JPH0862806A - Image forming method - Google Patents

Abstract

PURPOSE: To provide a method for forming an excellent image small in coloring of a non-image part by heat developing. CONSTITUTION: A photosensitive element contains a development suppressing agent precursor expressed by the formula, a coloring matter fixing element contains at least one kind of a surfactant selected from among a nonionic, betaine-based and cationic surfactants) and a mordant is a quaternary salt polymer. In the formula, PWR represents a group releasing Timet AF by reducing and AF represents a group functioning as a development suppressing agent after rereased. (Time) represents a group releasing AF through a reaction successively executed after Timet AF is released from PWR, and t represents 0 or integer of 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-developable color and black-and-white image forming method, and further to a light-sensitive element and a dye fixing element used in the image-forming method. In particular, in an image forming method of fixing a movable dye released or formed on an image to a dye fixing element, an image forming method useful for obtaining a positive image having an excellent S / N ratio and a photosensitive material used in the image forming method. The present invention relates to an element and a dye fixing element.

[0002]

2. Description of the Related Art Photothermographic materials are known in this technical field, and the photothermographic material and its process are described, for example, in "Basics of Photographic Engineering", Non-silver photography (ed. 1982, published by Corona Publishing Co., Ltd.). ~ Page 255.

Many methods have been proposed for obtaining a color image by heat development. For example, US Pat. Nos. 3,531,286, 3,761,270 and 4,212.
No. 40, Belgian Patent No. 802519, Research Disclosure Magazine (hereinafter abbreviated as RD) September 1975, pages 31 to 32, etc., proposes a method of forming a color image by combining an oxidant of a developer with a coupler. Has been done.

However, since the photothermographic material for obtaining the above-mentioned color image is a non-fixing type, silver halide remains after the image is formed, and the white background is gradually colored when exposed to strong light or stored for a long time. Is causing a serious problem. Further, the above-mentioned various methods generally have a drawback that it takes a relatively long time for development and an obtained image has only a high fog and a low image density.

In order to improve these drawbacks, a method has been proposed in which a diffusible dye is imagewise formed or released by heating, and the diffusible dye is transferred to a image-receiving material having a mordant with a solvent such as water. (US Patent No. 45
No. 00626, No. 4843914, No. 4503137
No. 4,559,920; JP-A-59-165054).

According to the above method, the developing temperature is still high, and the stability of the photosensitive material over time cannot be said to be sufficient. Therefore, a method of accelerating the development, lowering the development temperature, and simplifying the processing by heating and developing in the presence of a base or a base precursor and a small amount of water to transfer the dye is disclosed in JP-A-59-2.
18443, 61-238056, and European Patent 21.
No. 0660A2 and the like.

Many methods have been proposed for obtaining a positive color image by heat development. Among them, in U.S. Pat. No. 4,559,290, a so-called DRR compound is present in the presence of an oxidation type compound having no color image releasing ability and a reducing agent or a precursor thereof, and the reducing agent is added depending on the exposure amount of silver halide by heat development. A method has been proposed in which the diffusible dye is released by oxidizing the dye and reducing it with a reducing agent remaining without being oxidized. Further, in European Patent Publication No. 220746 and JP-A No. 64-13546, an N—X bond (X represents an oxygen atom, a nitrogen atom or a sulfur atom) as a compound that releases a diffusible dye by a similar mechanism. A heat-developable color light-sensitive material using a compound which releases a diffusible dye by reductive cleavage of is described, and it shows promise. This method comprises at least a photosensitive silver halide, a binder, an electron transfer agent, and / or a precursor thereof, an electron donor and / or a precursor thereof, and a reduced substance which is reduced to release a diffusible dye on a support. Heat-developable color light-sensitive material having a multi-layered dye-donor compound is exposed and heated to oxidize an electron donor depending on the amount of silver halide, and the non-reducing dye-donor compound remains without being oxidized. In this method, a diffusible dye is released by reduction with an electron donor and transferred to a dye fixing material having a mordant to form a positive color image.

In the above-cited patent specifications, a compound which contains a sparingly soluble metal compound in a light-sensitive material and which releases a base by a complex formation reaction of the sparingly soluble metal compound with water as a medium in a dye fixing material ( (Hereinafter referred to as a complex-forming compound), the photosensitive material is exposed to light, water is applied thereto, and then the photosensitive material is superposed on the dye-fixing material and heated to form an image.

In the above positive type heat development color forming method, the white background of the color image is improved (Dmin is suppressed).
Therefore, it is necessary to accelerate silver development in the exposed area and quickly consume the electron donor. Further, in order to increase the image density (maximum density Dmax), it is necessary to suppress the development of the non-exposed area and reduce the fog in silver development. In the thermal development system, certain compounds, such as a nitrogen-containing heterocyclic compound or a mercapto compound, have both an effect of promoting development and an effect of suppressing development, but since the addition amount showing each effect is different, the same addition amount at the same time You cannot expect both significant effects.

On the other hand, in order to produce a high density image in the diffusion transfer type image forming method, a quaternary salt polymer having a strong mordant power is generally effective as a mordant used in the dye fixing element, but the thermal development and the dye fixing element are effective. In the case of simultaneously diffusing and fixing to the positive electrode, fogging of the silver development is likely to occur, so that in the positive color material system, Dmax is rather decreased. This tendency is particularly remarkable when the counter ion of the quaternary salt polymer is a chloride ion. There has been a demand for a method in which a quaternary salt polymer is used as a mordant and heat development, diffusion, and fixing are simultaneously performed, and silver development can be promoted and fog development can be suppressed.

Currently, as image information, there is a large shift from a monochrome image to a color image due to the large amount of information and a variety of expressions, but a monochrome image is preferred and used in a specific field such as a medical field. . Also in the printing field, as a light-sensitive material used in the step of forming a printing plate, one which forms a black and white image is usually used.

The photosensitive materials used in the medical field and printing field are mainly silver halide photographic photosensitive materials. Conventionally, in these fields, a silver halide photographic light-sensitive material is processed through image exposure, development, stopping, fixing, washing with water, and drying. Therefore, it takes time and labor for the treatment, and there is a concern that the treatment chemical may adversely affect the human body and the working environment, contaminate, and may cause pollution due to waste liquid treatment.

Therefore, the image forming method of the light-sensitive material using silver halide is changed from the conventional wet processing using a developing solution to
A technique has been developed which can easily and quickly obtain an image by changing to a dry process such as heating. For such a photothermographic material, for example, Japanese Patent Publication No. 43-4921
And Japanese Examined Patent Publication No. 43-4924, and as a product, "Dry Silver" of 3M Company is mentioned as a typical photosensitive material. The light-sensitive material is a silver halide, an organic silver salt,
And a reducing agent. In this system, unused silver halide and organic silver salt remain in the light-sensitive material, so if exposed to strong light or stored for a long time, the residual silver halide and organic silver salt react and the non-image area becomes colored. Come on.

Further, there is a method capable of dry-processing a black dye image.
Research Disclosure Magazine, September 1978, pages 49-51 (R
No. D17326), but this system also has the same drawbacks as the above because it is an unfixed type in which silver or silver halide is contained in the dye image.

As described above, it is possible to develop a method for forming a color image and a black-and-white image in which a high image has a high Dmax, a low Dmin and a non-image portion is not colored due to storage by simultaneous thermal development and transfer simultaneous processing. Was wanted.

[0016]

Therefore, the first aspect of the present invention
The purpose of is to simultaneously perform development transfer by heating without using a processing solution, and transfer and fix the diffusible dye released or formed by the development reaction to the dye fixing layer to obtain high image quality, high Dmax, and low Dmin. It is an object of the present invention to provide a novel imaging method for forming a color or substantially black or gray positive dye image. A second object of the present invention is that, even when the transferred image is stored under light irradiation or under high temperature and high humidity for a long period of time, discoloration of the image or coloring of the non-image portion does not occur.
It is an object of the present invention to provide a novel imaging method for forming a color or substantially black or gray dye image. A third object of the present invention is to provide a light-sensitive element and a dye-fixing element used in the above image forming method.

[0017]

The above and other objects are achieved by the constitution of the present invention shown below. That is, the present invention provides an imagewise photosensitive element containing at least a photosensitive silver halide, a sparingly soluble metal salt compound, a hydrophilic binder, and a dye-donor compound which releases or forms a diffusible dye in inverse correspondence to the exposure dose. After the exposure or at the same time as the imagewise exposure, the compound capable of complex-forming reaction with the metal ion constituting the sparingly soluble metal salt compound and the dye fixing element containing a mordant are superposed, and in the presence of a hydrophilic thermal solvent or water. In an image forming method of transferring and fixing a diffusible dye released or formed by heat development to a dye fixing layer, the photosensitive element contains a development inhibitor precursor represented by the following general formula [I], Further, the dye fixing element contains at least one kind of surfactant selected from nonionic, betaine and cationic surfactants, and the mordant is a quaternary salt polymer. It was achieved by a light-sensitive element and dye fixing element used in the image forming method and the image forming method according to.

[0018]

[Chemical 4]

The general formula [I] and the general formula [I described later
The compounds I] and [III] are known and are described, for example, in JP-A-63-264747.

In the general formula [I], PWR is US Pat. No. 4,139,389 or US Pat. No. 4,139,3.
79, an electron-accepting center and an intramolecular nucleophilic substitution reaction center in a compound which releases a photographic reagent by an intramolecular nucleophilic substitution reaction after reduction as disclosed in JP-A-59-189333. It may be the one corresponding to the portion, and is also disclosed in US Pat. No. 4,232,107, JP-A-59-
As disclosed in Japanese Patent Application No. 101649 or JP-A-61-88257, an electron-accepting quinonoid center in a compound capable of eliminating a photographic reagent by an intramolecular electron transfer reaction after being reduced and a photographic reagent combined with the quinoid center It may correspond to the portion containing the existing carbon atom. Also, JP-A-56-142530 and US Pat.
No. 43,893 and U.S. Pat. No. 4,619,884, an aryl group substituted with an electron-withdrawing group in a compound in which a single bond is cleaved to release a photographic reagent after reduction, and the photographic reagent. It may correspond to a portion containing an atom (a sulfur atom, a carbon atom, or a nitrogen atom) connecting with. Further, it corresponds to a nitro group in a nitro compound that releases a photographic reagent after electron acceptance as disclosed in US Pat. No. 4,450,223 and a portion containing a carbon atom connecting the nitro group and the photographic reagent. Or a dieminal dinitro moiety in a dinitro compound which eliminates the photographic reagent by B after electron acceptance as described in US Pat. No. 4,609,610 and a moiety containing a carbon atom connecting the same to the photographic reagent. May be equivalent to. However, in order to more fully achieve the object of the present invention, among the compounds of general formula [I], those represented by general formula [II] are preferred.

[0021]

[Chemical 5]

X in the general formula [II] is an oxygen atom (--O--),
A sulfur atom (-S-), an group -N containing nitrogen atom (-R ³⁾
Represents-. R ¹ , R ² and R ³ represent a group other than a hydrogen atom or a mere bond. R ¹ and R ³ are preferably substituted or unsubstituted alkyl groups, aryl groups, heterocyclic residues, acyl groups, sulfonyl groups and the like. R ² is preferably a substituted or unsubstituted acyl group or sulfonyl group. R ¹ , R ² and R ³ may combine with each other to form a 5- to 8-membered ring. The EAG will be described later.

In order to achieve the object of the present invention, among the compounds represented by the general formula [II], the general formula [III]
Those represented by are preferred.

[0024]

[Chemical 6]

Y in the general formula [III] is a divalent linking group.
Preferably -CO- or -SO ₂− X is front
Has the same meaning as described above, but preferably represents an oxygen atom.
You R^FourIs bonded to X and Y, and has 5 to 8 members including nitrogen atom
Represents a group of atoms that form a monocyclic or condensed heterocycle of
You

Preferred examples of the ring formed by —R ⁴ —X—N—Y— of the general formula [III] are described on pages (4) to (5) of JP-A-63-264747. .

For a detailed description of EAGs represented by the general formulas [I] to [III], see page (5) of JP-A-63-264747.
It is described on page (7).

-(Time) _{t-of the} general formulas [I] to [III]
A detailed description of AF is given on pages (8) to (9) of JP-A-63-264747.

As the development inhibitor precursor represented by the general formula [I], compounds AF-1 to AF-99 on pages (9) to (19) of JP-A-63-264747 can be used. However, typical examples of the compounds are shown below.

[0030]

[Chemical 7]

[0031]

Embedded image

[0032]

[Chemical 9]

[0033]

[Chemical 10]

The amount of the compound of the general formula [I] used depends on the kind of AF, but it is from 1 × 10 ^-7 mol to 1 mol of silver halide.
1 mol, preferably 1 × 10 ⁻³ mol to 1 × 10 ⁻¹
It is in the molar range. The positive dye-donating substance 1 described later
It is 1 × 10 ⁻³ mol to 1 × 10 ² mol per mol, preferably 1 × 10 ⁻² mol to 10 mol. The development inhibitor precursor may be used alone or in combination of two or more kinds. Moreover, you may use together with a well-known development inhibitor.

The dye-fixing element used in the present invention contains a mordant which fixes the movable dye that diffuses imagewise from the photosensitive element. As the mordant, a polymer containing a tertiary amino group or a polymer containing a nitrogen-containing heterocyclic moiety can be used, but it contains a polymer containing at least a quaternary cation group. Examples of the quaternary salt polymer include homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazole group, and homopolymers and copolymers containing a vinyl monomer unit having a quaternary ammonium salt.

Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazole group include British Patent Nos. 2,056,101, 1,594,961 and 2,093, 041, U.S. Pat. Nos. 4,124,386 and 4,115,12.
No. 4, No. 4,273,853, No. 4,450,2
Examples of the mordant include the mordants described in JP-A No. 24, JP-A-48-28325 and the like.

[0037]

[Chemical 11]

Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary amino group include US Pat. Nos. 3,709,690 and 3,898,08.
8, No. 3,958,995, JP-A-60-578.
No. 36, No. 60-60643, No. 60-5783
No. 6, No. 60-122940, No. 60-1229.
No. 42, No. 60-122942, No. 60-235.
The following are included, including the mordants described in No. 134 and the like.

[0039]

[Chemical 12]

Others, US Pat. No. 2,548,564
No. 2, 2, 484, 430, No. 3, 148, 16
Examples thereof include vinylpyridinium cationic polymers disclosed in No. 1 and No. 3,756,814.

The molecular weight of the polymer mordant used in the present invention is preferably 1,000 to 1,000,000, and particularly 10,000 to 200,000. Such a polymer mordant is used in the mordant layer in the dye fixing element in combination with a hydrophilic colloid as a binder described later.

The mixing ratio of the polymer mordant and the hydrophilic colloid and the coating amount of the polymer mordant can be determined by those skilled in the art depending on the amount of the dye to be mordant, the kind and composition of the polymer mordant, and the image forming method to be applied. It can be easily determined, but the mordant / hydrophilic colloid ratio is 20/80 to 8
0/20 (weight ratio), the amount of mordant applied is about 0.2 to about 2
0 g / m ² are suitable, preferably used in inter alia 1 to 10 g / m ^2.

The polymeric mordant can be used in combination with metal ions in the dye fixing element to increase the transfer density of the dye. This metal ion can be added to a mordant layer containing a mordant or a layer adjacent thereto (either on the side closer to the support carrying the mordant layer or on the side farther from the support). The metal ion used here is preferably colorless and stable to heat and light. Ie Cu
²⁺ , Zn ²⁺ , Ni ²⁺ , Pt ²⁺ , Pd ²⁺ , Co ³⁺ ions and other multivalent ions of a ring transfer metal are preferable, and Zn ^{2+ is} particularly preferable.
Is preferred. The metal ions in the form of ordinary water-soluble compounds, for example, be added in _{ZnSO 4, Zn (CH 3 CO} 2) 2, the amount added is suitably from about 0.01 to about 5 g / m ^2, preferably 0 0.1 to 1.5 g / m ² . A hydrophilic polymer can be used as a binder in the layer to which these metal ions are added. As the hydrophilic binder, hydrophilic colloids which are specifically listed later are useful. The mordant layer containing the polymer mordant may contain various surfactants for the purpose of enhancing coatability.

When a quaternary salt polymer is used as a mordant for a dye fixing element, a nonionic, betaine or / and cationic surfactant is preferably used as a dispersion stabilizer and a coating aid. In particular, when the surfactant is a fluorine-based one, uniform coating can be performed without uneven coating such as cissing and coating streaks. Furthermore, as a mordant for the dye fixing element, 4
When a graded salt polymer is used, a nonionic, betaine or / and cationic surfactant is used in the dye fixing layer, its adjacent layer or the protective layer to increase the transfer rate and increase the transfer concentration.

The amount of the nonionic, betaine or cationic surfactant added in the present invention is 1 to 50 as the total amount on the dye fixing element (excluding the back layer).
0 mg / m ^2, it is preferably 5 to 300 mg / m ^2, particularly preferably 10 to 200 mg / m ^2.

The nonionic surfactant used in the present _{invention, - (CH 2 CH 2 O} ) n - _{group, - (CH (CH 3)} C
H ₂ O) _n − group, glycerol group, saccharose group and the like are contained as water-soluble components, and alkyl group, perfluoroalkyl group, aryl group and the like are contained as hydrophobic components. Here, the above n is an integer of 1 or more, preferably 5 or more, particularly preferably 10 to 100, and an ethylene oxide nonionic surfactant is preferable. Examples of the nonionic surfactant used in the present invention include the following. WN-1: RCOO (CH ₂ CH ₂ O) _n H where n = 5 to 100 and R = C _{3 to} C ₂₂ alkyl group,
Perfluoroalkyl group of the following formula.

[0047]

[Chemical 13]

WN-2: R ₁ COO (CH ₂ CH ₂ O)
_n -OCOR ₂ wherein the alkyl group of _{R 1, R 2 = C 3} ~C 22, perfluoroalkyl group. n = 5~100 WN-3: RO (CH 2 CH 2 O) n H where the alkyl group R = C ₃ ~C _22, perfluoroalkyl group, cholesterol and the like. n = 3 to 100 WN-4: (ROOCCH ₂ ) ₂ (ROOC) CO (CH ₂
CH ₂ O) _n H where the alkyl group R = C ₃ ~C _22, perfluoroalkyl group. n = 3 to 100 WN-5: (ROOCCH ₂ ) (ROOC) CHO (CH
₂ CH ₂ O) _n H where the alkyl group R = C ₃ ~C _22, perfluoroalkyl group. n = 3 to 100 WN-6: RCH [COO (CH ₂ CH ₂ O) _n H] ₂ where R = C _{3 to} C ₂₂ alkyl group and perfluoroalkyl group. n = 3 to 100

WN-7: (R ₁ ) (R ₂ ) C ₆ H ₃ O (CH
₂ CH ₂ O) _n H wherein R _1, R ₂ = H, alkyl group of C ₁ -C _18, perfluoroalkyl group. n = 3~100 WN-8: R -N _{[(CH 2 CH 2 O) p} H ] [(CH
₂ CH ₂ O) _q H] wherein the alkyl group R = C ₃ ~C _22, a phenyl group, a naphthyl group, a perfluoroalkyl group or the like. p, q = 3~100 WN-9 : RCON _{[(CH 2 CH 2 O) p} H ] [(C
H ₂ CH ₂ O) _q H] wherein the alkyl group R = C ₃ ~C _22, perfluoroalkyl group. p, q = 3 to 100 WN-10: sorbitan esters For example, ATlas “span” 20, 8 manufactured by Kao Corporation
0, 60, 40, 62, 65, 85 etc. WN-11: Polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan monooleate (n = 5 to 50), ATlas “Tween” 6
5, 85 mag. WN-12: polyglycerin such as C ₁₂ H ₂₃ COO [CH ₂ CH (OH) CH ₂ O]
_n H (n = 4), etc.

The cationic surfactant used in the present invention is a compound having a partial structure of at least one quaternary ammonium group or quaternary phosphonium group represented by the following general formula in the molecule.

[0051]

Embedded image

In the above formula, R ₁ , R ₂ and R ₃ may be the same or different and each represents a group selected from an alkyl group, an aralkyl group, a cycloalkyl group, an aryl group and a heterocyclic residue. Further, these groups are further alkyl group, alkoxy group, aralkyl group, aryl group, aryloxy group, hydroxyl group, halogen atom, carboxyl group, sulfo group, cyano group, acyl group, acyloxy group,
Substituted with an acylamino group, sulfonylamino group, carbamoyl group, substituted carbamoyl group, sulfamoyl group, substituted sulfamoyl group, amino group, substituted amino group, mercapto group, alkylthio group, arylthio group, alkoxycarbonyl group and heterocyclic residue. Good. Further, R ₁ and R ₂ , R ₁ and R ₃ or R ₂ and R ₃ may be linked to form a heterocycle. X represents a nitrogen atom or a phosphorus atom. Y ⁻ represents an anion selected from halogen ion, sulfonate ion, alkyl sulfate ion, nitrate ion, hydrogen sulfate ion, perchlorate ion, tetrafluoroborate ion, carboxylate ion and ZuCl ₃ ion, Any one of R ₁ , R ₂ and R ₃ and Y
May be bonded.

The cationic surfactant used in the present invention can be synthesized by a known method. For example, by heating a tertiary amine or a tertiary phosphine together with various alkylating agents in a polar solvent such as alcohols and acetonitrile or a nonpolar solvent such as ether, ethyl acetate, benzene, and toluene, the target is obtained. The cationic compound is usually obtained in good yield. Examples of the alkylating agent that can be used here include alkyl halides (aralkyl), alkyl (aralkyl) esters of sulfuric acid and sulfonic acids, lactones, sultones, and the like. Regarding the anion portion, it is possible to introduce it directly by using an alkylating agent having the target anion portion, or to convert another anion into the target anion later.

Specific synthetic examples of cationic compounds are described in V.
Migrdichian, Organic Synthesis, Vol. 1 (R
ainhold, 1957) 476-479, etc.

Next, preferable specific examples of the cationic surfactant used in the present invention are shown.

[0056]

[Chemical 15]

[0057]

Embedded image

[0058]

[Chemical 17]

The betaine-based surfactant used in the present invention is a surfactant having both an anionic group and a cationic group in one molecule to form an inner salt, and has the following general formula: C] A ^-- C ⁺ (wherein A ^- is an anion residue containing an anionic group such as a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, C ⁺
Represents an organic cation residue. ).

The betaine surfactant used in the present invention preferably contains at least one saturated or unsaturated hydrocarbon group having 6 or more carbon atoms or its fluorine-substituted compound in one molecule. Particularly preferably, it contains at least one saturated or unsaturated hydrocarbon group having 10 to 24 carbon atoms or a fluorine-substituted product thereof.

Specific examples of the betaine-based surfactant used in the present invention are described below.

[0062]

[Chemical 18]

[0063]

[Chemical 19]

[0064]

Embedded image

[0065]

[Chemical 21]

The photosensitive element used in the present invention is basically a photosensitive silver halide, a sparingly soluble metal salt compound, a hydrophilic binder and a dye-donating compound (when the reducing agent also serves as a reducing agent as described below) on the support. In addition, a reducing agent (indispensable when the dye-donor substance does not have the property of a reducing agent), an organometallic salt oxidizing agent, and the like can be added as necessary. These components are often added to the same layer, but if they are in a reactive state, they can be divided and added to separate 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 light-sensitive element, but may be supplied from the outside by, for example, a method of diffusing from a dye-fixing element described later.

The photosensitive element can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer and a back layer.

The silver halide which can be used in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, 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. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 µ, and particularly preferably 0.2 to 1.5 µ. The crystal habit of silver halide grains is cubic, octahedral, 14
It may be a face piece, a flat plate having a high aspect ratio, or the like. Specifically, US Pat. No. 4,500,626 No. 5
Column 0, No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (19)
1978), any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion may be used as it is after ripening but it is usually chemically sensitized before use. Well-known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods and the like can be used alone or in combination for the emulsions for conventional type light-sensitive materials. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159). The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. 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, U.S. Pat. No. 4,617,257 and JP-A-59-180550.
No. 60-140335, RD17029 (197).
8 years) sensitizing dyes described on pages 12 to 13 and the like.
As the spectral sensitizing dye used in the present invention, an infrared sensitizing dye is preferably used especially for infrared laser light exposure. These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3). , 615, 641 and Japanese Patent Application No. 61-226294).

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 US Pat. Nos. 4,183,756 and 4,225,666, the nucleus of silver halide grains may be added. It may be before or after formation. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

In the light-sensitive element, an organic metal salt can be used as an oxidizing agent together with the light-sensitive silver halide.
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 U.S. Pat. No. 4,500,6.
There are benzotriazoles, fatty acids and other compounds described in No. 26, columns 52 to 53. In addition, JP-A-60-1
Silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in 13235, and JP-A-61-161
The acetylene silver described in No. 249044 is also useful. Two or more kinds of organic silver salts may be used in combination. The above organic silver salts are
0.01 to 10 per mol of photosensitive silver halide
Moles, preferably 0.01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 20 g / m ² in terms of silver.

Various antifoggants or photographic stabilizers can be used in the present invention. Examples thereof include azoles and azaindenes described in RD17643 (1978), pages 24 to 25, JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, the mercapto compound and its metal salt described in JP-A-59-111636, the acetylene compounds described in JP-A-62-87957, etc. may be used.

As the reducing agent used in the present invention, those known in the field of light-sensitive materials 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 the reducing agent used in the present invention include US Pat. No. 4,500,626, columns 49 to 50, and US Pat. No. 4,483,914, columns 30 to 30.
Column 31, Id. 4,330,617, Id. 4,590,
No. 152, (17) to (18) of JP-A-60-140335.
Pp. 57-40245, 56-138736,
59-178458, 59-53831, 5
9-182449, 59-182450, 60
-119555, 60-128436 to 60
-128439, 60-198540, 6
0-181742, 61-259253, 62
-2444044, 62-131253 to 62
-131256, European Patent 220,746A2
No. 78 to 96, etc., and reducing agent precursors. 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 an electron transferring agent may be optionally added in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, electron transfer agent precursors can be used in combination. 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 electron transfer agent is a compound that easily diffuses and moves. Therefore, the present invention exerts a great effect particularly in preventing coloring due to the transfer of the electron transfer agent to the dye fixing element.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any one of the above-mentioned reducing agents which does not substantially move in the layer of the photosensitive element.
Preferred are hydroquinones, sulfonamide phenols, sulfonamide phenols, JP-A-53-11.
Examples thereof include compounds described as electron donors in No. 0827, and dye-donating compounds having diffusion resistance and reducing properties described below. In the present invention, the reducing agent is added in an amount of 0.001 to 20 mol, and particularly preferably 0.01 to 10 mol, based on 1 mol of silver.

The dye-donor compound used in the present invention is a compound having a function of releasing or forming a diffusible dye imagewise corresponding to the exposure amount. Preferred compounds can be represented by the following general formula [L1]. (Dye-Y) _n -Z [L1] Dye represents a dye group, generally a short-wavelength dye group or dye precursor group, Y represents a simple bond or linking group, and Z represents an image latent image. Inversely corresponding to the photosensitive silver salt having a difference in the diffusivity of the compound represented by (Dye-Y) _n -Z, or releasing Dye, and released Dye and (Dye-Y) represents a group having a property of causing a difference in diffusibility from _n- Z, n represents 1 or 2, and when n is 2, two Dye-Y may be the same or different. .

Specific examples of Dye include azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes,
It is derived from styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes, and the like, and these dyes may be temporarily short-waved. Specific examples of the diffusible dye released from the dye-donor compound are described in EP No. 76,492, No. 24 to
Page 42, JP-A-59-165054, Nos. 4 to 4
10 pages, U.S. Pat. No. 4,975,361, Japanese Patent Application No. 5-1
09811, 5-109830, etc. can be mentioned.

In the present invention, when forming a black and white image,
Dye having different hue as the above-mentioned dye-donating compound 2
One or more compounds are used in combination in the photosensitive layer having the same color sensitivity. In the most preferred embodiment, three kinds of dye donating compounds having Dye of yellow, magenta and cyan are used together in the color-sensitive photosensitive layer.

A dye-donor compound in which Dye is a diffusible black dye can also be used in combination. As the diffusible black dye, various ones can be mentioned. For example, the dyes listed in Tables 12 and 13 of Chemical Handbook (Maruzen, 1980) P996, the direct dyes described in Dye Handbook (Maruzen, 1970) P382 to 390 (CIDirect Black 17,19,22,32,38,51,
56,62,71,74,75,77,94,105,106,107,108,112,113,117,1
18,132,133,146, etc.), acid dyes described in P511 to 526 (CIAcid Black 1,2,7,24,26,29,31,44,48,50,51,
52,58,60,62,63,64,67,72,76,77,84,107,108,109,110,1
12,115,118,119,121,122,131,132,139,140,155,156,15
7,158,159,191), basic dyes (CIBasic Black 2,8 etc.) described in P557 to 562, acidic mordant dyes (CIMordant Black 1,3,7,9,11,1) described in P588-597.
3,17,26,32,38,43,44,51,54,65,75,77,84,85,86,87
Etc.), and mordant dyes described in U.S. Pat. No. 4,357,411, British Patent No. 2,084,342, and Japanese Unexamined Patent Publication No.
The bisazo dyes described in JP-A-4-359,066 and the like are also useful. Furthermore, JP-A-54-
31737, 56-12641, 58-573.
No. 2, No. 52-42725, No. 53-46029,
56-12641, 56-38037, 57.
-11345, 57-84747, 57-84
449, U.S. Pat. Nos. 4,126,461 and 36,744.
And those described in British Patent No. 2044474 and the like.

Specific examples of the dye donating compound represented by the general formula [L1] include the following compounds (1) to (3). The following items (1) to (4) are for forming a diffusible dye image (positive dye image), which corresponds to the development of silver halide.

US Pat. Nos. 3,134,764, 3,362,819, and 3,597,200,
A dye developing agent described in U.S. Pat. No. 3,544,545 and U.S. Pat. No. 3,482,972 in which a hydroquinone-based developer 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 US 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 also be used. . Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479 and isoxazolones described in US Pat. No. 4,199,354. Examples of the compound include a compound that releases a diffusible dye by an intramolecular rewinding reaction of the ring.

US Pat. No. 4,559,290, European Patent 220,746A2, Open Technical Report 87-619
As described in 9 and the like, a non-diffusible compound which reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used. For example, US Pat. No. 4,
139,389, 4,139,379, JP-A-59-185333, JP-A-57-84453, etc., and a diffusible dye is obtained by a nucleophilic substitution reaction in the molecule after reduction. Releasing Compound, US Pat. No. 4,23
2,107, JP-A-59-101649, 61-
88257, RD24025 (1984) and the like, compounds that release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent 3,008,5
88A, JP-A-56-142530, U.S. Pat. Nos. 4,343,893, 4,619,884, etc., and the single bond is cleaved to release a diffusible dye after reduction. Compounds, nitro compounds described in US Pat. No. 4,450,223, which release diffusible dyes after electron acceptance, US Pat. No. 4,609,610, etc., diffusible dyes after electron acceptance And compounds that release Further, as more preferable ones, European Patent No. 220,746A2 and Published Technical Report 87-619.
No. 9, Japanese Patent Application Nos. 62-34953 and 62-34954.
Compounds having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in Japanese Patent Application No. 62-106885. SO ₂ -X (X is as defined above) and a compound having an electron-withdrawing group, a PO-X bond (where X is as defined above) and electron-withdrawing property in one molecule described in Japanese Patent Application No. 62-106895. A compound having a group, a C--X 'bond in one molecule described in Japanese Patent Application No. 62-106887 (where X'is synonymous with X or --S
O ₂ - compounds having an electron attractive group as a representative) and the like. 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) described in EP 220,746A2.
, (7) to (10), (12), (13), (15), (23) to (26), (3
1), (32), (35), (36), (40), (41), (44), (53) to (5
9), (64), (70), compound (1) of Open Technical Report 87-6199
1) to (23).

The dye-donor compound used in the present invention is
In particular, the above dye-donating compounds are preferably used.

The total coating amount of the dye-donor compound used in the present invention varies depending on the extinction coefficient of the diffusible dye released or formed from the dye-donor compound used, but is usually 0.5 to 20 g / m ² , and preferably It is 1 to 10 g / m ² .

Dye donating compounds are described in US Pat.
It can be incorporated into the layer of the photosensitive element by a known method such as the method described in No. 2,027. In this case, JP-A-59-83154, 59-178451 and 5
9-178452, 59-178453, 59
-178454, 59-178455, 59-
A high boiling point organic solvent as described in 178457,
If necessary, it can be used in combination with a low boiling point organic solvent having a boiling point of 50 ° C to 160 ° C. Japanese Patent Publication Sho 51-3985
No. 3, and the dispersion method using a polymer described in JP-A-51-59943 can also be used. The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, relative to 1 g of the dye-donor compound used. Also, 1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less is suitable for 1 g of the binder. In the present invention, preferably, three dye-donor compounds capable of releasing diffusible dyes of yellow, magenta, and cyan colors may be simultaneously emulsified in the same oil droplet and used as one emulsion. Alternatively, they may be prepared as separate dispersions and added to the same coating layer coating solution. 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. The above dispersion method can be used not only for the dye-donor compound but also for a hydrophobic compound in general. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-15
The surfactants listed on pages (37) to (38) of 7636 can be used.

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive element. The specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

The dye-fixing element of the present invention is placed in a stacking relationship with the light-sensitive element during thermal development transfer. That is, the dye-fixing element is placed in a relationship in which the dye-fixing layer-coated surface is in face-to-face contact with the photosensitive layer-coated surface of the photosensitive element at least during heat development transfer. The dye-fixing element of the present invention may be coated on a support separate from the photosensitive element, or may be coated on the same support as the photosensitive element. The relationship between the photosensitive element and the dye fixing element, the relationship with the support, and the relationship with the dye reflection layer are described in US Pat.
The relationship described in the 57th column of No. 626 can be applied to the present application. In the present invention, the dye fixing element is preferably coated on a support separate from the light-sensitive element, and the support is particularly preferably a transparent support.

The dye-fixing element has a dye-fixing layer on a support, and if necessary, auxiliary layers such as a protective layer, a peeling layer, an anti-curl layer and an undercoat layer can be provided.
In particular, it is useful to provide a protective layer. One or more of the above layers may include a hydrophilic thermal solvent, a plasticizer, an antifade agent,
A UV absorber, a slip agent, a matting agent, an antioxidant, a dispersed vinyl compound for increasing dimensional stability, and the like may be included.

In the present invention, the sparingly soluble metal salt compound and the compound capable of complex-forming reaction with the metal ions constituting the sparingly soluble metal salt compound (referred to as complex-forming compound) are described in JP-A-62-129848, U.S. Pat. No. 4,740,4
Used for base generation, as described in No. 45. That is, a sparingly soluble metal salt compound (for example, zinc oxide,
A method of reacting a basic zinc carbonate, calcium carbonate, etc.) with a complex-forming compound (eg, guanidine picolinate, etc.) in a hydrophilic thermal solvent or water as a medium to generate a water-soluble base is used in the present invention. In the present invention, a dispersion of a sparingly soluble metal salt compound is contained in the light-sensitive element, and a complex-forming compound is contained in the dye-fixing element, and both are brought into close contact with each other in the presence of a hydrophilic thermal solvent or water for thermal development transfer. Since a base can be generated during the heat treatment, it is particularly effective in terms of storability of the light-sensitive element and the dye-fixing element over time. Specific examples of the sparingly soluble metal salt compound and the complex-forming compound are described in JP-A-62-129848 and US Pat.
No. 0,445. Further, the addition amounts of these compounds can be determined with reference to the description in the above patent specifications. The sparingly soluble metal salt compound may be added to the photosensitive silver halide emulsion layer or may be added to the hydrophilic colloid layer adjacent to the emulsion layer. The complex-forming compound may be added to the mordant layer, or may be added to the other hydrophilic colloid layers.

In addition to the above-mentioned base generation method, in the present invention, as a base, alkali metal, quaternary alkylammonium hydroxide, carbonate, bicarbonate, borate, second and third phosphates, Inorganic bases such as metaborates; organic bases such as aliphatic amines, aromatic amines, heterocyclic amines, amidines, cyclic amidines, guanidines, cyclic guanidines and their carbonates, bicarbonates, You may use borate, 2nd and 3rd phosphate etc. together.

In the present invention, other base precursors may be used in combination. The base precursor as used herein is one that releases a basic component by thermal decomposition or electrolysis. For example, salts of thermally decomposable organic acids such as trichloroacetic acid, cyanoacetic acid, acetoacetic acid, α-sulfonylacetic acid and the organic bases, salts with 2-carboxycarboxamide described in US Pat. No. 4,088,496, etc. Can be mentioned. In addition, base precursors described in British Patent No. 998,945, US Pat. No. 3,220,846, JP-A No. 50-22625 and the like can be used.

Further, the following compounds can be mentioned as the compounds which generate a base by electrolysis. For example, electrolysis of various fatty acid salts can be mentioned as a representative method using electrolytic oxidation. By this reaction, carbonates of organic bases such as alkali metals, guanidines and amidines can be obtained very efficiently. As a method using electrolytic reduction, amines are produced by reduction of nitro and nitrone compounds, amines are produced by reduction of nitriles;
Examples include production of p-aminophenols, p-phenylenediamines, and hydrazines by reduction of nitro compounds, azo compounds, azoxy compounds and the like. p-
Aminophenols, p-phenylenediamines and hydrazines can be used not only as bases but also directly as color image-forming substances. Further, it is of course possible to use an alkaline component produced by electrolysis of water in the presence of various inorganic salts.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive element and the dye-fixing element. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, a protein such as gelatin derivative, or a cellulose derivative,
Natural compounds such as polysaccharides such as starch, gum arabic, dextran, pullulan and polyvinyl alcohol,
Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. In addition, JP-A-62-1
No. 245260 and the like, a superabsorbent polymer, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or a copolymerization of the vinyl monomers with each other or with other vinyl monomers. Combined (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L- manufactured by Sumitomo Chemical Co., Ltd.)
5H) is also used. These binders can be used in combination of two or more.

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, 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 1
It is preferably 20 g or less per m ² , particularly 10 g or less, and more suitably 7 g or less.

As the hardener used for the constituent layers of the light-sensitive element and the dye-fixing element, US Pat. No. 4,678,739, No. 4,
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane etc.), N
-Methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

Among the above hardeners, the hardener used for the dye-fixing element includes coating properties (that is, stability of the coating solution against dissolution with time, reactivity with an adjacent layer during coating, etc.) and film quality (formation). Epoxy hardeners are particularly preferred from the viewpoints of stability over time of the sample and hardenability) and photographic properties (transfer density etc.).
Specific examples of epoxy hardeners include JP-A-62-9
Hardening agents described in 1942 can be mentioned.

In the present invention, an image formation accelerator can be used in the light-sensitive 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 a light-sensitive material layer. Has a function of accelerating the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver Alternatively, they are classified into compounds that interact with 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.

The light-sensitive element and / or the dye-fixing element of the present invention have the following properties with respect to variations in processing temperature and processing time during development.
Various development stoppers can be used for the purpose of always obtaining a constant image. 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. More specifically, JP-A-62-253
159 (31)-(32).

The constituent layers (including the back layer) of the light-sensitive element or the dye-fixing element are used for the purpose of improving physical properties of the film such as dimensional stability, curl prevention, adhesion prevention, film cracking prevention, and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, 62-110066 and the like can be used. In particular,
The use of a polymer latex having a low glass transition point (40 ° C. or lower) in the mordant layer is effective in preventing cracking of the mordant layer and curling of the dye fixing element.

In the constituent layers of the light-sensitive 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 releasability of the light-sensitive element and the dye-fixing element. Specifically, (25) of JP-A-62-253159
Page, No. 62-245253 and the like.

Further, various silicone oils (all silicone oils from dimethylsilicone oil to modified silicone oils obtained by introducing various organic groups into dimethylsiloxane) can be used for the above purpose. For example, various modified silicone oils described in "Modified Silicone Oil" technical data P1-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective. The silicone oils described in JP-A Nos. 62-215953 and 62-23687 are also effective.

A fluorescent whitening agent may be used in the light-sensitive element and the dye-fixing element. In particular, it is preferable that the dye-fixing element contains a fluorescent whitening agent or is supplied from the outside of the light-sensitive element. For example, see “The Chemis” edited by K. Veenkataraman.
try of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
The compound described in 143752 etc. can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

In the constituent layers of the light-sensitive element and the dye-fixing element, various surfactants can be used for the purposes of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like. The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, and improving releasability. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-20
No. 944, No. 62-135826, or the like, or a fluorochemical surfactant such as a fluorochemical compound such as a fluorocarbon oil or a solid fluorochemical resin such as a tetrafluoroethylene resin. Can be mentioned.

A matting agent can be used in the light-sensitive element and the dye-fixing element. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
Japanese Patent Application No. 62-110064, such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like, in addition to the compounds described on page 1-88256 (29).
No. 62-110065.

In addition, the constituent layers of the light-sensitive 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).

As the support for the light-sensitive element and the dye-fixing element of the present invention, those which can withstand the processing temperature are used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those containing pigments such as titanium oxide in these films, and further from polypropion etc. Examples include film-type synthetic paper made, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), cloth, etc. For this, a transparent support is particularly preferably used. These can be used alone or as a support laminated on one or both sides with a synthetic polymer such as polyethylene. In addition to this, JP-A-62-25
The supports described in Nos. 3159 to (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

Examples of the method for exposing and recording an image on a light-sensitive element include a method of directly photographing a landscape or a person using a camera, a method of exposing through a reversal film or a negative film using a printer or a stretcher, A method of scanning and exposing an original image through a slit or the like using an exposure device of a copying machine, a method of exposing image information by emitting light from a light emitting diode or various lasers through an electric signal, a CRT, a liquid crystal display of image information, There is a method of outputting to an image display device such as an electroluminescence display and a plasma display and exposing directly or through an optical system, and the method of exposing using a laser beam, particularly a semiconductor laser is particularly preferable.

Further, the image information is a video camera,
An image signal obtained from an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC),
An image signal obtained by dividing an original image into a large number of pixels such as a scanner, an image signal created by using a computer typified by CG and CAD, various medical devices such as ultrasonic diagnostic devices, and X using an imaging plate Line diagnostic equipment, tomographic imaging equipment (MRI) using nuclear magnetic resonance
Alternatively, an image signal or the like obtained by a tomography apparatus (CT) using X-rays can be used.

In the present invention, the heat development transfer step is carried out in the presence of a hydrophilic heat solvent or water. This water need not be pure water, but tap water can also be used. Further, an inorganic or organic base may be contained, or a surfactant, an antifoggant, a complex-forming compound, a scale inhibitor (antibacterial / antifungal agent), etc. may be contained. Water can be used by a method of applying it to the dye-fixing element, the light-sensitive element or both, but since the dye-fixing element usually contains a complex-forming compound, it is preferably applied to the light-sensitive element. The amount used is less than or equal to the weight of the solvent corresponding to the maximum swelling volume of the entire coating film of the light-sensitive element and the dye-fixing element (in particular, the weight of the total coating dry film is subtracted from the weight of the solvent corresponding to the maximum swelling volume of the entire coating film). A small amount (less than or equal to the amount) is sufficient. Examples of the method of applying water to the photosensitive layer or the dye fixing layer include, for example, JP-A-61-114.
7244 (26) page. It is also possible to use the solvent by preliminarily incorporating it in the light-sensitive element or the dye-fixing element or both in the form of confining the solvent in crystal water or microcapsules.

The hydrophilic thermal solvent used in place of or together with water is a compound which is solid at room temperature and soluble at high temperature. The hydrophilic thermal solvent may be incorporated in either the photosensitive element or the dye fixing element, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and / or its adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alkenyls, oximes and other heterocycles. Specific examples of the hydrophilic thermal solvent and particularly preferred specific examples thereof include the compounds described on pages 149 to 158 of JP-A-58-42092. Further, examples of the hydrophilic thermal solvent include U.S. Pat. Nos. 3,347,675, 3,667,959, 3,438,776, 3,666,477 and Research Disclosure (No. 17). , 643), JP-A-51-19525, 53-24829, and 53.
-60223, 58-1186640, 58-
198038, 59-229556 and 59-6.
8730, 59-842236, 60-191.
No. 251, No. 60-232547, No. 60-1422.
No. 41, No. 61-52643, No. 62-785554.
No. 62-42153, No. 62-44737, No. 63-53548, No. 63-161446, JP-A No. 1-224751, No. 2-863, and European Patent Publication 5.
The thermal solvent described in each gazette of 45,433 etc. can also be mentioned. Further, in order to promote dye transfer, a high boiling organic solvent may be contained in the photosensitive element and / or the dye fixing element. The hydrophilic thermal solvent may be used alone or in combination of two or more kinds. The hydrophilic thermal solvent is 10 to 300% by weight of the total coating film thickness excluding the hydrophilic thermal solvent in the light-sensitive element or the dye fixing element in terms of weight,
Preferably 20-200% by weight, particularly preferably 30-
It can be used in the range of 150% by weight.

The heating method in the developing and / or transferring step is as follows: contact with a heated block or plate, contact with a heat plate, hot presser, heat roller, halogen lamp heater, infrared or far infrared lamp heater, etc. It may be allowed to pass through, or may be transmitted through a high temperature atmosphere. Alternatively, a resistance heating volume may be provided in the light-sensitive element or the dye fixing element, and electricity may be supplied to the resistance heating volume for heating. As the heat generation volume, those described in JP-A-61-145544 can be used.

The heating temperature in the heat development step varies depending on the film pH adjusted by a base or a base precursor, but it can be developed at about 25 ° C to about 250 ° C, but is 50 ° C.
-100 degreeC is preferable, and 70-98 degreeC is especially useful. The heating pattern can be heating at a constant temperature or two-step heating of high temperature → low temperature or low temperature → high temperature. Further, a pressure condition and a method for applying pressure when superimposing a light-sensitive element and a dye-fixing element and bringing them into close contact are described in JP-A-61-61.
The method described on page 147244 (27) can be applied.

Any of the known heat developing apparatus can be used to process the photographic elements of this invention. For example, JP-A-59-7
No. 5247, No. 59-177547, No. 59-181.
No. 353, No. 60-18951, No. 62-259.
The device described in No. 44 etc. is preferably used.

[0117]

【Example】

Example 1 A method for preparing a zinc hydroxide dispersion 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 the following electron transfer agent, 0.5 g of polyethylene glycol nonylphenyl ether as a dispersant, and 0.5 g of the following anionic surfactant were added to a 5% gelatin aqueous solution, and glass beads having an average particle size of 0.75 mm were used in a mill. And crushed 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.

[0119]

[Chemical formula 22]

Next, the method for preparing the dye trapping agent dispersion will be described. The following polymer latex (1) (solid content 13
%) 108 ml, 20 g of the following nonionic surfactant, and 1232 ml of water were stirred, and 600 ml of a 5% aqueous solution of the following anionic surfactant was added over 10 minutes. The dispersion thus prepared was concentrated and desalted to 500 ml using an ultrafiltration module. Next 1500
Water of ml was added and the same operation was repeated once more to obtain 500 g of the dye trapping agent dispersion.

[0121]

[Chemical formula 23]

Next, a method for preparing a gelatin dispersion of a hydrophobic additive will be described. Cyan, magenta, and yellow dye-donor compounds and electron-donor gelatin dispersions were prepared according to the formulations shown in Table 1. That is, each oil phase component is about 60
Dissolve it in a uniform solution by heating it to ℃
The heated aqueous phase component was added to the mixture, stirred and mixed, and then dispersed by a homogenizer for 13 minutes at 12000 rpm. Water was added thereto, and the mixture was stirred to obtain uniform dispersions A, B, C and D.

[0123]

[Table 1]

[0124]

[Chemical formula 24]

[0125]

[Chemical 25]

[0126]

[Chemical formula 26]

[0127]

[Chemical 27]

[0128]

[Chemical 28]

Next, a method for preparing a photosensitive silver halide emulsion will be described. Photosensitive silver halide emulsion (1) Well stirred gelatin aqueous solution (in 500 ml of water, 20 g of gelatin, 0.5 g of potassium bromide, 3 g of sodium chloride)
g and 30 mg of the following chemical (A) were added and kept at 45 ° C.), 20 parts of solution (I) and solution (II) in Table 2 were simultaneously added.
Added at equal flow rate for 1 minute. After 6 minutes, solution (III) and solution (IV) in Table 2 were simultaneously added at the same flow rate for 25 minutes. Also (II
10 minutes after the start of addition of the solutions (I) and (IV), an aqueous solution of a gelatin dispersion of a dye (1 g of gelatin in 105 ml of water, 70 mg of the following dye (a), 139 mg of the following dye (b), and the following dye (c) ) Containing 5 mg and kept at 45 ° C.) 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 7.8, and 4-hydroxy-6-methyl-1,3,3.
3a, 7-tetrazaindene was added, and then sodium thiosulfate and chloroauric acid were added for optimum chemical sensitization at 68 ° C.,
Next, the following antifoggant (2) was added and then cooled. Thus, 635 g of a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.30 μm was obtained.

[0131]

[Chemical 29]

[0132]

[Table 2]

[0133]

[Chemical 30]

[0134]

[Chemical 31]

Photosensitive material 101 shown in Table 3 (using A as the coloring material emulsion) was prepared using the above materials.

[0136]

[Table 3]

[0137]

[Table 4]

[0138]

[Table 5]

[0139]

[Chemical 32]

Further, photosensitive materials 102 and 103 were prepared in the same manner as the photosensitive material 101 except that B and C were used instead of the color material emulsion A, respectively. Next, how to make the image receiving material will be described. A dye fixing material R101 having a constitution as shown in Table 6 was prepared.

[0141]

[Table 6]

[0142]

[Table 7]

[0143]

[Chemical 33]

[0144]

Embedded image

Further, the dye fixing material R1 as shown in Table 8 is used.
02 was produced.

[0146]

[Table 8]

[0147]

[Table 9]

[0148]

Embedded image

Further, in the dye-fixing element 102, dye-fixing elements 103 to 108 were prepared in the same manner except that the surfactant shown in Table 9 was used instead of the surfactant (7).

[0150]

[Table 10]

By combining the photothermographic materials 101 to 103 thus obtained and the dye fixing materials R101 and R108, a digital color printer "Fujix Pictrography PG-300" manufactured by Fuji Photo Film Co., Ltd.
0 "was used to perform exposure and processing as follows. As the image information, a tomographic imaging apparatus using nuclear magnetic resonance, so-called MR
The one obtained from I was used. The exposure was performed by scanning exposure using a semiconductor laser beam having an oscillation wavelength of 680 nm. The exposed light-sensitive material was dipped in water kept at 40 ° C. for 6 seconds, and then squeezed with a roller and immediately superposed so that the dye fixing material and the film surface were in contact with each other. Next, using a heat drum whose temperature has been adjusted so that the surface of the film that has absorbed water becomes 85 ° C., the dye fixing material is peeled off by heating for 45 seconds. A high-quality black and white image was obtained. Dye fixing materials R101 and R using a X-ray densitometer X-light 404
The black and white transmission image obtained on 102 was measured. The maximum and minimum concentrations are shown in Table 10.

[0152]

[Table 11]

As is apparent from these results, the light-sensitive material contains the compound represented by the general formula [I] of the present invention, and the dye fixing material contains a quaternary amine polymer as a mordant and a nonionic, cationic or betaine-based interface. Activator, especially the fourth
It can be seen that an image having a low Dmin and an extremely high Dmax can be obtained in the system containing the fluorine-containing betaine surfactant in the layer (uppermost layer).

Claims (6)

[Claims] 1. A light-sensitive element containing at least a light-sensitive silver halide, a sparingly soluble metal salt compound, a hydrophilic binder and a dye-donor compound which releases or forms a diffusible dye inversely corresponding to an exposure dose is imagewise formed. After the exposure or at the same time as the imagewise exposure, the compound capable of complex-forming reaction with the metal ion constituting the sparingly soluble metal salt compound and the dye fixing element containing a mordant are superposed, and in the presence of a hydrophilic thermal solvent or water. In an image forming method of transferring and fixing a diffusible dye released or formed by heat development to a dye fixing layer, the photosensitive element contains a development inhibitor precursor represented by the following general formula [I], The dye fixing element contains at least one surfactant selected from nonionic, betaine and cationic surfactants, and the mordant is a quaternary salt polymer. Image forming method. Embedded image 2. The image forming method according to claim 1, wherein the compound represented by the general formula [I] is represented by the general formula [II]. Embedded image 3. The image forming method according to claim 2, wherein the compound represented by the general formula [II] is represented by the general formula [III]. [Chemical 3] 4. The image forming method according to claim 2, wherein X is an oxygen atom. 5. The light-sensitive element contains at least two dye-donor compounds that release diffusible dyes having different hues in the same color-sensitive photosensitive layer, and the dye-fixing element is prepared by the image forming method. The image forming method according to any one of claims 1 to 4, wherein the dye image formed thereon is substantially a monochrome image. 6. The image forming method according to claim 1, wherein the at least one surfactant selected from the nonionic, betaine and cationic surfactants is a fluorinated surfactant.