JPH07214922A - Thermal transfer recording material - Google Patents

Abstract

PURPOSE:To provide a thermal transfer recording material enabling writing using a pencil or an aq. ball-point pen and capable of obtaining image recording not generating the lowering of image quality caused by the blur of a recording image during preservation without unreasonably damaging transfer density in a system performing thermal transfer recording using an electronic image signal. CONSTITUTION:In a thermal transfer recording material consisting of a thermal transfer dye donating material wherein at least a dye donating layer consisting of a thermal transfer dye and a binder resin is provided on a support and a thermal transfer dye image receiving material wherein a dye receiving layer containing dye acceptive substances is provided on a support, the thermal transfer dye is a dissociable dye donating a hydrogen atom to the dye acceptive substances by the transfer to the dye receiving layer to become an anion and at least one of the dye acceptive substances is inorg. solid fine particles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer recording material for recording an image by a thermal transfer system in which a dye is transferred from a dye-donor layer to a dye-receiving layer by heating in accordance with image information to record the dye. .

[0002]

2. Description of the Related Art In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and apparatuses suitable for the respective information processing systems have also been developed and adopted. As one of such recording methods, the thermal transfer recording method has been widely used recently because the apparatus used is light and compact, noise-free, excellent in operability and maintainability, and easy to colorize. . This thermal transfer recording method is roughly classified into two types, a heat melting type and a heat transfer type. In the latter method, a thermal transfer dye-donor material having a dye-donor layer containing a binder and a heat transferable dye on a support is superposed with a thermal transfer dye-image receiving material, and heat is applied from the support side of the dye-donor material, and heat is applied. In this method, a heat transferable dye is transferred in a pattern to a recording medium (heat transfer dye image receiving material) to obtain a transferred image. Here, the heat transferable dye means a dye which can be transferred from the thermal transfer dye-donor material to the thermal transfer dye image-receiving material by sublimation or diffusion in a medium. In such a thermal transfer recording method, color image information is set to yellow,
It is converted into magenta and cyan electric signals, transmitted to the thermal printer device, and recorded. To obtain the print, the dye-donor element is placed face-to-face with the image-receiving element and inserted between the thermal head and the platen roller. The thermal head is energized and heated according to the transmitted signal. The dye-donor element is heated from the back side by a thermal head. The dye in the dye-donor element migrates to the image-receiving element,
The image is recorded. In the case of a color image, this operation is followed by sequential heating with yellow, magenta, cyan and optionally black dye-donor elements to give a color hard copy corresponding to the original color image.

[0003]

However, the thermal transfer image receiving material used in this thermal transfer type thermal transfer recording method has the following problems. One of the problems that should be improved by the conventional sublimation type thermal transfer recording method is that you can write with an oil-based pen, but with a water-based pen or pencil, the writing performance is very poor, and the ink on the line of the character separates or you cannot write at all. It is pointed out that there is no. Therefore, there is a further demand for development of a sublimable dye and / or development of a receiving layer which is excellent in writability and does not deteriorate transferability of the sublimable dye to the receiving layer. Therefore, the first object of the present invention is to form an image receiving layer having excellent writability,
Another object of the present invention is to provide a thermal transfer recording material in which the transferability of the sublimable dye to the receiving layer is not deteriorated. Further, when the transferability of the conventional thermal transfer image-receiving material is improved, the dye tends to be thermally diffused in the image-receiving layer, so that the recorded image becomes bleed after storage. Therefore, a second object of the present invention is to provide an image receiving material in which the recorded image after storage does not bleed even if the transferability of the thermal transfer image receiving material is improved.

[0004]

The above problems are caused by a thermal transfer dye-providing material having a dye-donating layer comprising at least a heat transferable dye and a binder resin on a support, and a dye containing a dye-receiving substance on the support. In a material for thermal transfer recording comprising a thermal transfer dye image-receiving material provided with a receiving layer, the heat transferable dye may transfer to the dye receiving layer to donate a hydrogen atom to the dye receiving material to become an anion. A dissociative dye, and at least one of the dye-receptive substances
This was solved by a thermal transfer recording material, which is an inorganic solid fine particle.

The contents of the image-receiving material for thermal transfer recording and the thermal transfer dye-donating material used in the present invention will be specifically described below. The thermal transfer dye image receiving material is provided with an image receiving layer. This image-receiving layer accepts the heat-transferable dye transferred from the heat-transfer dye-providing material at the time of printing, and the substance capable of receiving the heat-transferable dye having the function of dyeing the heat-transferable dye alone. , Or 0.5 to 5 including with its binder material
It is preferable that the film has a thickness of about 0 μm.

The inorganic solid fine particles of the present invention will be described in detail. As the inorganic solid fine particles of the present invention, potassium chloride, potassium carbonate, calcium carbonate, slaked lime, barium sulfate, barium carbonate, lithobon, aluminum sulfate, activated alumina, lead white, zinc white, zinc sulfate, manganese sulfate, nickel sulfate, Examples thereof include titanium oxide, titanate, phosphate, boric acid, borate, sodium silicate, zeolite and the like. Preferably, potassium carbonate, calcium carbonate, barium sulfate, barium carbonate, aluminum sulfate,
Titanium oxide, titanate, phosphate, borate, silicic acid, sodium silicate, and zeolite, and more preferably calcium carbonate, barium carbonate, titanium oxide, and silicic acid are used.

The inorganic solid fine particles of the present invention are preferably used by being dispersed or dissolved in the resins listed below. As the resin, one that acts as a dye-receptive substance may be used. Dye-receptive resins are those that accept (or share) hydrogen atoms from dissociative dyes.
Those having a molecular weight of 2 × 10 ² to 1 × 10 ⁶ are preferable, and those having a molecular weight of 5 × 10 ² to 2 × 10 ⁵ are particularly preferable. The coating amount is preferably 0 to 50 parts by weight, preferably 0 to 30 parts by weight, and 0.2 to 15 g / m ² with respect to 1 part by weight of the inorganic solid acid, activated clay and solid fine particles of the present invention. And preferably used at 0.5 to 8 g / m ² . Representatively, JP-A-60-260060 and JP-A-60-260
381, Japanese Patent Application No. 61-52995, Japanese Patent Laid-Open No. 1-1883.
91, JP-A-3-83685, Japanese Patent Application No. 5-137463.
Those having a primary and / or secondary and / or tertiary amino group, those having a nitrogen-containing heterocyclic group disclosed in 4 and
Preferred compounds are those having a primary cation group and inorganic or organic basic compounds. Further, as a commercial product, Epomin manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd. and AEA “Sankyo” manufactured by Sankyo Co., Ltd. are also preferred compounds. In addition to the above compounds and polymers, dimers, mixtures, copolymers and the like of these can also be used.

As the resin used for dispersing or mixing the inorganic solid fine particles of the present invention described below, various known synthetic resins and water-soluble binder resins can be used. As the synthetic resin, an ordinary synthetic resin can be used as long as it accepts the dye transferred from the transfer sheet. Specific examples of the synthetic resin used in the present invention together with the above-mentioned dye-receptive substance are shown below. (A) Those having an ester bond. Dicarboxylic acid components such as terephthalic acid, isophthalic acid, and succinic acid (these dicarboxylic acid components may be substituted with sulfonic acid groups, carboxyl groups, etc.), ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol Polyester resin obtained by condensation of bisphenol A, polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate, etc., or polymethacrylic acid ester resin, polycarbonate resin, polyvinyl acetate resin, styrene Acrylate resin,
Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395, 63-7971 and 63-
7972, 63-7973, 60-29486
No. 2 can be mentioned. As commercially available products, Toyon Byron 290, Byron 200,
Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130, Kao's ATR-2009, ATR-2010, Unitika's Elitel UE3500, UE3210, XA-815.
3, Polyester TP-220, R- manufactured by Nippon Synthetic Chemical Industry
188 etc. can be used. (B) Those having a urethane bond. Polyurethane resin etc. (C) Those having an amide bond. Polyamide resin, etc. (D) Those having a urea bond. Urea resin etc. (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 above synthetic resins, mixtures or copolymers of these can also be used. In the present invention, various known water-soluble and / or water-dispersible polymers can be used as the water-soluble binder used together with the above-mentioned dye-receptive substance. Polymers are preferable, and gelatins are particularly preferable. In the present invention, the receiving layer of the thermal transfer image receiving material is
It may be configured so as to be supported by being mixed with 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 group capable of undergoing a crosslinking reaction with a hardening agent is preferable, and more preferably the water-soluble polymer described below. Binder and gelatin are good.

[0009]

[Chemical 1]

[0010]

[Chemical 2]

The molecular weight of the water-soluble binder of the present invention is 1 ×
10 ³ to 1 × 10 ⁶ is suitable, and particularly 1 × 10 ⁴ to 2
× 10 ⁵ is preferable. The coating amount is 0 to 50 parts by weight per 1 part by weight of the inorganic solid fine particles of the present invention.
30 parts by weight is preferred.

A protective layer, a peeling layer, and
An auxiliary layer such as an anti-curl layer can be provided. In particular, it is useful to provide a protective layer. The total thickness of the receiving layer is preferably 0.5 to 50 μm, particularly preferably 3 to 30 μm. 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 receiving layer may be composed of two or more layers.
In that case, it is preferable that the layer closer to the support contains a large amount of the inorganic solid fine particles of the present invention, and a high-boiling organic solvent and / or a thermal solvent is added to the receiving layer to enhance the dyeing property to the dye. You may make it the structure. A binder having a lower glass transition point, which is advantageous for heat transferable dyeing properties, is used in the layer closest to the outermost layer containing the dye-receptive substance, and the dyeing property during transfer is improved. May be. For the outermost layer, a synthetic resin having a higher glass transition point is used, or the amount of the high-boiling organic solvent and / or thermal solvent and / or the transfer accelerator of the present invention used is minimized or not used. It is desirable to have a structure that prevents failures such as stickiness, retransfer to another substance after adhesive transfer with another substance, and blocking with a thermal transfer donor material.

The heat transferable dye used in the present invention is a dissociative dye capable of donating a hydrogen atom to the dye receiving material to become an anion when the heat transferable dye moves to the dye receiving layer. As the dissociative substituent, the substituted dye preferably has a pka of 12 or less, and particularly preferably a pka of 7 or less. As the dissociative substituent, known substituents can be used as long as they have the above properties, and specifically, phenolic hydroxyl group, carboxylic acid group, sulfonic acid group, enolic hydroxyl group, sulfonylamino group, active methylene group. _{, -CONHCO -, - SO 2 NHCO} -, - S
And a heterocycle having a structure of O ₂ NHSO ₂ — or —NH—. Further, as conventionally known dissociative dyes, JP-A-3-90387, JP-A-3-114890, and JP-A-3-836 are known.
87, ibid. 3-83688, ibid. 3-83689, ibid. 3-9
The dyes of 2385 and 3-92386 can be used.

[0015]

[Chemical 3]

[0016]

[Chemical 4]

[0017]

[Chemical 5]

[0018]

[Chemical 6]

As a method for synthesizing the above-mentioned dyes used in the present invention, a conventional synthesizing method is used. For example, oxidative coupling (X ¹ is —N of a coupler compound and a p-hydroxyaniline compound for each dye is used. =)) Or a dehydration condensation reaction (when X is -CR ¹⁰⁰ =) between the coupler compound and p-hydroxyaryl aldehyde.

As the binder resin to be used together with the above-mentioned dye, any of the binder resins conventionally known for this purpose can be used, which usually has high heat resistance and migration of the dye when heated. The one that does not interfere with is selected. For example, polyamide resin, polyester resin, epoxy resin, polyurethane resin, polyacrylic resin (for example, polymethylmethacrylate,
Polyacrylamide, polystyrene-2-acrylonitrile), vinyl-based resins such as polyvinylpyrrolidone, polyvinyl chloride-based resins (for example, vinyl chloride-vinyl acetate copolymer), polycarbonate-based resins, polystyrene, polyphenylene oxide, cellulose-based resins ( For example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate), polyvinyl alcohol resin (for example, partially saponified polyvinyl alcohol such as polyvinyl alcohol and polyvinyl butyral). , Petroleum resin, rosin derivative, coumarone-indene resin, terpene resin, polyolefin resin (E.g., polyethylene, polypropylene) and the like. Such a binder resin is preferably used in a ratio of about 20 to 600 parts by weight, for example, per 100 parts by weight of the dye. In the present invention, a conventionally known ink solvent can be freely used as an ink solvent for dissolving or dispersing the above dye and binder resin.

The thermal transfer dye 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 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 Nos. -30247 and 62-136646 can be mentioned.

The support of the image-receiving sheet used in the present invention can withstand the transfer temperature, has a smoothness, a whiteness,
Any material can be used as long as it satisfies the requirements in terms of slipperiness, friction, antistatic properties, and dents after transfer. For example, synthetic paper (polyolefin-based, polystyrene-based, etc.), high-quality 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 (paper coated on both sides with polyethylene), and 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. As a support of an image receiving material for transmission observation (for example, OHP, etc.), if it has heat resistance enough to withstand thermal transfer processing, and if it has transparency enough to observe a transferred image, it is a generally known support. The body is used. Specifically, polyethylene, polypropylene, polyvinylidene chloride, polyvinyl alcohol, polyester, polycarbonate, polyamide, polystyrene, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ionomer, acetyl cellulose, cellulose ester, polyvinyl acetal. Resin films of polyvinyl chloride, polyphenylene sulfone, polyether sulfone, polyether ether ketone, polyether imide, polyacrylate, polymethyl methacrylate, etc. are used. In consideration of transparency, flexibility, heat resistance, etc., films of polyester, polycarbonate, polyamide, etc. are preferable. Of these, polyethylene terephthalate and polyethylene naphthalate films are particularly preferable. These resin films may be used alone or in the form of a laminated film. The thickness of these supports is usually 25 mμ to 360 μm, preferably about 75 mμ to 200 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 any one of a cushion layer, a porous layer, and a dye diffusion preventing layer or a layer having two or more functions depending on the constituent material, and also serves 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 prevention layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferable, and examples thereof include the above-mentioned binder for the receiving layer, particularly gelatin. The porous layer is a layer which prevents the heat applied during the thermal transfer from diffusing from the receiving layer to the support and plays a role of effectively utilizing the applied heat.

In the present invention, the cushion layer, the porous layer, the diffusion preventive layer, the adhesive layer and the like which constitute the thermal transfer image receiving material,
Contains the same or different inorganic fine particles of the present invention such as silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate, synthetic zeolite, zinc oxide, lithobone, titanium oxide, and alumina. May be.

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" Vol. V, Chapter 8, JP-A-61-1
The compounds described in No. 43752 and the like can be mentioned. 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.

As the support for the thermal transfer dye-providing material, any of those conventionally known can be used. 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-donor element is generally 2 to
It is 30 μm. 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.

The thermal transfer dye-providing material using a heat-transferable dye basically has a dye-providing layer containing a dye and a binder which are movable by heat on a support. This thermal transfer dye-providing material is prepared by dissolving or dispersing a dye and a binder resin which are conventionally known to be sublimated or become mobile by heat in a suitable solvent to prepare a coating solution,
This is applied to one side of the support of a conventionally known thermal transfer dye-donor element, for example, about 0.2 to 5 μm, preferably 0.4 to 2
It can be obtained by forming a dye-donor layer by coating and drying at a coating amount that results in a dry film thickness of μm. The dye-donor layer may be formed of a single layer, but may be formed of two or more layers for use in a method in which it is repeatedly used many times. In this case, the dye content and dye / binder ratio in each layer may be different. 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. Preferred in the present invention are those having a small molecular weight of about 150 to 800, and particularly preferred are heat transferable dyes having an electrophilic substituent and / or a substituent which is dissociated to be anionic and has a transfer temperature. , Hue, light resistance, solubility in ink and binder resin, dispersibility and the like. Dye application amount is 0.03-5
g / m ^2, preferably 0.1-2 g / m ^2.

A slipping layer may be provided to prevent the thermal head from sticking to the dye-donor element. The slipping layer is composed of a lubricating material, with or without a polymeric binder, such as a surfactant, a solid or liquid lubricant or mixtures thereof. The dye-donor material is preferably subjected to anti-sticking treatment on the side of the support on which the dye-donor layer is not provided, in order to prevent sticking due to heat from the thermal head when printing from the back side and to improve slippage. For example, it is preferable to provide a heat-resistant slip layer containing (1) a reaction product of a polyvinyl butyral resin and isocyanate, (2) an alkali metal salt or an alkaline earth metal salt of a phosphoric acid ester, and (3) a filler. Good. The polyvinyl butyral resin has a molecular weight of about 60,000 to 200,000, a glass transition point of 80 to 110 ° C., and a vinyl butyral portion having a weight percentage of 15 to 40% from the viewpoint of many reaction sites with isocyanate. Is good. As the alkali metal salt or alkaline earth metal salt of phosphoric acid ester, Gafac RD720 manufactured by Toho Kagaku Co., Ltd. is used, and 1 to 50% by weight, preferably 10% by weight based on the polyvinyl butyral resin.
It is recommended to use about 40% by weight. The heat-resistant slip layer is preferably accompanied by heat resistance in the lower layer, a combination of a synthetic resin that can be cured by heating and its curing agent, such as polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and titanium chelating agent, Alternatively, a combination of polyester and an organic titanium compound may be provided by coating.

The dye-donor element may be provided with a hydrophilic barrier layer for preventing the dye from diffusing toward the support. The hydrophilic dye barrier layer contains hydrophilic materials useful for the intended purpose. Generally good results are gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate grafted gelatin,
Ethyl methacrylate graft gelatin, cellulose monoacetate, methyl cellulose, poly (vinyl alcohol),
Poly (ethyleneimine), poly (acrylic acid), a mixture of poly (vinyl alcohol) and poly (vinyl acetate), a mixture of poly (vinyl alcohol) and poly (acrylic acid) or cellulose monoacetate and poly (acrylic acid) ). Especially preferred are poly (acrylic acid), cellulose monoacetate or poly (vinyl alcohol).

The dye-donor layer is formed by selecting hues 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 repeatedly printing each color according to the color separation signal, it is desirable that the hue when printed is cyan, magenta, and yellow, and such a hue is given. 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. In addition, it is preferable to provide a mark for position detection at the same time when any one of the dye-donor layers is formed during the formation of these dye-donor layers, because an ink or printing step different from the dye-donor layer formation is not required.

The dye-donor elements of the invention are used in sheet form or in continuous rolls or ribbons. If a continuous roll or ribbon is used, it may have areas of different dyes, such as cyan and / or magenta and / or yellow and / or black and other dyes that have only one type of dye or are heat transferable. 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 the present invention, in order to improve the releasability between the thermal transfer dye-donor element and the thermal transfer image-receiving element, in the layers constituting the dye-donor element and / or the image-receiving element, particularly preferably the surface where both materials come into contact with each other. It is preferable to include a release agent in the outermost layer corresponding to the above. As the release agent, solid or wax-like substances such as polyethylene wax, amide wax, fine powder of silicone resin, fine powder of fluororesin, etc .: Fluorine-based, phosphoric ester-based surfactants: paraffin-based, silicone Any conventionally known release agent such as system oil and fluorine oil can be used, but silicone oil is particularly preferable.

As the silicone oil, in addition to unmodified 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 an isocyanate) is also emulsified and dispersed in a water-soluble binder. Is a carboxy-modified silicone oil (for example, manufactured by 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 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 No. etc. are suitable for use. More specifically, aldehyde type hardener (formaldehyde etc.), aziridine type hardener, epoxy type hardener, vinyl sulfone type hardener (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardener (dimethylolurea, etc.), or polymer hardener (Japanese Patent Laid-Open Publication No. Sho 6-62).
2-234157 etc.).

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. Examples of anti-fading agents include antioxidants, ultraviolet absorbers, and certain metal complexes. Examples of the antioxidant include chroman compounds, coumarans compounds, phenol compounds (for example, 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 (U.S. Pat. No. 3,352,681
No.), benzophenone compounds (JP-A-56-278)
No. 4, etc.) and other JP-A Nos. 54-48535 and 62.
There are compounds described in Nos. -136641 and 61-88256. 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 4,24.
No. 5,018, columns 3 to 36, No. 4,254,195, columns 3 to 8, JP-A Nos. 62-174741 and 61-8.
8256, pages (27) to (29), JP-A-1-75
There are compounds described in JP-A No. 568, JP-A-63-199248 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272, pages 125-137. An anti-fading agent for preventing fading 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.

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.

Further, 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 the gelatin of the present invention and an aqueous polyvinyl resin solution. At this time, it is preferable to use a surfactant as a dispersion aid. For this purpose, in addition to the above-mentioned surfactant, 37 to 3 of JP-A-59-157636.
The surfactants described on page 8 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-63-2749.
44, and 63-274952.

The constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification and improving releasability. As typical examples of the organic fluoro compound, JP-B-57-9053, columns 8 to 17, JP-A-61-20944 and JP-A-62-13.
5826 and the like, or a hydrophobic fluorine compound such as an oily fluorine compound such as fluorine oil or a solid fluorine compound resin such as tetrafluoroethylene resin.

In the present invention, the thermal transfer dye-providing material is superposed on the thermal transfer image-receiving material and heat is applied in accordance with the image information from either side, preferably the back side of the thermal transfer dye-providing material, by means of heating means such as a thermal head. By applying energy, the dye in the dye-donor layer can be transferred to the thermal transfer image-receiving material according to the amount of heating energy, and a color image with excellent sharpness and resolution can be obtained. Further, an anti-fading agent can be similarly transferred. 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 sequentially for each color to transfer three colors. Form an image. Of course, when this process is performed in a single color, a monochrome transfer image is obtained.

The heating means is not limited to the thermal head, but laser light: ion gas laser such as argon or krypton, metal vapor laser such as copper, gold and cadmium, solid laser such as ruby or YAG, or 750. Lasers such as semiconductor lasers such as gallium-arsenide which emit in the infrared region of ~ 870 nm can be used.
However, practically, the semiconductor laser is effective in terms of small size, low cost, stability, reliability, durability and ease of modulation.

In laser-based systems, the thermal transfer dye-donor material preferably contains a material that strongly absorbs laser light. When a thermal transfer dye-donor material is irradiated with laser light, this absorbing material converts light energy into heat energy and transfers the heat to the dye in the immediate vicinity, and the dye is transferred to the heat transfer image-receiving material at a temperature (heat transfer temperature). ) Is heated up to. 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,
Only the areas of the dye that need to be present on the thermal transfer dye-donor material to reconstruct the original target color are heated and thermally transferred.

Thermal transfer In order to transfer a dye from a dye-donor material to a thermal transfer image-receiving material, a thermal head is energized in response to an electric signal or an ion gas laser such as argon or krypton, or a metal vapor such as copper, gold or cadmium. Laser, solid state laser such as ruby or YAG, or 7
Heating with several lasers can be used, such as semiconductor lasers such as gallium-arsenide, which emit in the infrared from 50 to 870 nm. However, in practice, semiconductor lasers are advantageous in terms of small size, low cost, stability, reliability, durability, and ease of modulation.

In the present invention, the thermal transfer dye-providing material is combined with a thermal transfer image-receiving material to form an image by printing using various printers of thermal printing system, facsimile, or magnetic recording system, magneto-optical recording system, optical recording system, etc. It can be used to create prints, prints from a television or CRT screen. For details of the thermal transfer recording method, the description in JP-A-60-34895 can be referred to.

[0047]

The present invention will be described in more detail with reference to the following examples, but the invention is not limited to the following specific examples as long as the gist of the invention is not exceeded. Example 1 [Preparation of thermal transfer dye-donating material]: Table-1: 1 to 18 A polyester film having a thickness of 6 μm and a width of 95 mm provided with a heat-resistant slip layer made of a thermosetting acrylic resin on one side was used as a support, and this support was used. On the surface of the body opposite to the side provided with the heat resistant slipping layer, a detection mark having a length of 20 mm was formed with a gravure ink for black plate and a dye-donating layer forming ink composition having the following composition was used to expose the dye for sublimation type thermal transfer. -2, the dye-donor elements 1 to 18 were coated in a face-sequential manner with a length of 170 mm so that the coating amount after drying was 1.2 g / m ^2.
It was created. (Ink Composition for Coating Thermal Transfer Dye Donating Layer) Dye [Table 1] 3 g Polyvinyl butyral resin 3 g (Denka Butyral 5000-A manufactured by Denki Kagaku) Silicone oil (KF-96 manufactured by Shin-Etsu Chemical) 0.05 ml Toluene 50 ml Methyl ethyl ketone 50 ml Polyisocyanate 0.05 ml (Takeda Pharmaceutical Takenate D110N)

[0048]

[Table 1]

[Preparation of Thermal Transfer Dye Image Receiving Material]: Table-3:
1-16 Synthetic paper with a thickness of 150 μm (Oji Yuka: YUPO-FP
G-150) on the support (V) or the support (W) shown in Table 2 and in the dye image-receiving layer coating liquid composition having the following composition, various dye-receptive resins as shown in Table 3 are used. On the contrary, the thermal transfer dye image receiving materials 1 to 1 are applied by a wire bar coating method so that the thickness after drying becomes 8 μm.
6 was produced. Sample size is 100mm × 140m
Cut to m.

[0050]

[Table 2]

(Composition for coating thermal transfer dye image-receiving material) Inorganic solid fine particles [Table 3] a (g) Resin [Table 3] b (g) Hardener [Table 3] c (g) Release agent [Table 3] d (g) solvent [Table 3] e (g)

[0052]

[Table 3]

Dye-donor element 1 obtained as described above
Nos. 18 to 18 and dye image-receiving materials 1 to 16 are combined in the combinations shown in Table 4 and Table 5 so that the dye-donor layer and the image-receiving layer are in contact with each other, and a thermal head is attached from the support side of the thermal transfer dye-donor material. Used, thermal head output 0.25W
/ Dot, pulse width 0.1 to 10 msec, and dot density 6 dots / mm were applied to heat, and the dye was dyed imagewise on the receiving layer of the image receiving material. The portion (D _max ) where the density of the recorded image-receiving material obtained at this time was saturated was used as a reflection densitometer (X Rite Inc., Status A).
The reflection density of the image was measured using a built-in filter).
It was tested with an HB pencil, a water-based ballpoint pen, etc. whether the characters can be written on the image-receiving sheet after recording with a pencil. Those that were writable were indicated by ○, those that were writable but had thin characters were indicated by △, and those that could not be written were indicated by ×. Then, the recorded image receiving material 60
The degree of image bleeding was observed after leaving it in an oven at 0 ° C. for 2 weeks. Judgment criteria are as follows: ◎: The image looks almost the same as it was before storage when viewed under an optical microscope with a magnification of about 200 times. ○: If the image is slightly blurred but hardly visually blurred,
What is visually perceived as slightly bleeding is indicated by Δ, and very bleeding and blurred is indicated by x. The results are listed below in order-
4, shown in Table-5.

[0054]

[Table 4]

[0055]

[Table 5]

As shown in Tables 4 and 5, when the sublimation type thermal transfer dye image-receiving material of the present invention is used, writing can be carried out with a pencil or a water-based ballpoint pen, and the transfer density of the image is not significantly impaired, and recording is possible. No image bleeding was observed during storage of the used image receiving material. However, when the image receiving material of Comparative Example was used, writing could not be performed with a pencil or a water-based ballpoint pen. When the dissociative dye was not used as the dye-donating material, the transfer density was low, and image bleeding and color transfer were observed during recording of the recorded image.

[0057]

EFFECT OF THE INVENTION By using the thermal transfer recording material of the present invention, it is possible to write with a pencil or a water-based ballpoint pen, and to record an image without bleeding the recorded image during storage without deteriorating the transfer density. Obtainable.

Claims (1)

[Claims] 1. A thermal transfer dye-receiving material comprising a support and a dye-receiving layer having a dye-receiving layer containing a dye-receiving substance on the support, and a dye-receiving layer comprising a dye-donor layer comprising a binder resin. A material for thermal transfer recording comprising a material, which is a dissociative dye capable of donating a hydrogen atom to the dye-receptive substance to become an anion when the heat-transferable dye migrates to the dye-receptive layer, and A material for thermal transfer recording, wherein at least one of the dye-receptive substances is an inorganic solid fine particle.