JP3126400B2 - Thermal transfer recording material and thermal transfer image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer recording material and a method for forming a thermal transfer image, and more particularly to a method for obtaining a positive image, improving the adhesion between a transparent original film and the thermal transfer recording material and improving the image quality. The present invention relates to a thermal transfer recording material and a thermal transfer image forming method.

[0002]

BACKGROUND OF THE INVENTION Conventionally, silver salt recording materials and photosensitive resin recording materials have been used to form high quality images. In such a recording material, processing using a liquid has been required after recording. That is, in the case of a silver salt recording material, a step of blackening the exposed silver particles or a step of coloring the coupler to a desired color is required. In most cases, such a processing requires a liquid processing liquid. there were. Further, in the case of a photosensitive resin recording material, an image is formed by using the property that the solubility in a developing solution and the permeability of the recording material are changed by exposure, so that a step of removing a non-image portion by the developing solution after the exposure is required. Was needed. The treatment using such a liquid generates a waste liquid, and is not preferable in terms of environmental hygiene.

Therefore, a thermal transfer recording method has attracted attention as an image forming method capable of performing dry processing. However, in the thermal transfer recording method using a thermal head, the recording resolution is limited by the degree of integration of the thermal head. Further, even if the degree of integration of the thermal head is increased, there is a limit in improving the image quality due to the influence of an adjacent head and the like. As a method of breaking through the limit of image quality by such a thermal head, application of a heat pattern by photothermal conversion can be considered. In this method, image information is given in the form of light and converted into a form of heat, thereby generating heat and causing thermal transfer.

As a thermal transfer recording method utilizing such light-to-heat conversion, a thermal fusion transfer ribbon having a thermal fusion ink layer in which carbon black is dispersed in a wax-based binder is used, and recording is performed by flash light through a transparent original (negative). A method for forming a transferred image has been proposed.

[0005]

However, in the case of such a method of transferring the exposed portion to the image receiving support, a positive image remains on the thin film support and a negative image is transferred to the image receiving support.
Since the thin film support has low physical strength and is easily damaged, it is difficult to use a substantially positive image as an image in a subsequent step.

In this method, since exposure is performed through a support of a thermal transfer recording material, when a support having a large thickness is used, image reproducibility deteriorates due to diffusion of light. When a support having a thin film thickness is used, light diffusion is suppressed, but the rigidity of the support is insufficient, and local poor adhesion to a document is likely to occur. Dimensional deviation easily occurs. In particular, it has been found that such poor adhesion or dimensional deviation is likely to occur when attempting to create a large area image.

Accordingly, an object of the present invention is to provide a thermal transfer recording material and a method for forming a thermal transfer image which are capable of positive type recording, hardly cause poor adhesion to an original image, hardly cause dimensional deviation, and have good image reproducibility. To provide.

[0008]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have reached the present invention.

That is, the first thermal transfer recording material according to the present invention comprises a support having a thickness of 30 μm or more and 500 μm or less, a thermal transfer layer, a light-to-heat conversion layer, and a release support laminated by a melt extrusion method or a coating method or laminated. A thermal transfer recording material having this order, wherein the release support has a thickness of 1
It is characterized in that it has a property of being separated from the support together with the thermal transfer layer and the light-to-heat conversion layer at a thickness of not less than μm and not more than 20 μm, and has a property of not being separated from the heat transfer layer and the light-to-heat conversion layer.

The second thermal transfer recording material according to the present invention comprises a support having a thickness of 30 μm or more and 500 μm or less, a thermal transfer layer, a release support or a light-to-heat conversion layer laminated by a melt extrusion method or a coating method or laminated. A thermal transfer recording material having this order, wherein the release support has a thickness of 1
It is characterized in that it has a property of being separated from the support together with the thermal transfer layer and the light-to-heat conversion layer at a thickness of not less than μm and not more than 20 μm, and has a property of not being separated from the heat transfer layer and the light-to-heat conversion layer.

Further, the method for forming a thermal transfer image according to the present invention comprises:
The first or second thermal transfer recording material is exposed to high-intensity light from the release support side, and the release support is peeled off, and at the same time, the exposed portion of the thermal transfer layer is removed from the support side.

[0012]

According to the present invention, a thermal transfer recording material having a thermal transfer layer, a light-to-heat conversion layer and a release support on a support in this order or a thermal transfer recording material having a thermal transfer layer, a release support and a light-to-heat conversion layer on a support in this order. Because of this, exposure was performed from the side of the peeling support, so that a thick-film support could be used, the adhesion was improved, the image quality was improved, and the dimensional deviation was further improved. Further, by using the thermal transfer recording material of the present invention, positive recording was made possible.

[0013]

The present invention will be described below in detail. (Thermal Transfer Recording Material) The first embodiment of the thermal transfer recording material of the present invention has a layer structure having a thermal transfer layer 2, a light-to-heat conversion layer 3, and a release support 4 on a support 1 in this order as shown in FIG. In the second embodiment, as shown in FIG. 2, a thermal transfer layer 2 is provided on a support 1.
It has a release support 4 and a light-to-heat conversion layer 3 in this order. Further, in the first embodiment, the thermal transfer layer 2 and the light-to-heat conversion layer 3 may be the same layer, and a release layer 5 is provided between the support 1 and the thermal transfer layer 2. Layer 5
It is preferable to have a thermal softening layer between the thermal transfer layer 2 and the light-to-heat conversion layer 3, and an intermediate layer between the thermal transfer layer 2 and the light-to-heat conversion layer 3.

Further, in the second embodiment, the support 1
Having a release layer 5 between the heat transfer layer 2 and the heat transfer layer 2, having a heat softening layer between the support 1 and the release layer 5, and having an intermediate layer between the heat transfer layer 2 and the release support 4. , Light-to-heat conversion layer 3
It is preferable to have a heat insulating layer on the surface.

As the support, synthetic paper (Yupo (manufactured by Oji Yuka), peach coat (manufactured by Nisshinbo), etc.), high-quality paper, art paper, coated paper, cast coated paper, resin coated paper, synthetic resin impregnated resin Paper, latex impregnated paper, etc., polyester, polyamide, polyimide, polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyacrylate, polyolefin, polycarbonate, polystyrene, phenolic resin, cellulose triacetate, etc. Various plastic films or sheets, glass, metals (aluminum, stainless steel, etc.) are used.

The thickness of the support is preferably large from the viewpoint of improving the adhesion between the original and the thermal transfer recording material.
It is not less than 0 μm and not more than 500 μm.

These plastic films or sheets may contain a pigment or air for coloring or for increasing the bending strength of the film or sheet. Examples of pigments include alkaline earth metal carbonates, Ti
O ₂ , MgO, ZnO, alumina, silica, carbon black and the like can be mentioned.

The thermal transfer layer used in the present invention may be either a fusion transfer layer or a sublimation transfer layer. The melt transfer layer only needs to have a property of being melted by heat and exhibiting adhesiveness to the light-to-heat conversion layer, and is composed of a dye, a pigment, a wax, a thermoplastic resin, an additive, and the like.

Dyes and pigments include alkaline earth metal carbonates, TiO ₂ , MgO, ZnO, alumina, silica, carbon black, nigrosine dye, Sudan black SM, Fast Yellow G, Benzidine Yellow, Pigment Yellow , Oil Yellow GG, Zapon First Yellow CGG, Sumiplast Yellow GG, India First Orange, Sumiplast Orange G, Pigment Orange R, Zapon Fast Orange GG, Irgazine Red, Paranitroaniline Red, Toluidine Red, Lisor Red 2G, Lake Red O,
Oil scarlet, Zapon first scarlet O
G, Eisen Spiron Red BEH, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Fast Gen Blue 5007, Victoria Blue F4
Known dyes and pigments such as R, Sudan Blue, Oil Peacock Blue, Brilliant Green B, and Phthalocyanine Green can all be used.

The waxes include carnauba wax,
Examples include montan wax, beeswax, rice wax, candelilla wax, lanolin wax, paraffin wax, microcrystalline wax, polyethylene wax, sasol wax, oxidized wax, amide wax, and silicone wax.

Examples of the thermoplastic resin include polyamide resin (eg, nylon), polyester resin, poly (meth) acrylate resin (eg, polymethyl methacrylate, polyethyl acrylate), polyurethane resin, polyvinyl chloride resin, and polyvinylidene chloride. Resin, polystyrene resin, polyvinyl acetate resin, polyvinyl chloride-vinyl acetate resin, polystyrene-acryl resin, polyethylene-vinyl acetate resin, polyethylene resin, polypropylene resin, polybutadiene resin, polyvinyl alcohol resin, phenol resin, cellulose resin (methyl cellulose) , Ethyl cellulose, carboxymethyl cellulose, nitrocellulose, acetyl cellulose, etc.), polyvinyl ether resin, polyvinyl pyrrolidone resin, polyvinyl aniline resin, Risaruhon resin, polycarbonate resin, ionomer resin, polysiloxane resin,
Acetal resins (polyvinyl butyral, polyvinyl acetal, polyvinyl formal, etc.), petroleum resins,
Rosin-based resins, cumarone-indene resins, terpene-based resins, styrene-butadiene rubber, isoprene rubber, nitrile rubber, and the like are included.

Examples of additives include various surfactants, higher fatty acids (stearic acid, palmitic acid, lauric acid, etc.), long-chain alcohols (stearyl alcohol, etc.),
Examples include metal salts of long-chain fatty acids (such as calcium stearate and zinc palmitate), antioxidants, various plasticizers, and silicone oil.

The sublimation transfer layer comprises a sublimation dye, a binder,
It is composed of additives and the like. The sublimable dye may include any of a yellow dye, a magenta dye, and a cyan dye, and may be one or two depending on the color tone of an image to be formed.
More than one species can be used in combination.

The yellow dyes include: Kayaset Yellow AG, Kayaset Yellow 963, MS Yellow V
P, MS Yellow VPH, MS Yellow HSO-24
6, Macrolex Yellow 6G, Foram Brilliant Yellow S-6GL, SYS-1, JP-A-59-78896
No. 60-27594, No. 60-31560, No. 60-53565, No. 61
Dyes such as methine dyes, quinophthalone dyes, and azo dyes described in JP-A-12394 and JP-A-63-122594, and examples of the magenta dye include: Kayaset Red TD
-FB, MS Magenta VP, MS Magenta HM-145
0, MS magenta HSO-147, MS magenta HM-
1450, MS Red G, Macrolex Red Violet R, Kayaset Red 130, SMS-2, SM
S-3, SMS-4, JP-A-60-30392, JP-A-60-30394
No. 60-253595, No. 61-262190, No. 63-5992,
Anthraquinone dyes, azomethine dyes, azo dyes and the like described in JP-A-63-205288, JP-A-64-159, JP-A-64-63194 and the like, and cyan dyes include:
Kaya Set Blue 714, Kaya Set Blue FR, Kaya Set Blue 136, Kaya Set Blue 814, Kaya Set T Blue 776, MS Cyan VPG, MS Cyan H
M-1238, MS Cyan HSO-144, MS Cyan HSO-16, Ceres Blue, SCM-1, JP-A-59-7
8896, 59-227948, 60-24996, 60-53563
No. 60-130735, No. 60-131292, No. 60-239289
Nos. 61-19396, 61-22993, 61-31292, 61
-31467, 61-35994, 61-49893, 61-148269
No. 62-191191, No. 63-91288, No. 63-91287, No.
Examples include naphthoquinone-based dyes, anthraquinone-based dyes, and azomethine-based dyes described in each publication such as 63-290793.

Examples of the binder include a thermoplastic resin, a melamine resin, an epoxy resin, a polyphenylene oxide resin, and a polyarylate resin used in the above-mentioned melt transfer layer.

The light-to-heat conversion layer is a layer that absorbs light irradiated in an image form and raises the temperature. It is preferable to add a pigment or a dye to this layer in order to effectively use the energy of high illuminance light such as laser light or flash light. Any pigment or dye used for this purpose can be used as long as it converts a pattern of high illuminance light into a heat pattern.

When flash light is used for exposure, a pigment having a wide absorption range is preferred. In particular, carbon black, carbon graphite, phthalocyanine pigments, iron powder, graphite powder, iron oxide powder, lead oxide, pigments having absorption in the visible and near infrared regions such as blackened silver are preferred, and carbon black is particularly preferably used. .

When a laser is used for exposure, dyes and pigments having a laser emission wavelength can be used. When using a laser that does not have a light-emitting region in the visible region, such as an infrared semiconductor laser, it is not necessary to use a dye or pigment that has absorption in the visible region. Can be used. Needless to say, dyes and pigments which are preferable when the flash light is used are also suitably used.

The light-to-heat conversion layer is prepared by dissolving or dispersing the above dye and pigment in a suitable binder to prepare a coating solution, and applying the coating solution on the above-mentioned heat transfer layer or the release support by a coating means such as a wire bar. It is formed.

The intermediate layer dissolves or melts the resin material,
It may be provided by coating, or may be used by laminating a film previously formed by an extrusion method, a casting method, or the like. The intermediate layer preferably has a lower light-to-heat conversion material content than the light-to-heat conversion layer, and has a lower thermoplasticity or thermal fusibility than the heat transfer layer. The resin suitable for the intermediate layer is not particularly limited as long as it has the above characteristics. The thickness of the intermediate layer is not particularly limited, but is preferably
0.5 to 5 μm.

In the thermal transfer recording material of the first embodiment, when the thermal transfer layer and the light-to-heat conversion layer are formed in the same layer, the above-mentioned light-to-heat conversion material, thermoplastic resin (binder) or the like is used to perform the heat transfer and light-to-heat conversion. What is necessary is just to form the layer which has both properties.

The peeling support in the present invention has a property of peeling off from the support for recording together with the thermal transfer layer, and has a property of not peeling off from the thermal transfer layer. The release support is composed of a synthetic resin layer or a synthetic resin film.

The thickness of the release support is 1 μm or more and 20 μm or less. When this thickness is less than 1 μm,
If the physical strength is not sufficient, peeling may not be performed well. If it exceeds 20 μm, loss of applied energy, light diffusion, etc. may occur, which may undesirably lower print quality.

The release support is made of a composition containing a resin and a filler, or a composition further containing a solvent, by a known means,
For example, melt extrusion method (T die, inflation method),
It is obtained by a coating method or based on a laminating method.

Examples of the above resin include polyolefin resins such as polyethylene and polypropylene, polyvinyl alcohol, polycarbonate, polyamide resins, polyamideimide, polyester resins, polysulfone resins, polyimide resins, nitrocellulose, cellulose diacetate, cellulose Suitable examples include cellulose resins such as triacetate, polyethylene phthalate, polyethylene naphthalate, polybutylene naphthalate, polyphenylene sulfide, polyphenylene oxide, polyparabanic acid, phosphazene resin, polyvinylidene chloride, and polyether ether ketone.

When a synthetic resin film is used, the film may be subjected to a stretching treatment or a film subjected to a corona discharge or other known surface treatment.

Further, when a synthetic resin film containing ferromagnetic powder is used as a filler, an anisotropy can be given to the thermal conductivity of the film by applying a strong magnetic field vertically to the film at the time of film formation. .

In forming the synthetic resin film, the mixing of the synthetic resin and the filler can be performed using, for example, a Banbury mixer, a mixing roll, an extruder, or the like.

When the above-mentioned peeling support is used for the thermal transfer recording material of the first embodiment, a light-transmitting one is used, but in the case of the second embodiment, it is not necessary to be light-transmitting.

The release layer preferably formed between the support and the thermal transfer layer is prepared by combining waxes, thermoplastic resins and additives used for the thermal transfer layer. It may be a layer which itself can be cohesively broken by melting or softening upon heating, or a resin which has a relatively low adhesive strength in combination with another resin, for example, a silicon resin, a fluorine resin ( Teflon, fluorine-containing acrylic resin, etc.), polysiloxane resin, acetal resin (polyvinyl butyral, polyvinyl acetal, polyvinyl formal, etc.), ethylene resin (ethylene vinyl acetate resin, ethylene acrylate resin, ethylene acrylate resin, ionomer resin) ) May be used.

However, in the case of the latter layer structure made of a resin that does not easily show an adhesive force, the material of the release layer greatly changes depending on the composition of the layer adjacent thereto, and the above example is merely an example. . This release layer is preferably heat-softening.

Alternatively, a heat softening layer may be separately provided between the support and the release layer. The release layer or the heat-softening layer having a heat-softening property is made of a thermoplastic resin, and has a property of softening at a temperature during thermal transfer. The thermoplastic resin preferably has a softening point of -30 to 150 ° C. The softening point temperature shown here is the VICAT softening point or a value indicated by the ring and ball method. Specifically, polyolefins such as polyethylene and polypropylene: ethylene and vinyl acetate, ethylene and acrylate, ethylene copolymer such as ethylene and acrylic acid: polyvinyl chloride: vinyl chloride and vinyl chloride copolymer such as vinyl acetate : Polyvinylidene chloride: Vinylidene chloride copolymer: Polystyrene: Styrene copolymer such as styrene and maleic anhydride: Acrylate ester copolymer such as acrylate and vinyl acetate: Polymethacrylate: methyl methacrylate And vinyl acetate, methacrylate copolymers such as methyl methacrylate and acrylic acid: polyvinyl acetate: vinyl acetate copolymer: vinyl butyral resin: polyamides such as nylon, copolymerized nylon, N-alkoxymethylated nylon Resin: Synthetic resin : Petroleum resin: chlorinated rubber: Polyethylene glycol: polyvinyl alcohol hydrogel Gin phthalate: cellulose derivatives, cellulose acetate phthalate, cellulose acetate succinate: Shellac: can be mentioned wax.
The heat-softening layer can be provided on the support by using a known method, and the thickness of the heat-softening layer is suitably in the range of 1 to 50 µm, and particularly preferably in the range of 5 to 30 µm.

In the present invention, the preferably formed heat insulating layer means a layer for preventing heat conduction from an original image. For example, a resin having a low heat conductivity such as a resin is used, and the structure of the heat insulating layer is formed in a space. Are preferred. More preferably, at the contact surface between the heat insulating layer and the original image, the original image is partially held by the material forming the heat insulating layer, and the other portions are in contact with air.

The heat insulating layer can be provided by any method. For example, when the heat-insulating layer is provided by coating, the heat-insulating layer coating solution may be any as long as it does not substantially adversely affect the light-to-heat conversion layer physically or chemically.

According to a preferred embodiment of the present invention, the heat insulating layer is a layer that is mechanically matted or a resin layer containing a matting agent.

As a method of mechanically matting the surface of the heat insulating layer, there are a method of applying the heat insulating layer so as to obtain a coating layer having an uneven pattern, and a method of mechanically roughening the surface to form a heat insulating layer. .

Specific examples of the method include a method in which a heat insulating layer is coated with a gravure roll having a concavo-convex pattern, and a method in which resin particles are sprayed and thermally fused to obtain a concavo-convex pattern. As a specific example, there is a method of forming a mat by providing a heat insulating layer and then pressurizing with a pressure roller having an uneven surface having a hardness higher than the hardness of the heat insulating layer. Alternatively, the release support or the light-to-heat conversion layer itself may be formed into a mat by applying pressure.

The thickness of the heat insulating layer is preferably 2 to 30 μm. When the heat insulating layer is thinner than 2 μm, the heat insulating effect is not sufficient. If the thickness of the heat insulating layer is greater than 30 μm, the adhesion to the original image is incomplete and a clear image cannot be obtained.

When a matting agent is used, the particle size of the matting agent is suitably in the range of 2 to 30 μm, and particularly preferably in the range of 4 to 20 μm, because of the above-mentioned disadvantages.

According to a preferred embodiment of the present invention, the surface roughness of the heat insulating layer is 0.3 to 2.0 μm in center line average roughness.
It is. When the center line average surface roughness is smaller than 0.3 μm, the heat insulating effect is small. If it is larger than 2.0μm,
A clear image may not be obtained due to incomplete adhesion to the original image. (Method of Forming Thermal Transfer Image) Next, a method of forming a thermal transfer image according to the present invention will be described. First, imagewise exposure is performed from the side of the peeling support of the thermal transfer recording material.

As a light source for exposure, a xenon lamp, a halogen lamp, a tungsten lamp, a laser, an LE
D, CRT, etc., and any light source having a high light intensity can be used without being limited by the emission wavelength. A flash light source or a laser light source is preferably used as a light source. As a flash light source, emission half width is
A xenon flash having an emission intensity of 10 W / cm ² or more for 10 ms or less is preferable. 50mW output power as a suitable laser light source
The above-mentioned argon laser, helium neon laser, semiconductor laser and the like can be mentioned.

The exposure method using such a light source includes contact exposure and scanning exposure.

In the case of contact exposure, the original transmission original and the recording material are brought into close contact with each other, and the exposure is performed with the high illuminance light from the transmission original side. The exposure time in this case is preferably 10 ms or less. If the exposure time is longer than 10 ms, the image quality deteriorates due to the diffusion of the thermal pattern. When a transparent original recorded on a photographic negative film is used, the emulsion layer side, that is, the recording layer side is brought into close contact with a release support or a heat insulating layer.

In the case of the scanning exposure method, a cylindrical scanning optical system or a plane scanning optical system is used as a recording optical system. Among them, the cylindrical outer surface scanning optical system is most preferable because the loss of the light source is small and the beam can be narrowed down easily.

Next, after the exposure, the release support is peeled off, and at the same time, the exposed portion of the thermal transfer layer is removed from the support side to form a thermal transfer image.

The present invention may include a step of transferring the image formed on the support to the final support, in which case a printing plate or the like can be formed. Here, the final support is preferably a material that can be set in a normal lithographic printing machine and can withstand a load applied during printing, such as a metal plate of aluminum, zinc, copper, steel, and chromium, zinc. Metal plate, paper, plastic film and glass plate, resin-coated paper, paper with metal foil such as aluminum, plastic film subjected to hydrophilization, etc., plated or vapor-deposited with copper, nickel, aluminum and iron Can be Of these, an aluminum plate is preferable. When an aluminum plate is used, graining treatment such as graining treatment and anodic oxidation treatment may be performed. The thickness of the final support is preferably from 50 to 400 µm, more preferably from 100 to 300 µm.

[0057]

According to the present invention, since the exposure is performed from the side of the release support having a thickness of 1 to 20 μm, the thickness is 30 to 500 μm.
It is possible to use a support having a thick film, thereby improving the adhesion to the document, improving the image quality, and improving the dimensional deviation. Further, by using the thermal transfer recording material of the present invention, positive recording was made possible.

By providing a release layer between the support and the thermal transfer layer, the exposed portion of the thermal transfer layer can be easily removed from the support side, and furthermore, the heat softening between the support and the release layer can be achieved. By having a layer, transfer to the final support is further facilitated. Further, by having the heat insulating layer, the occurrence of heat fogging due to uneven exposure can be further prevented, and the resolution of an image is improved.

[0059]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples of the present invention, but the present invention is not limited to these examples. In the following, "parts" means parts by weight unless otherwise specified.

Example 1 A coating liquid for a release layer having the following composition was applied on a 100 μm-thick polyethylene terephthalate using a wire bar so that the weight after drying was 10 mg / dm ² .

<Releasing layer composition> Paraffin wax emulsion 50 parts Low molecular weight polyethylene resin 50 parts On this releasing layer, a light-to-heat conversion heat transfer layer having the following composition (a layer in which the light-to-heat conversion layer and the heat transfer layer are integrated) is provided. Provided.

<Composition of light-to-heat conversion thermal transfer layer> Carbon black aqueous dispersion (solid content: 50%) 20 parts Paraffin wax emulsion 20 parts Ethylene vinyl acetate copolymer emulsion 20 parts A polycarbonate film was laminated (coating method) as a release support.

A positive transmissive original is overlaid on the separation support side of the recording material, adhered in vacuum, and a xenon flash light source FX-
Using a 180 (manufactured by Riso Kagaku Kogyo Co., Ltd.), exposure was performed from the original side with an energy of 0.3 J / cm ² .

Next, when the release support was peeled off, the exposed portion of the photothermal conversion thermal transfer layer was removed simultaneously with the release support, leaving a positive image with good image quality on the support side.

Example 2 A 25 μm-thick ethylene vinyl acetate copolymer resin layer (EVAFLEX F-1405 manufactured by Du Pont-Mitsui Polychemicals, a vinyl acetate content of 14%, a VICAT softening point of 68 ° C.) on a 100 μm-thick polyethylene terephthalate film ) Was provided by extrusion lamination. On this release layer, a thermal transfer layer was provided so as to have a dry film thickness of 20 mg / dm ² from a dispersion having the following composition.

<Thermal transfer layer composition> The following pigment 10 parts Stearyl acrylate / methacrylic acid copolymer 20 parts Paraffin wax 10 parts Isopar G 200 parts (Pigment) Cyan pigment Cyanine Blue 4920 (manufactured by Dainichi Seika) Yellow pigment Seika First Yellow 2400 (manufactured by Dainichi Seika) Magenta pigment Seika Fast Carmine 1483 (manufactured by Dainichi Seika) Black pigment Carbon black MA-100 (manufactured by Mitsubishi Kasei) On the other hand, using a dispersion of the following composition on a polypropylene film 8 μm thick, A light-to-heat conversion layer was provided so as to have a thickness of 15 mg / dm ² .

<Light-to-heat conversion layer composition> Carbon black 50% aqueous dispersion 20 parts Polyvinyl alcohol 20% aqueous solution 100 parts Glyoxal 4 parts Water 50 parts

The heat transfer layer side of the polyethylene terephthalate film and the light-heat conversion layer side of the polypropylene film are brought into close contact with each other, and the distance between a pair of nip rolls heated to 50 ° C.
The polypropylene film was passed through at a speed of 50 cm / min under a pressurized condition of kg / cm ² , and the polypropylene film was laminated on a polyethylene terephthalate film to prepare a recording material of the present invention.

The recording material of the present invention thus obtained was brought into close contact with the emulsion surface of a positive transmission original of a silver halide film having been subjected to YMCK four-color separation on the polypropylene film side, and was adhered in a vacuum to obtain a xenon flash light source FX-180 (Ride Kagaku). (Manufactured by the company) with an energy of 0.3 J / cm ² from the original side.

Next, when the polypropylene film was peeled off, the exposed portion of the heat transfer layer was removed simultaneously with the polypropylene film, and a positive image was formed on the polyethylene terephthalate film side.

Further, the image side of the polyethylene terephthalate film on which the positive image was formed was brought into close contact with the art paper,
It passed between a pair of nip rolls heated to 90 ° C. at a speed of 50 cm / min under a pressure of 5 kg / cm ² . The image on the polyethylene terephthalate film was transferred to art paper.

By repeating such an operation for four colors of YMCK, a full-color image could be formed on art paper.

Example 3 A 25 μm thick ionomer resin film (Himilan 1707, VICAT softening point 59, manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.) was placed on a 100 μm thick polyethylene terephthalate film.
C) was provided as a release layer by dry lamination. Using a dispersion having the following composition on this release layer, a dry film thickness of 20 mg / d
The light-to-heat conversion thermal transfer layer was provided so as to have an area of m ² .

<Composition of photothermal conversion thermal transfer layer> Carbon black (MA-100: manufactured by Mitsubishi Kasei) 10 parts Stearyl acrylate / methacrylic acid copolymer 20 parts Paraffin wax 10 parts Isopar G 200 parts The above photothermal conversion thermal transfer layer and thickness A 6 μm polypropylene film is closely adhered and passed between a pair of nip rolls heated to 50 ° C. at a pressure of 5 kg / cm ² at a speed of 50 cm / min, and the polypropylene film is laminated on a polyethylene terephthalate film. A thermal transfer recording material of the invention was prepared.

The thus-obtained thermal transfer recording material of the present invention was brought into close contact with the emulsion side of a silver halide film positive transmission original on the polypropylene film side of the heat-transfer recording material, and was vacuum-adhered to the xenon flash light source FX-180 (Riso Kagaku). Used, 0.3
The exposure was performed from the original side with an energy of J / cm ² . Next, when the polypropylene film is peeled off, the light-to-heat conversion layer of the exposed portion is removed simultaneously with the polypropylene film,
A positive image was formed on the polyethylene terephthalate film side.

Further, the image side of the polyethylene terephthalate film on which the positive image was formed and the grain side of a 0.24 mm thick aluminum plate subjected to graining and hydrophilization were brought into close contact with each other, and the distance between a pair of nip rolls heated to 90 ° C. was 5 kg. It passed at a speed of 30 cm / min under a pressure condition of / cm ² . The image on the polyethylene terephthalate film was transferred to an aluminum plate.

The obtained aluminum plate could be printed on an offset printing machine as a lithographic printing plate.

Example 4 In Examples 1 to 3, a coating solution of a heat insulating layer having the following composition was applied on a release support so that the weight after drying was 5 mg / dm ^2, and an image was formed in the same manner. However, a better image having excellent resolving power was formed.

<Insulating layer coating liquid> 12.5% aqueous dispersion of polymethyl methacrylate particles (average particle diameter 10 μm) 1 part 5% aqueous polyvinyl alcohol solution 10 parts Water 10 parts

Example 5 In Example 1, a heat-softening layer having the following composition was provided between the support and the release layer so as to have a dry film thickness of 20 mg / dm ² , and an image was formed in the same manner. A good image is formed,
Further, the image side on the formed polyethylene terephthalate film and the art paper were brought into close contact with each other, and a pair of nip rolls heated to 90 ° C. were pressed at a pressure of 5 kg / cm ^{2 at} a pressure of 50 cm / cm ^2.
Minutes passed through. The image on the polyethylene terephthalate film was transferred to art paper.

<Thermo-softening layer composition> Ethylene ethyl acrylate copolymer resin (EVAFLEX-EEA A-709 EA content 35% VICAT softening point 23 ° C or less: manufactured by Mitsui Dupont Polychemical Co., Ltd.) 10 parts THF 20 parts

Example 6 In Example 2, an intermediate layer having the following composition was provided between the thermal transfer layer and the light-to-heat conversion layer so as to have a dry weight of 5 mg / dm ² , and an image was formed in the same manner. A clear image with no image was obtained.

<Intermediate layer composition> Polyester resin (Vylon 200: manufactured by Toyobo) 10 parts Cyclohexanone 90 parts

Example 7 A release layer coating solution having the following composition was coated on a 100 μm-thick polyethylene terephthalate film using a wire bar so that the weight after drying was 10 mg / dm ² .

Paraffin wax emulsion 50 parts Low molecular weight polyethylene resin 50 parts A dispersion having the following composition having a weight of 20
The thermal transfer layer was provided by coating so as to be mg / dm ² .

Aqueous dispersion of cyan pigment (50% solid content) 20 parts Paraffin wax emulsion 20 parts Ethylene vinyl acetate copolymer emulsion 20 parts An 8 μm thick polycarbonate film was laminated (melt extrusion method) on this thermal transfer layer. . Next, a coating solution having the following composition was applied on a polycarbonate film using a wire bar so that the weight after drying was 10 mg / dm ² , to form a light-to-heat conversion layer.

Carbon black methyl ethyl ketone dispersion (solid content: 40%) 50 parts Polyester resin 50 parts A negative transmission original is overlaid on the light-to-heat conversion layer side of this recording material, adhered in vacuum, and a xenon flash light source FX-180 (Riso Kagaku Kogyo Co., Ltd.) Was exposed from the original side at an energy of 0.3 J / cm ² .

Next, when the release support was peeled off, the exposed portion of the thermal transfer layer was removed simultaneously with the release support, leaving a positive image on the support side.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a first embodiment of the thermal transfer recording material of the present invention.

FIG. 2 is a sectional view showing a second embodiment of the thermal transfer recording material of the present invention.

[Explanation of symbols]

 1: Support 2: Thermal transfer layer 3: Light-to-heat conversion layer 4: Release support 5: Release layer

Continuation of the front page (56) References JP-A-63-104881 (JP, A) JP-A-1-99877 (JP, A) JP-A-60-225793 (JP, A) JP-A-1-158432 (JP) JP-A-61-189535 (JP, A) JP-A-48-48137 (JP, A) JP-A-56-77194 (JP, A) JP-A-49-98225 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (3)

(57) [Claims] 1. A thermal transfer recording material comprising a support having a thickness of 30 μm or more and 500 μm or less, a thermal transfer layer, a light-to-heat conversion layer, and a release support laminated in this order by a melt extrusion method or a coating method. The thermal transfer recording wherein the support has a thickness of 1 μm or more and 20 μm or less and has a property of peeling off from the support together with the heat transfer layer and the light-to-heat conversion layer, and a property of not being peeled off from the heat transfer layer and the light-to-heat conversion layer. material. 2. A thermal transfer recording material comprising a thermal transfer layer, a peeling support and a light-to-heat conversion layer laminated in this order on a support having a thickness of 30 μm or more and 500 μm or less by a melt extrusion method or a coating method. The thermal transfer recording, wherein the support has a thickness of 1 μm or more and 20 μm or less and has a property of peeling off from the support together with the thermal transfer layer and the light-to-heat conversion layer, and a property of not peeling off from the heat transfer layer and the light-to-heat conversion layer. material. 3. Exposing the thermal transfer recording material according to claim 1 or 2 with high illuminance light from the side of the release support, removing the release support and simultaneously removing the exposed portion of the thermal transfer layer from the support side. A method for forming a thermal transfer image.