JPH05201140A - Thermal transfer image receiving material - Google Patents

Abstract

PURPOSE:To obtain a recording image having high transfer density and favorable frictional resistance, by a method wherein an infrared absorption coloring matter is contained within a coloring matter receiving layer or a layer coming into contact with the coloring matter receiving layer as a light and heat conversion agent. CONSTITUTION:Laser beams corresponding to an image signal are applied to a heat transfer coloring matter giving material in a heat transfer image receiving material containing a light and heat conversion agent which absorbs a heat transfer coloring matter and the laser beams and converts them into heat, the light absorbed by the light and heat conversion agent within the coloring matter giving material is converted into the heat, the heat transfer coloring matter transferred away from the coloring matter giving material is received and an image is recorded. A coloring matter receiving layer receiving the heat transfer coloring matter is provided on a substrate in the heat transfer image receiving material like this. In the coloring matter receiving layer or a layer which comes into contact with coloring matter is made to contain an infrared absorption coloring matter as the light and heat conversion agent. With this construction, a recording image which has high transfer density and is superior in wear resistance is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer image-receiving material for carrying out thermal transfer recording using a laser beam, and more particularly to a thermal transfer image-receiving material containing an infrared absorbing dye as a photothermal conversion agent.

[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 and the like. According to one method of obtaining such prints, the 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 yellow, magenta or cyan signals. This process is then repeated for the other two colors. In this way, a color hard copy corresponding to the original image 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 absorptive material may be present as a layer beneath the dye or may be mixed with the dye and present in the dye-donor layer. 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 reconstruct the color of the original image, causing a thermal transfer.

[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. As a method for solving this problem, Japanese Patent Laid-Open No. 3-2
No. 48855 describes an example of an apparatus in which a photothermal conversion layer is provided on a transparent image receiving material and a laser is irradiated from the image receiving material side. However, this method can only record on transparent materials. In addition, heat is transferred from the image-receiving material to the dye-donor material to transfer the dye, which requires a high laser irradiation light amount, which increases the load on the laser light source. 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-providing material containing a heat-transferable dye and a photothermal conversion agent that absorbs laser light and converts it into heat, by irradiating laser light corresponding to an image signal with the photothermal heat in the dye-providing material. The thermal transfer image-receiving material for converting the light absorbed by the converting agent into heat, receiving the heat-transferable dye transferred from the dye-donor element by this heat, and recording an image on the support, Use of a thermal transfer image receiving material having a dye receiving layer for receiving a transferable dye, and containing an infrared absorbing dye as a photothermal conversion agent in the dye receiving layer or in a layer in contact with the dye receiving layer Achieved by.

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. In particular, a support having good translucency and heat resistance is preferable. The thickness of the support of the thermal transfer dye-providing material is generally 2 to
It is 200 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 ~
5 g / m ^2, preferably 0.1-2 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, oil-soluble dyes, and the like. 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 combine with each other to form a ring, or D ⁸ and D ¹¹ or / and D ⁹ and D ¹² may combine with each other 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 12]

[0026]

[Chemical 13]

It is preferable to introduce the fading-preventing group described in JP-A-3-205189 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.

In the present invention, as the light-heat converting agent used in the dye-donor material, in addition to carbon black, an infrared absorbing dye, 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 an infrared laser is used, an infrared absorbing dye is preferable, for example, JP-A-3-2659.
No. 3, No. 3-97589, No. 3-97591, No. 3
No. 97590, No. 3-34891, No. 3-4228
No. 1, No. 3-30992, No. 3-36093, No. 3
-36095, 3-36094, 2-2074
No. 3-63185, U.S. Pat. No. 5,019,59.
No. 4, Japanese Patent Application No. 2-299902, No. 2-299007
The compounds described in Nos. 2-297165, 2-295304, 2-286958 and 2-295303 are preferable. Specific examples of the infrared absorbing dye compound are shown below.

[0031]

[Chemical 14]

[0032]

[Chemical 15]

[0033]

[Chemical 16]

[0034]

[Chemical 17]

[0035]

[Chemical 18]

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 dye, a dye having no heat transfer property, an ultraviolet absorber or the like is used in the photothermal conversion layer, these photothermal conversion agents are dissolved in an organic solvent or water together with the same binder as used in the dye donating layer. Alternatively, it can be dispersed and coated on a support to provide a photothermal conversion layer. The coating amount of these photothermal conversion agents is set so that the absorbance for light of the wavelength of the laser light used is 0.2 or more, preferably 0.5 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, if necessary. 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 another hue such as black may be added. It is preferable to provide a mark for position detection on the dye-donor material so as to detect the position of the first hue of thermal transfer.

In the present invention, if the support used for the thermal transfer image receiving material can withstand the transfer temperature and can satisfy the requirements in terms of smoothness, slipperiness, frictional property, antistatic property and dent after transfer. Anything 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) Having 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.

The infrared absorbing dye used as a photothermal conversion agent in the thermal transfer image-receiving material may be contained in the receiving layer or the support, or may be converted into the heat between the receiving layer and the support or on the surface of the receiving layer. It may be contained in the layer provided as a layer. It is preferably contained in the receiving layer. The coating amount of these infrared absorbing dyes is 0.01 to 5 g / m ² in any of the receiving layer, the support and the photothermal conversion layer.
Is preferable, and particularly preferably 0.5 to ² g / m ^2.
The range is. When the infrared absorbing dye is contained in the receiving layer, it can be dissolved or dispersed in the composition used for forming the receiving layer. When it is contained in the support, it may be contained in the composition when the support is formed. Particularly when resin-coated paper is used, it is preferably contained in the resin layer. When the photothermal conversion layer is formed separately from the receiving layer, it can be formed in the same manner as in the case of the dye-donor material. That is, the photothermal conversion layer can be provided by dissolving or dispersing the infrared absorbing dye in an organic solvent or water together with the same binder as that used in the receiving layer, and coating the same. The thickness of this photothermal conversion layer is preferably 0.1 to 5 μm, and particularly preferably 0.2 to 2 μm. The weight ratio of the infrared absorbing dye to the binder is preferably 0.1 to 5,
Particularly, 0.5 to 2 is preferable. As the infrared absorbing dye used as the photothermal conversion agent contained in the image receiving material, the compounds described in the infrared absorbing dye used for the dye providing material can be used.

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 serves to prevent 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 is used for the receiving layer, the light-heat converting layer, the cushion layer, the porous layer, the diffusion preventing layer, the adhesive layer and the like which constitute the thermal transfer image receiving material. , Barium sulfate, aluminum silicate, synthetic zeolite, zinc oxide,
Fine powders such as lithopone, titanium oxide, and alumina 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 surfaces of both materials contacting 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 non-modified silicone oil, modified silicone oil such as carboxy-modified, amino-modified, epoxy-modified, polyether-modified or 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 issued 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-donor element and thermal transfer image-receiving element used in the present invention may be hardened 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, antistatic property, 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, a fluorescent 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 and the image-receiving element in the present invention are used for forming a transferred image. Such a process consists of imagewise heating a dye-donor element as described above with a laser and transferring the dye image to an image-receiving material to form a transfer 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 multi-color 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 sequential repeating areas of a cyan dye, a magenta dye and a yellow dye, the steps being carried out sequentially for each color to give a three-part dye. 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.

When the laser beam applied to the dye-donor material is infrared light, the laser light not absorbed by the dye-donor material is absorbed by the infrared-absorbing dye in the image-receiving material and converted into heat. When the laser light applied to the dye-providing material is not infrared light, the infrared laser light absorbed by the infrared-absorbing dye in the image receiving material is applied at the same time. In this case, the laser beam for irradiating the image receiving material may be a laser beam whose intensity is modulated according to an image signal, or may be a laser beam having a uniform light amount. Lasers that can be used to transfer dye from the dye-donor elements of the invention are commercially available.

[0064]

EXAMPLES The effects of the present invention will be described in more detail below by showing specific examples of the present invention. Example 1 A 25 μm-thick polyester film (manufactured by Teijin) was used as a support, and a dye-donor layer-forming ink having the following composition was applied so that the coating amount after drying was 1.2 g / m ² ; C-1, M-1, and Y-1 were obtained.

Cyan ink composition for forming dye-donor layer Infrared absorption dye-A (Chemical formula 19 below) 1.5 g Cyan dye C-13 3 g Polyvinyl butyral resin 2.5 g (Denka Butyral 5000A: manufactured by Electrochemical Co., Ltd.) Polyisocyanate 0.1 g (Takenate D110N: manufactured by Takeda Pharmaceutical) Amino-modified silicone oil 0.004 ml (KF-857: manufactured by Shin-Etsu Silicone) Methyl ethyl ketone 50 ml Toluene 50 ml

[0066]

[Chemical 19]

Magenta Ink Composition for Forming Dye Donating Layer Infrared absorbing dye-B (Chemical Formula 20 below) 1.6 g Magenta dye M-3 2.5 g Polyvinyl butyral resin 2.5 g (S-Rex BX-1: Sekisui Chemical Co., Ltd.) Polyisocyanate 0.1 g (KP-90: Dainippon Ink and Chemicals) Amino-modified silicone oil 0.004 ml (KF-857: Shin-Etsu Silicone) Methyl ethyl ketone 70 ml Toluene 30 ml

[0068]

[Chemical 20]

Yellow ink composition for forming a dye-donor layer Infrared absorbing dye-C (Chemical Formula 21 below) 1.5 g Yellow dye Y-6 3 g Ethylcellulose 3 g Methylethylketone 50 ml Toluene 50 ml

[0070]

[Chemical 21]

(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 (1) for image receiving layer having the following composition was applied on 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 30 minutes in an oven at a temperature of 100 ° C. after temporary drying with a dryer.

Coating Composition (1) Infrared Absorbing Dye-D (Chemical Formula 22) 4 g Polyester Resin 22 g (Vylon-200: Toyobo) Polyisocyanate 4 g (KP-90 Dainippon Ink & Chemicals, Inc.) ) Amino-modified silicone oil 0.5 g (KF-857: manufactured by Shin-Etsu Silicone) Methyl ethyl ketone 85 ml Toluene 85 ml

[0073]

[Chemical formula 22]

Further, as comparative materials, ink compositions of cyan, magenta and yellow dye-donor materials and compositions obtained by removing the infrared absorbing dye from the coating composition of the image receiving material (1) were prepared. Donor materials C-a, M-
a, Ya and the image receiving material (a) were prepared.

The image-receiving material was fixed on the drum with the receiving layer facing outside, and the dye-donor layer was placed on the drum so that the dye-donor layer was in contact with the receiving layer of the image-receiving material, and the tape was fixed. next,
The combined material was irradiated with focused 830 nm laser light to transfer the 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 dye image corresponding to the image signal could be transferred. The results obtained are shown in Table A.

[0076]

[Table 1]

For the transfer density, an X-light reflection densitometer was used.
It was measured through a filter corresponding to the absorption of each dye.
The abrasion resistance was evaluated by rubbing the surface of the receptor layer of the image-receiving material after transfer recording with a finger and measuring the degree of dye repellency according to the following criteria. A: Almost no dye can be removed. Δ: The dye slightly adheres to the finger. X: Most of the dye can be removed.

[0078]

[Effects of the Invention] From this example, it is understood that when the material of the present invention is used, a recorded image having a high transfer density and excellent abrasion resistance can be obtained.

Claims (1)

[Claims] 1. A thermal transfer dye-providing material containing a heat transferable dye and a photothermal conversion agent that absorbs laser light and converts it into heat, is irradiated with laser light corresponding to an image signal, and photothermal conversion in the dye-providing material. The heat absorbed by the agent is converted into heat, and the heat transfer image receiving material for recording an image by receiving the heat transferable dye transferred from the dye-donor material by the heat is transferred onto the support. A thermal transfer image-receiving material having a dye-receiving layer for receiving a functional dye, and containing an infrared absorbing dye as a photothermal conversion agent in the dye-receiving layer or in a layer in contact with the dye-receiving layer.