4.
Compounds which release diffusible dyes by a nucleophilic substitution reaction in the molecule after reduction described in US Pat. No. 4,232,107, JP-A-59-101,64
9, No. 61-88,257, RD24,025 (1
984) 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-56-142,5.
30, U.S. Pat. Nos. 4,343,893 and 4,61
Compounds which release a diffusible dye by cleavage of a single bond after reduction as described in US Pat.
Nitro compounds releasing a diffusible dye after electron acceptance as described in U.S. Pat.
Examples thereof include compounds that release a diffusible dye after electron acceptance as described in JP-A No. 9,610.

As more preferable ones, European Patent No. 220,746, Open Technical Report 87-6,199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-201,6.
No. 53, No. 63-201, 654, No. 64-18, 5
No. 46, etc., a compound having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, one molecule described in JP-A-1-26,842. A compound having SO ₂ —X (where X has the same meaning as above) and a hand-withdrawing group, and a PO—X bond (where X has the same meaning as above) described in JP-A No. 63-271,344. ) And a compound having an electron-withdrawing group, JP-A-63-271341
C-X 'bond (X' is X as defined or or -SO ₂ - and represented) in one molecule described in JP compound having an electron attractive group is mentioned. Further, JP-A-1-161,237,
Compounds described in JP-A-1-161,842, in which a single bond is cleaved after reduction by a π bond conjugated with an electron-accepting group to release a diffusible dye, can also be used. Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include compounds (1) to (3), (7) to (10), (12), (1) described in EP 220,746 or US Pat. No. 4,783,396.
3), (15), (23) to (26), (31), (3
2), (35), (36), (40), (41), (4
4), (53) to (59), (64), (70), and compounds (11) to (11) described in Kokai Giho 87-6,199.
(23), compounds (1) to (84) described in JP-A-64-13546.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidant of a reducing agent. Specifically, British Patent No. 1,330,524, Japanese Patent Publication No. 48-39,165,
U.S. Pat. Nos. 3,443,940 and 4,474,86
No. 7, 483, 914 and the like. Reducible to silver halide or organic silver salt,
A compound that releases a diffusible dye when the other party is reduced (DR
R compound). Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. A typical example thereof is US Pat. No. 3,92.
8,312, 4,053,312, 4,05
5,428, 4,336,322, JP-A-59-
65,839, 59-69,839, 53-
3,819, 51-104,343, RD17,
465, U.S. Pat. Nos. 3,725,062 and 3,7.
28,113, 3,443,939, JP-A-58.
-116,537, 57-179,840, U.S. Pat. No. 4,500,626 and the like. DR
Specific examples of the R compound include the above-mentioned US Pat.
The compounds described in Columns 22 to 44 of No. 0626 can be mentioned. Among them, the compounds (1) to (3), (10) to (13), ( 16) ~
(19), (28) to (30), (33) to (35),
(38) to (40) and (42) to (64) are preferable.
The compounds described in US Pat. No. 4,639,408, columns 37 to 39 are also useful. In addition, as the coupler and the dye-donating compound other than the general formula [LI] described above, a dye silver compound in which an organic silver salt and a dye are bound (Research Disclosure May 1978 issue, pages 54 to 58, etc.), Azo dyes used in the heat developable silver dye bleaching method (US Pat. No. 4,235,957, Research Disclosure, 1976, No. 4, pages 30 to 32, etc.), leuco dyes (US Pat. No. 3,985, 565 and 4,02
2,617, etc.) can also be used.

Hydrophobic additives such as dye-donor compounds and diffusion-resistant reducing agents can be incorporated into the layers of the photothermographic element by known methods such as those described in US Pat. No. 2,322,027. it can. In this case, US Pat.
55,470, 4,536,466, 4,53
No. 6,467, No. 4,587, 206, No. 4,55
No. 5,476, No. 4,599,296, Japanese Examined Patent Publication 3-6
A high-boiling point organic solvent such as that described in No. 2,256 can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. In addition, two or more kinds of these dye donating compounds, diffusion resistant reducing agents, high boiling point organic solvents and the like can be used in combination. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, and more preferably 1 g to 0.1 g, relative to 1 g of the dye-donor compound used. Also, 1 cc or less per 1 g of binder, further 0.5 cc
Below, 0.3 cc or less is particularly suitable. See also
-39,853 and JP-A-51-59,943, dispersion methods using polymers and JP-A-62-30,2.
The method of adding a fine particle dispersion described in No. 42 etc. can also be used. In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained 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, Japanese Unexamined Patent Publication No. 59-157,636 (3)
The surfactants described in Research Disclosure, pages 7 to 38 can be used. In the heat-developable photosensitive element of the present invention, a compound capable of activating development and stabilizing an image at the same time can be used. The specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

In a system for forming an image by diffusion transfer of a dye, for the purpose of improving the white background of the obtained image by immobilizing or colorless an unnecessary dye or coloring matter in the constituent layers of the photothermographic element of the present invention. Various compounds can be added. Specifically, European Published Patent No. 353,741
No. 461,416, JP-A-63-163,345.
No. 62-203,158 can be used.

Various pigments and dyes can be used in the constituent layers of the heat-developable photosensitive element of the present invention for the purpose of improving color separation and increasing sensitivity. Specifically, the compounds described in Research Disclosure and European Published Patent No. 479,1
67, 502,508, JP-A-1-167,83.
No. 8, No. 4-343, 355, No. 2-168, 252
No. 6, JP-A-61-20,943, European Published Patent No. 47
The compounds and layer constitutions described in No. 9,167, No. 502,508 and the like can be used.

In a system for forming an image by diffusion transfer of a dye, a dye fixing element is used together with a photothermographic element. The dye fixing element is in the form of being separately coated on a support separate from the light-sensitive material. Regarding the relationship between the light-sensitive material and the dye fixing element, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention. The dye fixing element preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat. No. 4,50.
0,626, columns 58 to 59, JP-A-61-88,25.
No. 5, pages (32) to (41) and JP-A-1-161,23
No. 6, pages (4) to (7), the mordants described in US Pat. Nos. 4,774,162, 4,619,883, and 4,594,308. it can. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used. The binder used in the dye fixing element of the present invention is
The hydrophilic binders mentioned above are preferred. Further, it is preferable to use carrageenans as described in European Patent Publication No. 443,529 and latexes having a glass transition temperature of 40 ° C. or lower as described in Japanese Patent Publication No. 3-74,820. If necessary, a protective layer for the dye fixing element,
Auxiliary layers such as a release layer, an undercoat layer, an intermediate layer, a back layer and an anti-curl layer can be provided. In particular, it is useful to provide a protective layer.

In the constituent layers of the heat-developable photosensitive element and the dye fixing element, a high boiling point organic solvent can be used as a plasticizer, a slipping agent or an agent for improving the peelability between the light-sensitive material and the dye fixing element. Specific examples include those described in Research Disclosure and JP-A-62-245,253. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in “Modified Silicone Oil” technical data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective. Silicone oils described in JP-A Nos. 62-215,953 and 63-46,449 are also effective.

An anti-fading agent may be used in the photothermographic element and the dye fixing element. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a certain kind of metal complex, and the dye image stabilizer and the ultraviolet absorber described in the above Research Disclosure are also useful. Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. In addition, JP-A-61
The compounds described in -159,644 are also effective. As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794 etc.), 4-thiazolidone compounds (US Pat. No. 3,352,681 etc.), benzophenone compounds (JP-A-46- 2,784) and others, JP-A-54-48,535 and 62-1.
36,641 and 61-88,256. Further, the ultraviolet absorbing polymer described in JP-A-62-260,152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155 and 4,245.
No. 018, columns 3 to 36, No. 4,254,195, number 3
Column-8, JP-A-62-174,741 and 61-8
8, 256 (27) to (29), 63-199,
248, JP-A-1-75,568, 1-74,2
There are compounds described in No. 72 and the like.

The anti-fading agent for preventing the fading of the dye transferred to the dye fixing element may be contained in the dye fixing element in advance, or the dye may be externally applied such as the photothermographic element or a transfer solvent described later. You may make it supply to a fixed element. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination with each other. A fluorescent whitening agent may be used in the photothermographic element and the dye fixing element. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing element or supply it from the outside such as a photothermographic element or a transfer solvent. As an example, K. Veenkataraman edited "The Chem
istry of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61
The compound described in -143752 etc. can be mentioned. More specifically, a stilbene compound,
Examples include coumarin-based compounds, biphenyl-based compounds, benzoxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, and carbostyryl-based compounds.
The fluorescent whitening agent can be used in combination with an anti-fading agent or an ultraviolet absorber. Specific examples of these anti-fading agents, ultraviolet absorbers and fluorescent whitening agents are described in JP-A-62-215,27.
2 (125)-(137), JP-A-1-161,
No. 36, pages (17) to (43).

The hardener used in the constituent layers of the heat-developable light-sensitive element and the dye-fixing element is described in Research Disclosure, US Pat. Nos. 4,678,739, column 41, and 4,791,042. Sho 59-116,655
No. 62-245, 261, 61-18, 942.
And the hardeners described in JP-A-4-218,044 and the like. More specifically, aldehyde type hardener (formaldehyde etc.), aziridine type hardener, epoxy type hardener, vinyl sulfone type hardener (N, N'-ethylenebis (vinylsulfonylacetamide) ethane Etc.), N-
Examples thereof include methylol type hardeners (dimethylolurea etc.) and polymer hardeners (compounds described in JP-A-62-234157). These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of the coated gelatin. The layer to be added may be any layer of the light-sensitive material and the constituent layer of the dye fixing element, or may be divided into two or more layers and added.

Various antifoggants or photographic stabilizers and their precursors can be used in the constituent layers of the photothermographic element and the dye fixing element. Specific examples thereof include the aforementioned Research Disclosure, US Pat. Nos. 5,089,378, 4,500,627, 4,614,702, and JP-A 64-13,546 (7). (9) page, (57) to (71) page and (8
1)-(97), U.S. Pat. No. 4,775,610,
4,628,500, 4,983,494, JP-A-62-174,747, 62-239,148.
No. 63-264,747, JP-A-1-150,1.
No. 35, No. 2-110,557, No. 2-178,65
No. 0, RD17, 643 (1978) (24)-(2
5) The compounds described on page etc. are mentioned. These compounds are preferably used in an amount of 5 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, and more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, per mol of silver.

In the constituent layers of the heat-developable photosensitive element and the dye-fixing element, a coating aid, a peeling property improving property, a slip property improving property, an antistatic property,
Various surfactants can be used for the purpose of promoting development and the like. Specific examples of the surfactant include Research Disclosure, JP-A Nos. 62-173,463 and 62-62.
No. 183,457. The constituent layers of the heat-developable photosensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, antistatic properties, improving releasability and the like. As typical examples of the organic fluoro compound, JP-B-57-9058, columns 8 to 17, JP-A-61-209 can be used.
No. 44, No. 62-135826, or the like, or a fluorine-containing surfactant such as a fluorine-containing surfactant such as a fluorine-containing compound such as a fluorine oil or a solid fluorine-containing compound resin such as a tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the photothermographic element and the dye fixing element for the purpose of preventing adhesion and improving slipperiness. Matting agents such as silicon dioxide, polyolefin or polymethacrylate are disclosed in JP-A-61-88.
In addition to the compounds described on page 256 (29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, and the like are disclosed in JP-A-63-274944 and JP-A-63-274944.
There are compounds described in No. 274952. In addition, the compounds described in the above Research Disclosure can be used. In addition, the constituent layers of the photothermographic element and the dye fixing element may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32), JP-A-3.
-11,338, Japanese Patent Publication No. 2-51,496 and the like.

In the present invention, an image forming accelerator can be used in the photothermographic element and / or the dye fixing element. The image formation accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and photothermographic treatment. It has functions such as promoting the transfer of dyes from the element layer to the dye fixing layer. From the physicochemical functions, bases or base precursors, nucleophilic compounds, high boiling organic solvents (oils), thermal solvents, surfactants. , And compounds that interact with silver or silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof are described in US Pat. No. 4,678,739, columns 38 to 40.

In the present invention, various development stoppers can be used in the photothermographic element and / or the dye fixing element for the purpose of always obtaining a constant image with respect to variations in the processing temperature and the processing time during development. . The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or inhibits development by interacting with silver and a silver salt. Compound. Specific examples thereof 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. For more details, see JP-A-6
2-253, 159 (31) to (32).

In the present invention, the support for the heat-developable photosensitive element or dye fixing element is one that can withstand the processing temperature. Generally, papers and synthetic polymers (films) described in "Basics of Photographic Engineering-Silver Salt Photographs-edition" edited by The Photographic Society of Japan, published by Corona Publishing Co., Ltd. (1979) (223) to (240) pages. ) And other 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, Film method synthetic paper made from polypropylene etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass etc. Is used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. The laminate layer may contain pigments and dyes such as titanium oxide, ultramarine blue and carbon black as required. In addition, JP-A-62-253,159 (29)-(31), JP-A-1-161,236 (14)-(17), JP-A-63-316,848
No. 2, JP-A-2-22651, and JP-A-3-56,955.
No. 5,001,033 and the like can be used. The back surface of these supports may be coated with a hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents. Specifically, JP-A-63-220,24
The support described in No. 6 can be used. Further, the surface of the support is preferably subjected to various surface treatments and undercoats for the purpose of improving the adhesion with the hydrophilic binder.

As a method for exposing and recording an image on the photothermographic element, for example, a method of directly photographing a landscape or a person using a camera or the like, or exposing through a reversal film or a negative film using a printer or an enlarger is used. Method, scanning exposure of the original image through a slit, etc. using an exposure device of a copying machine, scanning exposure by causing image information to emit light through a light emitting diode, various lasers (laser diode, gas laser, etc.) Method (Japanese Patent Application Laid-Open Nos. 2-129,625 and 5-17611)
No. 4, No. 5-199872, etc.), a method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, and exposing directly or through an optical system. is there.

As described above, as a light source for recording an image on a photothermographic element, natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source, etc., US Pat. Kaihei 2-53,
The light source and the exposure method described in Nos. 378 and 2-54,672 can be used. Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material capable of exhibiting non-linearity between polarization and an electric field, which appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (KDP). ), Lithium iodate, inorganic compounds typified by BaB ₂ O ₄ , urea derivatives, nitroaniline derivatives, for example, nitropyridine-N such as 3-methyl-4-dichloropyridine-N-oxide (POM). -Oxide derivatives, JP-A-61-53462 and JP-A-62-2104
The compound described in No. 32 is preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. Further, the above-mentioned image information is an image signal obtained from a video camera, an electronic still camera, or the like, NTV signal standard (NT
For example, a television signal represented by SC), an image signal obtained by dividing an original image into a large number of pixels such as a scanner, or an image signal created by using a computer represented by CG or CAD can be used.

The heat-developable photosensitive element and / or dye fixing element of the present invention may have a form having a conductive heating element layer as a heating means for heat development and diffusion transfer of dye. The heat generating element in this case is disclosed in JP-A-61-114.
Those described in No. 5,544 can be used. The heating temperature in the heat development step is about 50 ° C to 250 ° C, and particularly about 60 ° C to 180 ° C is useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the end of the heat development process. 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 is particularly 50 ° C. or higher and about 10 ° C. higher than the temperature in the heat development step.
Up to low temperatures are preferred.

In the present invention, US Pat. No. 4,704,345
No. 4,740,445, JP-A-61-238,0.
The method described in No. 56, etc., in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is preferable. In this method, the heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, the temperature is preferably 50 ° C to 100 ° C. Examples of the solvent used for acceleration of development and / or diffusion transfer of dye include:
Water, a basic aqueous solution containing an inorganic alkali metal salt or an organic base (the bases described in the section of the image formation accelerator are used), a low boiling point solvent or a low boiling point solvent and water or the above base. A mixed solution with a polar aqueous solution may be mentioned. Further, a surfactant, an antifoggant, a complex-forming compound with a poorly soluble metal salt, an antifungal agent, and an antibacterial agent may be contained in the solvent. Water is preferably used as the solvent used in the steps of heat development and diffusion transfer, but any commonly used water may be used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the heat developing apparatus using the photothermographic element and the dye fixing element of the present invention, water may be used up, or may be circulated for repeated use.
In the latter case, water containing the components eluted from the material will be used. Further, JP-A-63-144,354 and 63
-144,355, 62-38,460, the apparatus and water described in Unexamined-Japanese-Patent No. 3-210,555 etc. may be used.

These solvents can be applied to the photothermographic element, the dye fixing element or both of them. The amount used may be not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coated film. As a method of giving this water,
For example, the methods described in JP-A-62-253,159, page (5) and JP-A-68-85,544 are preferably used. Also, the solvent is enclosed in microcapsules,
It can also be used by preliminarily incorporating it in the form of a hydrate in the photothermographic element or the dye fixing element or both. The temperature of the applied water may be 30 ° C to 60 ° C as described in JP-A-63-85,544. In particular, it is useful to set the temperature to 45 ° C. or higher for the purpose of preventing the growth of various fungi in water.

In order to promote dye transfer, a system in which a hydrophilic thermal solvent that is solid at room temperature and dissolves at high temperature is incorporated in the photothermographic element and / or the dye fixing element can also be adopted. The layer to be incorporated may be any of a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but a dye fixing layer and / or a layer adjacent thereto is preferable. Examples of hydrophilic thermal solvents are ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocycles.

As a heating method in the developing and / or transferring step, a heated block or plate is brought into contact with a heating plate, a hot presser, a heating roller, a heating drum, a halogen lamp heater, an infrared and far infrared lamp heater. There is a method of contacting with, etc., or passing through in a high temperature atmosphere. The method described in JP-A-62-253,159 and JP-A-61-147,244, page (27) can be applied to the method of superimposing the heat-developable photosensitive element and the dye fixing element.

Any of a variety of heat developing apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-7
5,247, 59-177,547, 59-1
81,353, 60-18,951, No. 62
-25,944, JP-A-6-95338 and 6-9.
The device described in No. 5267 and the like are preferably used. Further, as a commercially available apparatus, Pictrostat 100, Pictrostat 200, Pictrography 3000, Pictrography 2000, and the like manufactured by Fuji Photo Film Co., Ltd. can be used.

[0082]

The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 A method for preparing a dispersion of zinc hydroxide will be described. 12.5 g of zinc hydroxide having an average particle size of 0.2 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 ml of a 4% gelatin aqueous solution,
30 using glass beads with an average particle size of 0.75 mm in a mill
Grind for minutes. The glass beads were separated to obtain a zinc hydroxide dispersion.

Next, a method for preparing a dispersion of the electron transfer agent will be described. 10 g of electron transfer agent (1), 0.5 g of polyethylene glycol nonylphenyl ether as a dispersant, and 0.5 g of anionic surfactant (1) were added to a 5% aqueous gelatin solution, and glass beads having an average particle size of 0.75 mm were milled. Used for 60 minutes. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.35 μm.

[0085]

[Chemical 11]

[0086]

[Chemical 12]

Next, a method for preparing a dye trapping agent dispersion will be described. Polymer latex (1) (13% solid content)
108 ml, nonionic surfactant (1) 20 g, water 123
While stirring 2 ml of the mixed solution, 600 ml of a 5% aqueous solution of anionic surfactant (1) was added over 10 minutes. The dispersion thus prepared was concentrated and desalted to 500 ml using an ultrafiltration module. Next 1500 ml
Water was added and the same operation was repeated once again to obtain 500 g of a dye trapping agent dispersion.

[0088]

[Chemical 13]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described. The cyan, magenta, and yellow dye-donating compounds and the gelatin dispersion of the electron donor were adjusted according to the formulations shown in Table 1. That is, each oil phase component was heated and dissolved at about 60 ° C to form a uniform solution, and this solution and about 6
The aqueous phase components heated to 0 ° C were added, and the mixture was stirred and mixed, and then dispersed by a homogenizer for 13 minutes at 12000 rpm. Water was added to this and stirred to obtain a uniform dispersion.

[0090]

[Table 1]

[0091]

Embedded image

[0092]

[Chemical 15]

[0093]

Embedded image

[0094]

[Chemical 17]

[0095]

[Chemical 18]

[0096]

[Chemical 19]

[0097]

Embedded image

[0098]

[Chemical 21]

[0099]

[Chemical formula 22]

Next, a method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive silver halide emulsion (1) [For red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 3 g of sodium chloride in 480 ml of water).
g and 30 mg of silver halide solvent (1) were added, and the temperature was 45 ° C.
The solution (I) and the solution (II) shown in Table 2 were simultaneously added to the sample (which was kept warm) at a constant flow rate for 20 minutes. After 5 minutes, (III) in Table 2
Solution and (IV) solution were added simultaneously at the same flow rate for 25 minutes. Also (I
II), 10 minutes after the addition of the solution (IV), an aqueous solution of a gelatin dispersion of the dye (containing 105 g of water, 1 g of gelatin, 70 mg of the dye (1), 139 mg of the dye (2), and 5 mg of the dye (3) at 45 ° C.) Which was kept warm) was added over 20 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.2 and pAg to 7.7, and 4.1 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. 250 mg of -1,3,3a, 7-tetrazaindene and 1.8 mg of chloroauric acid were added, and the mixture was optimally chemically sensitized at 60 ° C and then cooled. Thus, a monodisperse cubic silver chlorobromide emulsion 635 having an average grain size of 0.30 μm
g was obtained.

[0103]

[Chemical formula 23]

[0104]

[Table 2]

[0105]

[Chemical formula 24]

Photosensitive Silver Halide Emulsion (2) [For red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (20 g of gelatin, 0.5 g of potassium bromide, 6 g of sodium chloride in 783 ml of water).
and 30 mg of silver halide solvent (1) were added, and the mixture was heated to 65 ° C.
The solution (I) and the solution (II) shown in Table 3 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 30 minutes. After 5 minutes, (III) in Table 3
Solution and (IV) solution were added simultaneously at an equal flow rate for 15 minutes. Also (I
II), 2 minutes after the start of the addition of solution (IV), an aqueous solution of a gelatin dispersion of dye (containing 0.9 g of gelatin, 76 mg of dye (1), 150 mg of dye (2), and 5 mg of dye (3) in 95 ml of water) (Incubated at 50 ° C.) was added over 18 minutes.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and pAg to 7.8, and sodium thiosulfate 2.8 mg and 4-hydroxy-6-methyl were added. -1,3,3a, 7-Tetrazaindene (175 mg) and chloroauric acid (1.2 mg) were optimally chemically sensitized at 60 ° C, and then antifoggant (2) (163 mg) was added, followed by cooling. Thus, the average particle size of 0.
635 g of 50 μm monodisperse cubic silver chlorobromide emulsion was obtained.

[0108]

[Table 3]

[0109]

[Chemical 25]

Photosensitive Silver Halide Emulsion (3) [For Green Sensitive Emulsion Layer] Well-stirred aqueous gelatin solution (20 g of gelatin in 690 ml of water, 0.5 g of potassium bromide, 4 parts of sodium chloride).
g and 15 mg of silver halide solvent (1) were added, and the temperature was 48 ° C.
The solution (I) and the solution (II) shown in Table 4 were simultaneously added to the sample (which was kept warm) at a constant flow rate for 8 minutes. 10 minutes later (III) in Table 4
Solution and (IV) solution were added simultaneously at the same flow rate for 32 minutes. Also (I
II), 1 minute after the addition of the solution (IV), an aqueous solution of a gelatin dispersion of a dye (2.5 g of gelatin and 250 mg of the dye (4) in 100 ml of water and kept at 45 ° C.) was added all at once. .

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and sodium thiosulfate 9.4 mg and 4-hydroxy-6-methyl were added. 263 mg of -1,3,3a, 7-tetrazaindene was added, optimal chemical sensitization was performed at 68 ° C, and 163 mg of antifoggant (2) was added, followed by cooling. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.27 μm was obtained.

[0112]

[Table 4]

[0113]

[Chemical formula 26]

Photosensitive Silver Halide Emulsion (4) [For Green Sensitive Emulsion Layer] Well-stirred gelatin aqueous solution (gelatin 20 g, potassium bromide 0.3 g, sodium chloride 6 in 700 ml of water).
g and 15 mg of silver halide solvent (1) are added, and the temperature is 55 ° C.
The solution (I) and the solution (II) shown in Table 5 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 20 minutes. After 10 minutes, (II in Table 5
Solution (I) and solution (IV) were added simultaneously at an equal flow rate for 20 minutes. In addition, 1 minute after the addition of the solutions (III) and (IV), an aqueous solution of a gelatin dispersion of a dye (a mixture of 1.8 g of gelatin and 180 mg of the dye (4) in 95 ml of water and kept at 45 ° C.) was collectively added. Was added.

After washing with water and desalting by a conventional method, 20 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7.6, and 1.0 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. 46 mg of -1,3,3a, 7-tetrazaindene and 0.6 mg of chloroauric acid were added for optimum chemical sensitization at 68 ° C, and then 163 mg of the antifoggant (2) was added, followed by cooling. Thus, the average particle size of 0.
635 g of a 45 μm monodisperse cubic silver chlorobromide emulsion was obtained.

[0116]

[Table 5]

Photosensitive Silver Halide Emulsion (5) [For blue-sensitive emulsion layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.5 g of potassium bromide, 5 g of sodium chloride in 690 ml of water).
g and 15 mg of silver halide solvent (1) were added, and the temperature was 51 ° C.
The solution (I) and the solution (II) shown in Table 6 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 8 minutes. After 10 minutes, (III) in Table 6
Solution and (IV) solution were added simultaneously at the same flow rate for 32 minutes. Also (I
One minute after the addition of the solutions (II) and (IV) is completed, an aqueous solution of the dye (water 95
The dye (5) (220 mg) and the dye (6) (110 mg), which were kept warm at 45 ° C., were added all at once to 100 ml of methanol and 5 ml of methanol.

After washing and desalting in a conventional manner, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.8, and sodium thiosulfate 4.8 mg and 4-hydroxy-6-methyl were added. -1,3,3a, 7-Tetrazaindene (250 mg) was added for optimum chemical sensitization at 68 ° C., and then antifoggant (2) (163 mg) and potassium iodide (94) were added.
After adding mg, it cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0119]

[Table 6]

[0120]

[Chemical 27]

Photosensitive Silver Halide Emulsion (6) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide and 9 g of sodium chloride in 695 ml of water).
g and 15 mg of silver halide solvent (1) were added, and the temperature was 63 ° C.
The solution (I) and the solution (II) shown in Table 7 were simultaneously added to the sample (which was kept warm) at an equal flow rate for 10 minutes. After 10 minutes, (II in Table 7
Solution (I) and solution (IV) were added simultaneously at the same flow rate for 30 minutes. One minute after the addition of the solutions (III) and (IV), an aqueous solution of the dye (66 mg of water and 4 ml of methanol, containing 155 mg of the dye (5) and 78 mg of the dye (6) and kept at 60 ° C.) was put together. Added.

After washing with water and desalting by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust the pH to 6.0 and pAg to 7.8, and 1.6 mg of sodium thiosulfate and 4-hydroxy-6-methyl were added. -1,3,3a, 7-Tetrazaindene (95 mg) and chloroauric acid (0.31 mg) were added for optimal chemical sensitization at 68 ° C, and then 163 mg of antifoggant (2) and 94 mg of potassium iodide were added. , Cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.55 μm was obtained.

[0123]

[Table 7]

Using the above materials, the photosensitive materials (K01) shown in Tables 8 to 10 were formed on the support (1) shown in Table 11.
made.

[0125]

[Table 8]

[0126]

[Table 9]

[0127]

[Table 10]

[0128]

[Table 11]

[0129]

[Chemical 28]

[0130]

[Chemical 29]

[0131]

[Chemical 30]

On the support (2) shown in Table 13, an image receiving material (R01) having the constitution shown in Table 12 was prepared.

[0133]

[Table 12]

[0134]

[Table 13]

[0135]

[Chemical 31]

[0136]

[Chemical 32]

[0137]

[Chemical 33]

[0138]

Embedded image

[0139]

Embedded image

[0140]

Embedded image

[0141]

Embedded image

[0142]

[Chemical 38]

[0143]

[Chemical Formula 39]

Next, exactly the same as the image receiving material R01 except that the compounds represented by the general formulas (1) and (2) are added in a predetermined amount to each layer of the dye fixing element as shown in Tables 14 to 17. Then, image receiving materials R02 to R44 were prepared. Next, as shown in Table 17, an image receiving material R45 was prepared in exactly the same manner as the image receiving material R01 except that a predetermined amount was added to each layer of the dye fixing element as shown in Table 17.

[0145]

[Chemical 40]

[0146]

[Table 14]

[0147]

[Table 15]

[0148]

[Table 16]

[0149]

[Table 17]

The above light-sensitive element (K01) and dye-fixing element (R01 to 45) were processed using the image recording apparatus described in JP-A-1-306852. That is, the original image is scanned and exposed through a slit, and the photosensitive element is exposed at 40 ° C.
After soaking it in water kept warm for 2.5 seconds, squeeze it with a roller, and then immediately superimpose it so that the dye fixing material and the film surface come into contact with each other. Used and heated for 17 seconds. Then, the light-sensitive element and the dye-fixing element were peeled off, and a clear color image corresponding to the original image was obtained on the dye-fixing material. The glossiness of the image surface of the obtained image was measured immediately after processing and after 2 days at 15 ° C. and 90%. The degree of decrease in glossiness after aging is evaluated on a scale of five, and if the decrease in glossiness is small, then 5,
The case where the decrease in gloss was remarkable was set as 1. Table 14 to Table 17
The results are shown in.

The experimental results shown in Tables 14 to 17 are summarized below. Unless otherwise specified, the compound represented by the general formula (1) was added to the second layer and the third layer of the dye fixing element. The same effect of suppressing gloss reduction was observed when any of the sodium salt, potassium salt, lithium salt and guanidinium salt of the compound of the general formula (2) was added. When two or more compounds of the general formula (2) were added, or when two or more compounds of the general formula (2) having different salts were added, the same effect of suppressing gloss reduction as when used alone was observed. The effect of suppressing the decrease in gloss was observed when the compound of the general formula (2) was added as follows. 1. When added to both the second layer and the third layer of the dye fixing element (R02 to 19) 1. When added only to the second layer of the dye fixing element (R2
2) 3. When added only to the third layer of the dye fixing element (R2
1) 4. When the amount of the compound represented by the general formula (2) added is 0.005 to 200 mol per 1 mol of the compound of the general formula (1) (R16 to
19) 5. 5. When the compound of the general formula (1) of the dye fixing element is added to any one of the first layer, the fourth layer and the fifth layer (R23 to 28) 6. 6. When the compound of the general formula (1) is arranged in the second layer of the dye-fixing element and the compound of the general formula (2) is added to the third layer, and vice versa (R31 to 44). When different compounds of the general formula (2) are added to the second layer and the third layer of the dye fixing element (R29, 3
0)

Instead of the above-mentioned photosensitive element (K01), Pictrostat donor PS-D manufactured by Fuji Photo Film Co., Ltd.
Pictrostat 200 and slide enlarging unit SE20 manufactured by Fuji Photo Film Co., Ltd.
0 and a processed positive image of Fuji Color Velvia, which is a standard image, was used for exposure, and a similar experiment was conducted using the image obtained by the processing. Was obtained. An image obtained by exposing and processing a standard printed image using a Pictrostat Donor PS-DII manufactured by Fuji Photo Film Co., Ltd. and a Pictrostat 100 manufactured by Fuji Photo Film Co., Ltd. is used. , When a similar experiment was conducted, almost the same result was obtained.

Example 2 An image receiving material R101 having the constitution shown in Table 18 was produced.

[0154]

[Table 18]

[0155]

Embedded image

[0156]

Embedded image

However, the compounds in Table 18 and Table 19 are
Other than the compounds shown in Chemical formulas 41 and 42, the compounds are the same as those used for the image receiving element R01 shown in Example 1. Further, in place of the guanidine picolinate (Compound 104 of the present invention) in the second layer and the fourth layer, the compounds shown in Table 19 were added in the amounts described, and in the same manner as in R101,
Dye fixing materials R102 to R116 were prepared. Fuji Photo Film Co., Ltd. Pictrostat Donor PS-DH and dye fixing materials R101 to 116 were used, and Fuji Photo Film Co., Ltd. Pictrostat 200 was used to expose and process with a standard image. The same experiment was performed using the obtained images. The same evaluation as in Example 1 was performed. However, although it was a transparent dye fixing material, the glossiness was evaluated by reflection. The results are shown in Table 19.

[0158]

[Table 19]

As shown in Table 19, it can be seen that the dye fixing materials (R105 to 116) in which the compound of the present invention was used in combination suppressed the decrease in gloss as compared with the comparative examples (R101 to 104).

Example 3 A method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive silver halide emulsion (21) [for red-sensitive emulsion layer] Well-stirred aqueous gelatin solution (800 g of gelatin, 12 g of potassium bromide, 80 g of sodium chloride and 80 g of compound (A) in 27 liters of water). The solution (I) and the solution (II) shown in Table 20 were simultaneously added at a constant flow rate for 19 minutes to 2 g of the solution (which was kept at 55 ° C.). After 5 minutes, (II in Table 20
Solution (I) and solution (IV) were added simultaneously at the same flow rate for 24 minutes.

After washing with water and desalting by a conventional method, 880 g of lime-treated ossein gelatin and 2.8 g of compound (B) were added to adjust pH to 6.2 and pAg to 7.7, and a ribonucleic acid decomposition product was obtained. 20.5 g and 51 mg of trimethylthiourea were added, and after optimal chemical sensitization at 60 ° C. for about 70 minutes, 9.0 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and a dye (A ) 3.2 g and KBr 20.5 g were sequentially added and then cooled. Thus, 29.5 kg of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm
I got

[0163]

[Table 20]

[0164]

[Chemical 43]

[0165]

[Chemical 44]

Photosensitive Silver Halide Emulsion (22) [For green emulsion layer] Well stirred gelatin aqueous solution (20 g of gelatin, 0.3 g of potassium bromide and 2 g of sodium chloride in 600 ml of water).
g and 30 mg of the compound (A) were added and kept at 46 ° C.), the solutions (I) and (II) in Table 21 were simultaneously added at an equal flow rate for 10 minutes. After 5 minutes, liquid (III) and (I
Solution V) was added simultaneously at an equal flow rate for 30 minutes. Also (III),
1 minute after the addition of the (IV) solution, 60 ml of a dye solution in methanol was added.
(Including 360 mg of dye (B1) and 73.4 mg of dye (B2)) were added all at once.

After washing with water and desalting by a conventional method (performed with a precipitating agent (B) at pH 4.0), 22 g of lime-treated ossein gelatin was added, and appropriate amounts of NaCl and H ₂ SO ₄ were added to adjust the pH.
Was adjusted to 6.0 and pAg was adjusted to 7.6, 1.8 mg of sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3
180 mg of a, 7-tetrazaindene was added to optimally perform chemical sensitization at 60 ° C., and then 90 mg of an antifoggant (B) was added, followed by cooling. Compound (B) 70 mg as a preservative
And 3 ml of compound (W) was added. Thus, a monodisperse cubic silver chlorobromide emulsion 635 having an average grain size of 0.30 μm
g was obtained.

[0168]

[Table 21]

[0169]

[Chemical formula 45]

[0170]

[Chemical formula 46]

Photosensitive Silver Halide Emulsion (23) [For Blue Sensitive Emulsion Layer] Well stirred gelatin aqueous solution (1582 g of gelatin, 127 g of KBr and 660 mg of compound (A) were added to 29.2 liters of water, and the mixture was heated to 70 ° C.). Solution (I) and solution (II) having the composition shown in Table 22 were added to the solution (which was kept warm), and after 10 minutes, solution (I) was added over 30 minutes each. Further, 5 minutes after the addition of the (II) solution, the (IV) solution was added, and 10 minutes after that, the (III) solution was added, the (III) solution was 27 minutes and 50 seconds, and the (IV) solution was added.
The liquid was added over 28 minutes.

Then, after washing with water and desalting by a conventional method (performed at pH 3.9 using 32.4 g of precipitating agent (A)), 1230 g of lime-treated ossein gelatin and 2.8 g of compound (B) were added. PH 6.1, pAg 8.5
According to. Then, after adding 27.7 mg of sodium thiosulfate and optimally chemically sensitizing at 65 ° C. for about 70 minutes, 17.5 g of dye (C), 2.8 g of antifoggant (C) and 117 ml of compound (W) were added. After adding sequentially, it was cooled. The silver halide grains of the obtained emulsion were octahedral, the grain size was 0.55 μm, and the yield was 29.1 kg.

[0173]

[Table 22]

[0174]

[Chemical 47]

[0175]

[Chemical 48]

Next, a method for preparing a gelatin dispersion of the compound (E) will be described. Compound (E) 0.4 g, high boiling solvent (A) 1.1 g, high boiling solvent (B) 0.1 g, surfactant (A) 0.2 g, surfactant (B) 0 .2
g was weighed, ethyl acetate (9.5 cc) was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution and 60 g of a 16% solution of lime-processed gelatin were mixed by stirring, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. After the dispersion, 29 cc of water for dilution was added. This dispersion is referred to as a dispersion of compound (E).

[0177]

[Chemical 49]

A method for preparing a dispersion of zinc hydroxide will be described. Zinc hydroxide with an average particle size of 0.2 μm 12.5
g, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate as a 4% gelatin aqueous solution 10
In addition to 0 ml, it was ground 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 zinc hydroxide dispersion.

Next, a method for preparing a gelatin dispersion of a dye-donor compound will be described. Cyan dye-donor compound (A
1) 7.3 g, cyan dye-donor compound (A2) 11.0 g, surfactant (B) 0.8 g, compound (G) 1 g, compound (F) 1.3 g, compound ( U)
4.4 g, compound (V) 2.2 g, high-boiling solvent (B) 7 g, high-boiling solvent (C) 3 g, ethyl acetate 26 ml was added and dissolved by heating at about 60 ° C. It was a solution. This solution and a 16% solution of lime-processed gelatin 65
g and 87 cc of water by stirring and mixing, and then 10 with a homogenizer
Dispersed at 10,000 rpm for minutes. After the dispersion, 220 cc of water for dilution was added. This dispersion is referred to as a cyan dye-donor compound dispersion.

[0180]

Embedded image

[0181]

[Chemical 51]

[0182]

[Chemical 52]

3. The magenta dye-donating compound (B)
50 g, compound (D) 0.05 g, compound (G) 0.05 g, surfactant (B) 0.094 g, high boiling point solvent (C) 2.25 g, and ethyl acetate 10 ml was added, It was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 15.2 g of a 16% solution of lime-processed gelatin and 2 parts of water
After mixing 3.5 cc with stirring, the mixture was dispersed with a homogenizer at 10,000 rpm for 10 minutes. After the dispersion, 42 cc of water for dilution was added. This dispersion is called a dispersion of a magenta dye-donor compound.

[0184]

Embedded image

The yellow dye-donor compound (C) was added in an amount of 15
g, 3 g of the compound (E), 1.5 g of the compound (G), 1.4 g of the surfactant (B), 7.5 of the high boiling point solvent (A).
3.9 g of the compound (T) was weighed and 40 ml of ethyl acetate was added.
Was added and dissolved by heating at about 60 ° C. to obtain a uniform solution. This solution, 53 g of a 16% solution of lime-processed gelatin and 8 parts of water
After mixing 5.7 cc with stirring, the mixture was dispersed with a homogenizer at 10,000 rpm for 10 minutes. After the dispersion, 83.7 cc of water for dilution was added. This dispersion is called a yellow dye-donor compound dispersion.

[0186]

[Chemical 54]

From these, on the support (4) of Table 25,
Photosensitive materials (K02) shown in Tables 23 and 24 were prepared.

[0188]

[Table 23]

[0189]

[Table 24]

[0190]

[Table 25]

[0191]

[Chemical 55]

[0192]

[Chemical 56]

[0193]

[Chemical 57]

[0194]

[Chemical 58]

The above photosensitive element (K02) was used as a BGR three-color separation filter (R: 600) using a tungsten bulb.
~ 700 nm, G: 500-590 nm, B: 400-49
It was constructed using a bandpass filter of 0 nm. 2) and exposed at 2500 lux for 1/10 seconds. Fountain solution (about 1 ml / m ² ) was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar, and then the dye fixing element (R01) used in Example 1 was used.
~ 45) and the film surface were in contact with each other. Use a heater that is adjusted so that the surface of the membrane that is supplied with water reaches 83 ° C.
Heated for seconds. Then, the light-sensitive element and the dye-fixing element were peeled off, and a clear color image corresponding to the reverse image of the original image was obtained on the dye-fixing material. The glossiness of the image surface of the obtained image was measured immediately after the treatment and after aging for 3 days at 45 ° C. and 80%. The degree of decrease in glossiness after the lapse of time was evaluated on a scale of five, and the case where the decrease in glossiness was small was 5 and the case where the decrease in glossiness was remarkable was 1. The results are shown in Tables 26 to 29.

[0196]

[Table 26]

[0197]

[Table 27]

[0198]

[Table 28]

[0199]

[Table 29]

The results obtained were almost the same as the results obtained in Example 1.

Further, the photosensitive element (K02) and the dye fixing element (R01 to 45) are combined with Fuji Photo Film Co., Ltd. Pictrostat 200 and A4 proof unit P.
When a similar negative image was exposed using a processed negative of Fuji Color Super HG400, a standard image of which was taken using F300, and a similar experiment was performed using the image obtained by the processing, almost the same result was obtained. Further, when the dye-fixing element (R02 to 19, 21 to 44) in which the compound of the present invention was used in combination, an image having more excellent color reproducibility could be obtained.

Example 4 A method for preparing a photosensitive silver halide emulsion will be described.

Photosensitive Silver Halide Emulsion (1) [Emulsion for Fifth Layer (680 nm Photosensitive Layer)] Aqueous solutions having the compositions shown in Table 30 and (I) and (II) having the compositions shown in Table 31 were stirred well. ) Solution was added simultaneously over 13 minutes, and 10 minutes later, (II) of the composition shown in Table 31 was added.
Solution I and solution IV were added over 33 minutes.

[0204]

[Table 30]

[0205]

[Table 31]

[0206]

Embedded image

Also, 13 minutes after the start of addition of the liquid (III), 27
150 cc of an aqueous solution containing 0.350% of the sensitizing dye (a) was added over a period of time.

[0208]

Embedded image

After washing with water and desalting (pH was set to 4.1 using the precipitating agent (a)) by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 6.0 and pAg to 7. After adjusting to 9, chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are shown in Table 32. The yield of the obtained emulsion was 630 g, which was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 10.2%, and the average grain size was 0.20 μm.

[0210]

[Chemical formula 61]

[0211]

[Table 32]

[0212]

Embedded image

Photosensitive Silver Halide Emulsion (2) [Emulsion for Third Layer (750 nm Photosensitive Layer)] Solution (I) and (II) having the composition shown in Table 34 were added to an aqueous solution having the composition shown in Table 33 and being well stirred. Solution) was added simultaneously for 18 minutes, and 10 minutes after that, Solution (III) and Solution (IV) having the compositions shown in Table 34 were added over 24 minutes.

[0214]

[Table 33]

[0215]

[Table 34]

After washing with water and desalting (pH was set to 3.9 using the precipitating agent (b)) by a conventional method, calcified lime-treated ossein gelatin (calcium content: 150 p
22 g, and redispersed at 40 ° C., 0.39 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene is added to adjust pH to 5.9 and pAg to 7 Adjusted to .8. Then, chemical sensitization was performed at 70 ° C. using the chemicals shown in Table 35. At the end of the chemical sensitization, a sensitizing dye was added as a methanol solution (solution having the composition shown in Table 36). Further, after chemical sensitization, the temperature was lowered to 40 ° C. and 200 g of a gelatin dispersion of a stabilizer described later was added,
Stir well and store. The yield of the obtained emulsion is 938.
It was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 12.6% in g and an average grain size of 0.25 μm.

[0219]

[Table 35]

[0218]

[Table 36]

[0219]

[Chemical formula 63]

[0220]

[Chemical 64]

Photosensitive Silver Halide Emulsion (3) [Emulsion for First Layer (810 nm Photosensitive Layer)] Aqueous solutions having the compositions shown in Table 37 and (II) and (II) having the compositions shown in Table 38 were stirred well. Solution) was added simultaneously for 18 minutes, and 10 minutes after that, Solution (III) and Solution (IV) having the compositions shown in Table 38 were added over 24 minutes.

[0222]

[Table 37]

[0223]

[Table 38]

After washing with water and desalting (pH was set to 3.8 using the precipitating agent (a)) by a conventional method, 22 g of lime-treated ossein gelatin was added to adjust pH to 7.4 and pAg to 7. After adjusting to 8, chemical sensitization was performed at 60 ° C. The compounds used for the chemical sensitization are as shown in Table 39. The yield of the obtained emulsion was 680 g, which was a monodisperse cubic silver chlorobromide emulsion having a coefficient of variation of 9.7%, and the average grain size was 0.32 μm.

[0225]

[Table 39]

A method for preparing a gelatin dispersion of colloidal silver will be described.

To the well-stirred aqueous solution having the composition shown in Table 40, the solution having the composition shown in Table 41 was added over 24 minutes. Then, after washing with water using the precipitating agent (a), 43 g of lime-treated ossein gelatin was added to adjust the pH to 6.3. The average particle size is 0.02 μm and the yield is 51.
It was 2 g. (Dispersion containing 2% silver and 6.8% gelatin)

[0228]

[Table 40]

[0229]

[Table 41]

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described.

Gelatin dispersions of the yellow dye-donor compound, the magenta dye-donor compound and the cyan dye-donor compound were prepared according to the formulations shown in Table 42. That is, each oil phase component was dissolved by heating at about 70 ° C. to form a uniform solution, and the aqueous phase component heated at about 60 ° C. was added and mixed with stirring, and then dispersed with a homogenizer at 10,000 rpm for 10 minutes. Water was added to this and stirred to obtain a uniform dispersion.
Further, a gelatin dispersion of a cyan dye-donating compound was added to an ultra loca module (ultra loca module manufactured by Asahi Kasei: ACV
-3050) was repeatedly diluted with water and concentrated, and the amount of ethyl acetate was reduced to 17.6 times the amount of ethyl acetate in Table 42.

[0232]

[Table 42]

A gelatin dispersion of reducing agent was prepared according to the recipe in Table 43. That is, each oil phase component was dissolved by heating at about 60 ° C., the aqueous phase component heated at about 60 ° C. was added to this solution, and the mixture was stirred and mixed, and then mixed with a homogenizer for 10 minutes for 100 minutes.
Dispersion was carried out at 00 rpm to obtain a uniform dispersion. Further, ethyl acetate was removed from the obtained dispersion using a vacuum deorganization solvent apparatus.

[0234]

[Table 43]

A gelatin dispersion of the stabilizer was prepared as per the formulation in Table 44. That is, each oil phase component was dissolved at room temperature, the aqueous phase component heated to about 40 ° C. was added to this solution, and the mixture was stirred and mixed, and then mixed with a homogenizer for 10 minutes at 10000 r.
dispersed at pm. Water was added to this and stirred to obtain a uniform dispersion.

[0236]

[Table 44]

A gelatin dispersion of zinc hydroxide was prepared according to the recipe in Table 45. That is, after mixing and dissolving each component, a glass mill with an average particle size of 0.75 mm
Acid separated for a minute. Further, the glass beads were separated and removed to obtain a uniform dispersion. (Zinc hydroxide has an average particle size of 0.
The one having a thickness of 25 μm was used. )

[0238]

[Table 45]

Next, a method for preparing a gelatin dispersion of the matting agent added to the protective layer will be described. A liquid prepared by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, and dispersed by stirring at high speed. Subsequently, methylene chloride was removed using a vacuum desolventizer to obtain a uniform dispersion having an average particle size of 4.3 μm.

[0240]

[Chemical 65]

[0241]

[Chemical formula 66]

[0242]

Embedded image

[0243]

[Chemical 68]

[0244]

[Chemical 69]

[0245]

Embedded image

[0246]

Embedded image

[0247]

Embedded image

[0248]

Embedded image

[0249]

[Chemical 74]

[0250]

[Chemical 75]

Photosensitive materials K03 shown in Tables 46 and 47 were prepared using the above materials.

[0252]

[Table 46]

[0253]

[Table 47]

[0254]

[Chemical 76]

[0255]

Embedded image

[0256]

Embedded image

[0257]

Embedded image

[0258]

Embedded image

Using the above light-sensitive material (K03) and the dye-fixing materials R01 to R45 used in Example 1, a full color black image and a built-in image were obtained using a digital color printer, Fujis Pictogram 3000, manufactured by Fuji Photo Film Co., Ltd. The ribbing pattern was output.

The output image was left under the condition of 35 ° C. and 80% RH for 2 weeks. The glossiness of the entire black image before and after that was measured in the same manner as in Example 1. In Tables 48 to 51, the decrease in glossiness was evaluated in the same manner as in Example 1. R02 to 19 and 21 to 44 using the compound of the present invention show a decrease in glossiness as compared with Comparative Examples (R01, 20) in the case where the compound of the present invention is not used in combination and Comparative Example (R45) using the comparative compound. You can see that it is small.

[0261]

[Table 48]

[0262]

[Table 49]

[0263]

[Table 50]

[0264]

[Table 51]

The sample for which the calibration pattern was output was stored under the conditions of 80 ° C. and 70% RH, and the increase in white background density was evaluated. In Table 48 to Table 51, the test time 7
The results of measuring the daily concentration increase using FCD3 manufactured by Fuji Photo Film Co., Ltd. are shown. It can be seen that when the compound of the present invention is used in combination, a slight increase in white background density is suppressed.

As a light-sensitive material, Fuji Photo Film Co., Ltd.
When the same test was performed using PICTROGRAPHIC DONOR PG-D, almost the same results as above were obtained.

Example 5 A solution as shown in Table 52 was prepared using the compound of the present invention. About 20 mg of guanidine picolinate crystals was added to 20 ml of the aqueous solution, and stored in an open system at 10 ° C. for 24 hours. The state of precipitation of crystals in the aqueous solution in that state was evaluated as follows. ◯: No crystals are seen. Δ: Some crystals are seen. X: Many crystals are seen.

[0268]

[Table 52]

When the compound of the present invention is not used in combination (S01
In Nos. 03 to 03), precipitation of crystals is often seen. In addition, when the compounds of the general formula (1) of the present invention are used in combination and the compounds of the general formula (2) are used in combination (S04, S05), precipitation is often observed. On the other hand, when the compound of the present invention is used in combination (S06 to 11), the precipitation of crystals is little or no, and the solution stability is excellent. Particularly, two or more compounds of the general formula (2) are used in combination (eg: S09,
The effect is remarkable with S10 and S11).

[0270]

The image forming method of the present invention has an effect of suppressing a decrease in glossiness after image formation.

Claims (1)

[Claims] 1. An image forming method for forming an image using a light-sensitive element and an image-receiving element, wherein one of the light-sensitive element and the image-receiving element contains at least one compound represented by the general formula (1) and a compound represented by the general formula: An image forming method comprising at least one compound represented by (2) and at least one metal compound hardly soluble in water represented by the general formula (3). Embedded image In the general formula (1), E is -S-, -O-, or-.
NR ¹ — (R ¹ represents a hydrogen atom, an alkyl group, an aryl group, or a bond for forming a double bond between N and an atom adjacent to N), and is represented by C as shown above. Adjacent. C represents a carbon atom. Z represents an atomic group necessary for forming a heterocycle with C and E and has no substituent other than D ⁻ . D ^- represents a substituent of C, -CO ₂ ^{-, -}
Indicates SO ₂ ²⁻ or —SO ₃ ²⁻ . Bk ⁺ represents an alkali metal ion, an alkaline earth metal ion, a substituted or unsubstituted guanidinium ion, an aminidium ion, or a quaternary ammonium ion. Embedded image In the general formula (2), E and C are the same as those in the general formula (1). Z represents a group of atoms necessary for forming a heterocycle with C and E, and has substituents X and Y. X
Is -CN, -CHNOH or D ^- Bk ⁺ in the general formula (1).
The group represented by is shown. Y represents a substituent on the heterocycle and represents an alkyl group, an aryl group, a carboxyl group, an alkyloxycarbonyl group, a hydroxy group, an alkyloxy group, an aryloxy group, a halogen atom, a cyano group or an amidoxime group. n represents an integer of 1 to 4. However, X
Is -CN or -CHNOH, n represents an integer of 0 to 4. [Chemical 3] In the general formula (3), M represents a metal other than an alkali metal, W represents an oxide ion, a hydroxide ion, a carbonate ion,
Represents silicate ion, borate ion or aluminate ion. p and m represent integers with which the atomic values of M and W can be balanced, respectively. Note that M _p W _m may have water of crystallization and may form a double salt.