JPH0558044A - Thermal transfer recording method using laser - Google Patents

Abstract

PURPOSE:To stably form a sharp high density image free from color irregularity in a thermal transfer recording method using laser irradiation. CONSTITUTION:In a thermal transfer system obtaining a color print from an electron image, laser beam is used in place of a thermal head and a dye donating material wherein a photothermal converting agent is contained in a thermal transfer dye donating material is brought into contact with an image receiving material and the image receiving material is heated at the time of the irradiation with laser beam.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for performing thermal transfer recording using a laser beam, and more particularly to thermal transfer recording by a laser characterized by heating a thermal transfer image receiving material during laser irradiation. Regarding the method.

[0002]

2. Description of the Related Art In recent years, thermal transfer systems have been developed for obtaining prints from images electronically formed by color video cameras. According to one method of obtaining such prints, an electronic image is first color separated with color filters. Next, the color-separated images are exchanged for electrical signals. Subsequently, these signals are manipulated to generate yellow, magenta and cyan electrical signals. These signals are then transmitted to the thermal printer. To obtain the print, a yellow, magenta or cyan dye-donor element is placed face-to-face with a dye-image receiving element. Subsequently, the both are inserted between the thermal head and the platen roller. A line type thermal head is used to heat from the back side of the dye-donor element. The thermal head has multiple heating elements and is heated up sequentially in response to the yellow, magenta and cyan signals. This process is then repeated for the other two colors. In this way, a color hard copy corresponding to the original image viewed on the screen is obtained.

An alternative method of obtaining a thermal print using the aforementioned electrical signals is to use a laser instead of a thermal head. In this system, the dye-donor element contains a material that strongly absorbs the laser beam. When a dye-donor material is irradiated with a laser beam, this absorbing material converts light energy into heat energy and immediately transfers that heat to nearby dyes, heating them to a heat transfer temperature to transfer the dye to the image-receiving material. To do. The absorbent material is layered below the dye and / or is mixed with the dye. The laser beam is modulated with an electrical signal that represents the shape and color of the original image, heating only the areas of the dye that need to be present on the dye-donor material to reconstitute the original target color and heat transfer. A more detailed description of this process can be found in British Patent 2,083,726A.

[0004]

The heat obtained from the laser light by the photothermal conversion material in the dye-donor element is used to transfer the heat-transfer dye through the dye-donor element and is in contact therewith. It is also used for transfer of dye to the dye receiving layer. However, if the contact between the dye-donor element and the image-receiving element is insufficient, the heat transfer to the receiving layer will be insufficient, the transfer of the dye into the dye-receiving layer will not be sufficient, and the dye on the surface of the receiving layer will not be transferred. I will stay. For this reason,
The obtained image is unstable, and if it is rubbed or overlapped with another sheet, it is easily peeled off or transferred to another sheet. The object of the present invention is to find a recording method which does not have these drawbacks.

[0005]

The above and other objects are achieved by the present invention described below. That is, the present invention provides a thermal transfer dye-donor material containing a heat-transfer dye and a photothermal conversion agent that absorbs laser light and converts it into heat, and a dye that migrates from the thermal transfer dye-donor material on one side of a support. By combining with a thermal transfer image-receiving material provided with a dye-receiving layer and irradiating a laser beam corresponding to an image signal, the light absorbed by the photothermal conversion agent in the dye-donating material is converted into heat, and this heat In a method for transferring an image by transferring a heat transferable dye in a dye-donor material to a dye-receiving layer in the heat transfer image-receiving material, the heat transfer image-recording material is heated during laser irradiation, and thermal transfer recording by a laser is performed. Regarding the method.

Any conventionally known support can be used as the support of the thermal transfer dye-providing material. Examples thereof include polyethylene terephthalate, polyamide, polycarbonate, glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide, polyphenylene sulfide, polypropylene, polysulfone, and cellophane. The thickness of the support of the thermal transfer dye-providing material is generally 2 to
It is 30 μm. An undercoat layer may be provided if necessary.

A thermal transfer dye-donor element using a heat-transferable dye basically has a dye-donor layer containing a dye and a binder which are movable by heat on a support. This thermal transfer dye-donating material is prepared by dissolving or dispersing a conventionally known dye that becomes sublimable or becomes mobile and a binder resin in an appropriate solvent to prepare a coating solution, and prepares a coating liquid from the conventionally known thermal transfer dye-donating material. On one side of the support for the material, for example about 0.2-5 μm, preferably 0.4-2 μm.
It can be obtained by coating and drying at a coating amount to give a dry film thickness of m to form a dye-donor layer. The dye-donor layer may be formed of one layer, but may be formed of two or more layers for use in a method of repeatedly using a large number of times.
In this case, the dye content and dye / binder ratio in each layer may be different. Dye application amount is 0.03 ~
1 g / m ^2, preferably from 0.1 to 0.6 g / m ^2.

As the dye useful for forming such a dye-donor layer, any of the dyes conventionally used in thermal transfer dye-donor materials can be used, but a particularly preferred dye in the present invention is about 150 to 800. Has a small molecular weight, and is selected in consideration of transfer temperature, hue, light resistance, solubility in ink and binder resin, dispersibility and the like. Specific examples include disperse dyes, basic dyes and oil-soluble dyes. Further, it is preferable to use a yellow dye represented by the following general formula (Y).

[0009]

[Chemical 1]

(Wherein D ¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, a cyano group or a carbamoyl group, and D ² represents a hydrogen atom,
It represents an alkyl group or an aryl group, D ³ represents an aryl group or a heteryl group, and D ⁴ and D ⁵ represent a hydrogen atom or an alkyl group. The above groups may be further substituted. ) Specific examples of compounds are shown below.

[0011]

[Chemical 2]

[0012]

[Chemical 3]

[0013]

[Chemical 4]

As the magenta dye, the dye of the following general formula (M) is preferable.

[0015]

[Chemical 5]

(Wherein D ^{6 to} D ¹⁰ are hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, cyano group, acylamino group, sulfonylamino group, ureido group, alkoxycarbonylamino group,
It represents an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group or an amino group, and D ¹¹ and D ¹² represent a hydrogen atom, an alkyl group or an aryl group. D ¹¹ and D ¹² may be bonded to each other to form a ring, or D ⁸ and D ¹¹ or / and D ⁹ and D ¹² may be bonded to form a ring. X, Y and Z represent = C (D ¹³ )-or a nitrogen atom (D ¹³ represents a hydrogen atom, an alkyl group, an aryl group,
Represents an alkoxy group, an aryloxy group, and an amino group). When X and Y are ═C (D ¹³ ) −, or when Y and Z are ═C (D ¹³ ) −, two D ^{13 s} may combine with each other to form a saturated or unsaturated carbocycle. .. The above groups may be further substituted. ) Specific examples of compounds are shown below.

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

As the cyan dye, the following general formula (C) is used.
Are preferred.

[0022]

[Chemical 10]

(In the formula, D ^{14 to} D ²¹ are synonymous with D ^{6 to} D ¹⁰ , and D ²² and D ²³ are synonymous with D ¹¹ and D ^12. ) Specific examples of compounds are shown below.

[0024]

[Chemical 11]

[0025]

[Chemical formula 12]

[0026]

[Chemical 13]

It is preferable to introduce the anti-fading group described in Japanese Patent Application No. 1-271078 into the compounds of the above general formulas (Y), (M) and (C) since the light fastness is improved.

As the binder resin to be used together with the above-mentioned dye, any of the binder resins known in the art for such purpose can be used, and usually has high heat resistance and migration of the dye when heated. The one that does not interfere with is selected. For example, polyamide-based resin, polyester-based resin, epoxy-based resin, polyurethane-based resin, polyacrylic-based resin (eg, polymethylmethacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl-based resin such as polyvinylpyrrolidone, polychlorinated Vinyl resin (for example, vinyl chloride-vinyl acetate copolymer), polycarbonate resin, polystyrene, polyphenylene oxide, cellulose resin (for example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, Cellulose acetate butyrate, cellulose triacetate), polyvinyl alcohol resins (eg polyvinyl alcohol, polyvinyl) Partially saponified polyvinyl alcohol) such as butyral, petroleum resins, rosin derivatives, coumarone - indene resins, terpene resins, polyolefin resins (e.g. polyethylene, polypropylene) and the like.

Such a binder resin is preferably used in a proportion of, for example, about 20 to 600 parts by weight per 100 parts by weight of the dye. In the present invention, conventionally known ink solvents can be freely used as the ink solvent for dissolving or dispersing the dye and the binder resin.

As the photothermal conversion agent of the present invention, in addition to carbon black, an infrared absorbing agent, a dye having no heat transfer property, an ultraviolet absorbing agent and the like are used. It is preferable to use a photothermal conversion agent that preferably absorbs the wavelength of the laser light used. When using an infrared laser, an infrared absorber is preferable, for example, Japanese Patent Application Nos. 2-273573 and 2-286958.
The compounds described in Nos. 2-295303 and 2-299007 are preferred.

The photothermal conversion agent may be contained in the dye-donating layer, or a photothermal conversion layer may be separately provided. For example,
The photothermal conversion layer may be provided between the support and the dye-donor layer or on the side of the support opposite to the dye-donor layer. Further, it may be contained in the support.

When an infrared absorbing agent, a dye having no heat transfer property, an ultraviolet absorbing agent or the like is used in the photothermal conversion layer, these photothermal converting agents are dissolved in an organic solvent or water together with the same binder as that used in the dye donating layer. A photothermal conversion layer can be provided by dispersing and coating on a support. The coating amount of these photothermal conversion agents is set so that the absorbance for the light of the wavelength of the laser light used is 0.3 or more, preferably 1.0 or more. Usually 0.01 g / m ² to 1 g / m ²
Is preferred. Further, the ratio of the binder to the photothermal conversion agent is preferably from 0.1 to 5, and particularly preferably from 0.5 to 2. Further, the light-heat conversion layer containing these light-heat conversion agents,
It is preferably provided between the support and the dye-donor layer.

Next, the case where carbon black is used for the photothermal conversion layer will be described. The carbon black of the photothermal conversion layer is preferably dispersed in a hydrophilic binder. As the hydrophilic binder, a transparent or translucent hydrophilic colloid is typical, and for example, gelatin, a gelatin derivative,
It includes natural substances such as proteins such as cellulose derivatives and starch, polysaccharides such as gum arabic, and synthetic polymer substances such as water-soluble polyvinyl compounds such as polyvinylpyrrolidone and acrylamide polymers. Of these, gelatin and polyvinyl alcohol are preferable, and gelatin is particularly preferable. In particular, when carbon black having a large oil absorption amount is dispersed using a hydrophilic binder, the carbon black is less likely to aggregate and the quality of the transferred image does not deteriorate. Further, by providing a photothermal conversion layer between the dye-donor layer and the support,
It can prevent fusion and ablation of carbon black. The amount of carbon black in the photothermal conversion layer is 0.1 g /
m ² ~50g / m ² are preferred, 0.5g / m ² ~20
Particularly good results can be obtained when g / m ^{2 is} used. When the carbon black is dispersed in the hydrophilic binder, it is preferable to use a surfactant as the dispersant. As the surfactant, any of anionic type, cationic type and nonionic type can be used, but nonionic type is particularly preferable.

The dye-donor element may have an intermediate layer provided between the support and the photothermal conversion layer or between the photothermal conversion layer and the dye-donating layer. Preferred specific examples include (acrylonitrile / vinylidene chloride / acrylic acid) copolymer (weight ratio 14: 80: 6), (butyl acrylate / -2-aminoethyl methacrylate / -2-hydroxyethyl methacrylate) copolymer. Polymer (weight ratio 30:20:50),
Linear / saturated polyester such as BOSTIC 7650
(M Heart, Bostic Chemical Group)
Alternatively, a chlorinated high density poly (ethylene-trichloroethylene) resin may be used. The coating amount of the intermediate layer is not particularly limited, but it is usually used in an amount of 0.1 to 2.0 g / m ² .

The dye-donor layer is formed by selecting a dye so that a desired hue can be transferred when printed, and by arranging two or more dye-donor layers having different hues side by side with one thermal transfer dye-donor material. May be. For example, when an image such as a color photograph is formed by repeating printing of each color according to the color separation signal, it is desirable that the hue when printing is cyan, magenta, and yellow, and such a hue is provided. Line up the three dye-donor layers containing the dye. Alternatively, in addition to cyan, magenta, and yellow, a dye-donor layer containing a dye that imparts a black hue may be added. It is preferable to provide a mark for position detection at the same time when any one of the dye-donor layers is formed at the time of forming these dye-donor layers, because an ink or a printing step different from the dye-donor layer formation is not required.

In the present invention, the support used for the thermal transfer image-receiving material can withstand the transfer temperature and satisfies the requirements in terms of smoothness, whiteness, slipperiness, frictional property, antistatic property and dent after transfer. Anything that can be used can be used. For example, synthetic paper (polyolefin-based, polystyrene-based, etc.), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin Paper support such as paper, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene), various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene methacrylate, polycarbonate, etc. Films or sheets that have been treated to impart white reflectivity to the plastic, and laminates of any combination of the above may also be used.

The thermal transfer image receiving material is provided with a dye receiving layer. This receiving layer contains a substance capable of receiving the heat transferable dye which has a function of receiving the heat transferable dye transferred from the heat transfer dye-providing material at the time of printing and dyeing the heat transferable dye. Or with other binder substances, it is preferable that the coating has a thickness of about 0.5 to 50 μm. The following resins are examples of polymers that are typical examples of substances that can receive a heat transferable dye.

(A) having an ester bond: a dicarboxylic acid component such as terephthalic acid, isophthalic acid, succinic acid (these dicarboxylic acid components may be substituted with a sulfonic acid group or a carboxyl group), and ethylene. Polyester resin obtained by condensation of glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc .: polyacrylic acid ester resin or polymethacrylic acid ester resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate : Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395
No. 63, No. 63-7971, No. 63-7972, No. 63
No. 7973 and No. 60-294862 can be mentioned. As commercially available products, Toyon Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-14 are used.
0, Byron GK-130, ATR-200 made by Kao
9, ATR-2010, etc. can be used.

(B) Those having a urethane bond Polyurethane resin and the like. (C) Those having an amide bond Polyamide resin and the like. (D) Those having a urea bond, such as urea resin. (E) Those having a sulfone bond Polysulfone resin, etc. (F) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc. In addition to the synthetic resin as described above, a mixture or copolymer of these may be used.

The thermal transfer image-receiving material, particularly the receiving layer, may contain a high boiling organic solvent or a thermal solvent as a substance capable of receiving the heat transferable dye or as a diffusion aid of the dye. Specific examples of the high boiling point organic solvent and the heat solvent include JP-A Nos. 62-174754 and 62-24525.
No. 3, No. 61-209444, No. 61-200538
No. 6, No. 62-8145, No. 62-9348, No. 62
The compounds described in No. -30247 and No. 62-136646 can be mentioned.

In the present invention, the receiving layer of the thermal transfer image receiving material may have a structure in which a substance capable of receiving the heat transferable dye is dispersed and carried in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but water-soluble polymers having a group capable of undergoing a crosslinking reaction by a hardening agent are preferable, and gelatins are particularly preferable. The receiving layer may be composed of two or more layers. In that case, a synthetic resin having a low glass transition point is used for the layer closer to the support, or a dye having a high boiling point organic solvent or a heat solvent is used to enhance the dyeing property, and the outermost layer has a glass transition point. Use a synthetic resin with a higher point, reduce the amount of high boiling organic solvent or thermal solvent to the required minimum amount or do not use it, and make the surface sticky, adhere to other substances, re-transfer to other substances after transfer. It is desirable to have a structure that prevents troubles such as transfer and blocking with a thermal transfer dye-providing material. The total thickness of the receiving layer is 0.5 to 50 μm, especially 3 to 50 μm.
The range of 30 μm is preferable. In the case of a two-layer structure, the outermost layer preferably has a thickness of 0.1 to 2 μm, particularly 0.2 to 1 μm.

In the present invention, the thermal transfer image-receiving material may have an intermediate layer between the support and the receiving layer. The intermediate layer is a cushion layer, a porous layer, a dye diffusion preventing layer, or a layer having two or more of these functions depending on the constituent material, and may also serve as an adhesive in some cases. The dye diffusion preventing layer plays a role of preventing the heat transferable dye from diffusing into the support. The binder constituting the diffusion preventing layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferable, and examples thereof include the water-soluble binders mentioned above as the binder for the image-receiving layer, particularly gelatin. The porous layer is
This layer serves to prevent the heat applied at the time of thermal transfer from diffusing from the image receiving layer to the support and to effectively utilize the applied heat.

In the present invention, silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, etc. are used for the receiving layer, cushion layer, porous layer, diffusion preventing layer, adhesive layer and the like which constitute the thermal transfer image receiving material. Fine powders of aluminum silicate, synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina and the like may be contained.

A fluorescent whitening agent may be used in the thermal transfer image-receiving material. As an example, K. Veenkatarama
n edition "The Chemistry of Synth
"tic Dyes", Volume V, Chapter 8, JP-A-61-1
Examples thereof include compounds described in Japanese Patent No. 43752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, 2,5-dibenzoxazolethiophene compounds, etc. Can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

In the present invention, in order to improve the releasability of the thermal transfer dye-donor material and the thermal transfer image-receiving material, in the layers constituting the dye-donor material and / or the image-receiving material, particularly preferably, the surface where both materials come into contact with each other. It is preferable to add a release agent to the outermost layer corresponding to the above. As the release agent, polyethylene wax, amide wax, fine powder of silicone resin,
Solid or wax-like substance such as fine powder of fluorocarbon resin: Fluorine-based, phosphoric acid ester-based surfactants: Paraffin-based, silicone-based, fluorine-based oils, etc. However, silicone oil is particularly preferable.

As the silicone oil, in addition to the unmodified silicone oil, modified silicone oils such as carboxy-modified, amino-modified, epoxy-modified, polyether-modified and alkyl-modified can be used alone or in combination of two or more kinds. Examples thereof include various modified silicone oils described on pages 6 to 18B of “Modified Silicone Oil” technical data published by Shin-Etsu Silicone Co., Ltd. When used in an organic solvent-based binder, when an amino-modified silicone oil having a group capable of reacting with a crosslinking agent of the binder (for example, a group capable of reacting with isocyanate) is emulsified and dispersed in a water-soluble binder. Is a carboxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd .: trade name X-22-3710) or an epoxy-modified silicone oil (for example, Shin-Etsu Silicone Co., Ltd.).
Made by: Product name KF-100T) is effective.

The layers constituting the thermal transfer dye-providing material and the thermal transfer image-receiving material used in the present invention may be cured with a hardener. In the case of curing an organic solvent-based polymer, JP-A Nos. 61-199997 and 58-21539.
The hardeners described in No. 8 and the like can be used. It is particularly preferable to use an isocyanate type hardener for the polyester resin. For curing water-soluble polymers, U.S. Pat. No. 4,678,739, column 41, JP-A-59-1166.
55, 62-245261 and 61-18942.
The hardeners described in the publications are suitable for use. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardeners (dimethylol urea, etc.), or polymer hardeners (JP-A-6-61
2-234157 etc. are mentioned.

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a metal complex of some kind. Examples of antioxidants include chroman compounds, coumarane compounds, phenol compounds (eg, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds.
The compounds described in JP-A-61-159644 are also effective.

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.),
4-thiazolidone compounds (US Pat. No. 3,352,68
No. 1), benzophenone compounds (JP-A-56-2)
No. 784, etc.), Japanese Patent Laid-Open No. 54-48535,
There are compounds described in JP-A-62-136641, JP-A-61-188256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155 and 4,2,4.
45,018, columns 3 to 36, ibid., 4,254,195.
Nos. 3-8, JP-A-62-174741, 61-
88256, pages (27) to (29), JP-A-1-755.
68, JP-A-63-199248 and the like.

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

Various surfactants can be used in the constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, prevention of electrostatic charge, acceleration of 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-62-1734.
63, 62-183457 and the like.

When a substance capable of accepting a heat transferable dye, a release agent, an anti-fading agent, an ultraviolet absorber, an optical brightening agent, and other hydrophobic compounds are dispersed in a water-soluble binder, they are dispersed. It is preferable to use a surfactant as an auxiliary agent.
For this purpose, in addition to the above-mentioned surfactants, the surfactants described on pages 37 to 38 of JP-A-59-157636 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 the matting agent, in addition to the compounds described in JP-A-61-88256, page 29, such as silicon dioxide, polyolefin or polymethacrylate, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-27.
There are compounds described in Nos. 4944 and 63-274952.

As mentioned above, the dye-donor element of the invention comprises
Used to form transfer images. Such a process
Imagewise heating of the dye-donor element as described above using a laser to transfer the dye image to the image-receiving material to form the transferred image.

The dye-donor elements of the invention are used in sheet form or as continuous rolls or ribbons. If a continuous roll or ribbon is used, it may have only one type of dye or may be a zone of different dyes such as heat transfer cyan and / or magenta and / or yellow and / or black and other dyes. Have separately. That is, one-color, two-color, three-color, or four-color materials (or even multicolor materials) are included within the scope of the present invention.

In a preferred embodiment of the invention, the dye-donor element comprises a polyethylene terephthalate support coated in successive repeating regions of a cyan dye, a magenta dye and a yellow dye, the steps being carried out for each color in sequence. Form a color transfer image. Of course, when this process is performed in a single color, a monochrome transfer image is obtained.
For the thermal transfer of dyes from dye-donor elements to image-receiving materials, ion gas lasers such as argon and krypton, metal vapor lasers such as copper, gold and cadmium, ruby and YA.
Several lasers can be used, such as solid state lasers such as G, or semiconductor lasers such as gallium-arsenide that emit in the infrared region of 750 to 870 nm. However, in practice,
A semiconductor laser is advantageous in terms of small size, low cost, stability, reliability, durability, and ease of modulation.

For heating the image receiving material, a heating roller, heat sealing, hot air, an infrared heating lamp or the like is used.
A heating roller is preferable in order to improve the close contact with the dye-donor element and to heat it. For example, the image receiving material is wound on a roll containing a halogen lamp, and the dye-donor material is further wound on it. The object of the present invention can be achieved by irradiating laser light while rotating these.

[0058]

EXAMPLES The effects of the present invention will be described in more detail below by showing specific examples of the present invention. Unless otherwise specified, “part” means “part by weight”.

Example 1 A composition (1) for a photothermal conversion layer having the following composition was prepared by using a polyethylene terephthalate film having a thickness of 25 μm as a support.
The coating amount of carbon black after drying was applied to be 1.8 g / m ² .

Photothermal conversion layer composition (1) Carbon black 23 g Surfactant (Nissan Nonion NS208.5) 5% aqueous solution 27 g Hydrophilic binder (gelatin) 10% aqueous solution 350 g Polyethylene glycol (polymerization degree 1000) 12 g Succinic acid-2-ethylhexyl ester sodium sulfonate 10% solution (water / methanol = 1/1) 60 cc water 530 cc

Next, on the light-heat conversion layer, the inks (Ya, Ma, and Ca) for forming the dye-donating layer of yellow, magenta, and cyan having the following compositions were dried, and the dye coating amount was 0. The dye-donor materials (Y-, M-, C-) were obtained by coating so that the coating amount would be 0.4 g / m ² .

Ink for forming a yellow dye-donating layer (Ya) Dye (Y-10) 3 g Binder resin (Denka Butyral 5000A manufactured by Electrochemical) 2 g Curing agent (Takenate D110N manufactured by Takeda Pharmaceutical Co., Ltd.) 0.1 g Release agent Agent (amino-modified silicone oil KF-857 manufactured by Shin-Etsu Silicone) 0.004 g Methyl ethyl ketone 70 g Toluene 30 g

Ink for forming magenta dye-donating layer (M-a) Dye (M-5) 4 g Binder resin (Denka Butyral 5000A manufactured by Electrochemical) 3 g Curing agent (Takenate D110N manufactured by Takeda Pharmaceutical Co., Ltd.) 0.15 g Release agent (Amino-modified silicone oil KF-857 manufactured by Shin-Etsu Silicone) 0.004 g Methyl ethyl ketone 65 g Toluene 35 g

Ink for forming cyan dye-donating layer (Ca) Dye (C-2) 3.5 g Binder resin (Denka Butyral 5000A manufactured by Electrochemical) 3.5 g Curing agent (Takenate D110N manufactured by Takeda Pharmaceutical Co., Ltd.) 0. 18 g Release agent (amino-modified silicone oil KF-857 manufactured by Shin-Etsu Silicone) 0.004 g Methyl ethyl ketone 75 g Toluene 25 g

(Preparation of Thermal Transfer Image Receiving Material (1)) A synthetic paper having a thickness of 150 μm (made by Oji Yuka, YUPO-
Using FPG-150), the coating composition for receiving layer (1) having the following composition was applied to the surface by wire bar coating so that the thickness when dried was 8 μm to form a thermal transfer image receiving material (1). Drying was carried out for 15 hours in an oven at a temperature of 50 ° C. after temporary drying with a dryer.

Receptor layer coating composition (1) Polyester resin (Vylon-200 Toyobo) 22 g Polyisocyanate (KP-90 Dainippon Ink and Chemicals) 4 g Amino-modified silicone oil (KF-857 Shin-Etsu Silicone) 0.5 g methyl ethyl ketone 85 cc toluene 85 cc

The image-receiving material (1) was fixed on a drum having a 150 W halogen lamp built-in with the receiving layer facing the outside, and the dye-donor layer was formed on the drum so that the dye-donor layer was in contact with the receptor layer of the image-receiving material. Y-) were overlaid and taped.

The combined material was then irradiated with focused 830 nm laser light to transfer the yellow dye to the image receiving material. The laser light was generated from a semiconductor laser LN9880 manufactured by Matsushita Denshi, and the spot diameter was 20 μm and the irradiation time was 5 ms. The laser output was 75 mW. By rotating the drum and scanning the laser, the yellow dye image corresponding to the image signal could be transferred. The temperature of the drum at the time of laser light irradiation was measured by a thermistor and controlled to be about 80 ± 5 ° C.

When the dye-donor materials (Y-) were changed to the dye-donor materials (M-) and (C-) and thermal transfer was carried out in the same manner, magenta and cyan dye images could be transferred.

The results of the image formed on the image receiving material were as follows. The transfer density was measured with a Macbeth reflection densitometer, and the blue light density was 1.8 for the yellow image, the green light density was 1.9 for the magenta image, and the red light density was 1.7 for the cyan image. The recorded image was strong and could not be scraped with a finger.

On the other hand, when the transfer was carried out at room temperature (drum temperature: about 30 ° C.) without using the drum heater, the transferred dye remained on the surface of the receiving layer, and the part rubbed with the finger was peeled off. ..

Example 2 A 6 μm-thick polyester film (manufactured by Teijin) was used as a support, and an ink composition for forming a dye-donor layer having the following composition was applied such that the coating amount after drying was 1.2 g / m ^2. Thus, cyan, magenta, and yellow dye-donor elements were obtained.

Cyan ink composition for forming dye-donor layer Infrared absorbing dye-A (Chemical formula 14) 2.4 parts Dye (C-2) 3 parts Polyvinyl butyral resin 2.5 parts (Denka Butyral 5000A: manufactured by Electrochemical Co., Ltd. ) Polyisocyanate 0.1 part (Takenate D110N: manufactured by Takeda Pharmaceutical) Amino-modified silicone oil 0.004 part (KF-857: manufactured by Shin-Etsu Silicone) Methyl ethyl ketone 50 parts Toluene 50 parts

[0074]

[Chemical 14]

Magenta Ink Composition for Forming Dye Donating Layer Infrared Absorption Dye-B (Chemical Formula 15) 2.3 parts Dye (M-4) 2.5 parts Polyvinyl butyral resin 2.5 parts (Eslex BX-1 : Sekisui Chemical Co., Ltd.) Polyisocyanate 0.1 part (KP-90: Dainippon Ink and Chemicals Co., Ltd.) Silicone oil 0.004 part (KF-857: Shin-Etsu Silicone Co., Ltd.) Methyl ethyl ketone 70 parts Toluene 30 parts

[0076]

[Chemical 15]

Yellow ink composition for forming dye-donor layer Infrared absorbing dye-C (Chemical Formula 16 below) 2.5 parts Dye (Y-8) 5 parts Ethylcellulose 3 parts Methylethylketone 50 parts Toluene 50 parts

[0078]

[Chemical 16]

(Preparation of Thermal Transfer Image Receiving Material (2)) Thickness 20
Prepare resin-coated paper in which polyethylene is laminated to a thickness of 25 μm on both sides of 0 μm paper respectively, and apply a coating composition (2) for a receptive layer having the following composition to a dry thickness of 10 μm by wire barcotting, It was dried to prepare a thermal transfer image receiving material (2).

Receptor layer coating composition (2) Polyester resin (TP220 manufactured by Nippon Synthetic Chemical Industry) 25 g Amino-modified silicone oil (KF-857 manufactured by Shin-Etsu Silicone Co.) 0.8 g Polyisocyanate (KP-90 manufactured by Dainippon Ink & Chemicals, Inc.) ) 4 g methyl ethyl ketone 100 cc toluene 100 cc

A thermal transfer image was obtained using the above dye-donor material and image-receiving material (2) in the same manner as in Example 1 (the drum temperature during laser light irradiation was controlled to about 80 ± 5 ° C.).
The transferred image obtained by the thermal transfer recording method of the present invention was clear with no color unevenness. The image was sufficiently transferred to the image receiving layer and was stable.

Example 3 An infrared absorbing layer-forming ink composition having the following composition was coated on a polyethylene terephthalate support having a thickness of 25 μm so that the dried infrared absorbing layer had a thickness of 1.5 μm. Formed. Onto this layer, the dye-donor layer-forming inks (Ya, Ma, and Ca) of Example 1 were applied, and yellow,
Magenta and cyan dye-donor elements were made.

Ink Composition for Forming Infrared Absorption Layer Infrared Absorption Dye-D (Chemical Formula 17) 2.1 parts Polyvinyl butyral resin 2.5 parts (Denka Butyral 5000A: manufactured by Denki Kagaku) Methyl ethyl ketone 70 parts Toluene 30 parts

[0084]

[Chemical 17]

(Preparation of Thermal Transfer Image Receiving Material (3)) An organic solvent solution of the dye-receptive polymer having the composition (B) was emulsified and dispersed in a gelatin aqueous solution having the composition (A) below by a homogenizer to prepare a dye-receptive material. A gelatin dispersion was prepared.

(A) Gelatin aqueous solution Gelatin 2.3 g Sodium dodecylbenzenesulfonate (5% aqueous solution) 20 cc Water 80 cc

(B) Dye Receptive Polymer Solution Polyester Resin (Vylon 300, Toyobo) 7.0 g Carboxy-modified Silicone Oil (X-22-3710, Shin-Etsu Silicone) 0.7 g Methylethylketone 20 cc Toluene 10 cc Triphenylphosphine Fate 1.5 g

To the dispersion thus prepared, 0.5 g of the following fluorine-based surfactant (a) C ₃ F ₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK was added in water / methanol (1: 1). ) Mixed solvent 10
The solution dissolved in cc was added to obtain a receiving layer coating composition.

This coating composition was subjected to corona discharge on the surface to make a synthetic paper having a thickness of 150 μm (manufactured by Oji Yuka: YUPO-SG).
G-150) was applied by a wire bar coating method so as to have a wet film thickness of 75 μm, and dried to prepare a thermal transfer image receiving material (3).

Using the obtained dye-donor material and image-receiving material (3), a transferred image was formed in the same manner as in Example 1 (the drum temperature during laser light irradiation was controlled to about 80 ± 5 ° C.). A SLD301 laser diode manufactured by Sony Corporation was used as the laser. The obtained image of each color was clear. As for the reflection densities measured by a Macbeth densitometer, the red density of the cyan image was 2.1, the green density of the magenta image was 2.2, and the blue density of the yellow image was 2.0. The obtained image was stable.

[0091]

INDUSTRIAL APPLICABILITY According to the present invention, an image is received by a thermal transfer recording method in which a dye-donor material containing a photothermal conversion agent and a heat transferable dye and an image receiving material are brought into contact with each other and a laser beam is irradiated to record an image while heating the image receiving material. It was possible to stably form a clear, high-density image having no color unevenness on the material.

Claims (1)

[Claims] 1. A thermal transfer dye-donor material containing a heat-transfer dye and a photothermal conversion agent that absorbs laser light and converts it into heat, and a dye transferred from the thermal transfer dye-donor material to one surface of a support. By combining with a thermal transfer image-receiving material provided with a dye-receiving layer and irradiating a laser beam corresponding to an image signal, the light absorbed by the photothermal conversion agent in the dye-providing material is converted into heat, and this heat causes the dye A thermal transfer recording method using a laser, which comprises heating the thermal transfer image receiving material during laser irradiation in a method for transferring an image by recording the thermal transferable dye in the donor material to the dye receiving layer in the thermal transfer image receiving material. ..