JPH05341472A - Heat developable photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a heat developable photosensitive material excellent in preservability and giving satisfactory image discriminating ability. CONSTITUTION:This heat developable photosensitive material has at least photosensitive silver halide, a binder and a precursor of a reducing agent represented by general formula I or II on the base. In the formulae I, II, each of R<1>-R<4> is H, alkyl, aryl or a heterocyclic group and R<5> is aryl or a heterocyclic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to a photothermographic material which is excellent in raw storability and is capable of obtaining an image having good discrimination.

[0002]

2. Description of the Related Art Photothermographic materials are known in this technical field, and the photothermographic materials and their processes are described, for example, in "Basics of Photographic Engineering", Non-silver photography (ed. P. 255. Many methods have also been proposed for obtaining a color image by heat development. For example, US Pat. No. 3,531,286
Issue 3, Issue 3,761,270, Issue 4,021,240
No., Belgian Patent No. 802,519, Research Disclosure (RD) 9 September 1975
A method for forming a color image by combining an oxidant of a developing agent with a coupler is proposed on pages 31 to 32 of the moon. However, since the photothermographic material for obtaining the above color image is a non-fixing type, silver halide remains after the image formation,
When exposed to strong light or stored for a long period of time, it causes a serious problem that the white background gradually becomes colored. Further, the above-mentioned methods generally have a drawback that it takes a relatively long time for development and an obtained image has only a high fog and a low image density.

In order to remedy these drawbacks, a method has been proposed in which a diffusible dye is imagewise formed or released by heating, and this diffusible dye is transferred to an image-receiving material having a mordant with a solvent such as water. ing. (US Patent 4,
500,626, 4,483,914 and 4,5
03,137, 4,559,290; JP-A-59.
In the above method, the developing temperature is also high, and the temporal stability of the photosensitive material cannot be said to be sufficient. Therefore, a method for promoting development, lowering the development temperature, and simplifying processing by heat-developing in the presence of a base or a base precursor and a small amount of water to transfer the dye is disclosed in JP-A-59-218,443. , No. 61-238056, European Patent No. 210,660A2, and the like.

Many methods have been proposed for obtaining a positive color image by heat development. For example, in U.S. Pat. No. 4,559,290, a so-called DRR compound, which is an oxidized type having no dye releasing ability, is made to exist in the presence of a reducing agent or a precursor thereof, and the reducing agent is oxidized by thermal development according to the exposure amount of silver halide. A method of releasing the diffusible dye by reducing with a reducing agent remaining without being oxidized has been proposed. In addition, European Patent Publication No. 220746 and Technical Report 87
-6199 (Vol. 12, No. 22), a compound releasing a diffusible dye by a similar mechanism is diffused by reductive cleavage of an N—X bond (X represents an oxygen atom, a nitrogen atom or a sulfur atom). A heat-developable color light-sensitive material using a compound that releases a functional dye is described.

[0005]

In the photothermographic material as described above, when a reducing agent having the ability to reduce silver halide is present in the binder, the reducing agent is air during storage of the photosensitive material. Oxidation by oxygen and the like in the inside reduces the reduction in the amount of the light.
Known as No. 7029 and the like. A reduction in reducing agent during live storage results in a reduction in the rate at which silver halide is developed into silver during processing, as well as the total amount of developed silver, which leads to poor image discrimination.

As a means for avoiding this, a technique of blocking the active site of a reducing agent and using it as a precursor is disclosed in JP-A-59-182449 and JP-A-59-1824.
50, 61-34540, JP-A-1-13855.
No. 8 and the like. A technique of using a reducing agent and a reducing agent precursor in combination is disclosed in JP-A-1-138556.

However, as a result of a detailed study by the present inventors on the use of a reducing agent precursor in a photothermographic material, the reducing agent precursor specifically exemplified in the above-mentioned literature shows that the reducing agent precursor at the time of processing is It was found that the reducing reaction rate of the reducing agent was slow and that it substantially did not function as a reducing agent. As a result, the discrimination of the image becomes worse.

(Object of the Invention) An object of the present invention is to provide a photothermographic material which is excellent in raw storability and is capable of obtaining an image giving good discrimination.

[0009]

The object of the present invention is to contain at least a photosensitive silver halide, a binder, and a reducing agent precursor represented by the following general formula (I) or (II) on a support. It was achieved by a photothermographic material characterized by General formula (I)

[0010]

[Chemical 3]

General formula (II)

[0012]

[Chemical 4]

In the formula, R ^{1 to} R ⁴ each include a hydrogen atom and an alkyl group (including those having a substituent. It preferably has 20 or less carbon atoms. For example, methyl, ethyl, propyl, butyl,
t-butyl, hexyl, octyl, t-octyl, decyl, dodecyl, hexadecyl, octadecyl, alkoxymethyl, hydroxymethyl, chloromethyl, bromomethyl, acyloxymethyl, etc., and aryl groups (including those having a substituent. 20 carbon atoms) The following are preferable: for example, phenyl, tolyl, xylyl, cumylhalogenophenyl, nitrophenyl, sulfophenyl, carboxyphenyl, alkoxyphenyl, alkylphenyl, naphthyl, anthryl and the like, or a heterocyclic group (having a substituent). It preferably has 20 or less carbon atoms, for example, pyridyl, quinolyl, methylpyridyl, thiophenyl, furyl, pyrrolyl and the like). R ⁵ represents an aryl group or a heterocyclic group (specific examples of both are the same as those in R ^{1 to} R ⁴ ).

Specific examples of the reducing agent precursor used in the present invention are shown below, but the reducing agent precursor usable in the present invention is not limited to these.

[0015]

[Chemical 5]

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

[0019]

[Chemical 9]

[0020]

[Chemical 10]

[0021]

[Chemical 11]

[0022]

[Chemical formula 12]

The reducing agent precursor used in the present invention as described above is easily synthesized by reacting the 1-phenyl-3-pyrazolidinone derivative, which is the corresponding reducing agent, with oxalyl chloride in the presence of a base. be able to. For example, (I-1) was synthesized as follows. 20 g of 1-phenyl-3-pyrazolidinone was dissolved in 100 ml of acetonitrile, and 18.8 ml of triethylamine was dissolved.
Was added. 5.4 ml of oxalyl chloride was added dropwise to this mixture under ice-cooling, and the mixture was left overnight at room temperature after completion of the addition.
Water was added to the reaction mixture and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried over sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (I-
10.2 g (yield 44%) of 1) was obtained. Melting point 201-3
° C. Other compounds can be similarly synthesized.

The light-sensitive material using the reducing agent precursor of the present invention as described above has excellent raw storability because the reducing agent precursor is not oxidized and reduced by oxygen in the air. At the time of processing, the hydrolysis reaction of the reducing agent precursor rapidly progresses to release the reducing agent, and the function as the reducing agent is sufficiently fulfilled, so that an image having good discrimination is provided.

Since the reducing agent precursor used in the present invention has high crystallinity and is hardly soluble in water, it can be incorporated into the light-sensitive material by fine particles dispersed by an emulsion dispersion method or a solid dispersion method.

In the present invention, a reducing agent may be used in combination with the reducing agent precursor. In this case, the reducing agent released from the reducing agent precursor and the reducing agent used in combination may be the same or different.

In the present invention, as the reducing agent used in combination with the precursor, those known in the field of photothermographic materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Examples of the reducing agent used in the present invention include U.S. Pat. No. 4,500,626, columns 49 to 50, and U.S. Pat. No. 4,483,914, number 30.
Column 31, No. 4,330,617, No. 4,59
0,152, JP-A-60-140335 (17)-
(18) pp. 57-40245, 56-138736.
No. 59-178458, No. 59-53831,
59-182449, 59-182450, 60-119555, 60-128436 to 60-128439, 60-198540,
No. 60-181742, No. 61-259253, No. 62-244044, No. 62-131253 to No. 62-131256, European Patent No. 220,746.
There are reducing agents described on pages 78 to 96 of A2. Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

When used in combination with a diffusion resistant reducing agent, the reducing agent released from the reducing agent precursor of the present invention promotes electron transfer between the diffusion resistant reducing agent and the developable silver halide. It functions as an electron transfer agent. If necessary, an electron transfer agent (non-precursor type) may be further used in combination.

The electron transfer agent can be selected from the above-mentioned reducing agents. It is desirable that the electron transfer agent has a mobility higher than that of a diffusion resistant reducing agent (electron donor). Of the diffusible reducing agents represented by electron transfer agents, particularly useful are 1-phenyl-3-pyrazolidinones,
A preferred example is JP-A 64-13546 (49)
To (63) page and the like.

The diffusion-resistant reducing agent (electron donor) used in combination with the diffusible reducing agent may be any of those reducing agents which do not substantially move in the layer of the light-sensitive material. Preferred are hydroquinones, sulfonamide phenols, sulfonamide naphthols, JP-A-53-
Examples thereof include compounds described as electron donors in No. 110827 and dye-donating compounds having diffusion resistance and reducing property described later.

In the present invention, the amount of the reducing agent including the precursor added is 0.001-2 with respect to 1 mol of silver as a whole.
The amount is 0 mol, particularly preferably 0.01 to 10 mol.
The diffusible reducing agent is preferably 40 mol% or less of the total reducing agent amount.

The photothermographic material of the present invention basically has a photosensitive silver halide, a binder and the above-mentioned reducing agent precursor on a support, and further, if necessary, a dye-providing compound and a base. A precursor etc. can be contained. These components are often added to the same layer, but if they are in a reactive state, they can be added separately to separate layers. For example, when a dye-providing dye compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented.

In the case of forming a color image, in order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, at least three halogenated layers having photosensitivity in different spectral regions are used. A combination of silver emulsion layers is used. For example, there are combinations of three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer. Each of the light-sensitive layers can take various arrangement orders known in a conventional type color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary. For the photothermographic material, a protective layer, an undercoat layer, an intermediate layer,
Various auxiliary layers such as a yellow filter layer, an antihalation layer and a back layer can be provided.

The silver halide usable 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 either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or a light fogging. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 µ, and particularly preferably 0.2 to 1.5 µ. The crystal habit of silver halide grains is cubic, octahedral, 14
It may be a face piece, a flat plate having a high aspect ratio, or the like.

Specifically, US Pat. No. 4,500,62
No. 6, Column 50, No. 4,628,021, Research
Disc lotion magazine (hereinafter abbreviated as RD) 1702
9 (1978) and any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used. The silver halide emulsion may be used as it is in an unripened state, but it is usually chemically sensitized before use. Well-known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods and the like can be used alone or in combination for the emulsions for conventional light-sensitive materials. These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159). The 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, organic silver salts are particularly preferably used. Organic compounds that can be used to form the above organic silver salt oxidizing agents include those described in US Pat.
There are benzotriazoles, fatty acids and other compounds described in Nos. 0,626, columns 52 to 53. In addition, JP-A-60
No. 113235, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate;
The acetylene silver described in 1-24944 is also useful.
Two or more kinds of organic silver salts may be used in combination. The above organic silver salt may be used in an amount of 0.01 to 10 mol, preferably 0.01 to 1 mol, per 1 mol of photosensitive silver halide. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg to 10 g / m ² in terms of silver.

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

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, U.S. Pat. No. 4,617,257 and JP-A-59-180550.
No. 60-140335, RD17029 (197).
8 years) Sensitizing dyes described on pages 12 to 13 and the like.
These sensitizing dyes may be used alone or in combination thereof, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. No. 3). , 615, 641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after the nucleation of silver halide grains. Good. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

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

When a system in which a small amount of water is supplied for thermal development is adopted, it is possible to quickly absorb water by using the above superabsorbent polymer. Further, when the super absorbent polymer is used in the dye fixing layer or its protective layer, the dye can be prevented from being retransferred from the dye fixing material to another after the transfer. In the present invention,
The binder coating amount is preferably 20 g or less per 1 m ² , particularly 10 g or less, and more preferably 7 g or less.

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

In the present invention, silver can be used as the image forming substance. Further, when a silver ion is reduced to silver under a high temperature condition, a compound that produces or releases a mobile dye corresponding to this reaction or vice versa, that is, a dye-donating compound may be contained. it can.

As an example of the dye-donating compound that can be used in the present invention, first, a compound (coupler) which forms a dye by an oxidative coupling reaction can be mentioned. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. This nondiffusible group may form a polymer chain. Specific examples of color developers and couplers are "The Theory of the Phot", 4th edition by James, "The Theory of the Photographic Process."
ographic process ") 291-334 layers, and 354-
Pp. 361, JP-A Nos. 58-123533 and 58-14.
9046, 58-149047, 59-111.
No. 148, No. 59-124399, No. 59-1748.
35, 59-231539, 59-23154.
No. 0, No. 60-2950, No. 60-2951, No. 6
0-14242, 60-23474, 60-6
6249 and the like.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye in an image form. This type of compound can be represented by the following general formula [LI]. (Dye-Y) _n -Z [LI] Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents an image latent image. Corresponding to or opposite to the photosensitive silver salt having a difference in the diffusivity of the compound represented by (Dye-Y) _n -Z, or releasing Dye and releasing Dye and (Dye- Y) _n -Z represents a group having a property of causing a difference in diffusivity, n represents 1 or 2, and when n is 2, two Dye-Y are the same or different. Good.

Specific examples of the dye-donating compound represented by the general formula [LI] include the following compounds (1) to (5). The following (1) to (3) are for forming a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and (4) to (5) are for silver halide. And a diffusible dye image (negative dye image) is formed in correspondence with the development of. (1) US Pat. Nos. 3,134,764 and 3,36
No. 2,819, No. 3,597,200, No. 3,5
No. 44,545, No. 3,482,972 and the like, a dye developing agent in which a hydroquinone type developing agent and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

(2) As described in US Pat. No. 4,503,137, etc., a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide. Can also be used. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479 and isoxazolones described in US Pat. No. 4,199,354. Examples thereof include compounds that release a diffusible dye by an intramolecular rewinding reaction of the ring.

(3) US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,78
As described in No. 3,396, Kokai Giho 6-6199, etc., a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent remaining unoxidized by development can also be used. An example is U.S. Pat. No. 4,139,389.
No. 4,139,379, JP-A-59-1853.
33, 57-84553 and the like, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, U.S. Pat. No. 4,232,107, JP-A-59- 101649, 61-88257, R
D24025 (1984) and the like, which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent 3,008,588A, JP-A-56-142530, U.S. Pat. Fourth 4,343,893
Nos. 4,619,884 and the like, compounds capable of cleaving a single bond after reduction to release a diffusible dye, and electron acceptors described in US Pat. No. 4,450,223 and the like. Examples thereof include a nitro compound which releases a diffusible dye later, and a compound which releases a diffusible dye after electron acceptance as described in US Pat. No. 4,609,610.

Further, as more preferable ones, European Patent No. 220,746A2, Open Technical Report 87-6199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-2016.
No. 53, No. 63-201654, etc., N—X bond in one molecule (X represents oxygen, sulfur or nitrogen atom).
And a compound having an electron-withdrawing group, Japanese Patent Application No. 62-1068
No. 85, a compound having SO ₂ —X (X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-27.
1344, a compound having a PO-X bond (X has the same meaning as above) and an electron-withdrawing group in one molecule.
C-X 'bond (X' in marked within one molecule in JP 3-271341 is X as defined either or -SO ₂ - represents a) include compounds having an electron-withdrawing group. Also, Japanese Patent Application Sho 62
Compounds releasing a diffusible dye in which a single bond is cleaved after reduction by a π bond conjugated with an electron-accepting group described in JP-A-319989 and JP-A-62-320771 can also be used. Among these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof are EP 220,746A2 or US Pat. No. 4,783,3.
Compounds (1) to (3), (7) to (10), (1
2), (13), (15), (23) to (26), (31), (32), (35), (3
6), (40), (41), (44), (53) to (59), (64), (70), and compounds (11) to (23) of Open Technical Report 87-6199.

(4) A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and which releases the diffusible dye by a reaction with an oxidant of a reducing agent. Specifically, British Patent No. 1,330,524 and Japanese Patent Publication No. 48-39,165.
U.S. Pat. Nos. 3,443,940 and 4,47.
4,867 and 4,483,914.

(5) A compound (DRR compound) which is reducing to a silver halide or an organic silver salt and releases a diffusible dye when the other is reduced. Since this compound does not need to use any other reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. Typical examples thereof are US Pat. Nos. 3,928,312 and 4,053,312.
No. 4,055,428, No. 4,336,32
2, JP-A-59-65839 and JP-A-59-69839.
No. 53-3819, 51-104, 343,
RD17465, U.S. Pat. No. 3,725,062,
No. 3,728,113, No. 3,443,939
No. 58-116,537 and 57-1798.
40, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626 in columns 22 to 44. Among them, the compounds (1) to (3), (10) to (13), (16) to (19),
(28) to (30), (33) to (35), (38) to (40), and (42) to (64) are preferable. Also, U.S. Pat. No. 4,639,408, No. 37-
The compounds described in column 39 are also useful.

In addition, as a dye-donor compound other than the above-mentioned coupler and general formula [LI], a dye silver compound in which an organic silver salt and a dye are bonded (Research Disclosure, May 1978, 54-58). , Etc., azo dyes used in the heat developable silver dye bleaching method (US Pat.
35,957, Research Disclosure, 1
(April 976, pages 30 to 32), leuco dyes (U.S. Pat. Nos. 3,985,565, 4,022,617, etc.) can also be used.

Hydrophobic additives such as dye-donor compounds and antidiffusive reducing agents can be incorporated into the layer of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154
No. 59-178451 and No. 59-178452.
No. 59-178453 and 59-178454.
No. 59-178455, No. 59-178457 and the like, a high-boiling point organic solvent can be used in combination with a low-boiling point organic solvent having a boiling point of 50 ° C. to 160 ° C., if necessary. The amount of the high-boiling organic solvent is 10 g or less, preferably 5 g, per 1 g of the dye-donor compound used.
It is below. Also, 1 cc or less for 1 g of binder,
Furthermore, 0.5 cc or less, particularly 0.3 cc or less is suitable.
The 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, fine particles can be dispersed and contained in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used.
For example, the surfactants listed on pages (37) to (38) of JP-A-59-157636 can be used. In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material. Specific compounds preferably used are described in US Pat. No. 4,500,
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 light-sensitive material. The dye fixing material may be applied separately on a support different from the photosensitive material, or may be applied on the same support as the photosensitive material. Regarding the relationship between the photosensitive material and the dye fixing material, the relationship with the support, and the relationship with the white reflective layer, the relationship described in column 57 of US Pat. No. 4,500,626 can be applied to the present application. The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat.
00,626, columns 58-59 and JP-A-61-18825.
No. 6, pages (32) to (41), mordants described in JP-A-62-24
No. 4043, No. 62-244036, etc. can be mentioned. Also, U.S. Pat. No. 4,463,0
A dye-accepting high molecular compound as described in No. 79 may be used.

If necessary, the dye fixing material may be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer. In the constituent layers of the light-sensitive material and the dye-fixing material, a high boiling point organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability of the light-sensitive material and the dye-fixing material. Specifically, JP-A-6
No. 2-253159, page (25), and No. 62-245253.

Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethylsiloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in “Modified Silicone Oil” technical data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective. The silicone oils described in JP-A Nos. 62-215953 and 63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive material and the dye-fixing material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a metal complex of some kind.
Examples of the antioxidant include chroman compounds, coumarans compounds, phenol compounds (for example, 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 compounds (US Pat. No. 3,533,794), 4-thiazolidone compounds (US Pat. No. 3,352,681),
Benzophenone compounds (JP-A-46-2784 and the like), other JP-A-54-48535 and JP-A-62-13
There are compounds described in No. 6641, No. 61-88256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155 and 4,245,018.
No. 3-36 columns, No. 4,254,195 No. 3-8
Column, JP-A Nos. 62-174741, 61-88256.
No. 27-29, 63-199248, Japanese Patent Application No. 62
-234103, 62-230595 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137). An anti-fading agent for preventing the fading of the dye transferred to the dye fixing material may be contained in the dye fixing material in advance,
The dye fixing material may be supplied from the outside such as a photosensitive material. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination with each other.

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

As the hardener used in the constituent layers of the light-sensitive material and the dye-fixing material, US Pat. No. 4,678,739, No. 4,
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide). ) Ethane etc.),
Examples thereof include N-methylol type hardeners (dimethylol urea and the like) and polymer hardeners (compounds described in JP-A-62-234157).

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, improvement of releasability, improvement of slipperiness, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like. The constituent layers of the light-sensitive material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving peelability and the like. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-20
Nos. 944 and 62-135826, or the like, or a fluorine-containing surfactant such as a fluorine-containing compound such as a fluorine-containing compound such as a fluorine oil or a solid fluorine-containing compound resin such as a tetrafluoroethylene resin, Can be mentioned.

A matting agent can be used in the light-sensitive material and the dye-fixing material. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
In addition to the compounds described on page 1-88256 (29), benzoguanamine resin beads, polycarbonate resin beads, A
Japanese Patent Application Nos. 62-110064 and 6 for S resin beads
There are compounds described in No. 2-110065. In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, a defoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are disclosed in JP-A-61-88256.
Nos. (26)-(32).

In the present invention, an image forming accelerator can be used in the light-sensitive material and / or the dye-fixing material. The image forming accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of promoting the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, it is a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver. Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a complex function, and usually have some of the above-mentioned accelerating effects together. These details are described in US Pat. No. 4,678,739, columns 38 to 40.

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is U.S. Pat. No. 4,51.
No. 1,493 and JP-A No. 62-65038. In a system in which heat development and transfer of a dye are carried out simultaneously while storing a small amount of water, it is preferable to add a base and / or a base precursor to the dye-fixing material in order to improve the storability of the light-sensitive material. In addition to the above, the sparingly soluble metal compounds described in European Patent Publication No. 210,660 and U.S. Pat. No. 4,740,445, and compounds capable of complex-forming reaction with metal ions constituting the sparingly soluble metal compound ( Complex-forming compound) and JP-A-61-23
The compounds that generate a base by electrolysis as described in No. 2451 can also be used as the base precursor. The former method is particularly effective. It is advantageous to add the hardly soluble metal compound and the complex-forming compound separately to the light-sensitive material and the dye-fixing material.

The light-sensitive material and / or the dye-fixing material of the present invention have the following properties with respect to fluctuations in processing temperature and processing time during development.
Various development terminators can be used for the purpose of always obtaining a constant image. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base to reduce the concentration of the base in the film to stop the development after proper development, or to inhibit development by interacting with silver and a silver salt. Compound. Specific examples thereof include an acid precursor that releases an acid by heating, an electrophilic compound that causes a substitution reaction with a coexisting base by heating, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. More specifically, JP-A-62-25
No. 3159, pages (31) to (32).

As the support for the light-sensitive material and the dye-fixing material of the present invention, those which can withstand the processing temperature are used. Generally, paper and synthetic polymer (film) are used. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetylserose) or those containing pigments such as titanium oxide in these films, and further from polypropylene etc. Made by film method synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially cast coated paper), metal, cloth, glass etc. are used .. These can be used alone or as a support having one or both sides laminated with a synthetic polymer such as polyethylene. In addition to these, the supports described in JP-A No. 62-253159, pages (29) to (31) can be used. A hydrophilic binder, a semiconductive metal oxide such as alumina sol and tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports.

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

As a light source for recording an image on a photosensitive material,
As described above, the light sources described in US Pat. No. 4,500,626, column 56, such as natural light, tungsten lamps, light emitting diodes, laser light sources, and CRT light sources can be used. Image exposure can also be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material that can develop the nonlinearity between the electric field and the polarization that appears when a strong optical electric field such as laser light is applied.
Lithium niobate, potassium dihydrogen phosphate (KDP),
Inorganic compounds represented by lithium iodate, BaB ₂ O _4, etc., urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM) , JP-A-6
The compounds described in 1-53462 and 62-210432 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. In addition, the above image information,
Image signals obtained from video cameras, electronic still cameras, etc., television signals represented by the Japanese television signal standard (NTSC), image signals obtained by dividing an original image into a large number of pixels such as a scanner, and represented by CG and CAD. An image signal created by using a computer can be used.

The light-sensitive 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 dye. The transparent or opaque heating element in this case is disclosed in JP-A-61-1.
Those described in the specification of No. 45544 and the like can be used. Note that these conductive layers also function as antistatic layers. The heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and development is possible, but about 80 ° C. to about 180 ° C. is particularly useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the heat development process is completed. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

Although the migration of the dye occurs only by heat,
Solvents may be used to facilitate dye transfer. Also,
As described in detail in JP-A-59-218443 and JP-A-61-238056, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful. is there. In this method, the heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, it is preferably 50 ° C. or higher and 100 ° C. or lower. Examples of the solvent used to accelerate development and / or transfer the diffusible dye to the dye-fixing layer include water or a basic water-soluble solvent containing an inorganic alkali metal salt or an organic base (as these bases, The one described in the section of the image formation accelerator is used.)
Can be mentioned. Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound, etc. may be contained in the solvent.

These solvents can be used by a method of applying them to the dye fixing material, the photosensitive material or both.
The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film). Examples of the method of applying a solvent to the photosensitive layer or the dye fixing layer include, for example, JP-A-61-147244 (26).
There is a method described on the page. Further, the solvent may be contained in a microcapsule or the like in advance and incorporated in the light-sensitive material or the dye-fixing material or both.

In order to promote dye transfer, a method of incorporating a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature into the light-sensitive material or the dye-fixing material can also be adopted. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material or the dye fixing material, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and / or its adjacent layer. Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alkenyls, oximes and other heterocycles. Further, a high boiling point organic solvent may be contained in the light-sensitive material and / or the dye-fixing material in order to promote dye transfer.

As a heating method in the developing and / or transferring step, a heated block or plate is brought into contact with a heating plate, a hot presser, a heating roller, a halogen lamp heater, an infrared or far infrared lamp heater or the like. Or passing through a high temperature atmosphere. JP-A-61-1 is a method for applying a pressure condition or pressure when the light-sensitive material and the dye-fixing material are superposed and brought into close contact.
The method described in page 47244 (27) can be applied. Any of a variety of thermal development apparatus can be used in processing the photographic elements of this invention. For example, JP-A-59-75247 and 59-59.
No. 177547, No. 59-181353, No. 60-
The devices described in No. 18951, No. 62-25944, etc. are preferably used.

[0074]

EXAMPLE A method for preparing a silver halide emulsion (III) for the fifth layer will be described. Well stirred gelatin aqueous solution [20 g of gelatin, 3 g of potassium bromide, 0.03 g of the following chemical A in 800 cc of water, and HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ O
0.25 g of H 2 was added and kept at 50 ° C.], the solutions (1) and (2) in Table A below were simultaneously added over 30 minutes.
Then, the following liquids (3) and (4) were simultaneously added over 20 minutes. In addition, 5 minutes after the addition of the liquid (3), 0.18 g of the following dye (a) and 0.06 g of the dye (b) were added to methanol 1
A dye solution dissolved in 60 cc was added over 18 minutes. After washing with water and desalting, 20 g of lime-treated ossein gelatin was added to adjust the pH to 6.2 and pAg to 8.5, and then sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3 were used.
Optimal chemical sensitization was performed by adding a, 7-tetrazaindene and chloroauric acid. Thus, the average particle size 0.40μ
600 g of monodisperse cubic silver chlorobromide emulsion of m were obtained.

[0075]

[Table 1]

[0076]

[Chemical 13]

A method for preparing the silver halide emulsion (IV) for the third layer will be described. Well stirred aqueous solution (water 73
20 g of gelatin, 0.30 g of potassium bromide, 6 g of sodium chloride and 0.015 g of the above-mentioned chemical A were added to 0 cc and kept at 60.0 ° C.) at the same time with the solutions (I) and (II) of Table B below. Added at equal flow rate over 60 minutes.
After the addition of the solution (I) was completed, a solution (III) of the following sensitizing dye (c) in methanol was added. Thus, a monodisperse cubic silver chlorobromide emulsion adsorbing a dye having an average grain size of 0.45 μm was prepared. After washing with water and desalting, 20 g of gelatin was added to adjust pH to 6.4 and pAg to 7.8.
Chemical sensitization was performed at 0.0 ° C. The chemicals used at this time were 1.6 mg of triethylthiourea and 100 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, and the aging time was 55 minutes. The yield of this emulsion is 6
It was 35 g.

[0078]

[Table 2]

[0079]

[Chemical 14]

A method for preparing the silver halide emulsion (V) for the first layer will be described. Well stirred gelatin aqueous solution (20g gelatin in 800cc water, 0.30 potassium bromide)
g, 6 g of sodium chloride, and 30 mg of the above-mentioned chemical A were added and kept at 50 ° C.), and the solution (I) and (I
Solution I) was added simultaneously at an equal flow rate over 30 minutes. After that, the following solutions (III) and (IV) were simultaneously added over 30 minutes. Three minutes after the addition of the solutions (III) and (IV) was started, a dye solution prepared by dissolving 67 mg of the following dye (d) and 133 mg of the dye (e) in 100 cc of methanol was added over 20 minutes. After washing with water and desalting, lime-treated ossein gelatin 22
After adjusting pH to 6.2 and pAg to 7.7 by adding g, sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and chloroauric acid were added. Optimal chemical sensitization was performed at 60 ° C. Thus, a monodisperse cubic silver chlorobromide emulsion having an average grain size of 0.38 μm was obtained. The yield was 635 g.

[0081]

[Table 3]

[0082]

[Chemical 15]

Next, a method for preparing a gelatin dispersion of zinc hydroxide will be described. 12.55 g of zinc hydroxide having an average particle size of 0.25 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 cc of a 4% gelatin aqueous solution, and glass beads having an average particle size of 0.75 mm were milled. Used for 30 minutes.
The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

Next, a method for preparing a dispersion of the electron transfer agent (1) will be described. 10 g of the following electron transfer agent (1), 0.5 g of polyethylene grylnonyl phenyl ether as a dispersant, and 0.5 g of the following anionic surfactant (2) were added to a 5% gelatin aqueous solution, and the average particle size was measured with a mill. Diameter 0.75
Milled for 60 minutes with mm glass beads. The glass beads were separated to obtain a dispersion of the electron transfer agent having an average particle size of 0.3 μm.

[0085]

[Chemical 16]

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described. The oil phase components shown in Table D below were each dissolved in 50 cc of ethyl acetate to form a uniform solution at 60 ° C. To this, add the water phase component heated to 60 ° C, and use a dissolver with a diameter of 8 cm for 30 minutes for 500 minutes.
Dispersed at 0 rpm. To this was added post-hydration and stirred to form a uniform dispersion. This is referred to as the hydrophobic additive gelatin dispersion.

[0087]

[Table 4]

Using the above materials, a heat developable color photosensitive material 101 having a multilayer structure shown in Table 1 was prepared.

[0089]

[Table 5]

[0090]

[Table 6]

[0091]

[Table 7]

[0092]

[Chemical 17]

[0093]

[Chemical 18]

[0094]

[Chemical 19]

[0095]

[Chemical 20]

[0096]

[Chemical 21]

[0097]

[Chemical formula 22]

Next, a method for producing the dye fixing material will be described. Dye fixing material R-1 having the constitution shown in Table 2 below was prepared using the paper support shown in Table E below.

[0099]

[Table 8]

[0100]

[Table 9]

[0101]

[Chemical formula 23]

[0102]

[Chemical formula 24]

[0103]

[Chemical 25]

With respect to the light-sensitive material 101 thus produced, as shown in Table 3 below, light-sensitive materials 102 to 115 having exactly the same composition as 101 except that the electron transfer agent (42) was changed to its precursor. I made each one. In the case of adding an electron transfer agent precursor, fine particles are dispersed and added in the same manner as the electron transfer agent (42), or added by a method of co-emulsifying and adding to an emulsion present in the addition layer. .

[0105]

[Table 10]

[0106]

[Chemical formula 26]

Further, the photosensitive materials 101 to 115
It was stored for 5 days under the condition that the temperature and humidity were 80%. Samples made in this way are 2 for each of 101-115.
01-215.

The above-mentioned multilayer color photosensitive materials 101 to 1
15 and 201-215 are tungsten bulbs,
It was exposed for 1/10 seconds at 5000 lux through B, G, R and gray color separation filters with continuously varying densities. While feeding this exposed light-sensitive material at a linear velocity of 20 mm / sec, 15 cc / m ² of water was supplied to the emulsion surface by a wire bar, and immediately thereafter, it was superposed so that the image-receiving material R-1 was in contact with the film surface. . Using a heat roller whose temperature was adjusted so that the water-absorbed film had a temperature of 85 ° C., it was heated for 15 seconds. Next, without peeling from the image receiving material, clear images of blue, green, red and gray were evenly obtained on the image receiving material corresponding to the color separation filters of B, G, R and gray. Table 4 shows the results of measuring the maximum density (Dmax) and the minimum density (Dmin) of cyan, magenta and yellow in the gray area.

[0109]

[Table 11]

From Table 4, it can be seen that the light-sensitive material using the compound of the present invention can produce an image excellent in discrimination before and after storage.

Claims (1)

[Claims] 1. A support having at least a photosensitive silver halide, a binder, and the following general formula (I) or (I
A photothermographic material comprising a reducing agent precursor represented by I). General formula (I): General formula (II) In the formula, R ^{1 to} R ⁴ each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. R ⁵ represents an aryl group or a heterocyclic group.