JPH1024660A - Thermal transfer recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a printed image with high transferability, excellent heat resistance, solvent resistance and abrasion resistance by adding half as much or more of epoxy resin with fluorene skeleton in terms of weight ration to the thermally fusible vehicle of a thermally fusible ink layer formed on a base. SOLUTION: A printed image with outstanding heat resistance, solvent resistance and superb fretting properties is obtained without adversely affecting ink transferability in spite of the use of resin as a main component of vehicle, by using epoxy resin with fluorene skeleton as the main component of the vehicle contained in thermally fusible ink. However, such epoxy resin is not necessarily used but it has only to beof such type that 50wt.% or more, above all, 70wt.% or more of the vehicle is equivalent to epoxy resin with fluorene skeleton. In addition, if the ratio of the epoxy resin with fluorene skeleton contained in the vehicle is not more than 50wt.%, the epoxy resin is not so fully effective in use than expected.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, solvent resistance,
The present invention relates to a thermal transfer recording material for forming an excellent printed image such as abrasion resistance.

[0002]

2. Description of the Related Art Conventional thermal transfer recording materials are generally capable of printing images of good quality on a base material coated with a hot-melt ink containing wax as a main component of a vehicle or on paper having poor surface smoothness. A hot-melt ink containing a resin as a main component of the vehicle is applied for forming or forming an image having good scratch resistance.

In recent years, thermal transfer recording materials have been used to print barcodes and the like used in the management of parts and products in the manufacturing process in manufacturing factories, product management in the distribution field, and article management in the field of use. Bar code printers and label printers are being used.

[0004] Some articles with such a bar code are exposed to high temperatures after the bar code is attached. For example, in the manufacturing process of a printed wiring board, 180
Since heat treatment is performed at about 250 ° C. in a semiconductor inspection process at about 250 ° C., heat resistance to withstand such a high temperature is required. Further, in the case of a bar code or the like used for product management in a manufacturing factory or the like, good contact with a solvent, oil, or the like is required, so that good solvent resistance is required. Further, in the case of barcodes used in the distribution field, etc., there are many occasions of rubbing, so that good rub resistance is required.

[0005] In addition to bar codes, in the field of commercial printing, outdoor advertisements, election posters, general posters, standing signs,
Stickers, catalogs, brochures, calendars, etc.
In the packaging field, light transfer bags, container labels for foods, beverages, chemicals, paints, etc., binding tapes, etc.In the clothing field, quality transfer labels, process control labels, product control labels, etc. Printers have come to be used, and there are cases where these are also required to have heat resistance, solvent resistance, abrasion resistance, and the like.

[0006]

However, none of the conventional thermal transfer recording materials can form a printed image which is excellent in transferability and satisfies all of heat resistance, solvent resistance, scratch resistance and the like. .

That is, in the case of a conventional thermal transfer recording material using a hot-melt ink mainly composed of wax as a vehicle, the transferability is good, but the obtained printed image is exposed to a high temperature of about 250 ° C. In some cases, it may be broken and become unreadable, and the solvent resistance and scratch resistance are also insufficient. In addition, those containing a resin such as an ethylene-vinyl acetate copolymer as a main component of the vehicle have relatively excellent heat resistance, solvent resistance, and abrasion resistance, but have a higher melt viscosity and a higher transferability than those mainly containing a wax. Inferior.

An object of the present invention is to provide a thermal transfer recording material which has good transferability and can form a printed image having good heat resistance, solvent resistance, scratch resistance and the like in view of the above points. It is in.

[0009]

According to the present invention, there is provided (1) a heat-fusible ink layer comprising at least a heat-fusible vehicle and a colorant provided on a substrate, wherein the heat-fusible vehicle comprises 50% epoxy resin having a fluorene skeleton
The present invention relates to a thermal transfer recording material characterized in that it is contained in an amount of at least 10% by weight.

According to the present invention, (2) the heat-fusible ink layer further contains 1 to 4 polytetrafluoroethylene particles.
(1) characterized by containing 50% by weight.
Item).

The present invention further provides (3) the thermal transfer recording according to (2), wherein the heat-fusible ink layer further contains wax particles in addition to the polytetrafluoroethylene particles. About the material.

The present invention further provides (4) a content of the hot-melt vehicle in the hot-melt ink layer of 40 to 40.
(1), (2), which is 95% by weight.
Alternatively, the present invention relates to the thermal transfer recording material according to (3).

The present invention further provides (5) an ink-enhanced layer comprising a binder resin, polytetrafluoroethylene particles and wax particles provided between the substrate and the hot-melt ink layer; Is contained in the ink-reinforced layer in an amount of 5 to 95% by weight, and relates to the thermal transfer recording material according to the above (1), (2), (3) or (4).

According to the present invention, (6) a layer made of wax is provided between the substrate and the ink-reinforced layer.
The thermal transfer recording material according to the above (5), wherein the penetration of the layer is 1 or less.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The hot-melt ink layer according to the present invention comprises a hot-melt vehicle and a colorant, and the hot-melt vehicle contains an epoxy resin having a fluorene skeleton in 50% (% by weight, hereinafter). Same as above).

In the present invention, by using an epoxy resin having a fluorene skeleton as the main component of the vehicle of the hot-melt ink, the transferability of the ink is impaired even though the resin is used as the main component of the vehicle. Instead, the heat resistance, solvent resistance and scratch resistance of the obtained printed image can be greatly improved. 50% of the epoxy resin having a fluorene skeleton in the vehicle
If it is less than this, the effect of using this epoxy resin is not sufficiently exhibited.

The epoxy resin having a fluorene skeleton used in the present invention has the formula (I):

[0018]

Embedded image

An epoxy resin represented by the formula: Commercial products have a softening point of about 70 to 90 ° C.

In the present invention, by forming the entire vehicle of the hot-melt ink with the epoxy resin having the fluorene skeleton, an image having particularly excellent heat resistance and solvent resistance can be obtained. It is not necessary that the epoxy resin has a fluorene skeleton for 50% or more, especially 70% or more of the vehicle.

Other vehicle components that can be used in the present invention include hot-melt resins containing epoxy resins other than epoxy resins having a fluorene skeleton.

Other epoxy resins which can be used in combination with the specific epoxy resin in the present invention include, for example, bisphenol A diglycidyl ether, brominated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, brominated bisphenol F diglycidyl ether, Examples include hydrogenated bisphenol A diglycidyl ether, tetraphenolethane tetraglycidyl ether, cresol novolak polyglycidyl ether, and naphthol-modified cresol novolak polyglycidyl ether. When these other epoxy resins are used, they can be used alone or in combination of two or more.

Examples of the heat-fusible resin other than the epoxy resin include ethylene-vinyl acetate copolymer resin, ethylene-alkyl (meth) acrylate copolymer resin, phenol resin, styrene-acryl copolymer resin, polyester resin, polyamide resin and the like. Is mentioned.

The other vehicle component is 5% of the total amount of the vehicle.
It is preferably used at 0% or less.

The entire vehicle has a softening temperature of 60 to 120 ° C. from the viewpoint of storage stability and transferability of the thermal transfer recording material.
Is preferable.

The content of the vehicle in the hot-melt ink layer is preferably from 40 to 95%, more preferably from 60 to 90%, from the viewpoint of transferability and the like.

In the present invention, the heat-fusible ink layer preferably contains polytetrafluoroethylene particles (hereinafter referred to as PTFE particles). By dispersing the PTFE particles in the epoxy resin as a vehicle, the sharpness of the ink layer during transfer is improved. Further, since the PTFE particles are present on the surface of the image obtained by the transfer, the scratch resistance is further improved. Here, the PTFE may be a homopolymer of tetrafluoroethylene or a copolymer of tetrafluoroethylene and a small amount of another modifying monomer.

The PTFE particles preferably have an average particle diameter in the range of 0.01 to 15 μm, especially 0.01 to 5 μm. If the average particle size is less than the above range, sufficient abrasion resistance tends not to be obtained, while if it exceeds the above range, transferability tends to be poor.

The content of the PTFE particles in the hot-melt ink layer is preferably 1 to 50%, more preferably 5 to 30%. If the content of the PTFE particles is less than the above range, the effect of improving the scratch resistance of the printed image may not be sufficiently exhibited. On the other hand, if it is more than the above range, the transferability tends to be poor.

The PTFE particles can be used in bulk form or in the form of a dispersion or emulsion dispersed in an organic solvent or water.

In the present invention, by using wax particles in addition to the PTFE particles, the scratch resistance of the obtained printed image is further improved. In the present invention, the wax particles are not included in the heat-fusible vehicle.

As the wax particles, those having an average particle diameter in the range of 0.01 to 15 μm, preferably 0.01 to 5 μm are preferable. If the average particle size is less than the above range, sufficient abrasion resistance tends not to be obtained, while if it exceeds the above range, transferability tends to be poor.

When PTFE particles and wax particles are used in combination, the total content of both particles in the hot-melt ink layer is preferably in the range of 1 to 50%, more preferably 5 to 30%. If the total content of both particles is less than the above range, the effect of improving the scratch resistance of the printed image may not be sufficiently exhibited. On the other hand, if it is more than the above range, the transferability tends to be poor.

When PTFE particles and wax particles are used in combination, the ratio of PTFE particles to the total amount of both particles is 5%.
The range is preferably from 0 to 90%, especially from 50 to 70%. If the proportion of the PTFE particles is less than the above range, the heat resistance and solvent resistance of the printed image may slightly decrease, while if it exceeds the above range, the effect of improving the scratch resistance may not be sufficiently exhibited.

Examples of the wax particles include plant waxes such as carnauba wax, candelilla wax and rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as montan wax and ceresin wax, paraffin wax, and microcrystalline. One or two kinds of wax particles composed of one or more kinds of synthetic hydrocarbon waxes such as petroleum wax such as wax, Fischer-Tropsch wax, polyethylene wax, polyethylene oxide wax, polypropylene wax, and polypropylene oxide wax. What consists of the above can be used. In particular, polyethylene wax, oxidized polyethylene wax, polypropylene wax, oxidized polypropylene wax, Fischer-Tropsch wax, and carnauba wax are preferred from the viewpoint of good slipperiness on the surface of the wax particles.

The wax particles can be used in bulk form or in the form of a dispersion or emulsion dispersed in an organic solvent or water.

The coloring agents used in the present invention include carbon black, azo pigments (insoluble azo, azo lake, condensed azo pigments), phthalocyanine pigments, nitro pigments, nitroso pigments, anthraquinone pigments, and nigrosine pigments. , Quinacridone pigments, perylene pigments, isoindolinone pigments, dioxazine pigments, titanium white, calcium carbonate, barium sulfate and various organic
Inorganic pigments can be used. A dye may be used in combination for adjusting the color tone. The content of the colorant in the ink layer is suitably from 5 to 50%, preferably from 10 to 40%.

When a multicolor or full-color image is formed by utilizing subtractive color mixture, a yellow, magenta, cyan and, if necessary, a black colorant are used.

As the yellow, magenta and cyan colorants, transparent pigments are preferably used. As the black colorant, an opaque pigment is usually used.

Examples of the yellow transparent pigment include naphthol yellow S, Hansa yellow 5G, Hansa yellow 3G, Hansa yellow G, Hansa yellow GR, Hansa yellow A, Hansa yellow RN, Hansa yellow R, benzidine yellow G, benzidine yellow G, benzidine yellow GR,
One or more organic pigments such as permanent yellow NCG and quinoline yellow lake can be used.

Examples of the magenta transparent pigment include permanent red 4R, brilliant fast scarlet, brilliant carmine BS, permanent carmine FB, lithol red, and permanent red F5.
One or more organic pigments such as R, brilliant carmine 6B, pigment scarlet 3B, rhodamine lake B, rhodamine lake Y, alizarin lake, and quinacridone red can be used.

As the cyan transparent pigment, for example, one or more organic pigments such as Victoria Blue Lake, metal-free phthalocyanine blue, phthalocyanine blue, and fast sky blue can be used.

Here, the transparent pigment is a pigment which gives a transparent colored ink when dispersed in a transparent vehicle.

As the black pigment, for example, one or more kinds of inorganic pigments such as carbon black having an insulating property and conductivity and organic pigments such as aniline black can be used.

The heat-fusible ink layer of the present invention may optionally contain a dispersant and the like in addition to the above components.

In the present invention, the heat-meltable ink layer is dissolved in a solvent that dissolves the specific epoxy resin, or is dispersed in a solvent that does not dissolve the specific epoxy resin, and further contains a colorant and, if necessary, PTFE. The particles can be formed by dissolving and dispersing particles (or PTFE particles and wax particles) and other additives to prepare a coating liquid, applying the coating liquid on a substrate, and drying.

In the present invention, the coating amount of the hot-melt ink layer (in terms of solid content, hereinafter the same) is usually 0.02 to 5 g / m 2.
² , more preferably 0.5 to 3 g / m ² .

Examples of the substrate include polyester films such as polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polybutylene naphthalate film, polyarylate film, polycarbonate film, polyamide film, aramid film, and polyethersulfone film. , Polysulfone film, polyphenylene sulfide film, polyetheretherketone film, polyetherimide film, modified polyphenyleneether film, polyacetal film, and various other plastic films commonly used as base film for this type of ink ribbon it can. Also, high-density thin paper such as condenser paper can be used. The thickness of the substrate is usually about 1 to 10 μm, and from the viewpoint that the heat diffusion can be reduced and the resolution can be increased,
A range of 6 μm is preferred.

When the thermal transfer recording material of the present invention is used in a thermal transfer printer provided with a thermal head, a silicone resin, a fluororesin, a nitrocellulose resin, or a silicone resin, It is possible to provide a conventionally known stick prevention layer made of various heat-resistant resins, such as silicone-modified urethane resin and silicone-modified acrylic resin, or a mixture of these heat-resistant resins with a lubricant. preferable.

In a preferred embodiment of the present invention, an ink reinforcing layer is provided between the substrate and the hot-melt ink layer. By providing the ink-enhanced layer, the ink-enhanced layer is present on the image surface after transfer, and the abrasion resistance is further improved.

The ink reinforcing layer is made of a binder resin, P
It is preferable that it is composed of TFE particles and wax particles. As the PTFE particles and the wax particles, those used in the hot-melt ink layer can be preferably used. As the binder resin, an acrylic resin, a polyester resin, or the like is particularly preferable from the viewpoint of improving the scratch resistance.

The proportion of each component in the ink-reinforced layer is such that 3-50% of PTFE particles, 2-45% of wax particles and 5-95% of binder resin are based on the total amount of the ink-reinforced layer.
Is preferable.

As the acrylic resin, for example, one or more of polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polyethyl acrylate, polybutyl methacrylate, polybutyl acrylate, and a copolymer thereof are used. it can.

The PTFE particles used in the ink reinforcing layer are preferably used in the form of a dispersion, especially a solvent dispersion. In preparing such a dispersion, it is preferable to use a fluorine-based surfactant as a dispersant in order to obtain good dispersibility. As this fluorine-based surfactant, a polymer fluorine-based surfactant is preferably used.
Examples of the polymer fluorosurfactant include an acrylic resin containing a perfluoroalkyl group (preferably having 6 to 10 carbon atoms), a copolymer of an acrylic monomer and ethylene oxide, and a perfluoroalkyl group (having a carbon number of 6 to 10 are preferable). Since such a polymer fluorine-based surfactant also functions as a binder resin, it can be used as all or a part of the binder resin.

The coating amount of the ink reinforcing layer is 0.3 to 2 g /
m ² , preferably 0.5 to 1.5 g / m ² . If the coating amount is less than the above range, the ink strengthening effect tends to be insufficient, while if it is more than the above range, the transferability tends to be poor.

The ink-strengthening layer can be formed by applying a coating liquid obtained by mixing PTFE particles and wax particles to a dispersion or solution of a binder resin on a substrate or a wax layer to be described later, and drying it.

In another preferred embodiment of the present invention, a wax layer having a penetration of 1 or less is provided between the substrate and the ink reinforcing layer. By providing the wax layer, the releasability of the ink reinforcing layer is improved, and the transferability is improved.

Examples of the wax include a mixture of one or more of carnauba wax, polyethylene wax and the like.

The wax layer can be formed by applying a solvent solution, a solvent dispersion or an aqueous emulsion of wax on a substrate and drying. Further, it can be formed by a hot melt coating method.

The coating amount of the wax layer is usually 0.01
To 2.0 g / m ² , more preferably 0.1 to 1.0 g / m ²
m ² is appropriate. If the amount of the wax layer applied is less than the above range, the desired effect tends to be hardly obtained, while if it is more than the above range, the transferability may be deteriorated.

The thermal transfer recording material of the present invention includes a thermal transfer recording material for forming a monochromatic print image and a color thermal transfer recording material for forming a multi-color or full-color print image by utilizing subtractive color mixture. It is.

A thermal transfer recording material for forming a monochromatic print image is a material in which a monochromatic heat-meltable ink layer is provided on a base material (or an ink-reinforced layer). Examples of the color of the heat-fusible ink layer include black, red, blue, green, yellow, magenta, and cyan.

One embodiment of a color thermal transfer recording material for forming multicolor or full-color images is as follows:
On a single substrate (or ink-enhanced layer), a yellow heat-meltable ink layer, a magenta heat-meltable ink layer, and a cyan heat-meltable ink layer, and if necessary, a black heat-meltable ink layer. They are arranged side by side. There are various modes for arranging the ink layers of the respective colors, which are appropriately selected according to the type of the printer.

FIG. 1 is a partial plan view showing one embodiment of the thermal transfer recording material of the above embodiment. In FIG. 1, on a single substrate 1, a yellow heat-fusible ink layer 2Y, a magenta heat-fusible ink layer 2M, and a cyan heat-fusible ink layer 2C are arranged side by side. The ink layers 2Y, 2M, and 2C each have a fixed size, and are arranged in the longitudinal direction of the base material 1 repeatedly in a fixed order as one repeating unit U. The order in which the three color ink layers are arranged in the repeating unit U is appropriately determined according to the transfer order of each color. A black ink layer may be added to the repeating unit U.

Another embodiment of a color thermal transfer recording material for forming a multi-color or full-color image is as follows.
A first thermal transfer recording material having a yellow heat-meltable ink layer provided on one substrate (or ink-reinforced layer), and a magenta heat-meltable ink layer provided on another substrate (or ink-reinforced layer). A second thermal transfer recording material, a third thermal transfer recording material having a cyan fusible ink layer provided on another substrate (or ink-enhanced layer), and optionally another substrate (or ink) And a fourth heat transfer recording material having a black heat-meltable ink layer provided on the reinforcing layer).

When the above-mentioned thermal transfer recording material for forming a color image is used, a multicolor or full-color image having excellent scratch resistance can be obtained. Furthermore, since the hot-melt ink layers of the respective colors in the present invention have good superposition properties, a color image with good color reproducibility can be obtained.

In order to form a printed image using the thermal transfer recording material of the present invention, an ink layer of the thermal transfer recording material is superposed on a transfer object, and thermal energy is applied to the ink layer in an image-like manner. A thermal head is generally used as a heat source for applying thermal energy, but any known one such as a laser beam, an infrared flash, and a hot pen can be used.

When the object to be transferred has a three-dimensional shape other than a sheet-like material, or when the surface thereof is a curved surface, thermal transfer by laser light is advantageous from the viewpoint of easy application of heat energy.

The formation of a multicolor or full-color image using the thermal transfer recording material for forming a color image of the present invention is usually carried out by a thermal transfer printer in accordance with the separated color signals of the multicolor image, ie, the yellow signal, the magenta signal and the cyan signal. The yellow ink dot, the magenta ink dot, and the cyan ink dot are sequentially overlaid and transferred in a predetermined order to form a yellow separated image, a magenta separated image, and a cyan separated image on a receiver. . The transfer order of the yellow, magenta, and cyan ink dots can be arbitrarily selected. In the case of a normal multi-color or full-color image, a three-color separation image is formed in accordance with the three-color signal, whereas when there are only two color signals, a corresponding two-color separation image is formed.

Thus, (A) a region in which a color is developed by subtractive color mixing of at least two of yellow, magenta and cyan, or (B) the region of (A) and the region of yellow, magenta and cyan A multi-color image including an area composed of a combination of at least one kind of single-color area is obtained. Here, the red color is at the overlapping portion of the yellow ink dot and the magenta ink dot, the green color is at the overlapping portion of the yellow ink dot and the cyan ink dot, and the blue color is at the overlapping portion of the magenta ink dot and the cyan ink dot. In addition, a black color is presented at the overlapping portion of the yellow ink dot, the magenta ink dot, and the cyan ink dot.

In the above, the black color is obtained by superimposing the yellow ink dot, the magenta ink dot and the cyan ink dot. However, the black color is obtained only by the black ink dots without using the three ink dots. You may do it.

The black ink dots may be superimposed on at least one of yellow ink dots, magenta ink dots, and cyan ink dots, or may be superimposed on at least two superimposed ink dots so as to exhibit a black color.

Since the thermal transfer recording material of the present invention gives an image having excellent heat resistance as described above, it is suitably used for forming an image on a transfer-receiving body which is subjected to a heat treatment at a temperature of 150 ° C. or more. You. If the temperature of the heat treatment applied to the transfer object is too high, the vehicle component tends to decompose and the form as a printed image tends to disappear, so the temperature of the heat treatment applied to the transfer object is about 280 ° C. or less. Is preferred.

When an image is formed by using the thermal transfer recording material of the present invention, the image may be formed directly on a target object to be transferred. After the image is formed, the image receiving member may be attached to a target transfer object by an appropriate means such as a heat-resistant adhesive.

As the sheet-like image receiving member, various heat-resistant sheet-like materials can be used, but those disclosed in JP-A-8-2131 are preferably used. This is an image receiving body provided with an image receiving layer containing a white pigment and an organic binder as essential components on one side of a substrate, and a heat resistant adhesive layer provided on the other side, wherein the organic binder is a phenoxy resin, Alternatively, it is composed of a phenoxy resin and a saturated polyester resin. In addition, sheet-like material of heat-resistant resin such as polyimide, cloth-like material of glass fiber or ceramic fiber, thing coated or impregnated with heat-resistant resin, sheet of glass or ceramic, sheet of metal, etc. Is mentioned.

The heat resistance, solvent resistance, and scratch resistance of the image formed on the transfer object using the thermal transfer recording material of the present invention are greatly improved by performing a heat treatment.

The heat treatment can be performed by heating the image in an atmosphere at 150 to 250 ° C. for 15 to 60 minutes. It is presumed that such heat treatment causes crosslinking of the epoxy resin, thereby improving the robustness.

In the case of a printed image such as a printed wiring board or a semiconductor, which is to be subjected to a heat treatment equivalent to the above-mentioned heat treatment in a later step, the heat treatment is not particularly required.

The thermal transfer recording material of the present invention gives an image having excellent heat resistance and solvent resistance. Therefore, the transferred material is used at a temperature of about 150 to 280 ° C. in a manufacturing process of a printed wiring board or the like or in an inspection process of a semiconductor or the like. It is particularly suitably used for forming a printed image on a material which is subjected to a heat treatment at a high temperature.

[0080]

Next, the present invention will be described with reference to examples.

Examples 1 to 7 and Comparative Examples 1 to 2 A polyethylene terephthalate film having a thickness of 5 μm was provided on one side with a stick preventing layer made of silicone resin having a coating amount of 0.25 g / m ² , and on the other side thereof, Table 1 was prepared. Is applied and dried at 70 ° C. to obtain a coating amount of 2
g / m ² of a heat-fusible ink layer was formed to obtain a thermal transfer recording material.

The average particle size of the particles shown in Table 1 is measured by a laser diffraction particle size distribution analyzer SALD-1 manufactured by Shimadzu Corporation.
It was measured at 100.

In Examples 5 to 7, the coating liquid for the ink-strengthening layer shown in Table 2 was applied on a substrate, dried at 70 ° C., and dried at a coating amount of 0.5 g / m ² . A layer was formed. Further, in Example 7, a wax layer coating liquid shown in Table 2 was applied on a substrate, and dried at 70 ° C. to obtain a wax having a penetration of 1 or less and a coating amount of 0.3 g / m ² . A layer was formed, and the ink-reinforced layer was formed thereon. The penetration was measured at 25 ° C. by a penetration measurement method specified in JIS K2235.

[0084]

[Table 1]

[0085]

[Table 2]

The heat resistance of each of the hot melt inks was
The transferability, solvent resistance,
Scratch resistance (clocking resistance, smear resistance) was evaluated by the following method. Table 3 shows the results.

[Heat resistance] About 10 mg of each ink after drying
After weighing with an electronic balance and heat-treating it in a hot oven at 250 ° C. for 1 hour, the weight was measured, and the ink residual ratio (%) represented by the following formula was obtained to evaluate the heat resistance. 80% residue ratio
If more. There is no practical problem.

Residual ink ratio (%) = (weight after heat treatment / weight before heat treatment) × 100 [Transferability] Using each of the above-mentioned heat transfer recording materials, a bar code printer of the heat transfer system (Tec Co., Ltd.) -30) and an image receiving body [Silver Name, manufactured by Lintec Co., Ltd. (a polyester film on which aluminum is deposited on one side and an adhesive layer is provided thereon to form an image on the polyester film surface)] ], A barcode pattern was formed under the following conditions. Applied energy: 22.6 mJ / mm ² Printing speed: 2 inches / second Platen pressure: Strong (specified by the printer used) RJS ENTERPRISE
S, INC bar code reader (Coder Scan I
The reading determination according to I) was performed. The criteria for the bar code reader are as follows. A: Completely readable. B Almost completely readable. C Can be read practically without any problem. D Partially readable. E Unreadable.

[Solvent resistance] In the same manner as in the transfer property test, a friction test was performed on the image of the bar code pattern formed on the silver namer under the following conditions. Reading was determined by a bar code reader in the same manner as in the case of the sex test. Testing machine: Atlas Electric Devices Co. A. A. T. C. C. Clock meter model CM-1 Friction material: cotton cloth (impregnated with ethanol, gasoline or kerosene) Pressure: 500 g / cm ² Number: 30 reciprocations [Scratch resistance (clocking resistance)] Transfer test In the same manner as in the above, a friction test was performed on the barcode pattern image formed on the silver namer under the following conditions,
With respect to the printed image after the friction test, reading judgment by a bar code reader was performed in the same manner as in the transferability test. Testing machine: Atlas Electric Devices Co. A. A. T. C. C. Crockmeter Model CM-1 Friction material: cotton cloth Pressure: 500 g / cm ² Number: 300 reciprocations [Scratch resistance (smear resistance)] Bar formed on silver namer in the same manner as in the transfer test described above. A friction test was performed on the image of the code pattern under the following conditions, and the image after the friction test was read by a bar code reader in the same manner as in the transferability test. Test machine: Love tester manufactured by Yasuda Seiki Seisakusho Co., Ltd. Friction material: Cardboard Pressure: 250 g / cm ² times Number: 300 reciprocations

[0090]

[Table 3]

[0091]

The thermal transfer recording material of the present invention has excellent transferability and gives a printed image having excellent heat resistance, solvent resistance and scratch resistance, and is therefore useful for printing bar codes and the like.

[Brief description of the drawings]

FIG. 1 is a partial plan view showing one example of an arrangement of ink layers of respective colors in one embodiment of a thermal transfer recording material of the present invention.

[Explanation of symbols]

 Reference Signs List 1 base material 2Y yellow ink layer 2M magenta ink layer 2C cyan ink layer

Claims (6)

[Claims] 1. A heat-fusible ink layer comprising at least a heat-fusible vehicle and a colorant is provided on a base material, wherein the heat-fusible vehicle contains 50% by weight of an epoxy resin having a fluorene skeleton. % Of the thermal transfer recording material. 2. The thermal transfer recording material according to claim 1, wherein the thermal fusible ink layer further contains 1 to 50% by weight of polytetrafluoroethylene particles. 3. The thermal transfer recording material according to claim 2, wherein the thermofusible ink layer further contains wax particles in addition to the polytetrafluoroethylene particles. 4. The thermal transfer recording material according to claim 1, wherein the content of the heat-fusible vehicle in the heat-fusible ink layer is 40 to 95% by weight. 5. An ink-reinforced layer comprising a binder resin, polytetrafluoroethylene particles and wax particles is provided between the substrate and the hot-melt ink layer, and the binder resin is contained in the ink-reinforced layer. 5. The thermal transfer recording material according to claim 1, wherein the thermal transfer recording material is contained in an amount of 5 to 95% by weight. 6. A method according to claim 1, wherein the base material and the ink-enhanced layer are
6. The thermal transfer recording material according to claim 5, wherein a layer made of wax is provided, and the penetration of the layer is 1 or less.