JPH05262039A - Laser thermal transfer recording medium - Google Patents

Abstract

PURPOSE:To obtain a laser thermal transfer recording medium capable of obtaining a uniform transfer image by low energy and having a wide color reproducing region. CONSTITUTION:In a laser thermal transfer recording medium wherein a light reflecting layer and an ink layer containing a photothermal conversion material are laminated on a support, an image receiving material transparent or pervious to light having the wavelength of laser beam to be used is superposed on the surface of the ink layer of the recording medium or arranged so as to be extremely close thereto and, in this state, the recording medium is irradiated with laser beam through the image receiving material to obtain a uniform transfer image by a low energy.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method for forming an image using a laser, and more particularly to a thermal transfer recording method using a laser.

[0002]

2. Description of the Related Art Conventionally, for thermal transfer recording, a thermal transfer ink sheet having a heat-fusible coloring material layer or a coloring material layer containing a heat sublimable dye provided on a substrate and a recording medium are opposed to each other to form a thermal head. There is a method in which a heat source controlled by an electric signal such as an energizing head is pressure-bonded from the ink sheet side to transfer and record an image.

Thermal transfer recording has features such as noise-free, maintenance-free, low cost, easy colorization and digital recording, and is used in various fields such as various printers, recorders, facsimiles and computer terminals. There is.

On the other hand, in recent years, there has been a demand for a recording method having a high resolution, capable of high-speed recording, and capable of image processing, that is, so-called digital recording, in the medical and printing fields.

However, in the conventional thermal transfer recording method using a thermal head or a current-carrying head as a heat source, it is difficult to increase the density in terms of the life of the head heating element. In order to solve this, thermal transfer recording using a laser as a heat source is disclosed in JP-A-49-15437, 49-17743, 57-87399 and 59-143659.
It has been proposed in the issue.

In thermal transfer recording using a laser as a heat source, the resolution can be increased by narrowing the laser spot. However, in the case of recording with a laser, scanning recording is generally performed, and in scanning recording, the recording speed is slower than the batch exposure using a mask material and the recording method using a line head in terms of recording speed. There is a drawback.
In order to increase the recording speed, it is necessary to increase the scanning speed of the laser. For that purpose, a high-power laser is used or an ink sheet that requires less energy for thermal transfer is required. Water cooled YA for high power laser
Although there are G lasers, water-cooled Ar lasers, etc., all of them are water-cooled lasers, so that equipment for circulating water is required and the size of the device becomes large, so that the places and conditions of use are limited. Therefore, there is a need for a high-sensitivity laser thermal transfer recording material capable of high-speed recording by using an air-cooled laser or a semiconductor laser, which has few restrictions on use conditions.

As a method for increasing the sensitivity of a laser thermal transfer recording medium, a photothermal conversion material is introduced into the ink layer so that the heat generating portion and the ink layer are made the same layer. To further reduce the energy required for transfer, it is conceivable to reduce the thickness of the ink layer, but in heat mode recording by laser irradiation, reducing the thickness of the ink layer reduces the photothermal conversion substance. This means that the absorption efficiency decreases and the sensitivity does not increase so much. It is possible to increase the proportion of the photothermal conversion substance in order to increase the absorption efficiency, but there is an upper limit of addition to the binder for forming the layer. That is, in the sublimation type laser thermal transfer recording medium, when the proportion of the dye is lowered, the sensitivity is lowered, and when the proportion of the binder is lowered, the storability is deteriorated, so that the addition amount of the photothermal conversion material is limited.

In the melting type laser thermal transfer recording medium, since the ink layer is wholly transferred together with the binder, when a color image is to be obtained, a colorless photothermal conversion substance is introduced or a non-transferable photothermal conversion layer and an ink layer are used. It must be stratified. However, since a completely colorless infrared absorbing agent is not known, there is a limit to the amount of the infrared absorbing agent that can be introduced into the ink layer, and the sensitivity is generally lowered when two layers are formed. Further, in the case of fusion type thermal transfer recording, when the laser irradiation from the image receiving side is carried out, the temperature near the interface between the ink layer and the image receiving layer rises most, which is advantageous in terms of transfer efficiency. However, since the laser beam has an intensity distribution and the temperature at the center is higher than that at the periphery, the temperature at the center of the beam spot becomes too high and melts and flows out,
There was a problem that the transferability of the central part deteriorates.

[0009]

SUMMARY OF THE INVENTION The object of the present invention was made in view of the above problems, and is used for laser recording capable of transferring with low energy, having a wide color reproduction range, and capable of obtaining a uniform transferred image. It is intended to provide a laser thermal transfer recording medium.

[0010]

As a result of studies conducted to achieve the above object of the present invention, a laser thermal transfer recording medium having a light reflecting layer and an ink layer containing a photothermal conversion material laminated on a support is used. By irradiating a laser beam through the image receptor with the surface provided with the ink layer and the image receptor transparent or transmitting the light of the wavelength of the laser beam to be used are superposed or arranged in the immediate vicinity. It was found that a uniform transferred image can be obtained with low energy.
Further, by providing the light reflecting layer, it becomes possible to reduce the addition amount of the photothermal conversion agent, and the color reproduction range in the fusion type thermal transfer is widened.

The present invention will be described in detail below. The laser used in the present invention is generally known solid laser such as ruby laser, YAG laser, glass laser, He-Ne laser, He-Xe laser, ion laser, nitrogen laser, carbon dioxide laser, carbon monoxide. Laser, other discharge-excited molecular laser, gas laser such as excimer laser, chemical laser, dye laser, semiconductor laser and the like can be used. In particular, when used for thermal transfer recording, one that oscillates infrared rays having a wavelength in the range of 0.7 to 30 μm is preferable. Solid-state lasers such as YAG laser (1.06 μm), Nd glass laser (1.06 μm), and He-Ne laser (1.15 μm, 3.39 μ) that emit infrared light
m), hydrogen / fluorine laser (2.6-3.0 μm), carbon dioxide laser (9-11 μm), carbon monoxide laser (5.0 μm)
m) gas laser, dye laser (~ 1 μm), In
GaP laser (0.65-1.0 μm), AlGaAs laser (0.7-1.0 μm), GaAsP laser (0.7-1.0 μm)
m), InGaAs laser (1.0 to 3.5 μm), InAs
P laser (1.0 to 3.5 μm), InAsSb laser (3.1 to 5.4 μm), PbCdS laser (2.5 to 4.0 μm)
m), PbSSe laser (4.0-8.5 μm), PbSnT
e laser (6.3-32 μm), PbSnSe laser (8.
5 to 34 μm), CdSnP ₂ laser (1.01 μm), GaS
b laser (1.53μm), Cd ₃ P ₂ laser (2.12μ
m), InAs laser (3.1 μm), Te laser (3.7
μm), (Hg, Cd) Te laser (3.9 to 4.1 μm),
PbS laser (4.3μm), InSb laser (5.2μ
m), PbTe laser (6.5 μm), PbSe laser (8.5 μm), or other semiconductor laser. In particular, a semiconductor laser is preferable because it is small and lightweight, has low power consumption, and can directly perform high-speed modulation. To use these as a laser light source, laser light may be condensed by a lens or the like so as to have a required recording diameter.

The laser irradiation is preferably carried out via an image receptor. By performing laser irradiation through the image receptor, in the case of an ink layer containing a colorant and a photothermal conversion agent, the temperature rise near the interface between the ink layer and the image receiving layer is maximized, which is advantageous for transfer. Further, even with an ink layer composed of two layers, a colorant layer and a photothermal conversion layer, the temperature rise near the interface between the ink layer and the photothermal conversion layer is maximum, and it is more advantageous to irradiate the laser from the laser thermal transfer recording medium side. ..

The layer structure of the fusion type laser thermal transfer recording medium of the present invention is basically composed of a light reflecting layer for reflecting a laser beam used for recording on a support and an ink layer capable of absorbing the laser beam and converting it into heat. Are laminated. Furthermore, the ink layer is a layer containing a photothermal conversion agent and a coloring material, or a layer containing a photothermal conversion agent (hereinafter referred to as a photothermal conversion layer) and a layer containing a coloring material (hereinafter referred to as a coloring material layer), or It comprises a thin film adhesive layer and a layer containing a photothermal conversion agent and a coloring material, or a thin film adhesive layer, a coloring material layer and a photothermal conversion layer.

In general, it is more advantageous to increase the sensitivity when the photothermal conversion agent is added to the ink layer and the photothermal conversion layer. However, the photothermal conversion agent often has absorption in the visible region, and when a color image is obtained, it is better to divide the photothermal conversion layer and the colorant layer into color reproducibility. On the other hand, by providing the light reflection layer under the ink layer, the laser light that cannot be completely absorbed by the ink layer is reflected and passes through the ink layer again. Therefore, the optical path length is doubled, and the addition amount of the photothermal conversion agent can be reduced or the film thickness of the photothermal conversion layer can be reduced. This improves color reproducibility and sensitivity. Transferability can be further improved by providing a release layer on the laser thermal transfer recording medium of the present invention. The release layer can be provided between the ink layer and the light reflection layer, between the photothermal conversion layer and the colorant layer, and between the support and the light reflection layer. When it is provided between the support and the light reflecting layer, it is transferred together with the light reflecting layer. By using this as a transmission image, a high-density transmission image can be easily obtained.

Further, the transferability is increased by providing the adhesive layer on the ink layer. The content ratio of the photothermal conversion material and the dye in the ink layer is different when obtaining a color image and when obtaining a monochrome image, but the photothermal conversion agent needs to have absorption in the near infrared region which is the oscillation wavelength of the semiconductor laser, Generally, these materials also have absorption in the visible region. Therefore, in the case of obtaining a color image, it is preferable to select a material having a small absorption in the visible region and reduce the addition amount. However, when the addition amount is small, the absorption efficiency for laser light is low, the content ratio of the photothermal conversion agent and the dye combined with the binder is in the range of 10 to 80% by weight, preferably 20 to 70% by weight. Within the range of.

When the content ratio of the photothermal conversion material and the dye exceeds 80% by weight, the ratio of the binder becomes relatively too small and the function as the binder cannot be sufficiently exhibited. The addition amount of the photothermal conversion agent depends on the thickness of the ink layer, but the transmittance of the ink layer for the light of the wavelength of the light source is in the range of 0 to 20%,
More preferably, it is added within the range of 0 to 5%. If the content of the photothermal conversion material is too low, the absorption efficiency of the laser light is poor and the sensitivity of the laser thermal transfer recording medium becomes low. If the content of the dye in the color image is low, the image reproduction range becomes small.

In the present invention, the thickness of the ink layer is usually
It is in the range of 0.1 to 5 μm, preferably in the range of 0.2 to 2 μm. If the thickness of the ink layer is too thick, the sensitivity will be low, and if it is too thin, the sensitivity will be high but uniform transferability will be difficult to obtain.

Next, materials constituting each layer will be described. Examples of the binder of the colorant layer or the ink layer containing the colorant, the photothermal conversion agent, and the colorant include a heat-meltable substance and / or a thermoplastic resin. Specific examples of the heat-melting substance include plant waxes such as carnauba wax, wood wax, auricury wax and espal wax; animal waxes such as beeswax, insect wax, shellac wax and whale wax; paraffin wax, microcrystal wax, polyethylene. Petroleum waxes such as waxes, ester waxes and acid waxes; and montan wax,
Mention may be made of waxes such as mineral waxes such as ozokerite and ceresin, and in addition to these waxes, higher fatty acids such as palmitic acid, stearic acid, margaric acid and behenic acid; for example palmityl alcohol. , Higher alcohols such as stearyl alcohol, behenyl alcohol, marganyl alcohol, myricyl alcohol and eicosanol; higher fatty acid esters such as cetyl palmitate, myricyl palmitate, cetyl stearate and myricyl stearate;
Examples thereof include amides such as acetamide, propionic amide, palmitic acid amide, stearic acid amide, and amide wax; and higher amines such as stearylamine, behenylamine, and palmitylamine.

Examples of the thermoplastic resin include ethylene copolymers, polyamide resins, polyester resins, polyurethane resins, polyolefin resins, acrylic resins, vinyl chloride resins, polyvinyl alcohol resins, polyvinyl acetal resins. Resins such as resins, cellulosic resins, rosin resins, ionomer resins and petroleum resins; elastomers such as natural rubber, styrene butadiene rubber, isoprene rubber, chloroprene rubber and diene copolymers; ester gum, rosin maleic acid Resins, rosin derivatives such as rosin phenol resins and hydrogenated rosins; and polymer compounds having a softening point of 50 to 150 ° C. such as phenol resins, terpene resins, cyclopentadiene resins and aromatic hydrocarbon resins. Kill.

The heat-meltable substance and the thermoplastic substance are
They can be used in combination with each other, and one kind or two or more kinds can be used from each.

When the heat-melting substance and the thermoplastic substance are appropriately selected, an ink layer having a desired heat softening point or heat melting point can be formed.

As the photothermal conversion material, any conventionally known material can be used. In the preferred embodiment of the present invention, since a semiconductor laser beam is used to generate heat, a near-infrared absorber having an absorption maximum in the wavelength band of 0.7 to 30 μm and no or little absorption in the visible region is preferable when forming a color image. When forming a monochrome image, carbon black or the like having absorption from the visible region to the near infrared region is preferable.

As the near-infrared absorber, cyanine-based, polymethine-based, azurenium-based, squarylium-based, thiopyrylium-based, naphthoquinone-based, anthraquinone-based organic compounds such as dyes, phthalocyanine-based, azo-based, thioamide-based organic metal complexes, etc. And the like are preferably used, and specific examples thereof include the compounds described in JP-A-63-319191 and JP-A-3-103476.

These may be used alone or in combination of two or more.

Examples of the coloring matter include pigments such as inorganic pigments and organic pigments, and dyes (cyan, magenta, yellow, black). As the inorganic pigment, for example, titanium dioxide, zinc oxide, Prussian blue, cadmium sulfide, iron oxide and chromates of lead, zinc, barium and calcium, carbon black and the like can be preferably used.

As the organic pigment, for example, azo-based, thioindigo-based, anthraquinone-based, anthanthrone-based, triphendioxazine-based pigments, vat dye pigments, phthalocyanine pigments such as copper phthalocyanine and its derivatives, and quinacridone pigments are preferably used. Can be used.

Examples of color proofing pigments include Rionol Blue FG-7330 (Toyo Ink Co., Ltd.) and Rionol Red 6BFG-4219X (Toyo Ink Co., Ltd.) Rionol Yellow No. 1206 (Toyo Ink Co., Ltd.) Lionol Yellow No. Pigments such as 1406G (Toyo Ink Co., Ltd.) are used.

The dyes include acid dyes, direct dyes,
Disperse dyes, oil-soluble dyes, metal-containing oil-soluble dyes and the like can be preferably used.

Each of the above-mentioned dyes may be used alone or in combination of two or more.

Further, as a developer which is appropriately used,
Typical examples are clay, oxalic acid, benzoic acid, phenolic resins, bisphenol A, 2,2-bis (4-hydroxyphenyl) heptane, etc. One or more of these may be used in combination with the above dye. it can.

The ink layer contains one or more additives such as surfactants, higher fatty acid derivatives, higher aliphatic alcohols, higher aliphatic ethers and phosphates, organic fillers and inorganic fillers. It may be.

Examples of the light reflection layer used in the present invention include metals and metal oxides, SnO ₂ , Co ₂ O ₃ , CdO,
It is obtained by applying or vapor depositing a light-transmitting semiconductor such as In ₂ O ₃ or the like, titania, a ferrite film or the like. These light-reflecting layers may be layers capable of reflecting the light of the wavelength of the light source, and of these, the metal vapor deposition film is particularly preferable. Preferred metals for the metal vapor deposition film include gold, silver, copper, aluminum, etc. Among these, the aluminum vapor deposition film is preferred.

As a method for forming a metal vapor deposition film, as long as the initial properties of the support are not impaired, the metal vapor deposition film is, for example, a thermal vapor deposition method, a sputtering method, an ion beam vapor deposition method, a plasma CVD method, as long as the heat resistance thereof is allowed. Although various vapor deposition methods such as laser photochemical vapor deposition can be employed, the presently preferred method is the sputtering method. The thickness of the metal vapor deposition film is usually 100 to 10000Å, preferably 500 to 1000.
It is Å. When the film thickness is 100 Å or less, the light reflectance decreases, and the function as a light reflecting layer is lost. On the other hand, 1
If it exceeds 0000Å, the thermal conductivity of the light reflecting layer cannot be ignored and the sensitivity is lowered.

In the case of transferring the light reflecting layer together with the heat-sensitive transfer recording medium of the present invention, it is possible to increase the transmission density of the image by reflection of the light reflecting layer, and the content of the coloring material contained in the ink layer. Since it is possible to obtain a transmission image having a sufficient density even if the amount is small, it is effective for making a mask material and the like.

The release layer is made by combining the waxes, the thermoplastic resin and the additives used in the melt transfer layer. It may be a layer which itself can cohesively break by being melted or softened when heated, or a resin such as a silicone resin, a fluorine resin (for example, a silicone resin, which is relatively difficult to show an adhesive force in combination with other resins). Teflon,
A layer using a polysiloxy acid resin such as a fluorine-based acrylic resin or an acetal resin (for example, polyvinyl butyral, polyvinyl acetal, polyvinyl formal, etc.) may be used. However, in the latter case of a layer structure made of a resin that does not easily exhibit adhesive strength, 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.

The adhesive layer has a softening point (measured by the ring and ball method).
Can be selected from thermoplastic resins having a temperature of 40 to 200 ° C. and can be used alone or in a blend.
Specific examples of these thermoplastic resins include, for example, polyvinyl butyral, polyvinyl formal, polyethylene, polypropylene, polyamide, ethyl cellulose,
Examples thereof include cellulose acetate, polystyrene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, ethylene vinyl acetate copolymer, acrylic resins such as polymethylmethacrylate, rosin derivatives such as polyisobutylene and ester gum.

Further, the support used in the present invention may be any one as long as it has good dimensional stability and can withstand heat during recording. For example, thin paper such as condenser paper or glassine paper, polyethylene terephthalate, polyethylene. A heat resistant plastic film such as naphthalate, polyamide, polyimide, polycarbonate, polysulfone, polyvinyl alcohol cellophane, or polystyrene can be used. The thickness of the support is usually preferably 2 to 100 μm. The shape of the support is not particularly limited, and may be any shape such as a wide sheet or film, a narrow tape or a card. A backing layer may be provided on the back surface of the support (on the side opposite to the adhesive layer) for the purpose of imparting properties such as running stability, heat resistance, and antistatic properties.

The thickness of this backing layer is usually 0.1-1.
μm.

In order to produce the melt type laser thermal transfer recording medium of the present invention, the various components forming the ink layer are mixed by heat or dispersed or dissolved in a solvent to prepare an ink layer forming coating liquid. Prepare. Then, the ink layer-forming coating liquid is applied to the surface of the support, and the solvent is dried if necessary, whereby the desired laser thermal transfer recording medium can be obtained. The binder is used by dissolving it in one or two or more kinds of solvents or dispersing it in a latex form.

As the solvent of the coating liquid, water, alcohols (eg ethanol, propanol), cellosolves (eg methyl cellosolve, ethyl cellosolve), aromatics (eg toluene, xylene, chlorobenzene),
Examples thereof include ketones (eg acetone, methyl ethyl ketone), ester solvents (eg ethyl acetate, butyl acetate etc.), ethers (eg tetrahydrofuran, dioxane), chlorine solvents (eg chloroform, trichloroethylene) and the like.

For the coating, conventionally known gravure roll coating methods, extrusion coating methods, wire bar coating methods, roll coating methods and the like can be adopted.

The ink layer may be formed as a layer containing a monochromatic dye on the entire surface or a part of the surface of the support, or a yellow ink layer containing a binder and a yellow dye, and a binder. A magenta ink layer containing a magenta dye and a cyan ink layer containing a binder and a cyan dye may be formed on the entire surface or a part of the surface of the support at regular intervals along the plane direction. ..

Further, in addition to the three ink layers arranged in the plane direction, a black ink layer containing a black image forming substance may be interposed.

It should be noted that the thermal transfer recording ink sheet can be conveniently used by forming perforations or providing detection marks for detecting the positions of areas of different hues.

The material to be transferred must be transparent or capable of transmitting the laser light used for recording, and it is desirable that it has further excellent heat resistance and high dimensional stability. Examples of the material include polyethylene, polypropylene, polyethylene terephthalate, polystyrene,
Examples thereof include resin films such as polyvinyl chloride and polyimide. It is also possible to obtain a reflection image by using a recording medium in which a release layer and a transfer layer are laminated on these resin films and retransferring only the transfer layer to another white support after the recording is completed. .. The thickness of these transferred materials is usually 1 μm or more, and more preferably 3 to 500.
The range of 0 μm is preferable. If the thickness is less than 1 μm, the self-supporting property may be lost. The shape of the material to be transferred is appropriately determined according to the application of heat-sensitive recording, and for example, a tape shape or a sheet shape can be adopted.

In order to form an image on a recording medium, the fusion laser thermal transfer recording medium (ink layer side) of the present invention and the recording medium are brought into close contact with each other and a laser is irradiated through the recording medium. When laser irradiation is performed through the image receptor, the photothermal conversion material contained in the ink layer absorbs the laser light to generate heat, but the amount of heat generated in the vicinity of the interface between the ink sheet and the image receptor is maximized, and thus transfer efficiency is improved. Further, since the laser light that could not be absorbed due to the thin ink layer is reflected by the light reflection layer, the same effect as the optical path length of the laser passing through the ink layer is doubled, and the ink to be heated The transfer energy is very small because the volume of the layer is small. In addition, since the light reflecting layer is formed by vapor deposition or coating on a support such as a resin film, it cannot substantially reflect without changing the beam diameter and energy intensity distribution of the laser beam. The energy density of the central portion of the laser beam supplied to the thermal transfer recording medium is lowered, and a transferred image without a void can be obtained.

The layer structure of the sublimation type laser thermal transfer recording medium in the present invention is basically the same as that of the melting type laser thermal transfer recording medium. However, if a sublimable or heat diffusible material is not used as the photothermal conversion agent, the photothermal conversion agent will not be transferred even if it is in the same layer as the sublimation dye. A layer containing and may have higher sensitivity. Further, the sensitivity of the sublimation-type thermal transfer ink sheet greatly depends on the ratio of the sublimable dye to other ink layer constituents. The higher the ratio of the sublimable dye, the higher the sensitivity, and the binder ratio is the storage stability of the ink sheet. The higher the binder ratio, the better the storage stability. Therefore, a smaller amount of the photothermal conversion agent is more advantageous in terms of sensitivity and storability. Providing the light reflecting layer is effective in the above points.

Examples of sublimable dyes include cyan dyes, magenta dyes, and yellow dyes. Examples of the cyan dye include, for example, JP-A-59-78896 and 59-227.
948, 60-24966, 60-53563, 6
0-130735 publication, 60-131292 publication, 60-239289 publication, 61-19396 publication, 61-22993 publication, 61-31292.
No. 61, No. 61-31467, No. 61-35994, No. 61-4
9893 publication, 61-148269 publication, 62-191191 publication,
Examples thereof include naphthoquinone dyes, anthraquinone dyes and azomethine dyes described in JP-A-63-91288, JP-A-63-91287 and JP-A-63-290793. Examples of the magenta dye include JP-A-59-78896, JP-A-60-30392, JP-A-60-30394, JP-A-60-253595, and JP-A-61-262190. Gazette, JP
63-5992, JP 63-205288, JP 64-159
And anthraquinone dyes, azo dyes, azomethine dyes and the like described in Japanese Patent Laid-Open No. 64-63194 and the like. Examples of yellow dyes include JP-A-59
-78896, JP-A-60-27594, JP-A-60-31560
JP-A No. 60-53565, JP-A No. 61-12394, JP-A No. 63-122594, etc. methine dyes, azo dyes, quinophthalone dyes, Examples include anthryothiazole dye. Particularly preferred as the sublimable dye is azomethine obtained by a coupling reaction of a compound having an open-chain or closed active methylene group with an oxidized form of a p-phenylenediamine derivative or an oxidized form of a p-aminophenol derivative. An indoaniline dye obtained by a coupling reaction with a dye and an oxidized form of a phenol or naphthol derivative or a p-phenylenediamine derivative or an oxidized form of a p-aminophenol derivative. The sublimable dye contained in the sublimable dye-containing ink layer may be any of a yellow dye, a magenta dye, and a cyan dye as long as the image to be formed is a single color. Whichever dye compound is used, depending on the color tone of the image to be formed, any two or more of the above three dyes or another sublimable dye may be contained.

The amount of the sublimable dye used is usually 0.1 to ²⁰ g, preferably 0.2 to 5 g, per 1 m ^{2 of} the support. As the binder of the ink layer, for example, a cellulose-based compound such as a cellulose addition compound, a cellulose ester, or a cellulose ether; polyvinyl alcohol, polyvinyl formal, polyvinyl acetoacetal, polyvinyl butyral, a polyvinyl acetal resin, polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl acetate, or the like. Acrylamide, styrene resin, poly (meth) acrylic acid ester, poly (meth) acrylic acid, vinyl resin such as (meth) acrylic acid copolymer, rubber resin, ionomer resin, olefin resin, polyester resin, etc. Is mentioned.

Among these resins, polyvinyl butyral, polyvinyl acetoacetal, and cellulosic resins which are excellent in storage stability are preferable. The various binders may be used alone or in combination of two or more. As the light-heat conversion material, those used in the above-mentioned fusion type laser thermal transfer recording medium are similarly used. However, in the case of sublimation type thermal transfer, it is necessary that the photothermal conversion material has neither sublimation property nor transfer property. Further, various additives can be appropriately added to the ink layer. As the additive, for example, silicone resin, silicone oil (reaction hardening type is also possible), silicone modified resin, fluororesin, surfactant, and peelable compound such as wax, metal fine powder, silica gel, metal oxide, Carbon black, a filler such as resin fine powder, a curing agent capable of reacting with a binder component (for example, a radiation active compound such as isocyanates, acryls and epoxies), and the like can be mentioned.

Further, as an additive, a heat-melting substance for promoting transfer, for example, a compound described in JP-A-59-106997, such as wax or higher fatty acid ester, can be mentioned.

As the support for the sublimation type laser thermal transfer recording medium, the support for the fusion type laser thermal transfer recording medium can be used. As the light reflection layer for the sublimation type laser thermal transfer recording medium, the light reflection layer of the fusion type laser thermal transfer recording medium can be used.

The sublimation type laser thermal transfer recording medium is not limited to the structure described above, and other layers may be formed. For example, an overcoat layer may be provided on the surface of the ink layer in order to prevent fusion with the recording medium and settling (blocking) of the heat diffusing dye. Further, the support may have an undercoat layer for the purpose of improving the adhesiveness with the binder and preventing the transfer of the dye to the support side and the dyeing.
Further, a backing layer may be provided on the back surface of the support (on the side opposite to the ink layer) for the purposes of running stability, dimensional stability, heat resistance, antistatic and the like. The thickness of the overcoat layer, the undercoat layer and the backing layer is usually 0.05 to 1 μm. The sublimation laser thermal transfer recording medium is prepared by preparing an ink layer forming coating liquid by dispersing or dissolving the various components forming the ink layer in a solvent, coating this on the surface of the support, and drying. It can be manufactured. In addition,
The binder is used alone or as a mixture of two or more thereof dissolved in a solvent or dispersed in a latex form. Examples of the solvent include water, ethanol, tetrahydrofuran, methyl ethyl ketone, toluene, xylene, chloroform, dioxane, acetone, cyclohexane, butyl acetate and the like.

For the coating, conventionally known methods such as a surface sequential coating method using a gravure roll, an extrusion coating method, a wire bar coating method and a roll coating method can be employed.

The ink layer may be formed on the entire surface or a part of the surface of the support as a layer containing a monochromatic heat diffusible dye, or a yellow ink containing a binder and a yellow dye. A layer, a magenta ink layer containing a binder and a magenta dye, and a cyan ink layer containing a binder and a cyan dye are formed on the entire surface or a part of the surface of the support at regular intervals along the plane direction. May be. In addition to the three ink layers arranged along the plane direction, a black ink layer containing a black image forming substance may be interposed. With respect to the black ink layer, a clear image can be obtained by either the diffusion transfer type or the melt transfer type. The thickness of the ink layer thus formed is usually 0.2 to 10 μm, preferably 0.3 to 3 μm.

Incidentally, the thermal transfer recording ink sheet can be conveniently used by forming perforations or providing detection marks for detecting the positions of areas having different hues.

The base material in the sublimation type laser thermal transfer recording medium has a function as a support for the image receiving layer.
As the base material that can be used here, the recording medium used for the fusion laser thermal transfer recording medium can be used. The image receiving layer in the laser thermal transfer recording medium of the present invention is not particularly limited, and may have various materials, compositions, layer configurations, etc. depending on the purpose of use and the like.
For example, it may be the same as the image-receiving layer having various materials, compositions, layer constitutions, etc., which have been proposed for the conventional image-receiving sheet for thermal transfer recording of this kind, or as those obtained by appropriately improving them. Good. At least the image receiving layer,
It contains a resin binder that receives the sublimable dye upon heating. Examples of such resins include polyvinyl chloride resins, copolymer resins of vinyl chloride and other monomers (for example, alkyl vinyl ether, allyl glycidyl ether, vinyl propionate, etc.), polyvinylidene chloride resins, polyester resins, Acrylic ester, methacrylic acid ester, epoxy resin, phenoxy resin, polyvinyl butyral, polyvinyl pyrrolidone, polycarbonate, polysulfone, polyarylate, polyparabanic acid, cellulose triacetate, styrene acrylate resin, vinyltoluene acrylate resin, polyurethane resin, polyamide resin, urea Resin, polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin and the like can be mentioned. These resins may be used alone or in a combination of two or more. The above various resins may be newly synthesized and used, or commercially available products may be used. In the formation of the image receiving layer, the above-mentioned various resins utilize their reaction active points (if there are no reaction active points, they are imparted to the resin), and are crosslinked by radiation, heat, humidity, a catalyst, or the like. It may be cured. In that case,
Radiation-active monomers such as epoxies and acrylics, and crosslinking agents such as isocyanates can be used. If necessary, additives such as a release agent, an antioxidant, a UV absorber, a light stabilizer, a filler (inorganic fine particles, organic resin particles) and a pigment may be added to the image receiving layer. Further, a plasticizer, a heat-fusible substance or the like may be added as a sensitizer. The release agent is for improving the releasability between the laser thermal transfer recording medium for thermal transfer recording and the image receiving sheet for thermal transfer recording, and in the case of the present invention, it is preferably contained in the outermost layer. Examples of such release agents include silicone oils (including those called silicone resins); solid waxes such as polyethylene wax, amide wax, Teflon powder; fluorine-based and phosphoric ester-based surfactants, etc. Among them, silicone oil is preferable. This silicone oil is classified into a type that is simply added (simple addition type) and a type that is cured or reacted (curing reaction type). In the case of the simple addition type, it is preferable to use a modified silicone oil (for example, polyester modified silicone resin, urethane modified silicone resin, acrylic modified silicone resin, etc.) in order to improve the compatibility with the resin. The addition amount of these simple addition type silicone oils cannot be uniformly determined because it may change variously depending on the type, but generally speaking, it is usually relative to the image receiving layer resin. It is 0.1 to 50% by weight, preferably 0.5 to 20% by weight.

As the curing reaction type silicone oil,
Examples thereof include a reaction-curable type (for example, one obtained by reacting and curing an amino-modified silicone oil and an epoxy-modified silicone oil), a photo-curable type, and a catalyst-curable type. The amount of these curable silicone oils added is 0.5 to 3 of the resin for the image receiving layer.
0% by weight is preferred. The release agent layer may be provided on a part of the surface of the image receiving layer by dissolving or dispersing the release agent in an appropriate solvent and applying the solution, followed by drying. Next, examples of the antioxidant include those disclosed in JP-A-59-1.
82785, 60-130735, and the antioxidants described in JP-A No. 1-127387, and compounds known to improve the image durability of photographs and other image recording materials can be mentioned. Examples of the UV absorbers and light stabilizers include those disclosed in JP-A-59-158287, JP-A-63-74686, JP-A-63-145089, and JP-A-63-145089.
-196292, 62-229594, 63-122596, 61-283595, 61-283595, compounds described in JP-A 1-204788 and the like, and compounds known as those for improving the image durability in photographs and other image recording materials. be able to. Examples of the filler include inorganic fine particles and organic resin particles.
Examples of the inorganic fine particles include silica gel, calcium carbonate, titanium oxide, acid clay, activated clay, alumina, and the like, and organic fine particles include, for example, fluororesin particles, guanamine resin particles, acrylic resin particles, and silicon resin particles. Resin particles may be mentioned. These inorganic / organic resin particles vary depending on the specific gravity, but 0-30
Preference is given to addition by weight.

Typical examples of the pigment include titanium white, calcium carbonate, zinc oxide, barium sulfate, silica, talc, clay, kaolin, activated clay and acid clay.

Examples of the plasticizer include phthalic acid esters, trimellitic acid esters, adipic acid esters, and other saturated or unsaturated carboxylic acid esters,
Examples thereof include citric acid esters, epoxidized soybean oil, epoxidized linseed oil, epoxy stearic acid epoxies, orthophosphoric acid esters, phosphite esters, glycol esters and the like. Examples of the heat-fusible substance include alcohols such as terpineol, menthol, 1,4-cyclohexanediol, phenol, amides such as acetamide and benzamide, coumarin, esters such as benzyl cinnamate, diphenyl ether, crown ether and the like. Ethers, camphor, ketones such as p-methylacetophenone, aldehydes such as vanillin and dimethoxybenzaldehyde, hydrocarbons such as norbornene and stilbene, higher fatty acids such as margaric acid, higher alcohols such as eicosanol, cetyl palmitate, etc. Higher fatty acid esters, higher fatty acid amides such as stearic acid amide, monomolecular compounds represented by higher amines such as behenylamine, carnauba wax, beeswax, paraffin wax, ester wax, montan wax, Waxes such as midwax, ester gum, rosin maleic acid resin, rosin derivative such as rosin phenol resin, phenol resin, ketone resin, epoxy resin, diallyl phthalate resin, terpene resin, aliphatic hydrocarbon resin, cyclopentadiene resin, Examples thereof include polymer compounds represented by polyolefin resins such as polyolefin resins, polyethylene glycol and polypropylene glycol.

In the present invention, the above-mentioned heat-meltable substance preferably has a melting point or softening point of 10 to 150 ° C. Incidentally, in the present invention, the total amount of the additive is usually
It is preferably selected in the range of 0.1 to 30% by weight based on the resin for the image receiving layer. The thickness of the image receiving layer is usually 3 to 30 μm.
It is suitable to select m, preferably 5 to 20 μm. Further, the image receiving layer may be a single layer, or may be provided as a multilayer structure of two or more layers having the same composition or different compositions, if necessary. It is also possible to obtain a reflection image by providing a peeling layer below the image receiving layer and retransferring only the image receiving layer to an arbitrary support after recording is completed. The method of forming the image receiving layer is not particularly limited, and it can be formed by various methods such as known methods. For example, the image-receiving layer is a coating method in which the forming components are dispersed or dissolved in a solvent to prepare an image-receiving layer forming coating liquid, and the image-receiving layer forming coating liquid is applied to the substrate and dried, It can be formed by a method such as a laminating method in which a mixture having components for forming an image receiving layer is melt extruded and laminated on the surface of the base material. Examples of the solvent used in the above coating method include water, alcohols (eg ethanol, propanol etc.), cellosolves (eg methyl cellosolve, ethyl cellosolve etc.), aromatics (eg toluene, xylene, chlorobenzene etc.), ketones. (Eg acetone, methyl ethyl ketone etc.), ester solvents (eg ethyl acetate, butyl acetate etc.), ethers (eg tetrahydrofuran, dioxane etc.), chlorine solvents (eg methylene chloride, chloroform, trichloroethylene etc.) and the like. For the coating, a conventionally known coating method using a gravure roll, extrusion coating method, wire bar coating method, roll coating method or the like can be adopted. After this coating, by drying appropriately,
An image receiving layer having a predetermined dry film thickness is formed.

In the recording medium of the present invention, in addition to the base material and the image receiving layer, if necessary, an intermediate layer is provided for the purpose of imparting properties such as adhesiveness between the image receiving layer and the base material. (Undercoat layer) may be provided. Further, an overcoat layer may be laminated on the surface of the image receiving layer for the purpose of preventing fusion of the laser thermal transfer recording medium and the recording medium. When the above-mentioned intermediate layer and overcoat layer are provided, it is preferable that the thickness of each layer is usually selected in the range of 0.1 to 20 μm. Further, on the back surface of the recording medium of the present invention (the surface of the base material opposite to the image receiving layer), if necessary, an antistatic layer,
You may provide backing layers, such as a writing layer and a curl prevention layer. There is no particular limitation on the material, structure, forming method, etc. of this backing layer, and it may be formed as the same as the backing layer used for a known recording medium of this type, or may be appropriately selected according to the purpose etc. You can also do it. In addition,
The backing layer is not limited to a single layer structure, and may have a structure of two or more layers. The backing layer is usually formed over the entire back surface of the base material, but in some cases, it may be formed on a part of the back surface. This backing layer may be formed at any point in the manufacturing process of the recording medium of the present invention. Of course, the recording medium of the present invention may be manufactured using a substrate having a predetermined backing layer in advance, or may be formed after the image receiving layer is formed.

In order to form an image, the ink layer of the sublimation type laser thermal transfer recording medium and the image receiving layer of the recording medium are superposed on each other, and the ink layer and the image receiving layer are imagewise irradiated with a laser from the transfer medium side. .. Then, the photothermal conversion material contained in the ink layer or in a layer provided in a part of the thermal transfer recording medium absorbs light to generate heat, thereby raising the temperature of the ink layer. The sublimable dye in the ink layer is vaporized or sublimated in an amount corresponding to the thermal energy, is transferred to the image receiving layer side and is received. As a result, a dye image is formed on the image receiving layer.

In this way, a monochromatic image can be formed. For example, yellow, magenta, cyan and, if necessary, black thermal transfer recording thermal sheets are sequentially replaced, and thermal transfer corresponding to each color is performed. It is also possible to obtain a color photographic tone color image consisting of a mixture of the respective colors. Then, the following method is also effective. That is, instead of using the sublimation type laser thermal transfer recording medium of each color as described above, the sublimation type thermal transfer recording medium having areas formed by separately coating the respective colors is used. Then, first, the yellow color-separated image is thermally transferred using the yellow area, then the magenta color-separated image is thermally transferred using the magenta area, and thereafter, the yellow, magenta, cyan, and necessary images are sequentially repeated. Then, the method of thermally transferring the black color separation image in order is adopted. This method can also obtain a color image having a color photographic tone, but more advantageously, this method has an advantage that the above-mentioned heat-sensitive transfer recording sheet need not be replaced.
Further, after forming an image by the method described above, heat treatment may be performed by the method described above for the purpose of improving the image storability.

[0065]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto. In the following, "part" means "part by weight".

Image formation: The recording medium is brought into close contact with the ink layer surface of the laser thermal transfer recording medium, and the semiconductor laser [LT09 is used from the rear surface of the recording medium through the recording medium.
Laser light of 0MD / MF (wavelength 0.83μm, maximum light output 100mW, manufactured by Sharp Corporation) is focused so that the beam diameter on the surface of the recording medium sample ink layer is 10μm, and the irradiation time is 2μs to 10μs. The laser power on the light-receiving surface was 60 mW.The exposure pattern formed lines with a pitch of 5 μm and printed several lines with a line pitch of 20 μm. It was peeled from the transfer medium and observed under a microscope to see if the state and lines of the image transferred on the recording medium could be resolved.

(Evaluation) With respect to each example, the sensitivity was evaluated with respect to the exposure pulse width required for recording, the transferability, the resolution, and the color tone of the transferred image. Further, the sublimation type thermal transfer recording medium was printed after the test of storage at 60 ° C. for 7 days, and the storage stability was evaluated. The results are shown together with the absorbance of the ink layer at 830 nm in Table 1 for the melting type laser thermal transfer recording medium and in Table 2 for the sublimation type laser thermal transfer recording medium.

The criteria for each evaluation are shown below.

Transferability ◯: A clear image was obtained Δ: An image was obtained, but there was a partial untransferred portion ×: An image was obtained, but many untransferred parts were seen Resolving power ○: Lines were well resolved △: Lines could not be partially resolved due to scattering of the photothermal conversion agent or surface transfer ×: Lines could not be resolved Color tone ○: Transferred image was photothermal conversion Almost no color turbidity due to the agent Δ: The transferred image is slightly turbid due to the photothermal conversion agent ×: The color tone of the transferred image is obviously changed by the photothermal conversion agent Storability (only for sublimable thermal transfer recording medium) ○: There is almost no change in performance after storage. Δ: Slight decrease in sensitivity or fogging occurs after storage. ×: Significant decrease in sensitivity or fogging occurs after storage.

Example 1 Production of Laser Thermal Transfer Recording Medium A melt type ink forming coating solution having the following composition was mixed and dispersed in a sand mill to prepare. Next, the melt type ink layer forming coating solution was vapor-deposited with aluminum to a thickness of 600 Å on a polyethylene terephthalate film [manufactured by Toray Industries, Inc.] with a thickness of 100 μm, and then the corona-treated surface was applied. Then, it was applied and dried using a wire bar to form an ink layer having a film thickness of 1 μm to obtain an ink sheet.

On the back surface of the polyethylene terephthalate film, a nitrocellulose layer containing a silicone-modified urethane resin (SP-2105, manufactured by Dainichiseika Co., Ltd.) was provided as a backing layer.

<Coating liquid for forming ink layer> Paraffin wax: 0.5 part [Nippon Seiro Co., Ltd., HNP-11] Rosin resin: 4.5 parts [DS-90 manufactured by Harima Kasei Co., Ltd.] Ethylene-vinyl acetate copolymer: 1 part [EV-40Y manufactured by Mitsui DuPont Polychemical Co., Ltd.] Magenta pigment dispersion ...・ 3.5 parts [manufactured by Mikuni dye Co., Ltd.] Infrared absorbing dye ・ ・ ・ 0.5 part [Exemplified compounds described in JP-A-3-103476] MEK ・ ・ ・ ・ ・ ・ ・ ・ ・ ・-90 parts Production of recording medium A 100 μm-thick polyethylene terephthalate film [manufactured by Toray Industries, Inc.] as a recording medium is coated with the following composition for forming an image receiving layer using a wire bar and dried. The film was formed to have a film thickness of 1 μm.

<Coating liquid for forming image receiving layer> EVA water dispersion: 10 parts [Toyo Morton Co., Ltd., AD37P295] Water: 90 parts (Example 2) Production of laser thermal transfer recording medium A release layer forming coating solution having the following composition was prepared. Next, the release layer-forming coating liquid was vapor-deposited with aluminum to a thickness of 600 Å on a polyethylene terephthalate film [manufactured by Toray Co., Ltd.] having a thickness of 100 μm, and further corona-treated on the surface. A laser heat transfer recording medium was obtained by applying and drying using a wire bar to form an ink layer having a film thickness of 1 μm, and forming an ink layer on the ink layer in the same manner as in Example 1. A backing layer similar to that in Example 1 was provided on the back surface of the polyethylene terephthalate film.

<Release layer forming coating liquid> Paraffin wax ・ ・ ・ ・ ・ ・ 9.5 parts [Nippon Seiwa Co., Ltd., HNP-11] Ethylene-vinyl acetate copolymer ・ ・ ・ 0.5 parts Evaflex EV210 manufactured by Mitsui Deupon Polychemical Co., Ltd. 85.0 parts of isopropyl alcohol Production of recording medium: The recording medium was prepared in the same manner as in Example 1.

Example 3 Production of Laser Thermal Transfer Recording Medium A 100 μm thick polyethylene terephthalate film [manufactured by Toray Industries, Inc.] was prepared by applying the release layer forming coating solution described in Example 2 to the film.
A wire bar is used for coating and drying to form a release layer having a thickness of 1 μm, and a 600Å-thick aluminum vapor deposition layer is formed on the release layer by a vacuum vapor deposition method, and corona treatment is performed.
An ink layer having a thickness of 0.5 μm was formed on the upper layer of the coating liquid for forming an ink layer described below in the same manner as in Example 1 to obtain a laser thermal transfer recording medium.

<Ink layer forming coating liquid> Paraffin wax: 0.5 part [Nippon Seiro Co., Ltd., HNP-11] Rosin resin: 5.5 parts [DS-90 manufactured by Harima Kasei Co., Ltd.] Ethylene-vinyl acetate copolymer ... 1 part [EV-40Y manufactured by Mitsui DuPont Polychemical Co., Ltd.] Carbon black ... 3 parts MEK ... 90 parts Manufacturing of recording medium: prepared in the same manner as in Example 1.

Example 4 Production of Laser Thermal Transfer Recording Medium An ink sheet prepared in the same manner as in Example 3 was coated with the following adhesive layer forming coating liquid on the ink layer upper layer and a wire bar on the upper layer. By coating and drying, an adhesive layer having a film thickness of 0.5 μm was formed to obtain a laser thermal transfer recording medium.

-Coating Liquid for Forming Adhesive Layer-Production of Recording Medium: It was prepared in the same manner as in Example 1.

Example 5 Production of Laser Thermal Transfer Recording Medium A polyethylene terephthalate film [made by Toray Industries, Inc.] having a thickness of 100 μm with an aluminum vapor deposition layer as described in Example 1 was added,
Apply the following photothermal conversion layer coating solution using a wire bar.
A light absorbing and heat generating layer having a film thickness of 0.5 μm is formed by drying, and an ink layer forming coating solution described below is applied to the upper layer using a wire bar and dried to form an ink layer having a film thickness of 1 μm. A laser thermal transfer recording medium was obtained.

<Photothermal conversion layer coating liquid> Polyvinyl alcohol: 7 parts [Nippon Gosei Chemical Co., Ltd., Gohsenol GL-05] Carbon black: 3 parts Water・ ・ ・ 90 parts <Coating liquid for ink layer formation> Paraffin wax ・ ・ ・ ・ ・ ・ 0.5 parts [NIPPON SEIWA CO., LTD., HNP-11 ] Rosin resin: 5 parts [Harima Kasei Co., Ltd., DS-90] Ethylene-vinyl acetate copolymer: 1 part [Mitsui-DuPont Polychemical Co., Ltd., EV-40Y] Magenta pigment dispersion ・ ・ ・ ・ ・ ・ 3.5 parts [Mikuni dye Co., Ltd.] MEK ・ ・ ・ ・ ・ 90 parts Manufacturing of recording medium: It was created in the same manner as in Example 1.

Example 6 Production of Laser Thermal Transfer Recording Medium A laser thermal transfer recording medium was obtained in the same manner as in Example 5 except that the following coating solution for light absorbing heat generating layer was used.

<Light absorbing heat generating layer coating liquid> Polycarbonate: 7 parts [Mitsubishi Gas Chemical Co., Ltd., Iupilon S-2000] IR absorbing dye: ... 3 parts [IR820B manufactured by Nippon Kayaku Co., Ltd.] MEK ... 90 parts Manufacturing of recording medium: prepared in the same manner as in Example 1.

Comparative Example 1 Production of Laser Thermal Transfer Recording Medium A 100 μm thick polyethylene terephthalate film [manufactured by Toray Industries, Inc.] was coated with the ink layer forming coating solution described in Example 1 using a wire bar.・ Dry, film thickness is 1μ
It was formed to be m.

Manufacture of recording medium: prepared in the same manner as in Example 1.

Comparative Example 2 Production of Laser Thermal Transfer Recording Medium A 100 μm thick polyethylene terephthalate film [manufactured by Toray Industries, Inc.] was coated with the coating liquid for ink layer formation described in Example 1 using a wire bar. -Dry to form a film having a thickness of 1 μm.

Production of Recording Medium: Created in the same manner as in Example 1.

Comparative Example 3 Production of Laser Thermal Transfer Recording Medium A polyethylene terephthalate film having a thickness of 100 μm (manufactured by Toray Industries, Inc.) was prepared by using the release layer forming coating solution described in Example 2.
Was coated and dried using a wire bar to form a peeling layer having a film thickness of 1 μm, and an ink layer similar to that of Example 3 was formed on the peeling layer to obtain a thermal transfer recording medium.

Production of Recording Medium: Created in the same manner as in Example 1.

Comparative Example 4 Production of Laser Thermal Transfer Recording Medium A release layer was formed on a polyethylene terephthalate film having a thickness of 100 μm in the same manner as in Example 3, and the following ink layer-forming coating liquid was formed on the release layer by a wire. Apply using a bar
An ink layer having a film thickness of 1 μm was formed by drying to obtain a laser thermal transfer recording medium.

<Ink layer forming coating liquid> Paraffin wax: 0.5 parts [Nippon Seiwa Co., Ltd., HNP-11] rosin resin: 4 parts [DS-90 manufactured by Harima Kasei Co., Ltd.] Ethylene-vinyl acetate copolymer ... 0.5 parts [EV-40Y manufactured by Mitsui DuPont Polychemical Co., Ltd.] Carbon black ... 5 parts MEK ... 90 parts Recording medium production: Prepared in the same manner as in Example 1.

Comparative Example 5 Production of Laser Thermal Transfer Recording Medium A coating solution for forming a photothermal conversion layer as described in Example 5 was prepared to a thickness of 100.
A photothermal conversion layer having a film thickness of 1 μm is formed by coating and drying on a polyethylene terephthalate film having a thickness of 1 μm (manufactured by Toray Industries, Inc.) using a wire bar, and an ink layer similar to that of Example 5 is formed thereon and laser thermal transfer is performed. A recording medium was obtained.

Production of Recording Medium: Created in the same manner as in Example 1.

Example 7 Production of Sublimation Type Laser Thermal Transfer Recording Medium A sublimation type ink forming coating solution having the following composition was mixed and dispersed in a sand mill to prepare a sublimation type ink thermal transfer recording medium. Then, the sublimation type ink layer forming coating liquid was vapor-deposited with aluminum to a thickness of 600 Å on a polyethylene terephthalate film [manufactured by Toray Industries, Inc.] having a thickness of 100 μm, and further corona-treated on the surface. Then, apply and dry with a wire bar to a film thickness of 1μ
An m ink layer was formed to obtain an ink sheet. A nitrocellulose layer containing a silicon-modified urethane resin (SP-2105, manufactured by Dainichiseika Co., Ltd.) was provided as a backing layer on the back surface of the polyethylene terephthalate film.

<Coating Liquid for Ink Layer Formation> Sublimation Dye ... 5.5 parts [Kayaset Blue 714, manufactured by Nippon Kayaku Co., Ltd.] Nitrocellulose・ ・ ・ 4 parts [Celnova BTH1 / 2 manufactured by Asahi Kasei Kogyo Co., Ltd.] Infrared absorbing dye ・ ・ ・ ・ ・ ・ 0.5 part [Exemplified compound described in JP-A-3-103476] Methyl ethyl ketone ・ ・ ・・ 80 parts Cyclohexanone ・ ・ ・ ・ ・ ・ ・ 10 parts Production of recording medium: 100 μm thick polyethylene terephthalate film [manufactured by Toray Industries, Inc.] and wire coated with a coating solution for forming an image receiving layer having the following composition By a bar coating method, a recording medium was obtained by coating and drying so that the film thickness after drying was 5 μm.

<Coating liquid for forming image receiving layer> Polyvinyl chloride resin: 9.5 parts [Shin-Etsu Chemical Co., Ltd., TK-300] Polyester modified silicone resin: 0.5 parts [Shin-Etsu Chemical Co., Ltd.] Mfg., X-24-8300] Methyl ethyl ketone ... 60 parts Dioxane ... 20 parts Cyclohexanone ... 10 parts (Comparative Example 6 ) Manufacture of sublimation type thermal transfer recording medium A sublimation type ink forming coating liquid having the following composition was mixed and dispersed in a sand mill to prepare a sublimation type thermal transfer recording medium. Next, the sublimation type ink layer forming coating liquid was applied to a polyethylene terephthalate film [manufactured by Toray Industries, Inc.] having a thickness of 100 μm using a wire bar.
An ink layer having a film thickness of 1 μm was formed by drying to obtain an ink sheet. A nitrocellulose layer containing a silicon-modified urethane resin (SP-2105, manufactured by Dainichiseika Co., Ltd.) was provided as a backing layer on the back surface of the polyethylene terephthalate film.

<Coating Liquid for Ink Layer Formation> Sublimation Dye ... 5 parts [Kayaset Blue 714 manufactured by Nippon Kayaku Co., Ltd.] Nitrocellulose・ ・ ・ 4 parts [Celnova BTH1 / 2 manufactured by Asahi Kasei Kogyo Co., Ltd.] Infrared absorbing dye ・ ・ ・ ・ ・ ・ 1 part [Exemplified compound described in JP-A-3-103476] Methyl ethyl ketone ・ ・ ・ ・ ・.. 80 parts cyclohexanone ... 10 parts Production of recording medium: Created in the same manner as in Example 6. The structural formulas of the infrared absorbing dye and magenta pigment used in the examples are shown below.

[0097]

[Chemical 1]

[0098]

[Chemical 2]

[0099]

[Table 1]

[0100]

[Table 2]

As shown in Tables 1 and 2, the thermal transfer recording medium of the present invention is effective in terms of sensitivity and color reproducibility, and is improved in transferability and resolution. Furthermore, the sublimation type laser thermal transfer recording medium is further improved. In, the binder ratio can be increased and the storage stability is improved.

[0102]

Industrial Applicability The laser thermal transfer recording medium of the present invention has excellent sensitivity and color reproducibility, good transferability and resolving power, and the sublimation type laser thermal transfer recording medium also has improved storage stability.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical indication 8305-2H B41M 5/26 B (72) Inventor Kosei Kojima 1 Sakuramachi, Hino City, Tokyo Konica Stock Association In-house

Claims (4)

[Claims] 1. The laser thermal transfer recording through the image receiving body in a state where a surface having a transfer layer of the laser thermal transfer recording medium and an image receiving body which is transparent or transmits a light of a wavelength of a laser light source are closely contacted or arranged in the vicinity thereof. A laser thermal transfer recording medium used in a thermal transfer recording method for recording by irradiating a medium with a laser, comprising laminating a light reflecting layer on a support and an ink layer absorbing a laser beam used for recording. Characteristic laser thermal transfer recording medium. 2. The laser thermal transfer recording medium according to claim 1, wherein a peeling layer is provided between the light reflecting layer and the ink layer. 3. The laser thermal transfer recording medium according to claim 1, further comprising a release layer provided between the support and the light reflecting layer. 4. An ink layer for absorbing a laser beam used for recording is a layer containing a light absorbing exothermic agent layer and a coloring material, a light absorbing exothermic layer and a coloring material layer, or a thin film adhesive layer and a light absorbing exothermic agent. The laser thermal transfer recording medium according to any one of claims 1 to 3, comprising a layer and a layer containing a coloring material, or a thin film adhesive layer, a coloring material layer and a light absorbing heat generating layer.