JPH05241304A - Heat transfer photographic element - Google Patents

Abstract

PURPOSE:To prevent the curl of an image obtd. after heat transfer of a heat developable photosensitive material and to prevent transfer trouble in an image forming device. CONSTITUTION:This heat transfer photographic element is made of a dyestuffting element with a substrate having 0.3-20g/m<2> rigidity coated with >=1g/m<2> hydrophilic binder and one or more image forming layers and/or a dye fixing element with an image receiving layer. The curl of this photographic element before processing is 10-60mm per 20cm<2> under the conditions of 25 deg.C and 60% relative humidity when the side with the image forming layers and the image receiving layer is set downward.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an image-forming layer and an image-receiving layer coated with at least 1 g / m ² of a hydrophilic binder, and is for heating to diffuse-transfer a movable dye to form an image. It relates to a thermal transfer photographic element.

[0002]

2. Description of the Related Art In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and apparatuses suitable for the respective information processing systems have also been developed and adopted. As one of such recording methods, the thermal transfer recording method has been widely used recently because the apparatus used is lightweight and compact, has little noise, is excellent in operability and maintainability, and can be easily colorized. .. This thermal transfer recording method is roughly classified into two types, a heat melting type and a heat transfer type. As the latter method, various methods have been proposed for obtaining a high-density transferred image by a thermal transfer recording method using a heat transferable dye.

Many methods have been proposed for obtaining a color image (color image) by thermal development. For example, U.S. Pat. Nos. 3,531,286 and 3,761, for a method of forming a color image by combining a coupler with an oxidized product of a developing agent produced by reduction of silver halide.
1,270, 4,021,240, Belgian Patent No. 802,519, Research Disclosure (hereinafter abbreviated as RD) 13742, and the like. Further, a method of forming a positive dye image by heat development by a silver dye bleaching method using silver halide is disclosed in US Pat.
235,957, RD14433, RD15227 and the like. Furthermore, a method of forming or releasing an imagewise diffusible dye from a dye-donor compound with heat development of silver halide, and transferring the diffusible dye to a dye fixing element having a mordant with a solvent such as water. , A method of transferring to a dye-fixing element with a high boiling point organic solvent, a method of transferring to a dye-fixing element with a hydrophilic thermal solvent incorporated in the dye-fixing element, a movable dye is heat diffusible or sublimable, and a support And the like have been proposed.

In this method, a negative dye image and a positive dye image with respect to the original can be obtained by changing the type of dye-donor compound used or the type of silver halide emulsion (US). Patent No. 4,4
63,079, 4,474,867, 4,47
8,927, 4,507,380, 4,50
0,626, 4,483,914, JP-A-58-
149046, 58-149047, 59-1
52440, 59-154445, 59-16
No. 5054, No. 59-180548, No. 59-168.
No. 439, No. 59-174832, No. 59-1748.
33, 59-174834, 59-17483.
5, No. 62-65038, No. 61-23245,
European Patent Publication Nos. 210,660A2 and 220,746
A2 etc.).

[0005]

In the above-mentioned image forming method, when a dye-donor element (also referred to as "photosensitive element") and a dye-fixing element are thermally transferred to form an image, the dye-donor element and the dye after thermal transfer are used. Since the curling of the fixing element is large, there is a problem that a conveyance problem occurs in the image forming apparatus and the commercial property is significantly impaired. This problem is remarkable when a hydrophilic binder is used. As a method for improving this problem, Japanese Patent Application Laid-Open No. 61-205935 proposes a method of coating an anti-curl layer on the back surface of a support, but it has been insufficient. Further, in recent years, a transfer image on the level of plain paper using a thin support has been required, and this problem has become more and more important. Accordingly, it is an object of the present invention to provide a thermal transfer photographic element with improved curl after processing.

[0006]

[Means for Solving the Problem] As a result of further diligent investigation, as a result of thermal transfer using a hydrophilic binder, the physical properties of the hydrophilic binder layer and the support change before and after thermal transfer, and the curl balance changes. It became clear.

Specifically, the hydrophilic binder layer tends to shrink due to heating, and this tendency becomes remarkable especially at low humidity. Further, the support is more likely to contract on the thermal transfer contact side with water contained in the hydrophilic binder layer due to heating, and thus is more likely to curl to the thermal transfer contact side. This indicates the peculiarity of curl change before and after thermal transfer. This tendency is particularly remarkable when the material of the support adjacent to the coating layer containing the hydrophilic binder is polyolefin.

Therefore, in consideration of the curl change amount before and after the thermal transfer, a method of applying a curl in the opposite direction to the thermal transfer photographic element before and after the thermal transfer is changed. That is, the above problem is that the rigidity is 0.3 to 20 g / m ^2.
At least 1 g / m ² of hydrophilic binder on the support
In a thermal transfer photographic element comprising a dye-donor element having one or more image-forming layers and / or a dye-fixing element having an image-receiving layer coated as described above, the curl of the thermal transfer photographic element before treatment is 25 ° C. and a relative humidity of 60. 20c under the condition that the surface having the image forming layer and the image receiving layer faces downward.
It was achieved by setting the rising curl of m square to 10 to 60 mm. If it is less than 10 mm, the curl after processing becomes large, and if it exceeds 60 mm, a conveyance problem occurs in the apparatus.

The curl of the present invention can be controlled by methods known in the art. That is, it is performed at the time of manufacturing the support, or by controlling the thickness of the image forming layer, the image receiving layer or the back layer, the elastic modulus, the moisture absorption coefficient, and the like.

Although the photographic element of the present invention can be subjected to various embodiments using thermal transfer, the photosensitive element having an image forming layer and the dye fixing element having an image receiving layer used in the photothermographic material will be described in detail.

The light-sensitive element used in the present invention basically has a light-sensitive silver halide, a binder and a dye-donor compound (which may also serve as a reducing agent as described later) on a support, Furthermore, if necessary, an organic metal salt oxidizing agent and the like can be added. These components are often added to the same layer, but if they are in a reactive state, they can be added separately to separate layers. For example, when a dye-providing dye compound is present in the lower layer of the silver halide emulsion, the reduction in sensitivity can be prevented. The reducing agent is preferably incorporated in the light-sensitive element, but may be supplied from the outside by, for example, a method of diffusing from a dye fixing element described later.

In order to obtain a wide range of colors in the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers sensitive to different spectral regions 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. The photosensitive element 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 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 μm, particularly preferably 0.2 to 1.5 μm. The crystal habit of silver halide grains is cubic, octahedral,
It may be a tetrahedron, a flat plate having a high aspect ratio, or any other shape. Specifically, U.S. Pat. No. 4,500,626, column 50, U.S. Pat. No. 4,628,021, Research Disclosure (hereinafter abbreviated as RD) 17029 (1).
1978), any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion may be used as it is after ripening, but it is usually chemically sensitized before use. Well-known sulfur sensitizing methods, reduction sensitizing methods, noble metal sensitizing methods, selenium sensitizing methods and the like can be used alone or in combination for emulsions for conventional type light-sensitive materials. These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-25315).
No. 9). 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, mercapto compounds and metal salts thereof described in JP-A-59-111636, 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 element and the dye-fixing element. As an example thereof, pages (26) to (2) of JP-A-62-253159.
8) The thing described in page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran and pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with A copolymer with a vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more.

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the above superabsorbent polymer. Also, the use of superabsorbent polymers in the dye-fixing layer or its protective layer can prevent the dye from retransferring from the dye-fixing element to another after transfer. In the present invention,
The coating amount of the binder is preferably 20 g or less per 1 m ² , particularly 10 g or less, and more preferably 7 g or less.

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

As the reducing agent used in the present invention, those known in the field of photosensitive elements can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property by itself but exhibits a reducing property by the action of a nucleophile or heat during the development process can also be used. Examples of the reducing agent used in the present invention include U.S. Pat. No. 4,500,626, columns 49 to 50, and U.S. Pat. No. 4,483,914, columns 30 to 30.
Column 1, No. 4,330,617, No. 4,590,152
Nos. (17) to (1) of JP-A-60-140335.
8), pages 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 and reducing agent precursors 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 a diffusion resistant reducing agent is used, an electron transfer agent and / or an electron transfer agent is optionally added to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination. The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the electron transfer agent or the precursor thereof has a mobility higher than that of the diffusion resistant reducing agent (electron donor). Particularly useful electron transfer agents are 1-phenyl-3-pyrazolidones or aminophenols. The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be one that does not substantially move in the layer of the photosensitive element among the reducing agents described above, and preferably hydroquinones, Examples thereof include sulfonamide phenols, sulfonamide naphthols, compounds described as electron donors in JP-A No. 53-110827, and dye-donating compounds having diffusion resistance and reducing properties described later. In the present invention, the reducing agent is added in an amount of 0.
001 to 20 mol, particularly preferably 0.01 to 10 mol.

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. 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. 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 developing agents and couplers are described in T.W. H. Jam
es "The Theory of the Pho"
"graphical Process" 4th edition 291
Pp. 334 and 354-361, JP-A-58-123
533, 58-149046, 58-1490.
No. 47, No. 59-111148, No. 59-12439.
No. 9, No. 59-174835, No. 59-231539.
No. 59, No. 231540, No. 60-2950, No. 60-2951, No. 60-14242, No. 60-2.
It is described in detail in Nos. 3474 and 60-66249.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye imagewise. This type of compound can be represented by the following general formula [LI]. (Dye-Y) _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) represents a group having a property of causing a difference in diffusibility from _n- Z, n represents 1 or 2, and when n is 2, two Dy
e-Y may be the same or different. General formula [LI]
Specific examples of the dye-donating compound represented by are the following compounds (1) to (4). In addition, the following
Is to form a diffusible dye image (positive dye image) corresponding to the development of silver halide, and is a diffusible dye image (negative dye image) to correspond to the development of silver halide.
Is formed.

US Pat. Nos. 3,134,764, 3,362,819, 3,597,200, 3,544,545, and 3,482,972 are described. , A dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide. As described in U.S. Pat. No. 4,503,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can also be used. An example is U.S. Pat. No. 3,983.
Compounds releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 4,199,
Compounds that release a diffusible dye by an intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354, etc.

US Pat. No. 4,559,290, European Patent 220,746A2, US Pat. No. 4,783,
As described in No. 396, Kokai Giho 6-6199, etc., a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used.
Examples thereof include U.S. Pat. Nos. 4,139,389 and 4,139,379, JP-A-59-185333,
Compounds that release diffusible dyes by nucleophilic substitution reaction in the molecule after reduction described in U.S. Pat. No. 4,232,107, JP-A-59-84453.
No. 101649, No. 61-88257, RD240
25 (1984) and the like, which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 3,008,588A, JP-A-56-
No. 142530, U.S. Pat. Nos. 4,343,893 and 4,619,884, which release a diffusible dye by cleavage of a single bond after reduction, U.S. Pat. Examples thereof include nitro compounds described in U.S. Pat. No. 223, which release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610, which release a diffusible dye after electron acceptance, and the like.

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 and the like, compounds having an N—X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group in one molecule, JP-A-1-268.
No. 42, a compound having SO ₂ —X (where X is as defined above) and an electron-withdrawing group in one molecule, JP-A-63-2
No. 71344, a PO-X bond (X
Has the same meaning as above) and a compound having an electron-withdrawing group, C-X 'in one molecule described in JP-A-63-271341.
Examples thereof include a compound having a bond (X ′ is synonymous with X or represents —SO ₂ —) and an electron-withdrawing group. In addition, JP-A-1
Compounds described in JP-A-161237 and JP-A-161342, which release a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated with an electron-accepting group, 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.
96-compounds (1)-(3), (7)-
(10), (12), (13), (15), (23)-
(26), (31), (32), (35), (36),
(40), (41), (44), (53) to (59),
(64), (70), compounds (11) to (23) described in Public Technical Report 87-6199, and the like.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and releases the diffusible dye by a reaction with an oxidant of a reducing agent. Specifically, British Patent No. 1,330,524, Japanese Patent Publication No. 48-39165, and US Patent Nos. 3,443,940 and 4,474,867.
No. 4,483,914 and the like. Reducible for silver halides or organic silver salts,
A compound that releases a diffusible dye when the other party is reduced (DR
R compound). 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. A typical example thereof is US Pat. No. 3,92.
8,312, 4,053,312, 4,05
5,428, 4,336,322, JP-A-59-
No. 65839, No. 59-69839, No. 53-381.
9, 51-104343, RD17465, U.S. Pat. Nos. 3,725,062 and 3,728,113.
No. 3,443,939, JP-A-58-11653.
7, 57-179840, U.S. Pat. No. 4,50.
No. 0,626, etc. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to
(3), (10) to (13), (16) to (19),
(28)-(30), (33)-(35), (38)-
(40) and (42) to (64) are preferable. The compounds described in U.S. Pat. No. 4,639,408, columns 37 to 39 are also useful. In addition, as a dye-donor compound other than the coupler and the general formula [LI] described above, a dye silver compound in which an organic silver salt and a dye are bound (Research Disclosure May 1978 issue, pages 54 to 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 diffusion resistant reducing agents can be incorporated into the layers of the light-sensitive element 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. Further, 1 cc or less, further 0.5 cc or less, and particularly 0.3 cc or less is suitable for 1 g of the binder. JP-B-51-39853, JP-A-51-59
A dispersion method using a polymer described in No. 943 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 element. Specific compounds preferably used are described in US Pat. No. 4,50.
0,626, columns 51-52.

In a system for forming an image by diffusion transfer of dyes, a dye fixing element is used together with a light-sensitive element. The dye-fixing element may be applied separately on a support different from the photosensitive element or may be applied on the same support as the photosensitive element. Regarding the relationship between the photosensitive element and the dye fixing element, 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 element 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-6-63
Examples thereof include those described in Nos. 2-244043 and 62-244036. Also, US Pat.
A dye-accepting high molecular compound as described in No. 63,079 may be used. The dye fixing element may be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer, if necessary. In particular, it is useful to provide a protective layer.

In the constituent layers of the light-sensitive element and the dye-fixing element, a high-boiling point organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability of the light-sensitive element and the dye-fixing element. A specific example is (2) in JP-A-62-253159.
5), No. 62-245253 and the like. Further, various silicone oils (all silicone oils from dimethyl silicone oils to modified silicone oils obtained by introducing various organic groups into dimethyl siloxane) can be used for the above purpose. Examples thereof include various modified silicone oils described in "Modified Silicone Oil" Technical Material P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X
-22-3710) and the like are effective. In addition, JP-A-62
The silicone oils described in JP-A-215953 and JP-A-63-46449 are also effective.

An anti-fading agent may be used in the light-sensitive element and the dye fixing element. 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, 4,245,018, columns 3 to 36, 4,254,195, columns 3 to 8, and JP-A-62-174741. 61-88256 (2
7)-(29), 63-199248, JP-A-1.
There are compounds described in, for example, -75568 and 1-74272.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137). The anti-fading agent for preventing the fading of the dye transferred to the dye-fixing element may be contained in the dye-fixing element in advance, or may be supplied to the dye-fixing element from the outside such as a light-sensitive element. . 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 element and the dye-fixing element. In particular, whether to incorporate a fluorescent whitening agent in the dye fixing element,
It is preferably supplied from the outside such as a photosensitive element. As an example, K. Venkataraman edition “Th
e Chemistry of Synthetic
Dyes ", Vol. V, Chapter 8, and compounds described in JP-A-61-143752 and the like. 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 element and the dye-fixing element, US Pat. No. 4,678,739, No. 4 is used.
Column 1, JP-A-59-116655 and JP-A-64-2452.
No. 61, No. 61-18942, etc. are mentioned. More specifically, aldehyde type hardeners (formaldehyde etc.), aziridine type hardeners, epoxy type hardeners, vinyl sulfone type hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane etc.), N
-Methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

In the constituent layers of the light-sensitive element and the dye-fixing element, various surfactants can be used for the purpose of coating aid, improvement of peeling property, improvement of sliding property, antistatic property, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like. The constituent layers of the light-sensitive element and the dye-fixing element may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, and improving releasability. As typical examples of organic fluoro compounds, JP-B-57-9053, columns 8 to 17, JP-A-61-20
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 element and the dye fixing element. 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, AS resin beads and the like are disclosed in JP-A-63-274944.
No. 63-274952. In addition, the constituent layers of the light-sensitive element and the dye-fixing element may contain a thermal solvent, an antifoaming agent, an antibacterial / antifungal agent, colloidal silica and the like. Specific examples of these additives are disclosed in JP-A-61-8.
No. 8256, pages (26) to (32).

In the present invention, an image forming accelerator can be used in the light-sensitive element and / or the dye fixing element. 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 photosensitive element layer. From the physicochemical functions, such as bases or base precursors, nucleophilic compounds, high boiling organic solvents (oils), thermal solvents, surfactants, silver Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. Details thereof 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. 4,511,493.
And JP-A-62-65038.

In a system in which heat development and transfer of a dye are simultaneously carried out in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye-fixing element in order to enhance the storage stability of the light-sensitive element. In addition to the above, European Patent Publication 210,660 and US Pat. No. 4,740,445.
Combination of a sparingly soluble metal compound and a compound capable of complexing reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex forming compound) described in JP-A-61-
The compounds that generate a base by electrolysis as described in No. 232451 can also be used as the base precursor.
The former method is particularly effective. The sparingly soluble metal compound and the complex-forming compound are advantageously added separately to the light-sensitive element and the dye-fixing element.

In the present invention, various development terminators can be used in the light-sensitive element and / or the dye-fixing element for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development. The term "development terminating agent" as used herein refers to a compound that immediately neutralizes or reacts with a base after proper development to lower the concentration of the base in the film to stop the 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 when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound and a precursor thereof. More specifically, JP-A-62-25
No. 3159, pages (31) to (32).

In the present invention, a support that can withstand the processing temperature is used as the support for the light-sensitive element and the dye-fixing element. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing a pigment such as titanium oxide are further prepared from polypropylene or the like. Film-processed synthetic paper, mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (particularly cast coated paper), metal, cloth, glass and the like are used. These can be used alone,
It can also be used 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-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.

Examples of the method for exposing and recording an image on a light-sensitive element include a method of directly photographing a landscape or a person using a camera, a method of exposing through a reversal film or a negative film using a printer or 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 the photosensitive element,
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 such as 3
-Methyl-4-nitropyridine-N-oxide (PO
Nitropyridine-N-oxide derivatives such as M) and compounds described in JP-A Nos. 61-53462 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. Further, the above-mentioned image information is an image signal obtained from a video camera, an electronic still camera or the like, a television signal represented by Nippon Television Signal Standard (NTSC), an image obtained by dividing an original image into many pixels such as a scanner. Signals, image signals created by using a computer represented by CG, CAD can be used.

The light-sensitive element and / or the dye-fixing element 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 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 for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases include an image). The one described in the section of the 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 may be contained in the solvent.

These solvents can be used by a method of applying them to the dye fixing element, the photosensitive element 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). A method for applying a solvent to the photosensitive layer or the dye fixing layer is described in, for example, JP-A-61-147244 (2).
6) There is a method described on page. Alternatively, the solvent may be contained in a microcapsule or the like in advance and incorporated in the light-sensitive element or the dye-fixing element or both.

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

As a heating method in the developing and / or transferring step, a heated block or plate is brought into contact, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater or the like is contacted. Or passing through a high temperature atmosphere. JP-A-61-1 is a method for applying a pressure condition or pressure when the light-sensitive element and the dye fixing element are superposed and closely contacted with each other.
The method described on page 27 of No. 47244 can be applied.

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

[0049]

The present invention will be described below with reference to examples, but the present invention is not limited thereto.

Example 1 A photosensitive element having the constitution shown in Table-A was prepared on the support (1) shown in Table-B and Table-C to obtain a photosensitive element (1).

[0051]

[Table 1]

[0052]

[Table 2]

[0053]

[Table 3]

[0054]

[Table 4]

[0055]

[Chemical 1]

[0056]

[Chemical 2]

[0057]

[Chemical 3]

[0058]

[Chemical 4]

On the support (1) shown in Table-B and Table-C, the dye-fixing element having the constitution shown in Table-D was prepared and designated as dye-fixing element (1).

[0060]

[Table 5]

Water-soluble polymer (1): Sumika gel L5-
H (Sumitomo Chemical Co., Ltd.) Water-soluble polymer (2): Copper-carrageenan (Taito Co., Ltd.) Water-soluble polymer (3): Dextran (molecular weight 70,000) Polymer dispersion (1): Nipol LX814 (Japan ZEON Co., Ltd.) Optical brightener (1): 2,5-bis (5-t-benzoxazol (2)) thiophene High boiling point organic solvent (1): Empara 40 (Ajinomoto Co., Inc.)
Made)

[0062]

[Chemical 5]

The film thickness of the backside PE layer of the support (1) used for the light-sensitive element (1) and / or the dye-fixing element (1) was changed as shown in Table E, and each of Experiment Nos. 1 to 13 was changed. A photothermographic material having the combination of

The above light-sensitive element and dye-fixing element were processed by using the image recording apparatus described in JP-A-2-84634. That is, an original image (a test chart on which yellow, magenta, cyan, and gray wedges having continuously changing densities are recorded) is scan-exposed through a slit, and this photosensitive element is exposed to water kept at 40 ° C. After soaking for 5 seconds, the particles were squeezed with a roller, and immediately thereafter they were superposed so that the dye-fixing element was in contact with the film surface, and heated for 25 seconds using a heat roller adjusted so that the water-absorbed film surface was 80 ° C. Then, the light-sensitive element and the dye-fixing element were peeled off, and a clear color image corresponding to the original image was obtained on the dye-fixing element.

The sample before processing the above-mentioned light-sensitive element and dye-fixing element was cut into a 20 cm square, and the sample was cut at 25 ° C.
After standing in an environment of 60% RH for 4 hours, the coated surface is faced downward and the averaged rising heights of the four curled corners are shown in Table-E. Further, the presence or absence of transport trouble of the photosensitive element and the dye fixing element before the heat treatment and the presence or absence of transport trouble of the photosensitive element and the dye fixing element after peeling and drying were observed, and the results are shown in Table-E. Further, the curl of the dye-fixing element after the photosensitive element and the dye-fixing element were peeled off and dried was measured, and the results are shown in Table-E. The curl was measured by cutting the dye-fixing element sample after peeling and drying into a 20 cm square and leaving it in an environment of 25 ° C. and 15% RH for 4 hours, and then, with the coated surface facing downward, rising of the curled four corners. The average height is shown.

[0066]

[Table 6]

[0067]

[Table 7]

As is clear from the results shown in Table E, the curl of the light-sensitive element or the dye-fixing element before processing is 10 to 60 m.
It can be seen that when m is m, there is no conveyance trouble, and the curl of the obtained image is small and the product is excellent in commercial property.

[0069]

The thermal transfer photographic element comprising the light-sensitive element and the dye-fixing element according to the present invention has excellent effects that there is no trouble in conveyance and curl of the obtained image is small.

Claims (2)

[Claims] 1. A stiffness 0.3 to 20 g / m dye-donor element having at least 1 g / m ² or more applied one or more layers of the image-forming layer was a hydrophilic binder on a ^second support and /
Alternatively, in a thermal transfer photographic element comprising a dye-fixing element having an image-receiving layer, the curl of the thermal transfer photographic element before processing is 2
A thermal transfer photographic element having a 20 cm square rising curl of 10 to 60 mm with the surface having the image forming layer and the image receiving layer facing downward under the conditions of 5 ° C. and 60% relative humidity. 2. A thermal transfer photographic element characterized in that the material of the support adjacent to the coating layer containing the hydrophilic binder of claim 1 contains polyolefin as a main component.