JP2699008B2 - Photothermographic material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a color photothermographic material capable of obtaining an image having excellent color separation for exposure in the near infrared to infrared region.

(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. In recent years, a technology has been developed that can obtain images simply and quickly by changing the image forming processing method for photosensitive materials using silver halide from conventional wet processing using a developing solution to dry processing such as heating. It has been.

Photothermographic materials are known in the art. For details of photothermographic materials and their processes, see, for example, Basics of Photographic Engineering (published by Corona Co., Ltd., 1979), p. 553, p.
Monthly Video Information, 40 pages, Handbook of Nebretts, Photographie and Reprographie, 7th Edition (Nebletts, Han
dbook of Photography and Reprography 7th Ed.) Van Nostrand Reinhold Company (Van)
Nostrand Reinhold Company), U.S. Pat.
No. 3,152,904, No. 3,301,678, No. 3,392,020, No. 3,45
7,075, British Patent Nos. 1,131,108 and 1,167,777, and Research Disclosure, June 1978, 9-15.
Page (RD-17029).

Various methods of obtaining a color image by heating are described in, for example, Research Disclosure Magazine, May 1978, pages 54 to 58 (RD-16966), and April 1976, pages 30 to 32 (RD-1966).
No. 4433), U.S. Pat.Nos. 3,985,655, 4,463,079,
4,474,867, 4,478,927, 4,507,380, 4,50
Nos. 0,626 and 4,483,914. Each of these methods produces or releases a dye by heating to form an image-like distribution of the dye, and has a feature that an image-like distribution of the dye can be obtained in a short time.

(Problems to be Solved by the Invention) However, conventionally used sensitizing dyes in the near-infrared to infrared regions show a decrease in the color sensitization sensitivity from a wavelength at which the color sensitization sensitivity is maximum toward a longer wavelength side. When the photosensitive material has a layer having a color sensitization sensitivity in a longer wavelength region than that of the photosensitive layer, the color separation from the layer is poor because the sensitivity is low (because the sharpness of the color sensitization sensitivity is poor). There was a problem.

Accordingly, an object of the present invention is to provide a color photothermographic material having excellent color separation in the near infrared to infrared region.

SUMMARY OF THE INVENTION An object of the present invention is to provide a support having at least three silver halide emulsion layers sensitive to different spectral regions, and each of the emulsion layers or a non-photosensitive layer adjacent thereto. In a color photothermographic material comprising yellow, magenta and cyan dye-donor compounds, the spectral sensitivity of at least one of the silver halide emulsion layers is maximized with respect to light having a wavelength of 700 nm or more. This is achieved by a color photothermographic material characterized in that the spectral sensitivity to light having a wavelength longer by 20 nm than the wavelength at which the spectral sensitivity has a maximum value is 1/10 or less of the maximum value of the spectral sensitivity.

By providing such spectral sensitivity characteristics, it is possible to improve color separation from other layers having sensitivity in the infrared region of longer wavelengths.

In one embodiment of the present invention, the spectral sensitization using the dicarboimidocyanine dye causes the maximum value of the spectral sensitivity to be larger than the wavelength at which the spectral sensitivity takes the maximum value by 20%.
A silver halide emulsion spectrally sensitized so that the spectral sensitivity to light having a longer wavelength of 10 nm or more can be obtained.

As the dicarboimidocyanine dye, a compound represented by the following general formula (I) is preferably used.

General formula (I) In the formula, R ₁ and R ₂ each independently represent an alkyl group having 1 to 8 carbon atoms, and Y ₁ and Y ₂ represent an atomic group for linking to complete a benzene nucleus, or represent a hydrogen atom or a halogen atom. Represents an atom, a cyano group or a perfluoroalkyl group. Y ₃ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a benzyl group or a phenyl group, X represents an anion, and p represents a number determined so that the number of positive charges and the number of negative charges are equal. Represents X
May combine with R ₁ or R ₂ to form an inner salt.

Hereinafter, the compound of the formula (I) will be described in more detail.

The alkyl group represented by R ₁ or R ₂ may be linear, branched, or cyclic, and includes a substituted alkyl group, and the substituent includes a halogen atom, an alkoxy group, an alkylthio group, a sulfonic acid group or a salt thereof, Examples thereof include a carboxyl group or a salt thereof.

Particularly preferred as R ₁ is an alkyl group having 1 to 4 carbon atoms, and is preferably an unsubstituted or substituted alkyl group substituted with a sulfonic acid group or a salt thereof.

Particularly preferred as R ₂ is an alkyl group having 1 to 4 carbon atoms, preferably an unsubstituted or substituted alkyl group substituted with a halogen atom or an alkoxy group having 1 to 4 carbon atoms.

Preferred as Y ₁ and Y ₂ are a hydrogen atom, a chlorine atom, a cyano group or a trifluoromethyl group, particularly Y ₁ is a chlorine atom, and Y ₂ is a chlorine atom, a cyano group or a trifluoromethyl group. Are preferred.

Preferred as the group represented by Y ₃ are a hydrogen atom, a methyl group, an ethyl group, and a butyl group, and a hydrogen atom is particularly preferred.

Preferred as the anion represented by X is a halide ion, a sulfonate ion or a carboxylate ion is particularly iodide ion, p-toluenesulfonate ion, acetate ion or substituted sulfonate ion on R ₁ . In these cases, p is 1.

Specific examples of the dicarboimidocyanine dye that can be used in the present invention are shown below, but the present invention is not limited thereto.

The sensitizing dye of the present invention 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 JP-A-63-23145).

The sensitizing dye of the present invention may be added to the emulsion during the formation of silver halide emulsion grains, at or before or after chemical ripening, or during the preparation of a coating solution. It is preferably added at the time of forming silver halide emulsion grains or at or before or after chemical ripening. The temperature at the time of addition may be 30 ° C. or higher, but it is preferable that the addition is performed at a temperature of 50 ° C. or higher and an adsorption time of 15 minutes or more is provided. More preferably, the addition is carried out at a temperature of 60 ° C. or higher, and the adsorption time is preferably 30 minutes or longer.

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

In the present invention, a silver halide emulsion spectrally sensitized with another sensitizing dye can be used in combination with silver halide spectrally sensitized with the above sensitizing dye. Other sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes known in the art.

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.

The photothermographic material of the invention basically has a photosensitive silver halide, a binder, and a dye-providing compound (which may also serve as a reducing agent as described later) on a support. And an organic metal salt oxidizing agent. 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 cyan, at least three silver halide emulsion layers sensitive to different spectral regions are used in combination.

In the present invention, for example, a combination of three layers of a near-infrared photosensitive layer (a layer subjected to spectral sensitization satisfying the requirements of the present invention), a red-sensitive layer and an infrared-sensitive layer, a green-sensitive layer, a red-sensitive layer, and a red-sensitive layer In the combination of the outer photosensitive layers, the green sensitive layer may further have near infrared sensitivity satisfying the requirements of the present invention. Each photosensitive layer can adopt various arrangement orders known for ordinary type color photosensitive materials. In addition, each of these photosensitive layers may be used as needed.
It may be divided into layers or more.

The photothermographic material can 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.

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

The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. A so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used. Particle size is 0.1 ~
2μ, especially 0.2-1.5μ, is preferred. 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. A known sulfur sensitization method, reduction sensitization method, noble metal sensitization method, selenium sensitization method, or the like can be used alone or in combination for an emulsion for a conventional light-sensitive material. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

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 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 ₃ 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 (for example, sodium methacrylate, ammonium methacrylate, Sumikagel L-manufactured by Sumitomo Chemical Co., Ltd.) 5H) is also used. These binders can be used in combination of two or more kinds.

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.

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 for the 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.

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 sulfonamide phenols, sulfonamido naphthols, compounds described as electron donors in JP-A-53-110827, and non-diffusive and reducing dye-providing compounds described later.

In the present invention, the amount of the reducing agent added is based on 1 mole of silver.
It is 0.001 to 20 mol, particularly preferably 0.01 to 10 mol.

In the present invention, silver can be used as the image forming substance. In addition, when silver ions are reduced to silver under high temperature conditions, they may contain a compound that generates or releases a mobile dye corresponding to this reaction or vice versa, that is, contains a dye-donating compound. it can.

First, examples of the dye-donating compound that can be used in the present invention include a compound (coupler) that forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Also,
A 2-equivalent coupler having a nondiffusible group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developers and couplers are described in James, The Theory of the Photographic Process, 4th Edition.
Edition (TH James “The Theory of the Photographic Pro
cess "), pages 291-334, and 354-361, JP-A-58-123.
No. 533, No. 58-149046, No. 58-149047, No. 59-11114
No. 8, No. 59-124399, No. 59-174835, No. 59-231539
No. 59-231540, No. 60-2950, No. 60-2951, No.
Nos. 60-14242, 60-23474, and 60-66249.

Further, as another example of the dye-donating compound, a compound having a function of releasing or diffusing a diffusion dye imagewise can be mentioned. Compounds of this type can be represented by the following general color [LI]:

(Dye-Y) nZ [LI] Dye represents a temporarily shortened dye group or dye precursor group for each dye, Y represents a simple bond or linking group, and Z represents an image-like 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 (2) form a diffusible dye image (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
No. 7,200, No. 3,544,545, No. 3,482,972, etc., a dye developer comprising a hydroquinone-based developer and a dye component linked thereto. 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, U.S. Pat.No.4,783,396, Published Technical Report 87-6199, etc. Non-diffusible compounds that release

Examples are U.S. Pat.Nos. 4,139,389 and 4,13
No. 9,379, JP-A-59-185333, compounds which release 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, RD24025 (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
Compounds which release a diffusible dye after electron acceptance described in No. 0 and the like are exemplified.

Also, as more preferred, EP 220,746A
No. 2, Published Technical Report 87-6199, U.S. Pat. No. 4,783,396, JP-A-63-201653, JP-A-63-201654, etc., in which NX bond (X is oxygen, sulfur or nitrogen) in one molecule. Represents an atom)
With a compound having an electron attractive group, compounds SO ₂ -X (X is as defined above) in one molecule described in Japanese Patent Application Sho 62-106885 having an electron attractive group, JP 63-271344 Compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule described in JP-A-63-271341, and C-X 'bond in one molecule described in JP-A-63-271341. X 'is the same as X or -SO
_2- )) and a compound having an electron-withdrawing group. Further, the compounds described in Japanese Patent Application Nos. 62-319989 and 62-320771, which release a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group can also be used.

Among them, a compound having an NX bond and an electron-withdrawing group in one molecule is particularly preferable. A specific example is European Patent No. 22
0,746A2 or compounds (1) to (3), (7) to (10), (12), (13) described in US Pat. No. 4,783,396.
(15), (23)-(26), (31), (32), (35),
(36), (40), (41), (44), (53)-(59),
(64), (70), Compounds (11) to of Published Technical Report 87-6199
(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, compounds (1) to (3) described in the above-mentioned U.S. Pat. (10)-(13), (16)-
(19), (28)-(30), (33)-(35), (38)-
(40), (42) to (64) are preferred. Also U.S. Pat.
The compounds described in 639,408, columns 37-39 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 Magazine, 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.

Hydrophobic additives such as a dye-providing compound and a diffusion-resistant reducing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154, JP-A-59-178451, and JP-A-59-178451.
-178452, 59-178453, 59-178454, 59-
High boiling organic solvents such as those described in JP-B-178455 and JP-B-59-178457 can be used in combination with a low-boiling organic solvent having a boiling point of 50 ° C to 160 ° C, if necessary.

The amount of the high boiling organic solvent is 1 g of the dye-donating compound used.
10 g or less, preferably 5 g or less. In addition, 1 cc or less of binder 1 g, further 0.5 cc or less, especially 0.
3cc or less is appropriate.

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 the hydrophobic compound in the hydrophilic colloid, 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.

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.

The silicone oils described in JP-A-62-215953 and JP-A-63-46449 are also 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-thiazolidone-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),
There are compounds described in JP-A-63-199248, JP-A-62-234103 and JP-A-62-230595.

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.

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.).

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. 62-173463 and 62-183457.

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 static charge, and improving releasability. 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 agent, colloidal silica, and the like may be included. Specific examples of these additives are disclosed in
No. 88256, pages (26) to (32).

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 the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of 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 U.S. Pat.
No. 9, columns 38-40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement, and the like. Specific examples thereof are described in U.S. Pat.
-65038 and the like.

In a system in which thermal development and transfer of a dye are performed 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 material.

In addition to the above, EP 210,660, U.S. Pat.
No. 40,445, a combination of a hardly soluble metal compound and a compound capable of forming a complex with a metal ion constituting the hardly soluble metal compound (referred to as a complex forming compound);
Compounds that generate a base by electrolysis described in JP-A 61-232451 can also be used as the 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, thereby suppressing development by interacting with a compound or silver and silver salt. Compound. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-253159 (31)-
It is described on page (32).

As a support pair of 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 synthetic polymers (films) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or a film containing pigment such as titanium oxide in these films, and polypropylene. For example, a mixed paper made from synthetic resin pulp such as polyethylene, a synthetic resin pulp such as polyethylene, and natural pulp, Yankee paper, baryta paper, coated paper (especially cast-coated paper), metal, cloth, glass and the like are used.

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

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

A hydrophilic binder, a semiconductor 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. Scanning and exposing the original image through slits using an exposure device, etc., exposing the image information by emitting light from a light emitting diode or various lasers via electrical signals, CRT, liquid crystal display, electroluminescence display And a method of outputting the image to an image display device such as a plasma display and exposing the image directly or via an optical system.

As a light source for recording an image on a photosensitive material, as described above, natural light, a tungsten lamp, a light emitting diode, a laser light source, a U.S. Pat.
The light sources described in the column can be used.

Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, a nonlinear optical material is a material that can exhibit nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, such as lithium niobate and potassium dihydrogen phosphate (KDP ), Inorganic compounds represented by lithium iodate, BaB ₂ O _{4 and the} like, urea derivatives, nitroaniline derivatives such as nitropyridine-N-oxide such as 3-methyl-4-nitropyridine-N-oxide (POM). Oxide derivatives, JP-A-61-53462, 6
The compounds described in 2-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful.

The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standard (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. Signals, image signals created using a computer represented by CG and CAD can be used.

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

The heating temperature in the thermal development step can be developed at 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 heat development, or may be performed after the heat development step. 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 detail in JP-A-59-218443, JP-A-61-238056, etc., a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water) is also available. Useful. In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower.
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 may be 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 may be contained in the photosensitive material or the dye-fixing material or both in advance, for example, by enclosing the solvent in microcapsules.

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 thermal solvent may be incorporated in any of the photosensitive material and the dye fixing material,
It may be built in both. Also, the layer to be incorporated is an emulsion layer,
Any of an intermediate layer, a protective layer, and a dye-fixing layer may be used, but it is preferable to be incorporated in the dye-fixing layer and / or a layer adjacent thereto.

Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alkenyls,
There are 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.

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

Any of a variety of thermal development equipment can be used to process the photographic elements of the present invention. For example, JP-A-59-75247, JP-A-59-75247
-17747, 59-181353, 60-18951, Shokai 6
An apparatus described in, for example, No. 2-25944 is preferably used.

Example 1 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, 6 g of NaCl dissolved in water to make a total of 300 ml) were simultaneously added over 30 minutes. Next, the temperature of the solution was lowered to 35 ° C., and an aqueous solution of silver nitrate (Ag
50 g of NO ₃ was dissolved in water to make a total of 300 ml) and an aqueous halide solution (31.5 g of KBr, 1.7 g of NaCl dissolved in water to make a total of 300 ml) were added simultaneously over 30 minutes.

After washing with water and desalting, lime-processed bone gelatin (guanine content 50
(ppm) 25 g and water 100 ml were added to adjust the pH to 6.3 and pAg7.9.

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 stirring (ash content 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. One minute after completion of the addition, sensitizing dye (A) 0.2
g and a dye solution obtained by dissolving 0.2 g of (B) in 120 ml of water and 120 ml of methanol were added. After 5 minutes, 10 ml of a 1% aqueous solution of potassium iodide was added.

Sensitizing dye (A) Sensitizing dye (B) 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 pAg7.6.

The obtained emulsion was kept at 60 ° C., and chemically ripened for 50 minutes using 2.5 mg of hypo. The yield of the emulsion was 500 g.

Next, how to prepare the silver halide emulsion (III) of the first layer 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 the pH to 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.

After 28 g of gelatin was dissolved in 1500 ml of water, a solution of 6.6 g of benzotriazole in 12.7 ml of methanol was added. This solution was kept at 40 ° C. and stirred. Silver nitrate in this solution
A solution of 8.5 g in 120 ml of water was added over 2 minutes. Further, a solution of 6.6 g of benzotriazole dissolved in 12.7 ml of methanol and 46.5 ml of 2N sodium hydroxide were added, and a solution of 8.5 g of silver nitrate dissolved in 1700 ml of water was added over 6 minutes.

The pH of this solution was adjusted and the silver benzotriazole emulsion was allowed to settle to remove excess salts. Thereafter, the pH was adjusted to 6.30 to obtain a silver benzotriazole emulsion with a yield of 420 g.

Organic silver salt (2) 20 g of gelatin and 5.9 g of 4-acetylaminophenylpropiolic acid were dissolved in 1000 ml of a 0.1% aqueous sodium hydroxide solution and 200 ml of ethanol.

 This solution was kept at 40 ° C. and stirred.

To this solution, a solution prepared by dissolving 4.5 g of silver nitrate in 200 ml of water was added over 5 minutes.

The pH of the dispersion was adjusted and settled to remove excess salts. Thereafter, the pH was adjusted to 6.3 to obtain a dispersion of organic desalting (2) in a yield of 300 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, and 1.5 g of the high-boiling organic solvent (1) was weighed, 45 ml of ethyl acetate was added, and the mixture was heated and dissolved 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 dispersion of the yellow pigment material.

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 cyan dye-donor substance (C) and 0.8 g of reducing agent
g, mercapto compound (1) 0.6 g, surfactant (4)
Was weighed, and 8.3 g of the high-boiling organic solvent (1) was weighed, 30 ml of ethyl acetate was added, and the mixture was heated and dissolved 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.

With these, the photothermographic material 100 as shown in the following table can be formed.

Preparation of the photosensitive material of the present invention The sensitizing dye of the specific example (9) described in the text of the present invention is used in place of the sensitizing dye (1) in the fifth layer of the photosensitive material 100, and the maximum sensitivity is the same as that of the photosensitive material 100. 3.3 × 10 ^-4 g /
except that m ² was added, to prepare a light-sensitive material 101 of to the present invention in the same manner as the photosensitive material 100.

Further, the silver halide emulsion (I) of the fifth layer of the light-sensitive material 100 was previously added to 70 ° C. at a specific example (9) described in the text of the present invention.
Sensitizing dye so that the maximum sensitivity is the same as that of photosensitive material 100
3.3 × 10 ^-4 g / m ^{2 was} added and a silver halide emulsion (I ′) adsorbed for 30 minutes was prepared. This was used in place of the silver halide emulsion (I), and a sensitizing dye was added. A light-sensitive material 102 of the present invention was prepared in the same manner as the light-sensitive material 100, except that no change was made.

 Next, a method of making the 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.

(Method of Sensitometry) Method for Measuring the Difference between the Maximum Spectral Sensitization Sensitivity and the Sensitivity at a Longer Wavelength of 20 nm Therefrom Each photosensitive material was exposed to a series of monochrome light for 5 seconds. 14 ml / m ² of water is applied to the film surface of these photosensitive materials,
The dye-fixing material and the film surface were brought into close contact with each other so as to overlap with each other, heated at 93 ° C. for 25 seconds, and then peeled off. Using the yellow image obtained in the dye fixing material, for the maximum value of the sensitivity,
The relative sensitivity (sensitivity difference, ΔlogE) at a wavelength 20 nm longer than the wavelength giving the maximum sensitivity was determined.

Measurement of Degree of Color Separation Using an exposure apparatus described in Japanese Patent Application Nos. 63-281418 and 63-204805, exposure was performed under the conditions shown in Table 1. This was treated as above. The difference ΔS = logE _Y −logEc between the exposure amount (logE _Y ) that gives the density of yellow fog + 0.1 obtained on the dye-fixing material and the exposure amount (logEc) that gives the density of Dmax−0.1 of cyan is obtained. I asked.

The results are shown in Table 2. The larger the value of ΔS, the better the color separation.

From Table 2, according to the present invention, with respect to the yellow layer, according to the present invention, the sample 101 of the present invention having a spectral sensitivity to light having a wavelength longer than 20 nm longer than the wavelength at which the spectral sensitivity takes the maximum value is 1/10 or more. , 102 have remarkably improved color separation from the cyan layer spectrally sensitized to a longer wavelength than the yellow layer.

Claims (1)

(57) [Claims] 1. A support having at least three silver halide emulsion layers sensitive to different spectral regions on a support, and each of the emulsion layers or a non-photosensitive layer adjacent thereto is provided with a yellow, magenta or cyan dye. In a color photothermographic material comprising a light-sensitive compound, the spectral sensitivity of at least one of the silver halide emulsion layers is maximum for light having a wavelength of 700 nm or more, and the spectral sensitivity is A color photothermographic material, wherein the spectral sensitivity to light having a wavelength longer than 20 nm than the wavelength at which the sensitivity takes a maximum value is 1/10 or less.