JPH0545834A - Heat developoable photosensitive material - Google Patents

Abstract

PURPOSE:To enhance color separability and to prevent desensitization with the lapse of time in an unexposed state by forming at least one infrared sensitive layer having spectral sensitivity peak to infrared rays of >=700nm wavelength and at least one infrared sensitive layer containing a specified compound. CONSTITUTION:The heat developable photosensitive material has at least one infrared sensitive layer having a spectral sensitivity peak in the infrared region of >=700nm and at least one of them contains a water-insoluble dye, and at least one infrared sensitive layer containing a compound represented by formula I in which A is a divalent aromatic residue; each of R1-R4 is H, OH, alkyl, alkoxy, aryloxy, or the like; at least A and R1-R4 has a sulfo group; each of W1 and W2 is -CH= or -N=; but at least one of W1 and W2 is -N=.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer heat-developable color light-sensitive material and, more particularly, to a heat-development color light-sensitive material having a small desensitization after aging and an excellent color separation property.

[0002]

2. Description of the Related Art The photographic method using silver halide is superior to other photographic methods such as electrophotography and diazo photographic method in photographic characteristics such as sensitivity and gradation control. Has been. In recent years, a technique has been developed in which a simple and quick image can be obtained by replacing the image forming method of a light-sensitive material using silver halide with a conventional dry processing using a developing solution or the like.

Photothermographic materials are known in the art, and regarding the photothermographic material and its process, for example, 553 of the foundation of photographic engineering (published by Corona Publishing Co. in 1979).
~ 555 pages, 40 pages of video information published in April 1978, Nebuletts, Handbook of Photography and Reprint, 7th Edition
prography 7th Ed.) Van Nostrand Reinhold Company
32-33, U.S. Pat. Nos. 3,152,904, 33.
01678, 3392020, and 3457075
No., British Patent Nos. 1131108 and 1167777 and Research Disclosure, June 1978.
The monthly issue is described on pages 9 to 15 (RD-17029).

Various methods of obtaining a color image by heating are described in, for example, Research Disclosure, 1978.
May issue, pages 54-58 (RD-16966), April 1976, pages 30-32 (RD-14433).
No.), US Pat. Nos. 3,985,655 and 4,463,079.
No. 4474867, 4478927, 45
07380, 4500626 and 4843914.
No. etc. These all generate or release a dye by heating to form an image-like distribution of the dye, and are characterized in that the image-like distribution of the dye can be obtained in a short time.

On the other hand, due to recent advances in office automation, advances in commercial image equipment, appearance of electronic still cameras, spread of video and facsimile, advances in computer graphics, advances in image sensors, advances in digital processing technology for original images, etc. Along with this, there is an increasing demand for obtaining a color hard copy from image information once converted into an electric signal.

Conventional color photosensitive materials usually have spectral sensitivities of blue, green, and red. To obtain an image by using image information once converted into an electric signal in such a color photosensitive material, a color CRT is used. It is common to use a (cathode ray tube) as an exposure light source, but a CRT is unsuitable for obtaining a large-sized print.

Further, as a writing head capable of obtaining a large size print, a light emitting diode (LED) is used.
And semiconductor lasers have been developed. However, none of these optical writing heads that efficiently emit blue light has been developed.

Thus, for example, a light emitting diode (LED)
When using, near infrared (800nm), red (670n
It is necessary to expose a color light-sensitive material having three layers spectrally sensitized to near infrared, red, and yellow by a light source combining three light emitting diodes of m), and yellow (570 nm). A system for performing image recording with such a structure is described in "Nikkei New Material", September 14, 1987, pages 47 to 57, and is partially put into practical use.

A system for recording on a color light-sensitive material having three light-sensitive layers having spectral sensitivity at respective wavelengths by a light source combining three semiconductor lasers emitting light of 880 nm, 820 nm and 760 nm is disclosed in Japanese Patent Laid-Open No. 61-61. 137
No. 149.

Generally, in a multilayer color light-sensitive material,
When yellow, magenta, and cyan colors are exposed to three different spectral regions to develop colors, it is an important technique for color reproduction to develop the colors without mixing.

In particular, when a light emitting diode (LED) or a semiconductor laser (LD) is used as an exposure light source, it is unavoidable to design three spectral sensitivities in a narrow spectral region, and how each spectral sensitivity is The key to improving color separation is to reduce the overlap.

Known techniques for solving these problems include:
For example, a technique using a water-insoluble dye as described in JP-A-2-258926 is known.

The heat-developable color light-sensitive material using the dye described in the above-mentioned publication has no transfer of the dye before and after the aging and is very excellent in white background.

However, most of these water-insoluble dyes are
Since it is a compound having a structure basically similar to that of the sensitizing dye, there is some interaction with silver halide. Therefore, it was found that over time, desensitization is assumed to be caused by the water-insoluble dye adsorbing to the silver halide, desorbing the original sensitizing dye, or changing the spectral shape of the spectral sensitivity. ..

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a heat-developable color light-sensitive material which is excellent in stability, such as excellent color separation and little desensitization during storage.

[0016]

Such an object is achieved by the following constitutions (1) to (3).

(1) In a heat-developable color light-sensitive material having at least a light-sensitive silver halide emulsion, a binder and a dye-donating compound on a support, an infrared ray having a spectral sensitivity peak to an infrared ray of 700 nm or more. At least one photosensitive layer, at least one of which contains a water-insoluble dye, and at least one infrared photosensitive layer containing the compound represented by Chemical formula 1 A heat-developable color photosensitive material.

[0018]

[Chemical 2]

[In Chemical Formula 2, A represents a divalent aromatic residue. R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an alkylthio group, an arylthio group, an amino group,
It represents an alkylamino group, an arylamino group, a heterocyclylamino group, an aralkylamino group, an aryl group, a heterocyclyloxy group or a mercapto group. However, A,
At least one of R ₁ , R ₂ , R ₃ and R ₄ has a sulfo group. Each W ₁ and W ₂ represent -CH = or -N =. However, at least _one of W ₁ and W ₂ represents -N =].

(2) In a heat-developable color light-sensitive material having at least a light-sensitive silver halide emulsion, a binder and a dye-donating compound on a support, an infrared ray having a spectral sensitivity peak for infrared rays of 700 nm or more. A silver halide emulsion prepared by having at least one photosensitive layer, containing a water-insoluble dye in at least one layer, and adding a sensitizing dye between grain formation and the end of chemical sensitization. A heat-developable color light-sensitive material having at least one light-sensitive layer containing

(3) In a heat-developable color light-sensitive material having at least a light-sensitive silver halide emulsion, a binder and a dye-donating compound on a support, an infrared ray having a peak of spectral sensitivity to an infrared ray of 700 nm or more. A heat-developable color photosensitive material comprising at least one photosensitive layer, at least one of which contains a water-insoluble dye, and at least one layer containing an organic silver salt.

[0022]

[Specific Structure] The specific structure of the present invention will be described in detail below.

The heat-developable color light-sensitive material of the present invention has at least a light-sensitive silver halide emulsion, a binder and a dye-donor compound on a support.

Then, at least one infrared photosensitive layer having a peak of spectral sensitivity to infrared light having a wavelength of 700 nm or more is provided, and at least one layer thereof contains a water-insoluble dye. Thereby, the color separation property is improved.

Further, in the present invention, at least one of the following (1) to (3) is adopted at this time.

(1) In the above, at least one infrared photosensitive layer containing the compound represented by Chemical formula 2 is further provided. The infrared photosensitive layer at this time may be an infrared photosensitive layer containing a water-insoluble dye or another infrared photosensitive layer.

In particular, it is preferable that the water-insoluble dye is contained in the infrared photosensitive layer, and further it is preferable that the water-insoluble dye is contained in the adjacent infrared photosensitive layer.

(2) In the above description, at least one photosensitive layer containing a silver halide emulsion prepared by adding a sensitizing dye is provided between the grain formation and the end of chemical sensitization. Any photosensitive layer may be used at this time, and it is particularly preferable to apply it to a photosensitive layer other than the infrared photosensitive layer.

(3) In the above, at least one layer containing an organic silver salt is further provided. Such an organic silver salt-containing layer may be a photosensitive layer, an intermediate layer, or a light-sensitive material constituent layer. Also, an organic silver salt-containing layer can be newly installed. Usually, it is preferable to add an organic silver salt to the infrared-sensitive layer containing the water-insoluble dye, and addition to the intermediate layer is also preferable.

Conventionally, although the effect of improving color separation is obtained by using a water-insoluble dye, since the water-insoluble dye and the sensitizing dye have similar structures, the silver halide and the water-insoluble dye are different from each other. It has been a problem that they interact with each other and cause desensitization due to their lifetime. Then, such desensitization occurs not only in the infrared photosensitive layer containing the water-insoluble dye but also in other photosensitive layers.

However, in the present invention, the above (1)-
This can be solved by applying any one of (3) or a combination thereof. Depending on the application of the above (1) and (2), desensitization of the application layer is mainly prevented. Further, depending on the application of (3), desensitization can be prevented not only in the applied layer but also in the adjacent layer or even in the photosensitive layer which is not directly adjacent.

In the heat-developable color light-sensitive material of the present invention, as described above, basically, a photosensitive silver halide, a binder and a dye-donating compound (in some cases, a reducing agent may also serve as the below-mentioned material may be used on the support. ), And if necessary, an organometallic salt oxidizing agent or the like can be added, for example, in the aspect of (3) above. These components are often added to the same layer, but if they are in a reactive state, they can be added separately to separate layers. For example, when a dye-providing dye 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 material, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing material described later.

The heat-developable color light-sensitive material may be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an antihalation layer and a back layer.

Next, the silver halide emulsion constituting the light-sensitive material of the present invention will be described.

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, but is preferably Silver chlorobromide or pure silver bromide containing 80 mol% or less of silver chloride or silver iodobromide containing 10 mol% or less of silver iodide.

The silver halide emulsion used in the present invention may be either 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 a light 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 is preferably a monodisperse emulsion, and two or more kinds of monodisperse emulsions may be mixed and used. The particle size is 0.1 to 2μ, especially 0.1 to
1.0 μ is preferable. More preferably 0.15 to 0.5
is μ. The crystal habit of silver halide grains is cubic, octahedral,
It may be a tetrahedron, a flat plate having a high aspect ratio, or the like.

Specifically, US Pat. No. 4,500,626, column 50, US Pat. No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (197).
8 years), any of the silver halide emulsions described in JP-A-62-253159 can be used.

The silver halide emulsion may be used as it is without being post-ripened, 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 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 emulsion used in the present invention is iridium (Japanese Patent Laid-Open No. 1-116637) for the purpose of improving reciprocity law failure under high illuminance or low illuminance, accelerating development speed, or preventing fog.
(See Japanese Laid-Open Patent Publication No. 2000), rhodium, platinum, cadmium, zinc, thallium, iron, chromium lead, palladium and the like.

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg / m ² 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, US Pat. No. 4,617,257
No. 59-180550, 60-14033.
No. 5, RD17029 (1978) pages 12 to 13 and the like.

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 Patent No. 3615641, Japanese Patent Application No. 6
No. 1-222694, etc.).

The time of adding these sensitizing dyes to the emulsion may be during or after chemical sensitization (ripening), or before or after the nucleation of silver halide grains according to US Pat. Nos. 4,183,756 and 4,225,666. ..

In the present invention, when the constitution (2) is adopted, a sensitizing dye is added between the grain formation and the end of chemical sensitization.

Next, a method of adding a sensitizing dye between the grain formation and the end of chemical sensitization in the silver halide emulsion will be described.

The method of adding the sensitizing dye is to put the sensitizing dye in a reaction vessel in advance before grain formation; to add the sensitizing dye all at once at one point during grain formation, or to add several sensitizing dyes. Method of adding sensitizing dye from the beginning of grain formation or from one point on the way at a constant flow rate or changing the flow rate from the beginning of grain formation: Add sensitizing dye in reaction vessel after grain formation Method: A method of adding a sensitizing dye at the beginning, the middle, and the end of desalting; in this case, the pH, temperature, etc. at the time of addition can be changed as necessary: before, during the chemical sensitization, A method of adding a sensitizing dye after completion; in this case, the pH, temperature, etc. at the time of addition can be changed as necessary: etc., but the present invention is not limited thereto.

When the sensitizing dye is added, it can be added in an organic solvent such as methanol, a mixed solvent of water and an organic solvent, or a gelatin dispersion. In addition, C ₁₂ H ₂₅ OSO ₃ Na
It can also be added as an aqueous solution solubilized with a surfactant as shown in (Japanese Patent Application No. 2-104671).
issue).

It is also effective to use a compound such as phenol, 2-phenoxyethanol or dimethylformamide (DMF) as the accelerating dye adsorption promoter.

The addition amount of the sensitizing dye in the present invention is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

The infrared-sensitive layer contained in the light-sensitive material of the present invention is
Although the silver halide is infrared spectrally sensitized, the infrared spectral sensitization is performed using an infrared spectral sensitizing dye.

Specific examples of the infrared spectral sensitizing dye used in the present invention are shown in Chemical formulas 3 to 24, but the invention is not limited thereto.

[0054]

[Chemical 3]

[0055]

[Chemical 4]

[0056]

[Chemical 5]

[0057]

[Chemical 6]

[0058]

[Chemical 7]

[0059]

[Chemical 8]

[0060]

[Chemical 9]

[0061]

[Chemical 10]

[0062]

[Chemical 11]

[0063]

[Chemical formula 12]

[0064]

[Chemical 13]

[0065]

[Chemical 14]

[0066]

[Chemical 15]

[0067]

[Chemical 16]

[0068]

[Chemical 17]

[0069]

[Chemical 18]

[0070]

[Chemical 19]

[0071]

[Chemical 20]

[0072]

[Chemical 21]

[0073]

[Chemical formula 22]

[0074]

[Chemical formula 23]

[0075]

[Chemical formula 24]

Next, in the present invention, the compound represented by the chemical formula 2 used when the constitution (1) is adopted will be described.

In the chemical formula 2, A represents a divalent aromatic residue. R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an alkylthio group, an arylthio group, an amino group and a substituent. Alternatively, it represents an unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted aralkylamino group, a heterocyclylamino group, an aryl group, a mercapto group, or a heterocyclyloxy group. However, A, R ₁ ,
At least one of R ₂ , R ₃ and R ₄ has a sulfo group.

W ₁ and W ₂ are each --CH = or --N
Represents =. However, at least _one of W ₁ and W ₂ represents -N =.

The compound represented by Chemical formula 2 is a compound known as a supersensitizer for sensitizing dyes in general light-sensitive materials for wet development processing (US Pat. No. 2875058, US Pat. No. 3,695,888, JP-A-59-192242
And Japanese Patent Application Laid-Open No. 59-191032) and also known as supersensitizers in photothermographic materials (see Japanese Patent Application Laid-Open No. 59-180550).

Next, the compound represented by Chemical formula 2 will be described in more detail.

In the formula, -A- represents a divalent aromatic residue,
These are --SO ₃ M groups (where M is a hydrogen atom or a cation that imparts water solubility (eg sodium, potassium, etc.)
Represents. ] May be included.

-A- represents, for example, in Chemical formulas 25 and 26
Those selected from those exemplified in A ₁ -or -A ₂ -of Chemical formula 27 are useful. However, when R ₁ , R ₂ , R ₃ or R ₄ does not include —SO ₃ M, —A— is
3 and the group of -A _1- of formula 24.

[0083]

[Chemical 25]

[0084]

[Chemical formula 26]

[0085]

[Chemical 27]

In -A _1-of Chemical formulas 25 and 26,
M represents a hydrogen atom or a cation that imparts water solubility.

In the chemical formula ₂ , R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a hydroxy group or a lower alkyl group (the number of carbon atoms is preferably 1 to 8, for example, methyl group, ethyl group, n -Propyl group, n-butyl group, etc.),
Alkoxy group (1 to 8 carbon atoms are preferable,
For example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), aryloxy group (eg, phenoxy group, naphthoxy group, o-troxy group, p-sulfophenoxy group, etc.), halogen atom (eg, chlorine atom, bromine atom, etc.), Heterocyclic nuclei (eg morpholinyl group, piperidyl group etc.), alkylthio groups (eg methylthio group, ethylthio group etc.), heterocyclylthio groups (eg benzothiazolylthio group, benzimidazolylthio group, phenyltetrazolylthio group etc.), arylthio groups (Eg phenylthio group, tolylthio group), amino group, alkylamino group or substituted alkylamino group (eg methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group) , Β-hydroxyethylamino group, di- (β-hydroxyethyl) amino group, β-sulfoethylamino group), arylamino group or substituted arylamino group (for example, anilino group, o-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, o
-Toluidino group, m-toluidino group, p-toluidino group, o-carboxyanilino group, m-carboxyanilino group, p-carboxyanilino group, o-chloroanilino group, m-chloroanilino group, p-chloroanilino group, p
-Aminoanilino group, o-anisino group, m-anisino group, p-anisino group, o-acetaminoanilino group,
Hydroxyanilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group, etc.), heterocyclylamino group (eg, 2-benzothiazolylamino group, 2-pyridylamino group, etc.), substituted or unsubstituted aralkylamino Groups (eg benzylamino group, o-
Anisylamino group, m-anisylamino group, p-anisylamino group and the like), aryl group (for example, phenyl group and the like), mercapto group and heterocyclyloxy group.
R ₁ , R ₂ , R ₃ and R ₄ may be the same or different from each other. -A- is -A ₂ - when selected from the group of,
At least one of R ₁ , R ₂ , R ₃ , and R ₄ needs to have at least one sulfo group (which may be a free acid group or may form a salt).

W ₁ and W ₂ are each -CH = or -N
Represents =. However, one of them is -N =.

Next, specific examples of the compound represented by Chemical formula 2 used in the present invention will be given. However, the present invention is not limited to these compounds.

(A-1) 4,4'-bis [4,6-di (benzothiazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt

(A-2) 4,4'-bis [4,6-di (benzothiazolyl-2-amino) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt

(A-3) 4,4'-bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt

(A-4) 4,4'-bis [4,6-di (naphthyl-2-oxy) pyrimidin-2-ylamino] bibenzyl-2,2'-disulfonic acid disodium salt

(A-5) 4,4'-bis (4,6-dianilinopyrimidin-2-ylamino) stilbene-2,
2'-disulfonic acid disodium salt

(A-6) 4,4'-bis [4-chloro-
6- (2-naphthyloxy) pyrimidin-2-ylamino] biphenyl-2,2'-disulfonic acid disodium salt

(A-7) 4,4'-bis [4,6-di (1-phenyltetrazolyl-5-thio) pyrimidine-
2-ylamino] stilbene-2,2′-disulfonic acid disodium salt

(A-8) 4,4'-bis [4,6-di (benzimidazolyl-2-thio) pyrimidin-2-ylamino] stilbene-2,2'-disulfonic acid disodium salt

(A-9) 4,4'-bis (4,6-diphenoxypyrimidin-2-ylamino) stilbene-
2,2'-disulfonic acid disodium salt

(A-10) 4,4'-bis (4,6-diphenylthiopyrimidin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt

(A-11) 4,4'-bis (4,6-dimercaptopyrimidin-2-ylamino) biphenyl-
2,2'-disulfonic acid disodium salt

(A-12) 4,4'-bis (4,6-dianilino-triazin-2-ylamino) stilbene-
2,2'-disulfonic acid disodium salt

(A-13) 4,4'-bis (4-anilino-6-hydroxy-triazin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt

(A-14) 4,4'-bis (4-naphthylamino-6-anilino-triazin-2-ylamino) stilbene-2,2'-disulfonic acid disodium salt

(A-15) 4,4'-Bis [2,6-di (2-naphthoxy) pyrimidin-4-ylamino] stilbene-2,2'-disulfonic acid disodium salt

(A-16) 4,4'-bis [2,6 di-
(2-Naphthylamino) pyrimidin-4-ylamino]
Stilbene-2,2'-disulfonic acid disodium salt

(A-17) 4,4'-bis (2,6-dianilinopyrimidin-4-ylamino) stilbene-
2,2'-disulfonic acid disodium salt

(A-18) 4,4'-bis [2- (2-
Naphthylamino) -6-anilinopyrimidin-4-ylamino] stilbene-2,2'-disulfonic acid disodium salt

(A-19) 4,4'-bis (2,6-diphenoxypyrimidin-4-ylamino) stilbene-
2,2'-disulfonic acid ditriethylammonium salt

(A-20) 4,4'-bis [2,6-di (benzimidazolyl-2-thio) pyrimidin-4-ylamino] stilbene-2,2'-disulfonic acid disodium salt

The compound represented by Chemical formula 2 is known or can be easily produced according to known methods.

The compound represented by Chemical formula 2 used in the present invention is about 0.01 g to 5 per mol of silver halide in the emulsion.
Advantageously used in amounts of g grams.

The ratio (weight ratio) of the infrared spectral sensitizing dye to the compound represented by Chemical formula 2 is preferably such that the range of dye / compound represented by Chemical formula 1 = 1/1 to 1/1000. In particular, the range of 1/2 to 1/500 is advantageously used.

The water-insoluble dye used in the present invention has, for example, a ballast group (a hydrophobic group containing many carbon atoms known in the field of photographic couplers) linked to a dye molecule, or a dye molecule having its absorption property. With a linking group that does not significantly affect
It is possible to use a dye or the like, which is linked by one or more, or is linked by a covalent bond with a polymer binder such as gelatin of a light-sensitive material, is polymerized, or has a mechanism of erasing by heat or pH during heat development. ..

On the other hand, examples of the chromogen structure of the water-insoluble dye include azo dyes, azomethine dyes (eg indophenol dyes), polymethine dyes (eg cyanine dyes, oxonol dyes, merocyanine dyes), azaannulene dyes (eg porphyrin dyes). , Phthalocyanine dyes, naphthalocyanine dyes), quinone dyes (for example, naphthoquinone dyes, anthraquinone dyes), and various heavy metal complexes. The larger the absorption coefficient per unit, the smaller the amount used, so the molecular absorption coefficient Polymethine dyes and azaannulene dyes having a large value are preferable.

Among them, the cyanine dye represented by Chemical formula 28 is particularly preferable in that it has a large molecular extinction coefficient, a narrow absorption band width, is stable, and does not bring about a photographic adverse effect.

[0116]

[Chemical 28]

In the formula 28, R ¹ , R ² , R ³ and R
⁴ , R ⁵ and R ^{6, which} may be the same or different, each represents an alkyl group, and Z ¹ and Z ² each represent a nonmetallic atom group necessary for forming a benzo-condensed ring or a naphtho-condensed ring. However, any one of the groups represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ R ⁶ , Z ¹ and Z ² contains at least one alkyl chain having 5 or more carbon atoms.

L represents a methine group, and X represents an anion. Specific examples of the anion represented by X include halogen ions (Cl, Br, I), p-toluenesulfonate ion, ethylsulfate ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion and the like. Can be mentioned.

N represents 1 or 2, and is 1 when the dye forms an inner salt.

The alkyl group represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is preferably an alkyl group having 1 to 18 carbon atoms (eg methyl, ethyl, n-propyl, n-). Butyl, isopropyl, n-pentyl) and includes those having a substituent (for example, an alkoxy group, an aryloxy group, an aralkyl group, an acyloxy group, a hydroxyl group). Specific examples of the alkoxy group include tetradecyloxy and hexadecyloxy, and examples of the aryloxy group include m-
Examples include pentadecylphenoxy, 2,4-di-t-pentylphenoxy, aralkyl groups such as benzyl group and phenylethyl group, and acyloxy groups including acyl groups such as stearoyl and palmitoyl.

The benzo-condensed ring or naphtho-condensed ring formed by the group of non-metal atoms represented by Z ¹ and Z ² includes those having a substituent, and the substituent includes a hydroxyl group, a halogen atom (for example, F, Cl, Br), a cyano group, a substituted amino group (for example, the dialkylamino group and the alkyl group are the same as those described above), or an alkyl group having 1 to 18 carbon atoms bonded to a ring directly or through a divalent linking group (substituent Including those having. For example, methyl, ethyl, propyl, butyl and the like (the substituent includes an alkoxy group, a halogen atom (as defined above), a hydroxyl group and the like)} and the like, and the divalent linking group is, for example, —O—, —NHCO. -, -N
_{HSO 2 -, - NHCOO -,} - NHCONH -, - C
OO -, - CO -, - SO 2 - is preferred.

The methine group represented by L includes those having a substituent, and the substituent includes a lower alkyl group having 1 to 5 carbon atoms (including those having a substituent. For example, methyl, ethyl, 3-hydroxy. Propyl, benzyl, 2-sulfoethyl), halogen atom (for example, F, Cl, Br), aryl group (including those having a substituent. For example, phenyl,
4-chlorophenyl), a lower alkoxy group (eg, methoxy, ethoxy), an amino group (including those having a substituent, for example, diphenylamino) are preferable. In addition, the substituents of the methine group represented by L may be bonded to each other to form a 6-membered ring (for example, 4,4-dimethylcyclohexene ring) or a 5-membered ring (for example, cyclopentene ring) containing three methine groups. Good.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Z
Of the groups having 5 or more carbon atoms which at least one of ¹ and Z ² has, particularly preferred are groups having 8 or more carbon atoms. The hydrophobic group used is called a ballast group.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Z
It is particularly preferable that ¹ and Z ^{2 do not} have an acid group (for example, a carboxyl group, a sulfonic acid group, a phosphonic acid group, and an anion group which is a conjugate base of these).
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Z ¹ and Z ²
Preferred combinations of groups represented by are: R ¹ ,
And R ⁴ , R ² and R ⁵ , R ³ and R ⁶ , and Z ¹ and Z ² are the same.

Specific examples of the dye compound represented by Chemical formula 28 used in the present invention are shown in Chemical formulas 29 to 57, but the scope of the present invention is not limited thereto.

[0126]

[Chemical 29]

[0127]

[Chemical 30]

[0128]

[Chemical 31]

[0129]

[Chemical 32]

[0130]

[Chemical 33]

[0131]

[Chemical 34]

[0132]

[Chemical 35]

[0133]

[Chemical 36]

[0134]

[Chemical 37]

[0135]

[Chemical 38]

[0136]

[Chemical Formula 39]

[0137]

[Chemical 40]

[0138]

[Chemical 41]

[0139]

[Chemical 42]

[0140]

[Chemical 43]

[0141]

[Chemical 44]

[0142]

[Chemical 45]

[0143]

[Chemical 46]

[0144]

[Chemical 47]

[0145]

[Chemical 48]

[0146]

[Chemical 49]

[0147]

[Chemical 50]

[0148]

[Chemical 51]

[0149]

[Chemical 52]

[0150]

[Chemical 53]

[0151]

[Chemical 54]

[0152]

[Chemical 55]

[0153]

[Chemical 56]

[0154]

[Chemical 57]

The dye represented by the chemical formula 28 has an absorption maximum in the wavelength range of 730 to 850 nm, and has the journal of the Chemical Society (J. Chem. Soc., 189 (1933)) and US Pat. No. 2,895,955. It can be synthesized with reference to the issue.

These water-insoluble dyes can be incorporated into the layer of the light-sensitive material by various methods.

For example, it can be introduced into the layer by making it into solid fine particles, dispersed and contained in a binder, or adsorbed to fine particles such as latex or fine particles of a metal compound.

In addition, after being dissolved in a low-boiling point organic solvent, it may be introduced into the layer by being precipitated and dispersed in gelatin or the like.

The water-insoluble dye described above, the dye-donating compound described below, and the hydrophobic additive such as the antidiffusive reducing agent may be incorporated in the layer of the light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. Can be introduced. In this case, JP-A-59-83154 and JP-A-59-17
No. 8451, No. 59-178452, No. 59-178.
No. 453, No. 59-178454, No. 59-1784.
No. 55, No. 59-178457 and the like can be used in combination with a high boiling organic solvent having a low boiling point of 50 ° C. to 160 ° C., if necessary.

A preferred introduction method is to disperse both the water-insoluble dye and the dye-donor compound in a hydrophilic colloid, which has the merit of suppressing the production cost.

The amount of the high-boiling organic solvent is preferably 20 to 500% by weight of the water-insoluble dye, and the absorption is high,
It is also suitable for narrowing the absorption band width. Further, more preferably, 200 to 400% by weight is desirable.

In the present invention, the organic silver salt in the case of adopting the constitution (3) will be described.

Organic compounds that can be used to form the organic silver salt used in the present invention are described in US Pat. No. 4,500.
There are benzotriazoles, fatty acids and other compounds described in No. 626, 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.

Further, a more preferable organic compound for forming the organic silver salt is represented by Chemical formula 58.

[0165]

[Chemical 58]

In Chemical Formula 58, Z ₁ represents an atomic group necessary for forming a 5-membered to 9-membered (especially 5-membered, 6-membered or 9-membered) heterocycle. The heterocycle completed by the above general formula Z ₁ is preferably a 5-membered, 6-membered or 9-membered heterocycle containing at least one nitrogen atom, particularly containing two or more nitrogen atoms or one nitrogen atom. Above, a 5-membered, 6-membered or 9-membered heterocycle containing an oxygen atom or a sulfur atom is preferable. Here, the heterocycle includes those condensed with a benzene nucleus or a naphthalene nucleus.

Examples of such compounds include benzotriazole, JP-A-58-118638 and JP-A-58-1.
No. 18639, benzotriazoles, benzimidazoles, and pyrazoloazoles described in JP-A No. 62-96940 {for example, 1H-imidazo [1,2-
b] pyrazoles, 1H-pyrazolo [1,5-b] pyrazoles, 1H-pyrazolo [5,1-c] [1,2,
4] Triazoles, 1H-pyrazolo [1,5-b]
[1,2,4] triazoles, 1H-pyrazolo [1,
5-b] [1,2,4] triazoles, 1H-pyrazolo [1,5-d] tetrazole and 1H-pyrazolo [1,5-a] benzimidazoles}, triazoles, 1H-tetrazole, Examples include carbazoles, saccharins, imidazoles, and 6-aminopurines.

The above organic silver salts are photosensitive silver halides.
0.01 to 10 moles per mole, preferably 0.1.
01 to 1 mol can be used in combination. The total coating amount of photosensitive silver halide and organic silver salt is 50 mg / m ^{2 in} terms of silver.
Approximately 10 g / m ² is suitable.

Various antifoggants or photographic stabilizers can be used in the invention. Examples thereof include azoles and azaindenes described on pages 24 to 25 of RD17643 (1978), 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 and the like can be used.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the dye-fixing material. As an example thereof, pages (26) to (2) of JP-A-62-253159.
8) The thing described in 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 polysaccharides such as starch, gum arabic, dextran and pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with A copolymer with a vinyl monomer (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.

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.
Further, when the super absorbent polymer is used in the dye fixing layer or its protective layer, the dye can be prevented from being retransferred from the dye fixing material to another after the 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 preferably 7 g or less.

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing material are used for the purpose of improving physical properties of the film such as dimensional stabilization, 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,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect can be obtained. ..

As the reducing agent used in the present invention, those known in the field of photothermographic 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 by itself but exhibits a 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:
U.S. Pat. No. 4,500,626, columns 49-50, 44
No. 83, col. 30, columns 31-43617;
No. 4,590,152, JP-A No. 60-140335, pages (17) to (18), Nos. 57-40245, 56.
-138736, 59-178458, 59-
No. 53831, No. 59-182449, No. 59-18
No. 2450, No. 60-119555, No. 60-128
436 to 60-128439, 60-1
No. 98540, No. 60-181742, No. 61-25.
9253, 624244044, 62-131
From 253 to 62-131256, there are reducing agents and reducing agent precursors described in EP 220746A2, 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, if necessary, an electron transfer agent and / or an electron transfer agent may be added in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the electron transfer agent or the precursor thereof has a mobility higher than that of the diffusion resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3
-Pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any of those reducing agents which do not substantially move in the layer of the light-sensitive material.
Hydroquinones, sulfonamide phenols, sulfonamide naphthols, JP-A-53-11 are preferred.
Examples thereof include compounds described as electron donors in No. 0827, and dye-donating compounds having diffusion resistance and reducing properties described later. 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.

In the present invention, a compound that produces or releases a mobile (diffusible) dye in response to this reaction or vice versa when silver ions are reduced to silver under high temperature conditions. That is, a dye-donor compound (also referred to as a dye-donor substance) is used.

Examples of the dye-donating compound that can be used in the present invention include compounds represented by the following general formula [LI]. (Dye-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 corresponds to a photosensitive silver salt having an imagewise latent image. Or, conversely, causes a difference in the diffusivity of the compound represented by (Dye-Y) nZ, or Dye
And a group having the property of causing a difference in diffusivity between the released Dye and (Dye-Y) n-Z, n represents 1 or 2, and when n is 2, Two
The two Dye-Y may be the same or different.

Specific examples of the dye-donating compound represented by the general formula [LI] include the following compounds (1) to (3). The following items (1) to (5) are for forming a diffusible dye image (positive dye image) in the opposite manner to the development of silver halide, and "and" are the diffusible dye image (corresponding to the development of silver halide). To form a negative dye image).

US Pat. Nos. 3,134,764 and 336.
2819, 3597200, and 3544545.
No. 3,482,972 and the like, a dye developer 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. 4,053,137, 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. For example, US Pat.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in 980479 and the like, US Pat. No. 4,1993.
No. 54 and the like, compounds that release a diffusible dye by an intramolecular rewinding reaction of the isoxazolone ring can be mentioned.

US Pat. No. 4,559,290, European Patent No. 220746A2, US Pat. No. 4,783,396,
As described in Published Technical Report 87-6199, 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.

As an example thereof, US Pat. No. 4,133,938.
No. 9, 4139379, JP-A-59-185333.
Nos. 57-84453 and the like, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, US Pat. No. 4,232,107, JP-A-59
No. 101649, No. 61-88257, RD240
25 (1984) and the like, which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3008588A, JP-A-56-14.
2530, US Pat. Nos. 4,343,893 and 4619.
Compounds which release a diffusible dye by cleavage of a single bond after reduction as described in US Pat.
Examples thereof include nitro compounds described in U.S. Pat. No. 223 and the like that release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610 and the like that release a diffusible dye after electron acceptance.

As more preferable ones, European Patent No. 220746A2, Open Technical Report 87-6199, US Pat. No. 4,783,396, and Japanese Patent Laid-Open No. 63-201653.
No. 63, 2016-654, etc.
A compound having an -X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, Japanese Patent Application No. 62-106885.
No. ₂ within one molecule of SO ₂ -X (X is as defined above)
And a compound having an electron-withdrawing group, JP-A-63-2713
A compound having a PO-X bond (X has the same meaning as described above) and an electron-withdrawing group in one molecule described in JP-A-44-
The compound having a C—X ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule described in No. 271341. Also, Japanese Patent Application Sho 62
Compounds described in JP-A-319989 and JP-A-62-320771, 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.

Of these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include European Patent No. 220746A2 or US Patent No. 47833.
96-compounds (1)-(3), (7)-
(10), (12), (13), (15), (23)-
(26), (31), (32), (35), (36),
(41), (44), (53) to (59), (64),
(70), Compound (11) to Open Technical Report 87-6199
(23) and so on.

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 oxidized form of a reducing agent. Specifically, British Patent No. 1330524, Japanese Patent Publication No. 48-39165, US Patent Nos. 3443940, 4474867, and 448.
3914 and the like.

A compound (DRR compound) which is reducible to a silver halide or an organic silver salt and releases a diffusible dye when its partner is reduced. Since this compound does not need to use any other reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. Typical examples thereof are U.S. Pat. Nos. 3,928,312, 40,53312, and 405.
No. 5428, No. 4336322, JP-A-59-658.
No. 39, No. 59-69839, No. 53-3819,
51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113, and 3,443.
939, JP-A-58-116537, and JP-A-57-17.
9840, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to (3) described in the above-mentioned U.S. Pat. (10) to (13), (1
6) to (19), (28) to (30), (33) to (3
5), (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 a dye-donor compound other than the above-mentioned general formula [LI], a dye silver compound in which an organic silver salt and a dye are bound (Research Disclosure 197) is used.
May 1988, pp. 54-58, etc.), azo dyes used in the heat-development silver bleaching method (US Pat. No. 4,235,957, Research Disclosure, April 1976, 3).
0-32 pages) etc. can also be used.

Hydrophobic additives such as a dye-donor compound and a diffusion-resistant reducing agent can be prepared according to the methods described above and in JP-B-51-3.
The dispersion method using a polymer described in JP-A-9853 and JP-A-51-59943 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.

In dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP-A-59-157636, (37) to (38)
The surfactants listed on the page 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 material. 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, a dye fixing material is used together with a light-sensitive material. The dye fixing material may be applied separately on a support different from the photosensitive material, or may be applied on the same support as the photosensitive material. Regarding the relationship between the light-sensitive material and the dye-fixing material, 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 application.

The dye fixing material 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. 4,500,626, columns 58 to 59 and JP-A No. 61-88256 (32).
The mordant described on page (41), JP-A-62-244043.
No. 62-244036 and the like. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used.

If necessary, the dye fixing material may be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive material and the dye-fixing material, a plasticizer, a slipping agent, or a high-boiling organic solvent can be used as an agent for improving the releasability of the light-sensitive material and the dye-fixing material. Specifically, JP-A-62-253159, (2
5), No. 62-245253 and the like.

Further, various silicone oils (all silicone oils from dimethylsilicone oil to modified silicone oil obtained by introducing various organic groups into dimethylsiloxane) 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.

Further, JP-A-62-215953 and 63
The silicone oil described in JP-A-46449 is also effective.

An anti-fading agent may be used in the light-sensitive material and the dye-fixing material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a metal complex of some kind.

Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (eg hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. The compounds described in JP-A-61-159644 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-46-2784)
Etc.) and others, JP-A-54-48535 and JP-A-62-
There are compounds described in Nos. 136641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

Examples of the metal complex include US Pat. No. 4,2411,
55, 42425018, columns 3 to 36, 4254.
195, columns 3 to 8, JP-A-62-174741, JP-A-61-88256, pages (27) to (29), and JP-A-63-1.
No. 99248, Japanese Patent Application Nos. 62-234103 and 62-
There are compounds described in No. 230595 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137).

The anti-fading agent for preventing the fading of the dye transferred to the dye-fixing material may be contained in the dye-fixing material in advance, or may be supplied to the dye-fixing material from the outside such as a light-sensitive material. May be.

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 light-sensitive material and the dye-fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing material or supply it from the outside such as a light-sensitive material. 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.

As the hardener used for the constituent layers of the light-sensitive material and the dye-fixing material, US Pat. No. 4,678,739, No. 41 is used.
Column, JP-A-59-116655 and JP-A-62-24526.
No. 1, No. 61-18942 and the like. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), N-
Examples thereof include methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

In the constituent layers of the light-sensitive material and the dye-fixing material, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of sliding property, prevention of electrification, 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 material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. Typical examples of the organic fluoro compounds include Japanese Examined Patent Publication No. 57-9053, columns 8 to 17,
Fluorine-based surfactants described in JP-A Nos. 61-20944 and 62-135826, oil-based fluorine-based compounds such as fluorine oil, and solid fluorine-containing compound resins such as tetrafluoroethylene resin. Hydrophobic fluorine compounds may be mentioned.

A matting agent can be used in the light-sensitive material and the dye-fixing material. 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 material and the dye-fixing material 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 No. 61-88256, pages (26) to (32).

In the present invention, an image forming accelerator can be used in the light-sensitive material and / or the dye-fixing material.
The image forming 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. From the physicochemical functions, such as bases or base precursors, nucleophilic compounds, high boiling organic solvents (oils), thermal solvents, surfactants, 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 promoting effects together. These details are described in US Pat. No. 4,678,739, columns 38 to 40.

Examples of the base precursor include salts of organic acids and bases which are decarboxylated by heat, compounds which release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is US Pat. No. 45114.
93, JP-A-62-65038 and the like.

In a system in which heat development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye-fixing material in order to enhance the storage stability of the light-sensitive material.

In addition to the above, European Patent Publication 210660
And US Pat. No. 4,740,445, a combination of a sparingly soluble metal compound and a compound capable of complex-forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex-forming compound), and JP-A-61-232451. Compounds that generate a base by electrolysis as described in No. 1 can also be used as the base precursor. The former method is particularly effective. It is advantageous to add the hardly soluble metal compound and the complex-forming compound separately to the light-sensitive material and the dye-fixing material.

In the light-sensitive material and / or the dye-fixing material of the present invention, various development terminators can be used for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development.

The term "development terminator" as used herein means, after proper development,
A compound that rapidly neutralizes or reacts with a base to lower the concentration of the base in the film to stop development, or a compound that interacts with silver and a silver salt to suppress development. In particular,
Examples thereof include acid precursors that release an acid upon heating, electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, or nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof. For more details, see JP-A-62-2531.
No. 59 (31) to (32).

As the support for the light-sensitive material and the dye-fixing material of the present invention, those which can withstand the processing temperature are used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate (P
ET), polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide, and synthetic film made by polypropylene or the like. Blended paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly Cascote paper), metal, cloth, glass and the like are used.

These can be used alone or
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene.

In addition, the supports described in JP-A No. 62-253159, pages (29) to (31) can be used.

On the surface of these supports, a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide,
You may apply carbon black and other antistatic agents.

As a method for exposing and recording an image on a light-sensitive material, for example, a method of directly photographing a landscape or a person with a camera or the like, a method of exposing through a reversal film or a negative film with a printer or an enlarger, 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, 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.

As a light source for recording an image on a photosensitive material,
As described above, US Patent No. 4 of natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
The light source described in 500626, column 56 can be used.

The light source used for exposing the color light-sensitive material of the present invention is a light emitting diode or a semiconductor laser. As the light emitting diode in the present invention, GaA
sP (red), GaP (red, green), GaAsP (red,
Yellow), GaAs (infrared), GaAlAs (infrared, red),
Various materials such as GaP (red, green, yellow) and SiC (blue) can be used.

It is also possible to use an infrared-visible conversion element that converts the infrared light of the infrared light-emitting diode into visible light with a phosphor as described above. As such a phosphor, a phosphor activated with a rare earth is preferably used, and as the rare earth, Er ³⁺ , Tm ³⁺ , Yb ³⁺ or the like can be used.

Specific examples of the semiconductor laser which can be used in the present invention include In _1-x as a light emitting material.
G _ax P (-700 nm), GaAs _1-x P _x (610-9)
00 nm), Ga _1-x Al _x As (690 to 900 nm),
InGaAsP (1100 to 1670 nm), AlGaA
A semiconductor laser using a material such as sSb (1250 to 1400 nm) can be given. Irradiation of light to the color light-sensitive material in the present invention may be performed by a YAG laser (1064 nm) in which Nd: YAG crystal is excited by a GaAs _x P _(1-x) light emitting diode, in addition to the above semiconductor laser.

Further, in the present invention, the second harmonic generation element (SHG element) is for converting the wavelength of the laser light into one half by applying the non-linear optical effect. For example, the non-linear optical crystal. Examples include those using CD ^* A and KD ^* P (Laser Handbook, edited by Laser Society, published December 15, 1982, pages 122 to 1).
(See page 39). Also, Li ⁺ is added to H ⁺ in the LiNbO ₃ crystal.
A LiNbO ₃ optical waveguide device having an optical waveguide ion-exchanged with can be used [NIKKEI ELECTRONIC
S, July 14, 1986 (No. 399) Nos. 89-90
See page].

The above-mentioned 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, or an image signal created by using a computer represented by CG and CAD can be used.

The light-sensitive material and / or the dye-fixing material are
It may have a form having a conductive heating element layer as a heating means for heat development or dye diffusion transfer. In this case, the transparent or opaque heating element is disclosed in JP-A-61
Those described in, for example, the specification of 145544 can be used.
Note that these conductive layers also function as antistatic layers.

The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but especially about 80 ° C. to about 180 ° C.
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 it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step. Although the transfer of the dye occurs only by heat, a solvent may be used to promote the transfer of the dye.

In addition, JP-A-59-218443 and JP-A-6-218443.
As described in detail in No. 1-238056 and the like, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. 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, it is preferably 50 ° C. or higher and 100 ° C. or lower.

Examples of the solvent used for promoting the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases). Examples thereof include those described in the section of the image formation accelerator). Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound, etc. may be contained in the solvent.

These solvents can be used by a method of applying them to a dye fixing material, a photosensitive material or both.
The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). Further, the solvent may be contained in a microcapsule or the like in advance and incorporated in the light-sensitive material or the dye-fixing material or both.

Further, in order to promote the dye transfer, a method in which a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature is incorporated in the light-sensitive material or the dye-fixing material can also be adopted. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material or the dye fixing material, 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, alcohols, oximes, and other heterocycles.

Further, a high-boiling point organic solvent may be contained in the light-sensitive material and / or the dye-fixing material in order to promote dye transfer.

As a heating method in the developing and / or transferring step, a heated block or plate is brought into contact, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater or the like is contacted. Or passing through a high temperature atmosphere.

[0244] The light-sensitive material and the dye-fixing material are superposed,
For the pressure condition and the method of applying the pressure for the close contact, see Japanese Patent Laid-Open No.
The method described in page 1-147244 (27) can be applied.

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
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.

[0246]

EXAMPLES The present invention will be specifically described with reference to examples.

Example 1 A method for preparing emulsions (1) to (3) will be described.

A method for preparing the silver halide emulsion (1) for the fifth layer will be described.

A well stirred gelatin aqueous solution (water 80
Lime treated deionized bone gelatin in 0 ml (Ca content 20
ppm) 20 g, sodium chloride 4 g and potassium bromide 0.
1 g and 0.015 g of the compound (A) of Formula 59 were dissolved and kept at 65 °), and an aqueous solution of silver nitrate (AgNO ₃
50 g dissolved in water to a total volume of 300 ml) and an aqueous halide solution (KBr 22.8 g, NaCl6)
g, dissolved in water and made up to 300 ml) were added simultaneously over a period of 30 minutes. Then, the temperature of the solution was lowered to 35 ° C., and an aqueous solution of silver nitrate (50 g of AgNO ₃ dissolved in water to make a total of 300 mm) and an aqueous solution of halide (31.5 g of KBr, 1.7 g of NaCl) were dissolved in water,
300 ml total) was added simultaneously over 30 minutes.

After washing with water and desalting, 25 g of lime-treated bone gelatin (guanine content 50 ppm) and 100 ml of water were added to pH 6.
3, adjusted to pAG 7.9.

The obtained emulsion was kept at 55 ° C., 0.8 mg of triethylthiourea, 4-hydroxy-6-methyl-1,
Optimum chemical sensitization was carried out using 100 mg of 3,3a, 7-tetrazaindene. The yield of emulsion was 650 g.

[0252]

[Chemical 59]

Next, the method for preparing the third layer silver halide emulsion (2) will be described.

Coal-treated bone gelatin (C
a content of 2500 ppm) aqueous solution (in 800 ml of water, 20 g of gelatin, 2 g of sodium chloride, and the compound of formula 59 (A))
0.015 g was dissolved and kept at 50 ° C.), and the solution A and the solution B shown in Table 1 were added at the same time.
Solution B was added over 8 minutes. 16 minutes after the addition of the solution A was completed, the solution D in Table 1 was added over a period of 44 minutes, and 20 minutes after the addition of the solution A was completed, the solution C in the table 1 was added over a period of 40 minutes. The pAg from the end of the addition of solution A to the start of the addition of solution C was 6.7.

After washing with water and desalting, coal-treated bone gelatin (Ca
PH 4000ppm) 25g and water 100ml, add pH
It was adjusted to 6.0 and pAg 7.7. Then, optimal chemical sensitization was carried out at 55 ° C. using 1.1 mg of triethylthiourea and 60 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. Emulsion yield is 650g
Met.

[0256]

[Table 1]

Next, the method for preparing the silver halide emulsion (3) for the first layer will be described.

Solution I and solution II shown in Table 3 were simultaneously added over 18 minutes to a well-stirred aqueous gelatin solution having the composition shown in Table 2. 5 minutes after the addition of solution I was completed, III shown in Table 3
Solution and Solution IV were added simultaneously over 42 minutes. Using a precipitating agent represented by the compound (B) of Chemical formula 60, washing with water (pH = 4.1)
Then, 22 g of gelatin was added, an aqueous solution of NaCl and NaOH was added, and pH = 6.1, pAg = 7.6 (40 ° C.).
Measurement). After that, triethylthiourea and 4
Optimal chemical sensitization was carried out at 60 ° C. using -hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. The obtained emulsion was a cubic emulsion having an average grain size of 0.26 μm, and the yield was 635 g. Further, this emulsion was a monodisperse emulsion having a variation coefficient of 8.5%.

[0259]

[Table 2]

[0260]

[Table 3]

[0261]

[Chemical 60]

Next, a method for preparing a gelatin dispersion of a dye-donor substance will be described.

A magenta dye-donor substance (A)
15.9 g, 0.85 of the reducing agent of Chemical formula 65, 0.20 g of the mercapto compound (1) of Chemical formula 66, 0.4 g of the surfactant (3) of Chemical formula 67, and a high-boiling organic solvent (2) 5.1g
Basic weight was added, and 70 cc of ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 100 g of a 10% solution of coal-treated gelatin, and 600 cc of water were mixed by stirring, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a dispersion of the magenta dye-donor substance.

A cyan dye-donor (B ₁ )
7.3 g of the cyan dye-providing substance (B ₂ )
10.6 g, the reducing agent of chemical formula 65 is 1.0 g, the mercapto compound (1) of chemical formula 66 is 0.3 g, the surfactant (3) of chemical formula 67 is 0.4 g, and the high boiling point organic solvent (1) is It weighed 9.8 g, added 50 cc of ethyl acetate, and heated and dissolved at about 60 ° C. to obtain a uniform solution. This solution, 100 g of a 10% solution of coal-treated gelatin, and 60 cc of water were mixed by stirring, and then dispersed by a homogenizer at 10,000 rpm for 10 minutes. This dispersion is referred to as a dispersion of a cyan dye-donor substance.

A yellow dye-providing substance (C) of Chemical formula 64
18.8 g and 2.1 g of the water-insoluble dye (D)
Chemical formula 65 reducing agent 1.0 g, chemical formula 66 mercapto compound (1) 0.13 g, chemical formula 67 surfactant (3) 1.5 g, high boiling organic solvent (1) 4.0 g Weigh,
45 cc of ethyl acetate was added and dissolved by heating at about 60 ° C. to obtain a uniform solution. 10% of this solution and coal-treated gelatin
After 100 g of the solution and 60 cc of water were mixed by stirring, they were dispersed by a homogenizer for 10 minutes at 10,000 rpm. This dispersion is called a yellow dye-donor substance dispersion.

The high boiling point solvent (1) is triisononyl phosphate, and the high boiling point solvent (2) is trihexyl phosphate.

[0267]

[Chemical formula 61]

[0268]

[Chemical formula 62]

[0269]

[Chemical 63]

[0270]

[Chemical 64]

[0271]

[Chemical 65]

[0272]

[Chemical 66]

[0273]

[Chemical 67]

From these, the heat-developable color photosensitive materials 100 shown in Tables 4 and 5 were produced. The first layer,
Sensitizing dyes (1), (2) in the third and fifth layers,
(3) was added only after the chemical sensitization of emulsions (1) to (3) was completed.

[0275]

[Table 4]

[0276]

[Table 5]

The water-soluble polymers shown in Tables 4 and 5 are
8 and the surfactant (1) is aerosol O.
T and surfactants (2) and (4) are compound 69 and compound 7, respectively.
0, the hardener is shown in Chemical formula 71, and the mercapto compound (2) is shown in Chemical formula 72. The sensitizing dye (1) is the same as that shown in Chemical formula 73, the sensitizing dye (2) is the same as the compound example (II-10) shown in Chemical formula 11, and the sensitizing dye (3) is the compound example shown in Chemical formula 4. It is the same as (I-4).

[0278]

[Chemical 68]

[0279]

[Chemical 69]

[0280]

[Chemical 70]

[0281]

[Chemical 71]

[0282]

[Chemical 72]

[0283]

[Chemical 73]

Next, in the light-sensitive material 100, the compound (A-
3) in the order of the first layer and the third layer, 5.4 × 10 ⁻³ g / m ² ,
A light-sensitive material 101 was prepared in exactly the same manner except that the coating amount was 4.3 × 10 ⁻³ g / m ² .

Next, a method for preparing the dye fixing material will be described.

Dye fixing material R-1 was prepared by coating the composition shown in Table 6 on a paper support laminated with polyethylene.

[0287]

[Table 6]

Surfactant * 2, polymer * in Table 6
5, * 7, high-boiling point organic solvent * 8, and matting agent * 10 are shown below.

Surfactant * 2: Aerosol OT polymer * 5: Vinyl alcohol-sodium acrylate copolymer (75/25 molar ratio) Polymer * 7: Dextran (molecular weight 70,000) High boiling point organic solvent * 8: Reophos 95 (Ajinomoto Co., Inc.
Matting agent * 10: Benzoguanamine resin (18 vol% of particles exceeding 10 μm)

The silicone oil * 1 is converted to
Surfactants * 3, * 4, and * 11 are 75 and 7 respectively.
6 and 77, mordant * 6 is shown in chemical formula 78, and hardener * 9 is shown in chemical formula 79.

[0291]

[Chemical 74]

[0292]

[Chemical 75]

[0293]

[Chemical 76]

[0294]

[Chemical 77]

[0295]

[Chemical 78]

[0296]

[Chemical 79]

Next, evaluation was performed by the following exposure and processing.

Using the laser exposure apparatus described in Japanese Patent Application No. 2-129625, exposure was carried out under the conditions shown in Table 7, and 12 cc / m ² of water was supplied to the emulsion surface of the exposed light-sensitive material with a wire bar. The dye fixing material and the dye fixing material were superposed so that the film surface was in contact. After heating for 20 seconds using a heat drum whose temperature is adjusted so that the temperature of the absorbed film becomes 90 ° C.,
The dye fixing material was peeled off from the light-sensitive material to obtain an image on the dye fixing material.

[0299]

[Table 7]

With respect to the above-mentioned light-sensitive materials 100 and 101, stability over time and color separation were evaluated as follows. The results are shown in Table 8.

Lifetime stability The sensitivity of the light-sensitive material 100 at room temperature for 3 days is 100.
Is displayed as relative sensitivity when
The relative sensitivity at a temperature of 45 ° C. and a relative humidity of 45% for 3 days was obtained and evaluated. The sensitivity was examined by fog +0.8.

Color Separation The degree of mixing of the color of the other layer into the color image having a density of 1.5 to 1.7 formed by laser exposure of a wavelength corresponding to the original spectral sensitivity of the own layer is determined by X-RITE. Judgment was made by measuring the density under the status A condition, and it was shown in the table without any problems.

[0303]

[Table 8]

As shown in the above results, by adding the compound of the formula 2 in the present invention to the first layer and the third layer, the desensitization of the yellow of the first layer and the cyan of the third layer during the life time is reduced. It can be seen that a photothermographic material having a small size and excellent color separation property can be obtained.

In the light-sensitive material 101, the compound (A-3) of chemical formula 2 was added to the first layer only in the same amount, and the compound of chemical formula 2 (A-3) was added to only the light-sensitive material 102 and the third layer. Photosensitive material 10 in which -3) is added to photosensitive material 101
3 was prepared, and the same treatment and evaluation as above were performed. As a result, in the photosensitive material 102, in yellow,
Further, in the light-sensitive material 103, the cyan desensitization after aging was small (45 ° C., 80% RH, relative sensitivity after 3 days RH:
It was found that the light-sensitive material 102: yellow 96, the light-sensitive material 103: cyan 98) and excellent in color separation.

In the light-sensitive material 101, instead of the compound (A-3) of Chemical formula 2, the compound (A-9) was used in the first layer at 4.2 × 10 ⁻³ g / m ² , and the compound (A-9) was used in the third layer (A-3). −9) to 3.3 × 1
^{3. The} light-sensitive material 104 added with 0 ^-3 g / m ² , and the compound (A-16) of 5.1 × 10 ^-3 g / m ^{2 in} the first layer and the compound (A-16) of 4. Photosensitive material 1 ^containing 1 × 10 ⁻³ g / m ²
No. 05 was prepared and subjected to the same processing and evaluation as above, and results similar to those of the photographic material 101 were obtained.

Example 2 Instead of using the emulsion (1) of the fifth layer and the sensitizing dye (1) of Chemical Formula 73 in the light-sensitive material 100 of Example 1,
A light-sensitive material 201 was prepared by using the following emulsion (4) so that the coating amount would be 0.20 g / m ² in terms of silver amount, and using this, the same processing as in Example 1 was performed and the same evaluation was performed. I did. The results are shown in Table 9 together with the light-sensitive material 100.

Emulsion (4) (for the fifth layer) In Emulsion (1), 1 minute after the completion of the second addition of the aqueous silver nitrate solution and the aqueous halide solution, 70 ml of a 0.5% methanol solution of sensitizing dye (1) was added. Was added, and the amount of triethylthiourea at the time of chemical sensitization was increased to optimize the emulsion, and an emulsion (4) was prepared in exactly the same manner as the emulsion (1).

[0309]

[Table 9]

As shown in the above results, by using the emulsion of the present invention in the fifth layer, the heat-developable color light-sensitive material having a small desensitization of magenta in the fifth layer during life, and having excellent color separation properties. It can be seen that

In the light-sensitive material 100, instead of using the emulsion (2) and the sensitizing dye (2) in the third layer,
A light-sensitive material 202 was prepared in the same manner except that the emulsion (5) of the present invention prepared from the emulsion (2) and the sensitizing dye (2) was added according to the emulsion (4). An evaluation was done. It was found that this product has a small desensitization of cyan in the third layer during the life time (relative sensitivity of 96 after 80 days of RH of 45 ° C. and 80% RH) and is excellent in color separation.

Also, instead of using the emulsion (3) and the sensitizing dye (3) in the first layer, a book prepared from the emulsion (3) and the sensitizing dye (3) according to the emulsion (4). A light-sensitive material 203 was prepared in the same manner except that the emulsion (6) of the invention was added, and the same processing and evaluation as above were carried out. With this product, the desensitization of the yellow of the first layer during the lifetime is small (45
It was found that the relative sensitivity after 3 days of storage at 80% RH and 97%) and the excellent color separation property were excellent.

Example 3 In the light-sensitive material 100 of Example 1, the organic silver salt was applied to the first layer by using the following organic silver salt dispersion so that the coating amount was 0.02 g / m ^{2 in} terms of silver amount. A light-sensitive material 301 was prepared in exactly the same manner as the light-sensitive material 100 except that the addition was performed as described above. Further, instead of the first layer of the light-sensitive material 301, the second layer and the fourth layer are respectively coated in this order in an amount of 0.0 in terms of silver amount.
2 g / m ^2, except that the addition of such a 0.01 g / m ^2, was prepared a photosensitive material 302 in a similar manner.

Preparation of Dispersion of Organic Silver Salt 28 g of gelatin and 13.2 g of benzotriazole were added to 3 parts of water.
It was dissolved in 000 ml. The solution was kept at 40 ° C. and stirred. A solution prepared by dissolving 17 g of silver nitrate in 100 ml of water was added to this solution over 4 minutes. Also, 1N aqueous solution of NaOH 1
00 cc was added over 3 minutes 1 minute and 30 seconds after the start of addition of the aqueous silver nitrate solution. The pH of the reaction solution was kept at 2 or higher.

The pH of this benzotriazole silver emulsion was adjusted and allowed to settle to remove excess salt. Thereafter, the pH was adjusted to 6.50 to obtain a yield of 400 g of an organic silver salt dispersion of benzotriazole silver.

The photosensitive materials 301 and 302 were processed in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 10 together with the light-sensitive material 100.

[0317]

[Table 10]

As shown in the above results, by using the organic silver salt of the present invention, not only the added layer but also the adjacent layer and other layers are less desensitized during life,
It can be seen that a heat-developable color light-sensitive material having excellent color separation property can be obtained.

A photosensitive material 303 was prepared in the same manner as in the photosensitive material 301 except that acetylaminophenylacetylene silver was used as the organic silver salt in place of silver benzotriazole in an amount of 0.03 g / m ² applied. When the processing and evaluation were performed, the same results as those of the photosensitive material 301 were obtained.

In the light-sensitive material 302, acetylaminophenylacetyl silver was used instead of benzotriazole silver as the organic silver salt, and the silver coating amount of this was 0.03 g / m ² in the ^second layer and 0 in the fourth layer. When a light-sensitive material 304 was prepared in the same manner except that the amount was 0.02 g / m ^2, and the same processing and evaluation were performed, the same result as that of the light-sensitive material 302 was obtained.

Example 4 In the photosensitive material 100 of Example 1, the first layer and the third layer were used.
The compound (A-15) represented by Chemical Formula 2 is contained in each layer.
In the order of the first layer and the third layer, 5.4 × 10 ⁻³ g / m ² , 4.
Add to a coating amount of 3 × 10 ^-3 g / m ² , and add
A light-sensitive material 401 was prepared in the same manner except that the emulsion (4) was added to the layer so that the coating amount was 0.20 g / m ² in terms of silver amount.

In the light-sensitive material 401, further,
Using the benzotriazole silver dispersion, the second and fourth layers were coated in this order in an amount of 0.0
2 g / m ^2, was added in an amount of 0.01 g / m ^2, was prepared a photosensitive material 402 in a similar manner.

The photosensitive materials 401 and 402 were processed in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 11 together with the photosensitive material 100.

[0324]

[Table 11]

As shown in the above results, by adopting the combination aspect of the present invention, it is possible to obtain a heat developable color light-sensitive material which is further less desensitized during aging and is further excellent in color separation. I understand.

In Examples 1 to 4, instead of using the compound of Chemical formula 29 as the water-insoluble dye, the compound of Chemical formula 30 and the compound of Chemical formula 38 were used in the same manner, and the same treatment and evaluation were carried out. As a result, the results equivalent to those of Examples 1 to 4 were shown.

[0327]

EFFECTS OF THE INVENTION According to the present invention, the color separation property is excellent, the desensitization with life time is small, and the stability is excellent.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] May 13, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0079

[Correction method] Change

[Correction content]

The compound represented by Chemical formula 2 is a compound known as a supersensitizer for sensitizing dyes in general light-sensitive materials for wet development processing (US Pat. No. 2875058, US Pat. No. 3,695,888, JP-A-59-192242
And Japanese Patent Application Laid-Open No. 59-191032) and also known as a supersensitizer in a thermosensitive color image light-sensitive material (See Japanese Patent Application Laid-Open No. 59-180550).

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0115

[Correction method] Change

[Correction content]

Among them, the cyanine dye represented by Chemical formula 28 is particularly preferable in that it has a large molecular extinction coefficient, a narrow absorption band width, is stable, and does not bring about a photographic adverse effect.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0124

[Correction method] Change

[Correction content]

In addition, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R
It is particularly preferable that ⁶ , Z ¹ and Z ^{2 do not} have an acid group (for example, a carboxyl group, a sulfonic acid group, a phosphonic acid group, and an anion group which is a conjugate base of these). As a preferable combination of the groups represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Z ¹ and Z ² , R is:
¹ and R ⁴ , R ² and R ⁵ , R ³ and R ⁶ , and Z ¹ and Z ² are the same.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0137

[Correction method] Change

[Correction content]

[0137]

[Chemical 40]

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0174

[Correction method] Change

[Correction content]

As the reducing agent used in the present invention, those known in the field of heat-developable color 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 by itself but exhibits a reducing property by the action of a nucleophile or heat during the development process can also be used.

[Procedure Amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0249

[Correction method] Change

[Correction content]

A well-mixed gelatin aqueous solution (80% water)
Lime treated deionized bone gelatin (Ca content 2
0 ppm) 20 g, 4 g of sodium chloride, 0.1 g of potassium bromide, and 0.015 g of the compound (A) of formula 59 were dissolved and kept at 65 °) in an aqueous solution of silver nitrate (AgN
O _{3 (} 50 g) was dissolved in water to make a total of 300 ml) and an aqueous halide solution (KBr 22.8 g, N 2
6 g of aCl was dissolved in water, and the total amount thereof was made up to 300 ml) was added simultaneously for 30 minutes. Then, the temperature of the solution was lowered to 35 ° C., and an aqueous solution of silver nitrate (50 g of AgNO ₃ dissolved in water to make 300 ml in total) and an aqueous solution of halide (31.5 g of KBr, 1.7 g of NaCl) were dissolved in water to obtain 300 ml of the whole. 3) at the same time
Added over 0 minutes.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0250

[Correction method] Change

[Correction content]

After washing with water and desalting, 25 g of lime-processed bone gelatin (guanine content 50 ppm) and 100 ml of water were added to pH.
It was adjusted to 6.3 and pAg 7.9.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0275

[Correction method] Change

[Correction content]

[0275]

[Table 4]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0281

[Correction method] Change

[Correction content]

[0281]

[Chemical 71]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0321

[Correction method] Change

[Correction content]

Example 4 In the photosensitive material 100 of Example 1, the first layer and the third layer were used.
The compound (A-3) represented by Chemical formula 2 is added to each of the layers,
5.4 × 10 ⁻³ g / m ² , in the order of the first layer and the third layer,
It was added so as to give a coating amount of 4.3 × 10 ⁻³ g / m ² , and emulsion (4) was added to the fifth layer at a coating amount of 0.
A light-sensitive material 401 was prepared in the same manner except that the addition amount was 20 g / m ² .

Claims (3)

[Claims] 1. A heat-developable color light-sensitive material having at least a light-sensitive silver halide emulsion, a binder and a dye-donor compound on a support, and infrared light having a peak of spectral sensitivity to infrared light of 700 nm or more. Having at least one layer, and at least one layer containing a water-insoluble dye,
A heat-developable color light-sensitive material having at least one infrared light-sensitive layer containing the compound represented by Chemical formula 1. [Chemical 1] [In Chemical Formula 1, A represents a divalent aromatic residue. R ₁ ,
R ₂ , R ₃ and R ₄ are each a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an alkylthio group, an arylthio group, an amino group, an alkylamino group. , An arylamino group, a heterocyclylamino group, an aralkylamino group, an aryl group, a heterocyclyloxy group or a mercapto group. However, A, R ₁ , R ₂ , R
_At least one of ₃ and R ₄ has a sulfo group. Each W ₁ and W ₂ represent -CH = or -N =. However, at least _one of W ₁ and W ₂ is -N =
Represents]. 2. A heat-developable color light-sensitive material having at least a light-sensitive silver halide emulsion, a binder and a dye-donating compound on a support, and infrared light having a peak of spectral sensitivity to infrared light of 700 nm or more. A silver halide emulsion prepared by having at least one layer, containing a water-insoluble dye in at least one layer, and further adding a sensitizing dye between grain formation and the end of chemical sensitization. A heat-developable color light-sensitive material having at least one light-sensitive layer contained therein. 3. A heat-developable color light-sensitive material having at least a light-sensitive silver halide emulsion, a binder and a dye-donating compound on a support, and infrared light having a peak of spectral sensitivity to infrared light of 700 nm or more. A heat-developable color light-sensitive material comprising at least one layer, at least one layer containing a water-insoluble dye, and at least one layer containing an organic silver salt.