JPH04169285A - Thermal transfer recording method - Google Patents

Abstract

PURPOSE:To obtain recording imparting a sharp spot by using laser having a wavelength capable of being absorbed by the dye of a colorant layer. CONSTITUTION:A thermal transfer dye donating material wherein a dye donating layer containing a thermal transfer dye is superposed on a thermal transfer image receiving material wherein an image receiving layer is provided on a support so that the dye donating layer and the image receiving layer come into contact with each other and, at the time of the thermal transfer due to laser, the laser having a wavelength capable of being absorbed by the dye contained in the dye donating layer is used. For example, as the laser used in an yellow dye donating layer wherein a dye absorbing wavelength region is 400-500nm, He-Cd laser is effectively used and, as the laser used in a magenta dye donating layer, copper vapor laser is effectively used and, as the laser used in a cyan dye donating layer, He-Ne laser is effectively used. By this method, it is prevented that the min. size to be transferred spreads so as to become larger than the spot size of laser beam and sharp recording is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of industrial application) The present invention relates to a thermal transfer recording method using a laser. In recent years, thermal transfer systems have been developed for the purpose of obtaining prints from images electrically produced by color video cameras and the like. According to one of the methods developed, first the colors of the electrical image are separated by color filters and each color image is converted into electrical signals, and then cyan, magenta and yellow electrical signals are extracted from these electrical signals. It is operated to create a signal and sends an electrical signal to the thermal transfer device.

Cyan, magenta and yellow dye-donor elements are placed in close proximity to the dye-receiver element for printing. These two elements are inserted between the thermal transfer head and a hot platen roller such that the linear thermal transfer head applies heat from the back side of the dye donor sheet. The linear thermal transfer head has a number of heating elements and is continuously heated in response to cyan, magenta and yellow electrical signals. The same operation is repeated for the remaining two colors. In this way, a color hard copy is obtained that corresponds to the original image on the screen. This process and apparatus for carrying out this process are described in U.S. Patent No. 4. 621. No. 271 provides further details.

Another way to obtain prints by heat using the electrical signals described above is to use a laser instead of a thermal print head. When using a conventionally known laser such as that disclosed in JP-A-2-202488, the dye-donating material contains a substance that exhibits strong absorption in the wavelength region of the laser. When the dye-donor material is irradiated with a laser, the absorbing material converts the laser energy into thermal energy, heating the dye in the immediate vicinity of the absorbing material to a transferable temperature and transferring it to the dye-receiving material. This absorbing material may be in a layer directly below the dye and may be mixed with 7' or the dye.

The laser beam is witsed by electrical signals corresponding to the shape and color of the original image. Such MiIff is performed to heat and transfer each dye to the required location. This allows the original image to be reproduced on the dye-receiving layer.

Details of this process are described in German Patent No. 2 083.726A.

(Problems to be Solved by the Invention) When the above-mentioned materials and a laser are used, there is a problem in that the minimum size to be transferred becomes larger than the spot size of the laser beam. Since the dye-donor layer contains an absorbing substance other than the dye, there is a problem in that the film thickness increases.

Further, there is a problem that the concentration of the composition of the dye-donating layer decreases, and the burden of creating the dye-donating layer increases.

(Means for solving problems) These problems are solved according to the invention.

Namely, 1) A thermal transfer dye-providing material having a dye-providing layer containing a heat-transferable dye on a support and a thermal transfer image-receiving material having an image-receiving layer on a support are stacked so that the colorant layer and the image-receiving layer are in contact with each other. In addition, the present invention is solved by a thermal transfer recording method in which thermal transfer is performed using a laser, wherein the wavelength of the laser is such that the dye contained in the coloring material layer can absorb light. In particular, the problem can be more effectively solved by a thermal transfer recording method characterized in that the laser consists of a combination of an oscillating section and a nonlinear optical element.

The laser used in the present invention is appropriately selected and used depending on the wavelength range absorbed by the dye to be transferred by a commercially available laser device.

For example, a laser used for a yellow dye-donating layer whose dye absorption wavelength range is from 400 nm to 500 nm is 44 nm.
He-Cd laser with oscillation wavelength at 2 nm, 488
An argon laser with an oscillation wavelength in the nm range is effective.

The laser used for the magenta dye donor layer, where the absorption wavelength range of the dye is from 500 nm to 600 nm, is 510 nm.
a copper vapor laser with an oscillation wavelength of m and 578 nm;
Argon laser with oscillation wavelength at 515 nm, 54
A He-Ne laser having an oscillation wavelength of 3 nm is used.

For the cyan dye donor layer, which has a dye absorption wavelength range from 600 nm to 700 nm, a He-Ne laser with an oscillation wavelength of 632 nm, a ruby laser with an oscillation wavelength of 694 nm, and a krypton laser with an oscillation wavelength of 647 nm are used. , an all-vapor laser with an oscillation wavelength of 628 nm, and A with an oscillation wavelength of 660 nm.
IGa1nP semiconductor laser etc. can be effectively used.

Further, if a dye laser is used, and the dye used in the laser is appropriately selected, a laser having an oscillation wavelength suitable for each dye-donating layer can be used.

It is also possible to use a so-called white laser that emits laser light of three wavelengths: red, green, and blue light.

Furthermore, it is also possible to obtain laser light of an appropriate wavelength by combining an element that converts the wavelength of laser light with a laser oscillation device. For example, if you combine a YAG laser that oscillates at 11064n and a second harmonic generator, you can generate 532nm.
can be used for magenta dye-donor elements. In addition to the above, a sum frequency/difference frequency generator or an optical parametric oscillator can also be used as the wavelength conversion element. Materials used for these wavelength conversion elements are generally known as nonlinear optical elements. For example, KDP, ADP.

Inorganic crystalline materials such as LjNbOi and β-BaB20+ are widely used.

Recently, it has been found that nonlinear optical elements made of organic materials have better performance than the above-mentioned inorganic materials.

Organic materials include p-nitroaniline (p-NA),
Examples include 2-methyl-4-nitroaniline (MNA).

In addition, NPP, MAP, POM, m-NA, m-
Also known as AP.

Regarding these materials, for example, “organic nonlinear optical materials”
(written by Shinsuke Umegaki, published by Funshin Publishing, 1990).

By combining these nonlinear optical materials with an 830 nm semiconductor laser, 415 nm laser light can be obtained.
It can be used as a yellow dye-providing material.

Use of these nonlinear optical materials is advantageous because a compact and inexpensive laser light source can be obtained.

Especially when combined with a semiconductor laser, it can be further miniaturized. Among nonlinear optical materials, organic materials have a higher wavelength conversion ability and are more advantageous than inorganic materials.

A thermal transfer dye-providing material using a thermally transferable dye basically has a thermal transfer layer on a support containing a dye that sublimes or becomes mobile by heat and a binder.

This thermal transfer dye-providing material is prepared by preparing a coating solution by dissolving or dispersing a dye that sublimes or becomes mobile by heat and a binder resin in a suitable solvent, and then applying this coating solution to the thermal transfer dye-providing material. On one side of the support for the material,
For example, about 0. It can be obtained by coating and drying to form a thermal transfer layer in a coating amount such that the dry film thickness is 2 to 5 microns, preferably 0.4 to 2 microns.

Dyes useful in forming such thermal transfer layers include:
Although any dye conventionally used in thermal transfer dye-providing materials can be used, particularly preferred in the present invention are dyes of about 15
It has a small molecular weight of about 0 to 800, and is selected in consideration of transfer temperature, hue, light resistance, solubility in ink and binder resin, dispersibility, etc.

Specifically, for example, disperse dyes, basic dyes, oil-soluble dyes, etc. can be mentioned, but in particular, Sumikaron Yellow E
4C; L, Dianix Yellow H2G-FS, Miketon Bolier Tell Yellow 3GSL, Kayasent Yellow 937, Sumikaron Red EFBL, Dianix Red ACE, Miketon Bolier Tell Red FB, Kayaset Red 126, Miketon Fast Brilliant Plue B, Kayaset Blue 136 or the like is preferably used.

In addition, a yellow dye represented by the general formula below (in the formula,
R1° represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, a cyano group, or a carbamoyl group, R2 represents a hydrogen atom, an alkyl group, or an aryl group, and R3 represents an aryl group or a heteryl group. R4 and R2 may be the same or different and each represents a hydrogen atom or an alkyl group. (The above substituents may be further substituted) A magenta dye of the following general formula (wherein R, R2 is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group,
Represents an arylthio group, aralkyl group, cyan group, acylamino group, sulfonylamino group, ureido group, alkylthio group, arylthio group, alkoxycarbonyl group, carbamoyl group, sulfamoyl group, sulfonyl group, acyl group, amino group, R,,R , represents an alkyl group, a cycloalkyl group, an aralkyl group, or an aryl group. R8 and R
4 may be combined with each other to form a ring, or R3 and R
-1R2 and R4 may be combined to form a ring. n is 0
Represents an integer from ~3. X, Y and R.

and Z represent 10= or a nitrogen atom (here R.

is a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an alkoxy group, an aryloxy group,
(represents an amino group).

Also, when X and Y, or Y and Z, are 10=, they may be bonded to each other to form a saturated or unsaturated carbon ring. (The above substituents may be further substituted) A cyan dye (R4) of the following general formula.

"Q,' (wherein, Q contains at least one nitrogen atom and represents an atomic group necessary to form a 5-membered or more nitrogen-containing heterocycle with the bonding carbon atom, and R3 is an acyl group or represents a sulfonyl group, R7 represents a hydrogen atom or an aliphatic group having 1 to 6 monomers, R8 represents a hydrogen atom or a halogen atom, an alkoxy group or an aliphatic group having 1 to 6 carbon atoms, R4
represents a halogen atom, an alkoxy group, or an aliphatic group having 1 to 6 carbon atoms, and n represents an integer of 0 to 4. R1 may be combined with R3, R2, or R4 to form a ring.

R6 and R1 represent a hydrogen atom, an aliphatic group having 1 to 6 carbon atoms, or an aromatic group. R6, R, may be combined with each other to form a ring. Also, R5 and 2' or R6 are R4
dyes such as (may be bonded to form a ring) are also suitably used.

Furthermore, as the binder resin used with the above dye, any binder resin conventionally known for this purpose can be used, and usually has high heat resistance and does not hinder the transfer of the dye when heated. things are selected. For example, polyamide resin, polyester resin,
Epoxy resins, polyurethane resins, polyacrylic resins (e.g. polymethyl methacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl resins including polyvinylpyrrolidone, polyvinyl chloride resins (e.g. vinyl chloride-acetic acid) vinyl copolymer), polycarbonate resin, polystyrene, polyphenylene oxide, cellulose resin (e.g. methylcellulose, ethylcellulose, carboxymethylcellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate), Polyvinyl alcohol resins (for example, partially saponified polyvinyl alcohols such as polyvinyl alcohol and polyvinyl butyral), petroleum resins, rosin derivatives, chroman-indene resins, terpene resins, polyolefin resins (for example, polyethylene and polypropylene), etc. are used.

It is preferable to use such a binder resin in an amount of, for example, about 80 to 600 parts by weight per 100 parts by weight of the dye.

In the present invention, any conventionally known ink solvent can be freely used as the ink solvent for dissolving or dispersing the above pigment and binder resin.

As the support for the thermal transfer dye-providing material, any conventionally known support can be used. For example, polyethylene terephthalate; polyamide; polycarbonate, glassine paper: condenser paper: cellulose ester difluorine polymer: polyether: polyacetal: polyolefin, polyimide: polypheidonthalene, polypropylene;
Examples include polysulfone and cellophane.

The thickness of the support of the thermal transfer dye-providing material is generally 2 to 30 mm.
μ. An undercoat layer may be provided if necessary. Further, a dye diffusion preventing layer made of a hydrophilic polymer may be provided between the support and the dye-donating layer. This further improves the transfer density. As the hydrophilic polymer, the water-soluble polymers described above can also be used.

The dye-donor element may also be provided with a hydrophilic barrier layer to prevent diffusion of the dye towards the support. The hydrophilic dye barrier layer contains a hydrophilic material that is useful for the intended purpose. Generally excellent results are obtained with gelatin, poly(acrylamide), poly(isopropylacrylamide),
Butyl methacrylate grafted gelatin, ethyl methacrylate grafted gelatin, cellulose monoacetate, methylcellulose, poly(vinyl alcohol), poly(ethyleneimine), poly(acrylic acid), mixture of poly(vinyl alcohol) and poly(vinyl acetate) , by using a mixture of poly(vinyl alcohol) and poly(acrylic acid) or a mixture of cellulose monoacetate and poly(acrylic acid). Particularly preferred is poly(
acrylic acid), cellulose monoacetate or poly(vinyl alcohol).

The dye-providing material may be provided with an undercoating layer. In the present invention, any undercoat layer may be used as long as it has the desired effect, but a preferred specific example is a (acrylonitrile-vinylidene chloride-acrylic acid) copolymer (weight ratio 14:8026).
), (butyl acrylate-2-aminoethyl methacrylate-2-hydroxyethyl methacrylate) copolymer (weight ratio 30:20:50), linear/saturated polyester such as Bostik 7650 (Emhart, Bostic) stick chemical group) or chlorinated high density poly(ethylene-trichloroethylene) resins.

There is no particular limit to the amount of undercoat layer applied, but it is usually 0.1
Used in amounts of ~2.0g, 7m.

For the dye-donating layer, the dye is selected so that the desired hue can be transferred when printed, and if necessary, two or more dye-donating layers with different dyes are arranged in one thermal transfer dye-donating material.
It may be formed by For example, when printing each color repeatedly according to color separation signals to form an image such as a color photograph, it is desirable that the hues of the print are cyan, magenta, and yellow. Three dye-donor layers containing the dye to be provided are arranged.

Alternatively, a dye-donating layer containing a dye that provides a black hue in addition to cyan, magenta, and yellow may be added. It is preferable to provide a mark for position detection at the same time as the formation of any of the dye-donating layers, since this eliminates the need for an ink or printing process separate from the formation of the dye-donating layer.

The support used in the thermal transfer image-receiving material of the present invention can withstand the transfer temperature and satisfies the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic property, and no dents after transfer. It can also be used with things like bato. For example, synthetic paper (polyolefin-based, polystyrene-based, etc.), high-quality paper, art paper, coated paper, cast coated paper,
wallpaper, lined paper, synthetic resin or emulsion impregnated paper,
Paper supports such as synthetic rubber latex-impregnated paper, synthetic resin-loaded paper, paperboard, cellulose fiber paper, polyolefin-coated paper (especially paper coated on both sides with polyethylene), polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate. Various plastic films or sheets such as nebolicarbonate, films or sheets treated to impart white reflective properties to the plastic, and laminates made of any combination of the above may also be used.

The thermal transfer image-receiving material is provided with an image-receiving layer. This image-receiving layer receives the heat-transferable dye that migrates from the heat-transferable dye-providing material during printing, and is made of a material capable of receiving the heat-transferable dye that has the function of dyeing the heat-transferable dye. Alone or together with other binder materials, the thickness 0.
It is preferable that the film has a thickness of about 5 to 50 μm. Typical examples of polymers that can accept heat-transferable dyes include the following resins.

(b) Those with ester bonds Dicarboxylic acid components such as terephthalic acid, isophthalic acid, and sohadaic acid (these dicarboxylic acid components may be substituted with sulfonic acid groups, carboxyl groups, etc.), ethylene glycol, diethylene glycol , propylene glycol, neopentyl glycol, bisphenol A
Polyester resins obtained by condensation such as: polyacrylic acid ester resins or polymethacrylic acid ester resins such as polymethyl methacrylate, polybutyl acrylate, polymethyl acrylate, polybutyl acrylate; polycarbonate resins: polyvinyl acetate resins: styrene acrylate resins; Vinyltoluene acrylate resin, etc. Specifically, JP-A No. 59-101395, JP-A No. 63-7971, JP-A No. 63-7972, JP-A No. 61797.
No. 3 and No. 60-294862. In addition, commercially available products include Toyobo's Byron 290, Byron 200, Byron 280, and Byron 3.
00, Byron 103, Byron GK-140, Byron GK-130, Kao ATR-2009, ATR-
2010 can be used.

(b) Those with urethane bonds polyurethane resin, etc.

(c) Those with an amide bond polyamide resin, etc.

(d) Those with urea bonds urea resin etc.

(e) Those with a sulfone bond Polysulfone resin.

(f) Others having highly polar bonds, such as polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc.

In addition to the synthetic resins mentioned above, mixtures or copolymers thereof can also be used.

The thermal transfer image-receiving material, particularly the image-receiving layer, may contain a high-boiling organic solvent or a thermal solvent as a substance capable of receiving heat-transferable dyes or as a dye diffusion aid.

The image-receiving layer of the thermal transfer image-receiving material of the present invention may have a structure in which a substance capable of receiving a heat-transferable dye is dispersed and supported in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but a water-soluble polymer having a vine group that can be crosslinked with a hardening agent is preferred. Among them, gelatin is particularly preferred.

The image receiving layer may be composed of two or more layers. In that case, the layer closer to the support should be made of a synthetic resin with a low glass transition point, or a high boiling point organic solvent or hot solvent should be used to increase dye dyeing properties, and the outermost layer should have a glass transition point. Avoid sticky surfaces, adhesion to other materials, and susceptibility to other materials after transfer by using synthetic resins with higher points or by minimizing or not using high-boiling point organic solvents or hot solvents. It is desirable to have a configuration that prevents failures such as transfer and blocking with the thermal transfer dye-providing material.

The total thickness of the image-receiving layer is 0.5 to 50 μm, particularly 3 to 30 μm.
A range of μm is preferred. In the case of a two-layer configuration, the outermost layer is 0.
1-2 μm, especially 0. The thickness is preferably in the range of 2 to 1 μm.

The thermal transfer image-receiving material of the present invention may have an intermediate layer between the support and the image-receiving layer.

The intermediate layer can be a cushion layer, a porous layer, or a
This layer has one of the functions of a dye diffusion prevention layer or a layer having two or more of these functions, and in some cases also serves as an adhesive.

The dye diffusion-preventing layer plays a role, in particular, in preventing the heat-transferable dye from diffusing into the support. The binder constituting this diffusion prevention layer may be water-soluble or organic solvent-soluble, but preferably a water-soluble binder.
Preferred examples include the water-soluble binders mentioned above as binders for the image-receiving layer, particularly gelatin.

The porous layer is a layer that prevents the heat applied during thermal transfer from diffusing from the image-receiving layer to the support and effectively utilizes the applied heat.

The image receiving layer, cushion layer, porous layer, diffusion prevention layer, adhesive layer, etc. constituting the thermal transfer image receiving material of the present invention include silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, Fine powders of synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina, etc. may also be included.

A fluorescent brightener may be used in the thermal transfer image-receiving material.

Examples include K. Veenkataraman!
il rTheChemjstry of 5ynth
etjc Dyes J Volume 5 Chapter 8, Unexamined Japanese Patent Publication 1986-
Examples include compounds described in No. 143752 and the like. More specifically, examples include stilbene compounds, coumarin compounds, biphenyl compounds, benzoxacylyl compounds, naphthalimide compounds, birapurin compounds, carbostyril compounds, and 2,5-dibenzoxazolethiophene compounds. It will be done.

Optical brighteners can be used in combination with antifade agents.

In the present invention, in order to improve the releasability of the thermal transfer dye-providing material and the thermal transfer image-receiving material, the dye-providing material and
, and/or the layers constituting the image-receiving material, particularly preferably the outermost layer corresponding to the surface where both materials come into contact contains a release agent.

As a mold release agent, solid or waxy substances such as polyethylene wax, amide wax, fine powder of silicone resin, fine powder of fluorine resin, etc. Surfactants such as fluorine type and phosphate ester type: Paraffin type and silicone Any conventionally known mold release agent such as fluorine-based or fluorine-based oils can be used, but silicone oil is particularly preferred. In addition to unmodified silicone oil, carboxy-modified and
Modified silicone oils such as amino-modified, epoxy-modified, polyether-modified, and alkyl-modified silicone oils can be used alone or in combination of two or more. Examples include various modified silicone oils described on pages 6 to 18B of the "Modified Silicone Oil" technical data published by Shin-Etsu Silicone ■. When used in an organic solvent-based binder, amino-modified silicone oil having a group that can react with the crosslinking agent of this binder (for example, a group that can react with isocyanate) is used after being emulsified and dispersed in a water-soluble binder. is a carboxy-modified silicone oil (for example, manufactured by Shin-Etsu Silicone ■).

(Product name:
-100T) is valid.

The layers constituting the thermal transfer dye-providing material and the thermal transfer image-receiving material used in the present invention may be hardened with a hardening agent.

When curing organic solvent-based polymers, JP-A-61
Hardeners described in Japanese Patent No. 199997 and No. 58-215398 can be used. For polyester resins, it is particularly preferable to use isocyanate-based hardeners.

For the curing of water-soluble polymers, U.S. Patent Box 4.678.7
No. 39, column 41, JP-A-59-116655, JP-A No. 62
The hardening agents described in Japanese Patent No. 245261 and Japanese Patent No. 8>18942 are suitable for use.

More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, vinylsulfone hardeners (N,N'-ethylene-bis(
(vinylsulfonylacetamido)ethane, etc.), N-methylol hardeners (dimethylol urea, etc.), and polymer hardeners (compounds described in JP-A-62-234157, etc.).

Antifading agents may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Antifading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of antioxidants include chroman compounds, coumaran compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds. Compounds described in JP-A-61-159644 are also effective.

Benzotriazole compounds (
U.S. Patent Box 3,533,794), 4-thiazolidone compounds (U.S. Patent Box 3,352,681, etc.)
, penbuphenone compounds (JP-A No. 56-278.4), and other JP-A Nos. 54-48535 and 6113
There are compounds described in No. 6641, No. 61-88256, and the like.

Further, the ultraviolet absorbing polymer described in JP-A-61-260152 is also effective.

As metal complexes, US Patent Box 4. 241. 155
No. 4.245,018, columns 3 to 36, No. 4,
No. 254,195, columns 3 to 8, JP-A-62-17474
There are compounds described in Japanese Patent Application No. 1, No. 61-88256, pages (27) to (29), Japanese Patent Application No. 62-234103, Japanese Patent Application No. 62-31096, and Japanese Patent Application No. 62-230596.

Examples of useful anti-fading agents are disclosed in JP-A No. 62-215272 (
125) to (137)X.

The anti-fading agent for preventing fading of the dye transferred to the image-receiving material may be included in the image-receiving material in advance, or it may be supplied to the image-receiving material from the outside by a method such as transfer from a dye-donating material. You can.

The above antioxidants, ultraviolet absorbers, and metal complexes may be used in combination.

Various surfactants can be used in the constituent layers of the thermal transfer dye-providing material and the thermal transfer image-receiving material for the purposes of coating aids, improving peelability, improving slipperiness, preventing electrification, accelerating development, and the like.

Nonionic surfactants, anionic surfactants, amphoteric surfactants, and cationic surfactants can be used. Specific examples of these are disclosed in JP-A-62-173463 and JP-A-62-173463.
It is described in No. 183457, etc.

In addition, when dispersing substances that can accept heat-transferable dyes, mold release agents, anti-fading agents, ultraviolet absorbers, optical brighteners, and other hydrophobic compounds in a water-soluble binder, the interface is used as a dispersion aid. Preferably, an activator is used. For this purpose, in addition to the above-mentioned surfactants, JP-A-59-15763
The surfactants described on pages 37-38 of No. 6 are particularly preferably used.

A matting agent can be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As a matting agent, silicon dioxide, polyolefin, polymethacrylate, etc.
In addition to the compounds described on page 29 of No. 1-88256, Japanese Patent Application No. 110064/1988, such as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads,
There is a compound described in No. 62-110065.

(Example) In the following Examples and Comparative Examples, production of a thermal transfer dye-providing material and a thermal transfer image-receiving material, printing using both materials, and testing of the thermal transfer image-receiving material were conducted as follows.

Example U (Preparation of thermal transfer dye-donating material) Using a transparent polyester film (manufactured by Teijin) with a thickness of 6 μm as a support, the dye-donating layer format ink having the following composition was applied in an amount of 1.2 g/' after drying. H! Cyan, macenta and yellow dye-providing materials were obtained.

Cyan ink composition dye-a for forming dye-donating layer
3 parts polyvinyl butyral resin (Denka Butyral 5000A: IE vaporization reproduction 2.5
Part polyisocyanate (Takenate DIION, manufactured by Takeda Pharmaceutical Co., Ltd.) 0, 1 part Amino-modified silicone oil (KF-857: Shin-Etsu Kagakuyu) 0.004 parts Methyl ethyl ketone 50 parts Toluene
50 parts Dye-a Dye-b 2.5 parts Polyvinyl butyral resin (Nislex BX-1: Sekisui Chemical Co., Ltd.) 2.5 parts Polyisocyanate (KP-90: Dainippon Ink Chemical Co., Ltd.) 0.1 part Silicone oil ( KF-857: Shin-Etsu Kagakuyu) 0.004 parts methyl ethyl ketone 70 parts toluene
30 parts dye-b dye-0 5 parts ethyl cellulose 3 parts methyl ethyl ketone 50 parts toluene
50 parts dye-b (preparation of thermal transfer image-receiving material) Synthetic paper with a thickness of 150 μm (Tamago Yuka Co., Ltd., YU
A thermal transfer image-receiving material (1) was prepared by applying a coating composition for an image-receiving layer (1) having the following composition to the surface using wire bar coating to a dry thickness of 8 μm. Formed. Drying was performed for 30 minutes in an oven at a temperature of 100°C after temporary drying with a hair dryer.

Coating composition for image layer (1) Polyester resin (Vylon-200 manufactured by Toyobo Co., Ltd.) 22 g Polyisocyanate (KP-90: manufactured by Dainippon Ink Chemical Co., Ltd.) 4 g Amine-modified silicone oil (KF-857 manufactured by Shin-Etsu Silicone Co., Ltd.) 0.5 g Methyl ethyl ketone 85NJ Toluene 85-Using the three color dye-providing materials and image-receiving material obtained as above, the dye-providing layer and the image-receiving layer were superimposed so that they were in contact with each other, and the dye-providing material was exposed to light with a spot diameter of 50 μm from the support side. time 1
The dye was transferred from the dye-providing material to the image-receiving material by scanning the laser beam under the condition of 0 m5ec. The irradiation energy was 30 μW/μm2 @ The laser used was He-N for the cyan dye donor material.
An e-laser was used, a combination of KDP and YAG laser as a wavelength conversion element was used for the magenta dye-donating material, and a He-Cd laser was used for the yellow dye-donating material.

The spots recorded by the transferred dye were sharp and clear.

Example 2 (Preparation of thermal transfer image-receiving material (2)) Resin-coated paper was prepared by laminating polyethylene to a thickness of 15 μm and 25 μm on both sides of a 200 μm paper, and an image-receiving layer having the following composition was placed on the 15 μm-thick laminated surface. The coating composition was applied by wire bar coating to a dry thickness of 10 μm, and dried to produce a thermal transfer image-receiving material (2).

Coating composition for image-receiving layer Polyester resin TP220 (8 bottles manufactured by Synthetic Kagaku) 25 g Amino-modified silicone oil (KF857: manufactured by Shin-Etsu Silicone) 0.8 g Polyisocyanate (KP-90 + manufactured by Dairomoto Ink) 4 g Methyl ethyl ketone 100-Toluene
100! When thermal transfer was performed using the following laser under the same conditions as in Example 1, clear and sharp image recording without fusion was obtained.

The laser used had a wavelength of 670 when the cyan dye donor material was used.
When using a magenta dye-donating material, a AYAG laser is combined with an MNA crystal as a wavelength conversion element, and when a yellow dye-donating material is used, a 83 nm semiconductor laser is used.
A 0 nm semiconductor laser and a POM crystal wavelength conversion element were used in combination.

Example 3 (Preparation of thermal transfer image-receiving material (3)) An organic solvent solution of a dye-receiving polymer having the composition of (B) was emulsified and dispersed in an aqueous gelatin solution of the following composition (A) using a homogenizer to obtain gelatin as a dye-receiving material. A dispersion liquid was prepared.

(A) Gelatin aqueous solution Gelatin 2.3g Sodium dodecylbenzenesulfonate (5% aqueous solution) 20 Donated water
80M1
(B) Dye-receptive polymer solution polyester resin (manufactured by Toyobo: Vylon 300) 7.0 g Carboxy-modified silicone oil (manufactured by Shin-Etsu Silicone: X-22-3710) 0.7 g Methyl ethyl ketone 20 m Toluene 10 paper Triphenyl phosphate 1.5 g Fluorine surfactant (a) of the dispersion thus prepared: CzFqSO
0.5g of JCHzCOOK was mixed with water and 7'methanol (1:
A solution of 1) dissolved in mixed solvent 10- was added to prepare a coating composition for a receptor layer.

This coating composition was corona discharged onto the surface to a thickness of 150 μm.
m synthetic paper (Tamago Yuka: YUP〇-3GG-150)
Wet M thickness 7 by wire bar coating method on top
It was applied to a thickness of 5 μm and dried.

Example 1 Using the obtained image receiving material and using the following laser
When the transfer was carried out under the conditions described in 1., a high-density image recording with sharp spots was obtained.

The laser used was a red semiconductor laser for the cyan dye-donating material, and a semiconductor laser-excited YAG laser for the magenta dye-donating material in combination with a fiber-type wavelength conversion element in which the following compound a was incorporated into a glass capillary. .

For the yellow dye-donor material, an 870 nm semiconductor laser and LiNb0. A waveguide-type wavelength conversion element using a waveguide was used in combination.

Compound-a H2 From the above examples, it can be seen that the thermal transfer recording method of the present invention is effective in obtaining clear recording with sharp spots. Furthermore, it can be seen that compact and inexpensive recording has become possible by combining nonlinear optical materials and semiconductor lasers.

Claims (1)

[Scope of Claims] 1) A thermal transfer dye-providing material in which a dye-providing layer containing a heat-transferable dye is provided on a support, and a thermal transfer image-receiving material in which an image-receiving layer is provided on a support as a colorant layer and an image-receiving layer. A thermal transfer recording method in which the laser beams are superimposed so that they are in contact with each other, and the laser beam is used for thermal transfer, the laser beam having a wavelength that allows light to be absorbed by the dye contained in the coloring material layer. . 2) The thermal transfer recording method according to claim (1), wherein the laser comprises a combination of an oscillating part and a nonlinear optical element.