JP2699017B2 - Transfer type heat developable color photosensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transfer type thermal development in a multilayer heat-developable color light-sensitive material, which has a dye having excellent diffusion resistance and is excellent in life time, color separation and white background. It relates to a color photosensitive material.

(Prior Art) A photographic method using silver halide has superior photographic characteristics such as sensitivity and gradation control as compared with other photographic methods such as electrophotography and diazo photographic method, and thus has been used most widely. Have been.

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

Conventional color light-sensitive materials usually have blue, green, and red spectral image sensations. To obtain an image using image information once converted into an electrical signal on such a color light-sensitive material, a color image is required.
It is common to use a CRT (cathode ray tube) as the exposure light source, but the CRT is not suitable for obtaining large-size prints.

Light-emitting diodes (LEDs) and semiconductor lasers have been developed as write heads capable of obtaining large-size prints. However, none of these optical writing heads efficiently generate blue light.

Therefore, for example, when a light emitting diode (LED) is used, a light source combining three light emitting diodes of near-infrared (800 nm), red (670 nm) and yellow (570 nm) separates the light into near-infrared, red, and yellow light. It is necessary to expose a color light-sensitive material having three sensitized layers, and a system for performing image recording in such a configuration is described in “Nikkei New Materials”, September 14, 1987, pp. 47-57. And some are in practical use.

JP-A-61-137149 describes a system in which a light source combining three semiconductor lasers emitting at 880 nm, 820 nm, and 760 nm records light on a spectral material at each wavelength.

In the case of conventional light-sensitive materials, a heat-developable color light-sensitive material is more excellent when a processing solution is used and a long processing time is required to quickly output an image from image information. Various types of heat-developable color light-sensitive materials are known.

For example, a method of forming a dye image by a coupling reaction between an oxidized form of a developing agent and a coupler is disclosed in U.S. Pat.
Nos. 1,270 and 4,021,240. But,
In this case, complicated processing is required for removing a silver image accompanying the formation of a color image, and the processing is not simple. Further, when the removal of silver is stopped, color reproduction is deteriorated.

A method of forming a positive dye image by silver dye bleaching is described in U.S. Pat. No. 4,235957. However, in this method, a dye image is bleached by a silver image,
Complicated processing steps are required.

Recently, a method of transferring an imagewise diffusible dye to a dye fixing element by heat development has been proposed. That is, it is a transfer type heat-developable color photosensitive material.

In this method, a negative dye image and a positive dye image can be obtained by changing the type of the dye-providing substance used. For further details, see U.S. Pat.
No. 4,503,137, No. 4,559,290, JP-A-58-149046
No., JP-A-60-133449, JP-A-59-218443, JP-A-61-2380
No. 56, European Patent Publication 220,746A, Published Technical Report 87-6199, European Patent Publication 210,660A and the like.

(Problems to be Solved by the Invention) In general, yellow,
When each color of magenta and cyan is exposed to three different spectral regions to form a color, it is an important technique in color reproduction to form each color without mixing colors.

In particular, when three spectral sensitivities must be designed in a narrow spectral range of 600 nm or more, how to reduce the overlap of each spectral sensitivity, in other words, how to sharpen the spectral sensitivity However, this has been the key to improving color separation.

As a known technique for solving these problems, for example, as described in U.S. Pat. No. 4,619,892, a technique of increasing the short-wave side sensitivity among two spectral sensitivities and introducing a filter layer is known. Have been.

However, in the case of a transfer type photosensitive material, when a dye or a dye is contained, it is important that the dye or the dye or a decomposition product thereof is not transferred during processing / transfer, in order to maintain a good white background. Has become.

Furthermore, it is also an important requirement that the dyes and dyes do not substantially change during storage of the light-sensitive material and do not change the spectral sensitizing properties and color separation properties.

Therefore, the object of the present invention is to provide a multicolor heat-developable color light-sensitive material, which has a dye having excellent diffusion resistance, and is excellent in aging, color separation and white background, and is a transfer-type heat-developable color light-sensitive material. Is to provide.

(Constitution of the Invention) An object of the present invention is to provide at least one or more photosensitive layers having a peak in spectral sensitivity to infrared light of 700 nm or more, and a water-insoluble compound represented by the following general formula [I]. This has been attained by a transfer-type heat-developable color light-sensitive material having at least one layer containing a dye.

General formula [I] In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and represent an alkyl group, and Z ¹ and Z ² are a benzo-fused ring or a naphtho-fused ring Represents a group of non-metallic atoms necessary to form Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
Any of the groups represented by 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 a halogen ion (Cl, Br, I), p-toluenesulfonic acid ion, ethyl sulfate ion, perchlorate ion and the like.

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 (eg, 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 the aryloxy group includes m-pentadecylphenoxy,
Examples of aralkyl groups such as 2,4-di-t-pentylphenoxy and the like include benzyl and phenylethyl groups, and examples of acyl groups of acyloxy groups include stearoyl and palmitoyl.

The benzo-fused ring or naphtho-fused ring formed by the nonmetallic atom group represented by Z ¹ and Z ² includes those having a substituent, and the substituent includes a hydroxyl group, a halogen atom (eg, F, Cl, Br), A cyano group, a substituted amino group (for example, a dialkylamino group and an alkyl group are the same as described above) or a carbon number of 1 to 1 bonded to a ring directly or via a divalent linking group;
Including those having 18 alkyl groups ｛substituents. For example, methyl, ethyl, propyl, butyl and the like (substituents include an alkoxy group, a halogen atom (same as described above), a hydroxyl group, etc.), etc., and the divalent linking group is, for example, -O-, -NHCO _{-, - NHSO 2 -, -} NHCOO -, - NH
CONH -, - COO -, - CO -, - SO 2 - is preferred.

The methine group represented by L includes those having a substituent, and examples of the substituent include lower alkyl groups having 1 to 5 carbon atoms (including those having a substituent. For example, methyl, ethyl,
3-hydroxypropyl, benzyl, 2-sulfoethyl), halogen atom (for example, F, Cl, Br), aryl group (including those having a substituent; for example, phenyl, 4-chlorophenyl), lower alkoxy group (for example, methoxy , Ethoxy), an amino group (including those having a substituent, for example, diphenylamino), and the like. Further, the substituents of the methine group represented by L may combine with each other to form a 6-membered ring (for example, a 4,4-dimethylcyclohexene ring) or a 5-membered ring (for example, a cyclopentene ring) containing three methine groups. . Among the groups having 5 or more carbon atoms of at least one of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Z ¹ and Z ² , a group having 8 or more carbon atoms is particularly preferable. For example, a hydrophobic group called a ballast group used for a color photographic coupler or a color material for forming a color image by a diffusion transfer method is exemplified.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Z ¹ and Z ^{2 each} represent an acid group (for example, a carboxyl group, a sulfonic group, a sulfonic group, and an anionic group which is a conjugate base thereof) ) Are particularly preferred.

Preferred combinations of the groups represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Z ¹ and Z ² include R ¹ and R ⁴ , R ² and R ⁵ , R ³ and R ⁶ , Z ¹
And Z ² are equal to each other.

Specific examples of the dye compound represented by the general formula (1) used in the present invention are shown below, but the scope of the present invention is not limited thereto.

The dye represented by the general formula (I) has an absorption maximum at a wavelength of 73.
In the range of 0 to 850 nm, the Journal of Chemical
Society (J. Chem. Soc., 189 (1933)) and U.S. Pat.
It can be synthesized with reference to 95,955.

The water-insoluble dye can be introduced into the column of the light-sensitive material by various methods.

For example, solid fine particles can be dispersed and contained in a binder, adsorbed on fine particles such as latex, or a metal compound, and introduced into a layer.

In addition, after dissolving in a low-boiling organic solvent, a substance precipitated and dispersed in gelatin or the like can be introduced into the column.

However, as a more preferable introduction method, a high-boiling organic solvent, or a low-boiling organic solvent, or a mixed solvent of the two, after dissolution, using various surfactants, dispersed in a hydrophilic colloid such as gelatin. can give.

The water-insoluble dye can be added to an emulsion layer, an intermediate layer, a protective layer, and an antihalation layer, if necessary.

When it is added to an emulsion layer, a mixture of the water-insoluble dye of a dye-providing compound described later can be dispersed in a hydrophilic colloid, which is advantageous in that the production cost can be reduced.

On the other hand, when it is added to the intermediate layer, the protective layer and the antihalation layer, there is an advantage that it can be introduced into the photosensitive material without suppressing the development of the adjacent emulsion layer.

The heat-developable color light-sensitive material of the present invention basically comprises a support having a photosensitive silver halide, a dye-providing compound (which may also serve as a reducing agent as described later), and a binder. An organic metal salt oxidizing agent, if necessary,
Etc. can be contained. These components are often added to the same layer, but may be added separately to another layer if they can react. For example, if a coloring dye-providing compound is present in the lower layer of the silver halide emulsion, the sensitivity can be prevented from lowering. 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.

In order to obtain a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta, and shiner, at least three silver halide emulsion layers having photosensitivity in different spectral regions are used in combination. For example, blue layer, green layer,
There are a combination of three red-sensitive layers, a combination of green-sensitive layers, red-sensitive layers, and infrared-sensitive layers. Each photosensitive layer can adopt various arrangement orders known for ordinary type color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary.

The photothermographic material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter, an antihalation layer, and a back layer.

Further, in the present invention, at least one layer containing the water-insoluble dye represented by the general formula (I) is provided, for the following reason.

For example, when a layer B spectrally sensitized to 750 nm is provided on a layer A spectrally sensitized to 810 nm, exposure to 750 nm light causes the color of layer A to be mixed in a high-exposure part, that is, a part with much light. And the color separation becomes insufficient. In particular, this tendency becomes remarkable when the sensitivity of the layer A spectrally sensitized to 810 nm is high.

Therefore, in the present invention, in the layer A and in the layer between the layer A and the layer B, there is no substantial absorption near the spectral sensitization peak of the layer A, and the spectral sensitization of the layer A is performed. By including a water-insoluble dye represented by the general formula (I) having a maximum absorption wavelength at a position which is shorter than the peak and can absorb light emitted from the light source used for the exposure of the layer B, the short wave of the layer A is obtained. The spectral sensitized part on the side is cut to improve color separation.

In the present invention, since a water-insoluble dye represented by the general formula (I) is used, a dye for improving color separation is not transferred when a dye for forming an image is transferred. Will be kept.

In the present invention, when the spectral sensitivities overlap between the two photosensitive layers providing the diffusible dyes having different hues, the photosensitive layer on the short wave side is provided in or on the photosensitive layer in charge of the long wave side. By providing a layer of the water-insoluble dye represented by the general formula (I) having the absorption maximum wavelength at the wavelength of the light source for exposing the color, color separation and color reproducibility can be improved.

Further, the dye represented by the structure of the present invention, although the reason is not well understood,
Small optical or chemical changes such as color increase, fading and discoloration. Therefore, it is possible to obtain a transfer-type heat-developable color light-sensitive material having a very small change in spectral characteristics or color separation.

As the light emitting diode of the light source used for exposing the heat developable color photosensitive material of the present invention, GaAsP (red), GaP (red,
Green), GaAsP: N (red, yellow), GaAs (infrared), GaAlAs (infrared, red), GaP: N (red, green, blue), GaSiSi (infrared), Ga
Various materials such as N (blue) and SiC (blue) can be used.

Further, an infrared-visible conversion element that converts infrared light of the infrared light-emitting diode into visible light by a phosphor can be used. As such a phosphor, a phosphor activated with a rare earth is preferably used.
r ³⁺ , Tm ³⁺ , Yb ^{3+ and the} like can be used.

As a specific example of a semiconductor laser that can be used in the present invention, In _1-x G _ax P (x700 n
m), GaAs _1-x P _x (610-900 nm), Ga _1-x Al _x As (690-900 nm)
nm), InGaAsP (1100-1670 nm), AlGaAsSb (1250-140
0 nm). Irradiation of light to the color photosensitive material in the present invention, in addition to the above-described semiconductor laser, Nd: YAG crystal GaAs _x P _(1-x)
A YAG laser (1064 nm) excited by a light emitting diode may be used.

In the present invention, the second harmonic generation element (SHG element) converts the wavelength of laser light to half by applying a nonlinear optical effect. For example, a CD ^{* is used} as a nonlinear optical crystal ^. Examples using A and KD ^* P (Laser Handbook, edited by Laser Society of Japan, December 1982)
Published on the 15th, pages 122 to 139). Also, in the LiNbO ₃ crystal
It is possible to use a LiNbO ₃ optical waveguide device having an optical waveguide in which Li ⁺ is ion-exchanged with H ⁺ (NIKKEI ELECTRONICS
1986.7.14. (No. 399) pp. 89-90.

As other light sources, light sources such as natural light, a tungsten lamp, and a CRT light source can be used.

The silver halide that can be used in the present invention may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide.

The silver halide emulsion used in the present invention may be a surface latent image emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Further, a so-called core-shell emulsion having a different phase between the inside of the grain and the grain surface layer may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used. Particle size is 0.1-2μ,
In particular, 0.2 to 1.5 µ is preferable. The crystal habit of the silver halide grains may be any of cubic, octahedral, tetrahedral, high aspect ratio tabular, and the like.

Specifically, U.S. Patent No.
Any of the silver halide emulsions described in No. 28,021, Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (1978), and JP-A No. 62-253159 can be used.

The silver halide emulsion may be used as it is after unripe, but usually it is used after chemical sensitization. Known sulfur sensitization methods, reduction sensitization methods, noble metal sensitization methods, and the like can be used alone or in combination for 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 coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / cm ² in terms of silver.

The silver halide used in the present invention may be spectrally sensitized with methine dyes or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

Specifically, U.S. Pat.No. 4,617,257, JP-A-59-180
No. 550, No. 60-140335, RD17029 (1978), pp. 12-13, and the like.

These sensitizing dyes may be used alone, or a combination thereof may be used.
Often used for supersensitization.

Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3,615,641). And those described in Japanese Patent Application No. 61-226294).

These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or may be added to U.S. Pat.
No. 4,225,666, before and after nucleation of silver halide grains. The addition amount is generally about 1 ^-8 to 10 ^-2 mol per mol of silver halide.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used.

Organic compounds that can be used to form the above-mentioned organic silver salt oxidizing agent include benzotriazoles, fatty acids and other compounds described in U.S. Pat. No. 4,500,626, columns 52-53. Also useful are silver salts of carboxylic acids having an alkynyl group such as silver phenylpropiolate described in JP-A-60-113235 and acetylene silver described in JP-A-61-249044. Two or more organic silver salts may be used in combination.

The above organic silver salts can be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of the photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is suitably from 50 mg to 10 g / m ² in terms of silver.

In the present invention, various antifoggants or photographic stabilizers can be used. An example is RD17643
(1978) Azoles and azaindenes described on pages 24 to 25, carboxylic acids and phosphoric acids containing nitrogen described in JP-A-59-168442, or mercapto compounds and metals thereof described in JP-A-59-111636 Salts and acetylene compounds described in JP-A-62-87957 are used.

As the reducing agent used in the present invention, those known in the field of photothermographic materials can be used. Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat during the development process can be used.

Examples of reducing agents used in the present invention include U.S. Pat.
Columns 49-50 of 4,500,626, 30-31 of 4,483,914
No. 4,330,617, 4,590,152, JP-A-60-14
Nos. 17- (18), Nos. 57-40245 and 56-1 of No. 0335
38736, 59-178458, 59-53831, 59-1824
No. 49, No. 59-182450, No. 60-119555, No. 60-128436
No. to No. 60-128439, No. 60-198540, No. 60-18
No. 1742, No. 61-259253, No. 62-244044, No. 62-1312
From No. 53 to No. 62-131256, there are reducing agents and reducing agent precursors described in EP 220,746 A2, pp. 78-96.

Combinations of various reducing agents can also be used, such as those disclosed in U.S. Pat. No. 3,039,869.

When a diffusion-resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent are optionally added to promote electron transfer between the diffusion-resistant reduction agent and the developable silver halide. Precursors 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 its precursor has a higher mobility than the diffusion-resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols.

The diffusion-resistant reducing agent (electron donor) to be used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the light-sensitive material among the aforementioned reducing agents, and is preferably a hydroquinone, Examples thereof include sulfonamidophenols, sulfonaminonaphthols, compounds described as electron donors in JP-A-53-110827, and non-diffusible and reducible dye-donating compounds described later.

In the present invention, the amount of the reducing agent added is based on 1 mole of silver.
It is 0.01 to 20 mol, particularly preferably 0.1 to 10 mol.

Examples of the dye donating compound used in the present invention include compounds having a function of releasing or diffusing a diffusible dye imagewise. This type of compound can be represented by the following general formula [LI].

(Dye-Y) nZ [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or a linking group, and Z represents a latent image. (Dye-Y) n-Z to cause a difference in the diffusivity of the compound represented by (Dye-Y) nZ, or to release Dye and to release the released Dye and (Dye- Y) represents a group having a property that causes a difference in diffusivity with n-Z, n represents 1 or 2, and when n is 2, two Dye-Ys are the same but different. Is also good.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds.
The following items (1) to (3) form a diffusible dye sensitizer (positive dye image) in reverse correspondence to the development of silver halide.
Is to form a diffusible dye image (negative dye image) corresponding to the development of silver halide.

U.S. Pat.Nos. 3,134,764, 3,362,819, 3,591
7,200, 3,544,545 and 3,482,972. A dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide.

As described in U.S. Pat. No. 4,503,137, non-diffusible compounds which release a diffusible dye in an alkaline environment but lose their ability when reacted with silver halide can also be used. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in U.S. Pat.No. 3,980,479 and the like, and an intramolecular reversion reaction of an isoxazolone ring described in U.S. Pat. Compounds that release diffusible dyes are included.

As described in U.S. Pat.No. 4,559,290, European Patent No. 220,746A2, Published Technical Report 87-6199, etc., a non-diffusible substance which reacts with a reducing agent remaining unoxidized by development to release a diffusible dye Can also be used.

Examples are U.S. Pat.Nos. 4,139,389 and 4,13
No. 9,979, JP-B-59-185333, and compounds capable of releasing a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in U.S. Pat.
No., JP-A-59-101649, JP-A-61-88257, RD24035 (19
1984), a compound that releases a diffusible dye by an electron transfer reaction in the molecule after being reduced.
No. 3,008,588A, JP-A-56-142530, U.S. Pat.
Nos. 893, 4,619,884, etc., compounds that release a diffusible dye by cleavage of a single bond after reduction, and release a diffusible dye after electron acceptance, as described in U.S. Pat. Nitro compounds, U.S. Pat.No. 4,609,61
No. 0, etc., which release a diffusible dye after accepting electrons, and the like.

Also, more preferably, EP 220,74
6A2, Published Technical Report 87-6199, Japanese Patent Application No. 62-34953, 62-349
Compounds having an NX bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule described in JP-A-34954, etc. To SO
_2- X (X is as defined above) and a compound having an electron-withdrawing group. A PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule described in Japanese Patent Application No. 62-106895. A compound having
Japanese Patent Application No. 62-1006887 discloses a 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.

Of these, compounds having an NX bond and an electron-withdrawing group in one molecule are sometimes preferred. A specific example is European Patent No. 22
Compounds (1)-(3), (7)-described in US Pat.
(10), (12), (13), (15), (23)-(26),
(31), (32), (35), (36), (40), (41),
(44), (53)-(59), (64), (70), Published Technical Report 87
-6199 compounds (11) to (23).

Compounds that have a diffusible dye as a leaving group and release a diffusible dye upon reaction with an oxidized reducing agent (DD
R coupler). Specifically, British Patent No. 1,330,524, JP-B-48-39,165, U.S. Patent Nos. 3,443,940, and 4,47
Nos. 4,867 and 4,483,914.

Is reducible to silver halides or organic silver salts,
A compound that releases a diffusible dye when the partner is reduced (DRR
Compound). Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. A representative example is U.S. Pat.No. 3,928,312
No. 4,053,312, No. 4,055,428, No. 4,336,32
No. 2, JP-A-59-65839, JP-A-59-69839, JP-A-53-3819
No. 51-104,343, RD17465, U.S. Pat.
No. 2, 3,728,113, 3,443,939, JP-A-58-1
Nos. 16,537, 57-179840 and U.S. Pat. No. 4,500,626. 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 described in the above-mentioned U.S. Patents, (1) to (3) ), (10)-(13), (1
6)-(19), (28)-(30), (33)-(35), (3
8) to (40) and (42) to (64) are preferred. The compounds described in U.S. Pat. No. 4,639,408, columns 37 to 39 are also useful.

Other examples of the above-mentioned couplers and dye-donating compounds other than the general formula [LI] include dye silver compounds in which an organic silver salt is combined with a dye (Research Disclosure, 1978, May 1978).
Monthly publications, pages 54 to 58), azo dyes used in the thermally developed silver dye bleaching method (US Pat. No. 4,235,957, Research Disclosure, April 1976, pages 30 to 32, etc.), leuco dyes (US Patent Nos. 3,985,565 and 4,022,617) can also be used.

The hydrophobic additives such as the dye-donating compound, the water-insoluble dye of the present invention, and the diffusion-resistant reducing agent can be introduced into the layer of the photosensitive element by a known method such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
Nos. 59-178451, 59-178452, 59-178453
No. 59-178454, No. 59-178455, High boiling organic solvents such as those described in No. 59-178457, if necessary in combination with a low boiling organic solvent having a boiling point of 50 ° C. to 160 ° C. , Can be used.

The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the hydrophobic additive such as the dye-donating compound used. Also, 1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less is suitable for 1 g of the binder.

A dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 can also be used.

In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method.

When dispersing in a hydrophilic colloid of a hydrophobic compound, various surfactants can be used. For example, JP-A-59
The surfactants listed on pages (37) to (38) of No. 157636 can be used.

In the present invention, a compound capable of activating development and simultaneously stabilizing an image can be used in the light-sensitive material. Specific compounds preferably used are described in U.S. Pat.
No. 626, columns 51-52.

In a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with a photosensitive material. The dye-fixing material may be in the form of being separately coated on a support separate from the photosensitive material, or may be in the form of being coated on the same support as the photosensitive material. The relationship between the photosensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer described in column 57 of US Pat. No. 4,500,626 can be applied to the present invention.

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 field of photography can be used, and specific examples thereof include U.S. Pat.
-88256, mordants described on pages (32) to (41);
Nos. 2-244043 and 62-244036. Further, a dye-receiving polymer compound as described in US Pat. No. 4,463,079 may be used.

The dye-fixing material may be provided with an auxiliary layer such as a protective layer, a release layer, and an anti-curl layer, if necessary. It is particularly useful to provide a protective layer.

As the binder for the constituent layers of the photosensitive material and the dye fixing material, hydrophilic binders are preferably used. Examples thereof include those described on pages (26) to (28) of JP-A-62-253159. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₂ M (M
Is a homopolymer of a vinyl monomer having a hydrogen atom or an alkali metal) or a copolymer of the vinyl monomers or other vinyl monomers (eg, sodium methacryl, ammonium methacrylate, Sumikagel manufactured by Sumitomo Chemical Co., Ltd.) L-5H) are also used. These binders can be used in combination of two or more.

When a system for performing thermal development by supplying a small amount of water is used, it is possible to quickly absorb water by using the above superabsorbent polymer. When the superabsorbent polymer is used for the dye-fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye-fixing material to another after transfer.

In the present invention, the coating amount of the binder is 1 m ² per 20g
The following is preferable, and particularly, it is suitably 10 g or less, more preferably 7 g or less.

Examples of the hardener used in the constituent layers of the light-sensitive material and the dye-fixing material include U.S. Patent No. 4,678,739, column 41, and JP-A-59-11665.
No. 5, 62-245261, 61-18942 and the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners Vinyl sulfone hardeners (such as N, N'-ethylene-bis (vinylsulfonylacetamide) ethane), N-methylol hardeners (such as dimethylol urea), or polymer hardeners (Japanese Patent Laid-Open No. Sho 62) -234157, etc.).

In the present invention, an image formation accelerator can be used for the light-sensitive material and / or the dye-fixing material. Examples of the image formation accelerator include a redox reaction between a silver salt oxidizing agent and a reducing agent, promotion of a reaction such as generation of a dye from a dye-providing substance or decomposition of the dye or release of a diffusible dye, and a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. See US Pat. No. 4,678,
No. 739, columns 38-40.

Examples of the base precursor include a salt of an organic acid and a base that are decarboxylated by heat, a compound that releases an amine by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement, and the like. Specific examples thereof are described in U.S. Pat.
2-65038.

In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in the dye-fixing material from the viewpoint of improving the storage stability of the photosensitive element.

In addition to the above, a combination of a sparingly soluble metal compound described in European Patent Publication No. 210,660 and a compound capable of forming a complex with a metal ion constituting the sparingly soluble metal compound (referred to as a complex forming compound); Compounds that generate a base by an electric field described in 61-232451 can also be used as a base precursor. In particular, the former method is effective. The sparingly soluble metal compound and the complex forming compound are advantageously added separately to the light-sensitive material and the dye-fixing material.

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

The term "development terminator" as used herein means that after appropriate development, the base is quickly neutralized or reacts with the base to reduce the base concentration in the film, and interact with a compound that stops development or silver and silver salts to suppress development. Compound. Specific examples include an acid precursor that releases a film when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. More specifically, JP-A-62-253159 (31) to (32)
Page.

Various polymers are included in the constituent layers (including the back layer) of the photosensitive material or the dye fixing material for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, film crack prevention, and pressure sensation. Latex can be included. Specifically, JP-A Nos. 62-245258, 62-136648, 62
Any of the polymer latexes described in JP-A-110066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or less) is used as a mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for the back layer, the curl prevention effect is reduced. can get.

The constituent layers of the photosensitive material and the dye fixing material include a plasticizer,
A high boiling organic solvent can be used as a slipping agent or an agent for improving the releasability of the photosensitive material and the dye fixing material. Specific examples include those described in JP-A-62-253159, page (25) and JP-A-62-245253.

Further, for the above purpose, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethyl siloxane) can be used. Examples thereof include various modified silicone oils described in Technical Data “Modified Silicone Oil” published by Shin-Etsu Silicone Co., Ltd., page 6-18B, especially carboxy-modified silicone (trade name: X-22-37).
10) is effective.

Also, silicone oils described in JP-A-62-215953 and Japanese Patent Application No. 62-23687 are effective.

An anti-fading agent may be used in the light-sensitive material and the dye-fixing material. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of the antioxidant include chroman compounds, coumaran 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.

Examples of ultraviolet absorbers include benzotriazole-based compounds (US Pat. No. 3,533,794, etc.), 4-quazolidone-based compounds (US Pat. No. 3,352,681), benzophenone-based compounds (JP-A-46-2784, etc.), and others. JP-A-54-
There are compounds described in JP-A-48535, JP-A-62-136641 and JP-A-61-88256. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective.

As metal complexes, U.S. Pat.Nos. 4,241,155 and 4,2
Nos. 45,018, columns 3-36, 4,254,195, columns 3-8, JP-A-62-174741 and JP-A-61-88256, pages (27) to (29),
Japanese Patent Application Nos. 62-234103 and 62-31096, Japanese Patent Application No. 62-23059
There are compounds described in No. 6, etc.

Examples of useful anti-fading agents are described in JP-A-62-215272 (125).
~ (137).

An anti-fading agent for preventing 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 outside such as a photosensitive material. .

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination with each other.

A fluorescent whitening agent may be used for the photosensitive material and the dye fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside such as a photosensitive material. For example, K. Veenkataraman ed., "The Chemistry of Synt
hetic Dyes, Vol. V, Chapter 8, and JP-A-61-143752. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given.

The fluorescent whitening agent can be used in combination with an anti-fading agent.

Various surfactants can be used in the constituent layers of the light-sensitive material and the dye-fixing material for the purpose of coating aid, improving releasability, improving slipperiness, preventing static charge, and accelerating development. Specific examples of the surfactant are described in JP-A Nos. 62-273463 and 62-183457.

The constituent layers of the photosensitive material and the individual dye material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17, JP-A-61-20944.
No. 62-135826, and hydrophobic surfactants such as fluorine surfactants described in JP-A No. 62-135826, or oily fluorine compounds such as fluorine oil or solid fluorine compound resins such as ethylene tetrafluoride resin. Can be

A matting agent can be used for the photosensitive material and the dye fixing material. As matting agents, in addition to the compounds described on page 29 of JP-A-61-88256 such as silicon dioxide, polyolefin or polymethacrylate, Japanese Patent Application No. 62-110064 such as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads. And No. 62-110065.

In addition, the constituent layers of the photosensitive material and the dye fixing material include:
A heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like may be included. Specific examples of these additives are disclosed in
No. 88256, pages (26) to (32).

As a support for the light-sensitive material and the dye-fixing material of the present invention,
Those that can withstand the processing temperature are used. Generally, paper and total polymer (film) are mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (eg, triacetylcellulose), or films containing pigments such as titanium oxide, and polypropylene. Synthetic paper made from pulp, mixed paper made from total resin pulp such as polyethylene and natural pulp, Yankee paper, Palita paper, coated paper (especially cast coated paper), metal, cloth, glass, etc. Can be

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

In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used.

A hydrophilic binder, a semiconductive metal oxide such as alumina sol or tin oxide, carbon black, or another antistatic agent may be applied to the surface of these supports.

Methods of exposing and recording images on photosensitive materials include, for example, a method of directly photographing landscapes and people using a camera, a method of exposing through a reversal film or a negative film using a printer or a enlarger, and a method of copier. A method of scanning and exposing an original image through a slit or the like using an exposure device or the like, or image information of a CRT, a liquid crystal display,
There is a method of outputting an image to an image display device such as an electroluminescence display or a plasma display and exposing the image directly or via an optical system.

The image information of the first half is image signals obtained from video cameras, electronic still cameras, etc. Television signals typified by the Nippon Television Signaling Standard (NTSC), and image signals obtained by dividing the original image into a number of pixels such as a scanner Image signals produced using a computer represented by CG, CG, and CAD.

The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and particularly about 80 ° C. to about 180 ° C. is useful. The dye diffusion transfer step may be performed simultaneously with the thermal development, or may be performed after the completion of the thermal development. In the latter case, the heating temperature in the transfer step is such that the transfer can be performed in the range from the temperature in the heat development step to room temperature, but it is particularly preferable that the heating temperature is 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

Dye transfer is caused only by heat, but a solvent may be used to promote dye transfer.

Further, as described in JP-A-59-218443, JP-A-61-238056, etc., a method in which development and transfer are carried out simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also useful. It is. In this method, the heating temperature is preferably not lower than 50 ° C. and not higher than the boiling point of the solvent. For example, when the solvent is water, 50 ℃ or more
100 ° C or less is desirable.

Examples of the solvent used for promoting 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 include Those described in the section of the formation accelerator are used. In addition, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound may be contained in the solvent.

These solvents can be used in a method for imparting to the dye fixing material, the photosensitive material, or both. The amount used is as small as not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, a method described in JP-A-61-147244, page (26). Further, the solvent can be used by being incorporated in the photosensitive element or the dye-fixing material or both in advance, for example, by enclosing the solvent in a microcapsule.

In order to promote dye transfer, a method in which a hydrophilic thermal solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the photosensitive material or the dye fixing material can be adopted. The hydrophilic heat solvent may be incorporated in either the photosensitive 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 is preferably incorporated in the dye-fixing layer and / or an adjacent layer.

Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, anneals, oximes and other heterocycles.

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

As a heating method in the development and / or transfer step, it is contacted with a heated block or plate, or in contact with a hot plate, hot presser, heat roller, halogen lamp heater, infrared and far infrared lamp heater, For example, passing through a high temperature atmosphere. Further, a resistive heating element layer may be provided on the photosensitive material or the dye fixing material, and the layer may be heated by being energized. As the heating element layer, those described in JP-A-61-145544 can be used.

The method described in JP-A-61-147244, page 27, can be applied as a pressure condition and a method of applying pressure when the photosensitive material and the dye-fixing material are overlaid and brought into close contact with each other.

In the processing of the light-sensitive material of the present invention, any of various heat developing apparatuses can be used. For example, JP-A-59-75147, JP-A-59-75147
-17747, 59-181353, 60-18951, Shokai 6
An apparatus described in, for example, No. 2-25944 is preferably used.

Hereinafter, specific examples will be described.
It is not limited to this embodiment.

Example A method for preparing a silver halide emulsion (I) of the fifth layer will be described.

A well-stirred gelatin aqueous solution (20 g of lime-treated deionized bone gelatin (Ca content 20 ppm) in 800 ml of water, 4 g of sodium chloride and 0.1 g of potassium bromide) 0.015 g dissolved in water and kept at 65 ° C) and silver nitrate aqueous solution (50 g of AgNO ₃ dissolved in water to make a total of 300 ml)
And an aqueous halogen solution (22.8 g of KBr and 6 g of NaCl dissolved in water to make a total of 300 ml) were simultaneously added over 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 ml) and an aqueous halide solution (31.5 g of KBr and 1.7 g of NaCl were dissolved in water to make the whole 300 ml. Was added simultaneously over 30 minutes.

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

Keep the obtained emulsion at 55 ° C and triethylthiourea 0.8m
g, 100 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was used for optimal chemical sensitization. The yield of the emulsion was 650 g.

Next, how to prepare the silver halide emulsion (II) of the third layer will be described.

Lime-processed bone gelatin with good agitation (lime 0.4%,
Adenine content 0.2ppm) aqueous solution (gelatin 50g in 800ml water)
And sodium chloride (10 g), potassium bromide (0.1 g) and sodium hydroxide (1N) (5 cc).
An aqueous solution of O ₃ (100 g of AgNO ₃ dissolved in water to make a total of 600 ml) and an aqueous halide solution (54.5 g of KBr and 2 g of NaCl dissolved in water to make a total of 600 ml) were simultaneously added over 30 minutes. 1 minute after completion of addition, sensitizing dye (A) 0.2
g, a dye solution obtained by dissolving 0.2 g of (B) in 120 ml of water and 120 ml of methanol is added.
ml was added.

After washing and desalting, lime-processed bone gelatin (adenine content 20
(ppm) and 50 ml of water were added to adjust the pH to 6.0 and pAg7.6.

The obtained emulsion was kept at 60 ° C., and
Chemical ripening was performed for minutes. The yield of the emulsion was 500 g.

Next, how to prepare the first layer silver halide emulsion (III) will be described.

Lime-processed bone gelatin (Ca content 2500pp
m) Aqueous solution (gelatin 20g and sodium chloride 2 in 800ml water)
g and compound 0.015 g was dissolved and kept at 50 ° C.), the following solution I and solution II were simultaneously added, and solution I was added over 12 minutes and solution II over 8 minutes. From 16 minutes after the completion of the addition of the solution I, the solution IV is added over a period of 44 minutes.
Added over minutes. The pAg from the end of the addition of the solution I to the start of the addition of the solution III was 6.7.

After washing with water and desalting, lime-processed bone gelatin (Ca content 4000pp
m) 25 g and 100 ml of water were added to adjust to pH 6.0 and pAg 7.7. Thereafter, chemical sensitization was optimally performed at 55 ° C. using 1.1 mg of triethylthiourea and 60 mg of 4-hydroxy 6-methyl-1,3,3a, 7-tetrazaindene. The yield of the emulsion was 650 g.

 How to make an organic silver salt is described.

Organic silver salt (1) A method for preparing a silver benzotriazole emulsion will be described.

28 g of gelatin and 13.2 g of benzotriazole were dissolved in 3000 ml of water. 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, 100 cc of a 1 N aqueous solution of NaOH was added over 3 minutes 1 minute and 30 seconds after the start of the addition of the aqueous silver nitrate solution. The pH of the reaction solution is 2
Kept above.

The pH of the benzotriazole silver emulsion was adjusted, allowed to settle, and excess salts were removed. Then adjust the pH to 6.50 and yield
400 g of silver benzosoliazole dispersion were obtained.

Organic silver salt (2) 12.8 g of potassium 4-acetylaminophenylpropiolate and 136 ml of a 10% aqueous solution of surfactant (0) are dissolved and mixed in 540 ml of ethanol and 1600 ml of water, and kept at 40 ° C.
Stirred.

To this solution, a solution in which 8 g of silver nitrate was dissolved in 120 cc of water was added over 3 minutes. Water is added to this dispersion, and the washing and desalination efficiency is about
Ultrafiltration and purification were performed to obtain 1/11, and an aqueous dispersion having a yield of 500 g was obtained. In addition, add 14g of gelatin and 96cc of water,
The dispersion was stirred at a high speed to obtain a dispersion of the organic silver salt (2) in a yield of 610 g.

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

15 g of yellow dye-providing substance (A), 1.2 g of reducing agent
g, 0.3 g of mercapto compound (1), surfactant (4)
Was weighed to 1.5 g and the high-boiling organic solvent (1) was weighed to 7.5 g. Ethyl acetate (45 ml) was added and dissolved by heating at about 60 ° C. to obtain a uniform solution. This solution and 100 g of a 10% solution of lime-processed gelatin and water
After stirring and mixing 30 ml, 10 minutes with a homogenizer, 10 minutes
Dispersed at 000 rpm. This dispersion is referred to as a yellow dye-providing substance dispersion.

15 g of magenta dye-providing substance (B) and 0.6 g of reducing agent
g, 0.15 g of mercapto compound (1), surfactant (4)
Was weighed, and 1.5 g of the high boiling organic solvent (2) was weighed, 25 ml of ethyl acetate was added, and the mixture was dissolved by heating at about 60 ° C. to obtain a uniform solution. 100 g of this solution and a 10% solution of lime-processed gelatin and 30
After stirring and mixing with a homogenizer for 10 minutes, 1000
Dispersed at 0 rpm. This dispersion is referred to as a magenta dye-providing substance dispersion.

15 g of a cyan dye-donating substance (C), 0.8 g of a reducing agent,
0.6 g of mercapto compound (1) and surfactant (4) in 1.
5 g, weigh 8.3 g of high boiling point organic solvent (1), and add ethyl acetate
30 ml was added, and the mixture was dissolved by heating at about 60 ° C. to obtain a uniform solution. 100 g of this solution and a 10% solution of lime-processed gelatin and 30
After stirring and mixing with a homogenizer for 10 minutes, 1000
Dispersed at 0 rpm. This dispersion is referred to as a dispersion of a cyan dye-donating substance.

By these, the transfer type photothermographic material 10 as shown in the following table is obtained.
0 can be configured.

High-boiling point organic solvent (2) Trihexyl phosphate Next, a method for producing a dye fixing material will be described.

The composition was coated on a paper support laminated with polyethylene according to the composition shown in the following table to prepare a dye fixing material R-1.

Next, the sample to be compared in the examples is a dye No. A having the following structure for comparison in the second layer of the transfer type photothermographic material 100.
And No. B, and dyes No. 1, No. 8, and No. 2 of the present invention.
Except that 6 was added as a gelatin dispersion, the transfer type photothermographic material 101 had the exact same configuration as the transfer type photothermographic material 100,
102, 103, 104 and 105 were produced.

Comparative dye No.A Incidentally, a gelatin dispersion of the dye was prepared as follows.

Each of the dyes of the present invention was weighed so as to have the coating amount shown in Table 1,
It was added to 7 ml of ethyl acetate together with 1 g of the high boiling point organic solvent (1) and dissolved by heating at about 60 ° C. to form a uniform solution.

This solution, 40 g of a 10% solution of lime-processed gelatin, 0.6 g of surfactant (4), and 70 ml of water were stirred and mixed, and then dispersed with a homogenizer at 15,000 rpm for 10 minutes to prepare a mixture.

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

Using the laser exposure apparatus No. Sho 63-281,418,63-204,805 described, was exposed under the conditions shown in Table 2, water 12 ml / m ² was supplied with a wire bar on the emulsion surface of the exposed light-sensitive material, thereafter The dye-fixing material and the film surface were overlapped so that the film surfaces were in contact with each other. After heating for 20 seconds using a heat roller whose temperature was adjusted so that the temperature of the absorbed film became 90 ° C., the dye fixing material was peeled off from the photosensitive material to obtain an image on the dye fixing material.

For 670nm and 810nm laser exposure,
In the present invention, no substantial change occurred.

The evaluation of aging was performed for 3 days at 60 ° C. and 60% relative humidity for 3 days at room temperature.

In the evaluation of the white background, unexposed portions were measured by X-RITE (status A).

Further, regarding the evaluation of the color separation property, the density of 1.5 to
The test was performed based on cyan density, which became a mixed color in yellow of 1.7.

The color separation was evaluated according to the criteria shown in the following table.

As shown in the above results, it can be seen that by containing the dye of the present invention, a transfer type photothermographic material excellent in aging property, color separation property and white background can be obtained.

Next, the water-insoluble dye No. 1 of the present invention was added to the first layer.
Dispersed together with the cyan dye-donating substance in the
A photosensitive material 106 was prepared in the same amount as in Example 1.

This was exposed and processed under the above conditions. As a result, the sensitivity of the first layer 810 nm was slightly lower than that of the photosensitive material 103, but other performances were equivalent.

In any case, it can be seen that the method of the present invention is excellent.

Claims (1)

(57) [Claims] 1. A layer having at least one photosensitive layer having a spectral sensitivity peak with respect to infrared light of 700 nm or more and containing a water-insoluble dye represented by the following general formula [I]. And a transfer type heat-developable color light-sensitive material comprising at least one layer of: General formula [I] In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and represent an alkyl group, and Z ¹ and Z ² are a benzo-fused ring or a naphtho-fused ring Represents a group of non-metallic atoms necessary to form Where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , Z ¹
And any of the groups represented by Z ² include at least one alkyl chain having 5 or more carbon atoms. L represents a methine group, and X represents an anion. n represents 1 or 2, and is 1 when the dye forms an inner salt.