JPS61295079A - Heat sensitive transfer material - Google Patents

Abstract

PURPOSE:To enable a clear printing of two-color recording on an ordinary paper, by providing a fine particle layer which does not fuse by heat energy of printing between the layers of heat fusion type ink of different color tones. CONSTITUTION:A heat transfer ink layer 5 is formed, from the side of its substrate, the first ink layer 2, a peel ply 3 and the second ink layer 4. The peel ply 3 is a dense layer of particle diameters 400mum or under of silicic anhydride, alumina, alumina hydrate etc., and desirable thicknesses of the layer are 0.01mum-2mum. If the second ink layer 4 only is required for transferring, a thermal head 7 moves toward right and the tape is reeled up, and immediately after the heat sensitive transfer material 6 passes the heater portion 7b from the body 8 to be recorded, and the head is separated, and red color recording 4a is produced on the body 8 to be recorded. Additionally, the head is applied with heat and is moved to the right, and after the heat sensitive transfer material 6 is rolled up, and immediately behind the member 10 the heat sensitive transfer material 6 is separated from the body 8 to be recorded, and the first ink layer 2, the peel ply 3 and the second ink layer 4 are transferred together to produce a black color recording 5a on the body 8 to be recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermal transfer material for obtaining recorded images of two different colors. Furthermore, the present invention relates to a thermal transfer material having good separation of two colors.

[Conventional technology]

The thermal transfer recording method has the general characteristics of the thermal recording method, such as the device used is compact, low-noise, and has excellent operability and maintainability. It is characterized by excellent durability of recorded images, and has recently begun to be widely used.

This thermal transfer recording method generally uses a thermal transfer material formed by coating a sheet-like support with a thermal transfer ink containing a colorant dispersed in a heat-melting binder. The thermally transferable ink layer is superimposed on the recording medium so as to be in contact with the recording medium, and heat is supplied from the support side of the thermal transfer material by a thermal head to transfer the melted ink layer onto the recording medium. A transfer ink image is formed according to the shape of heat supply.

Furthermore, there is a strong market demand for two-color printing while taking advantage of the advantages of the thermal transfer recording method, and various techniques for obtaining two-color printing have been proposed.

As a conventional two-color printing method using a thermal transfer recording method on plain paper, JP-A-56-148591 discloses two heat-melting high-melting ink layers A and 1 containing different colorants on a base material. Low melting point ink layer B is laminated sequentially from the substrate side, and in the case of low heat application energy, only the low melting point ink layer B is transferred onto the plain paper, and in the case of high heat application energy, both the heat melting ink layers A and B are transferred. A two-electrode thermal transfer recording element is disclosed which provides a two-color record. In this method, when the difference in melting point between layer A and layer B is small, it is difficult to separate the two layers because the same material is used for the ViA layer and layer B.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a thermal transfer material that can provide clear two-color recording prints on plain paper while eliminating the above-mentioned drawbacks and maintaining various thermal transfer performances.

[Failure to solve the problem]

In other words, the present invention comprises, on a support, a first heat-melting ink layer and a second heat-melting ink layer having mutually different color tones from the support side, and between the layers, printing is performed. The present invention relates to a thermal transfer material characterized in that it has a fine powder layer that does not melt in a bath due to thermal energy.

The present invention will be described in further detail below with reference to the drawings as necessary. In the description of (10) above, "Kan" representing the area ratio.
and "parts" are based on weight unless otherwise specified.

FIG. 1 is a schematic cross-sectional view in the thickness direction of a heat-sensitive transfer material in the most basic embodiment used in the recording method of the present invention.

That is, the thermal transfer material 6 is usually formed by forming a thermal transferable ink layer 5 on a support 1 in the form of a sheet. The thermally transferable ink layer 5 itself has a multilayer structure, with a first ink layer 2, a release layer 3, a second ink layer 4 provided in order from the support side.
Consisting of

As the support 1, conventionally known films and papers can be used as they are, such as films of relatively heat-resistant plastics such as polyester, polycarbonate, triacetylcellulose, nylon, polyimide, etc. Sulfuric acid paper and condenser paper can be suitably used.

The thickness of the support is preferably about 1 to 15 μm when considering a thermal head as a heat source during thermal transfer; however, for example, when using a heat source such as a laser beam that can selectively heat the thermal transferable ink layer. There are no particular restrictions.

In addition, when using a thermal head, a heat-resistant protective layer made of silicone resin, fluororesin, priimide resin, epoxy resin, phenol resin, melamine resin, nitrocellulose, etc. should be provided on the surface of the support that comes into contact with the thermal head. It is possible to improve the heat resistance of the support material, or it is also possible to use support materials that could not be used conventionally.The first ink layer 2 and the second ink layer 4 each have a heat-melting structure. It consists of a plasticizer, a dispersant, an oil agent, a filler, etc., as appropriate.

The colorants used in the first ink layer 2 and the second ink layer 4 have different tones, and the colorants in the release layer 3 have different color tones. In this case, an infusible fine powder such as silicic anhydride is used. It is a dense and thin layer composed of fine particles of alumina and alumina hydrate, and its function is to completely separate the first ink layer 2 and the second ink layer 4, resulting in two clear colors. This is to obtain printing.

First ink layer2. The heat-melting binder of the second ink layer 4 includes spermaceti wax, beeswax, and lanolin.

Natural waxes such as carnauba wax, candelilla wax, montan wax, and ceresin wax, petroleum waxes such as paraffin wax and microcrystalline wax, oxidized waxes, ester waxes, low molecular weight polyethylene, synthetic waxes such as Fischer Troglossox, and lauric acid. , higher fatty acids such as myristic acid, palmitic acid, stearic acid, behenic acid, stearyl alcohol, behenyl alcohol fx
Esters such as KR1 alcohol, sucrose fatty acid ester, sorbitan fatty acid ester, amides such as oleylamide, other polyolefin resins, polyamide resins, polyester resins, gopoxy resins, polyurethane resins, polyacrylic resins , PoIJ JM Chemical Chemical Nyl Resin Cellulose Resin, Polyvinyl Alcohol Resin, Petroleum Resin, Phenol Resin, Polystyrene Resin, Vinyl Acetate Resin, Natural Comb, Styrene Butanoene Rubber, Imprene Rubber, Chloroprene Rubber, etc. , polyisobutylene, polybutene, a plasticizer, and an oil agent such as mineral oil or vegetable oil, as appropriate.

As the coloring agent, various dyes and pigments widely used in the field of printing and recording are used.

The content of the colorant in each of the first ink layer 2 and the second ink layer 4 is suitably in the range of 1 to 80%. Also, the first ink layer 2. Additives such as a dispersant or a filler made of fine metal powder, fine inorganic powder, metal oxide, etc. may be added to the second ink layer 4 as required.

The thickness of the first ink layer 2 is preferably in the range of 0.5μ to 10μ.
Preferably, the total thickness of the thermally transferable ink layer 5 is 2 μ to 20 μ.

The release layer 3 provided to improve the separation between the first ink layer 2 and the second ink layer 4 may be made of, for example, silicic anhydride, which does not melt when heat is applied from a thermal head and has a good sharpness. It is a dense layer formed from particles of silicates, alumina, alumina hydrates, etc. with a particle size of 400 mμ or less. If the particle size exceeds 400 mμ, a dense layer will not be formed, and the function of binding the first ink layer 2 and the second ink layer 4 during non-printing will be difficult to achieve. Layer thickness is 0.01μ~
The thickness is preferably 2μ, more preferably 0.1μ to 1.5μ. If it is less than 0.001μ, the peeling effect will be weak, and if it exceeds 2μ, there is a risk that the second ink layer 4 will peel off during non-printing.

If you want to obtain the same color tone as the first ink layer 2 and the second ink layer 4, it is recommended to place a dark color such as black on the first ink layer 2 and a bright color such as yellow on the second ink layer 4. Good, second
The color tone of the ink layer 4, the color tone of the first ink layer 2, and the color tone of the second ink layer 4
When it is desired to obtain a color mixture of 40 tones in the ink layer, for example, if the first ink layer 2 is colored yellow and the second ink layer 4 is colored magenta, magenta and red can be obtained. In addition, by changing the pigment concentration or layer thickness ratio of each layer, various recordings of two different colors can be obtained. Furthermore, if either the first ink layer 2 or the second ink layer 4 is made white, it is possible to correct the small print using the same method.

In order to obtain the thermal transfer material 6 of the present invention, the above-mentioned heat-melting binder, colorant, and additives as necessary for each of the first ink layer 2 and the second ink layer 4 are added using a dispersion device such as an attritor. The first ink layer coating agent A and the second ink layer coating agent B are melted or kneaded together with a suitable solvent to form a heat-melting or solution or dispersion liquid.
get.

To form the peeling layer 3, colloidal particles of silicic acid anhydride or alumina obtained by a gas phase method are dispersed in water or an organic solvent and mixed as necessary to form a coating material C, or by a liquid phase method. The silica sol or alumina sol produced in step 1 is mixed as necessary to prepare coating material C.

Next, the ink is coated on the support in the order of coating material A, coating material C, and coating material B, and if necessary, heated and dried to form the first ink layer 2, the release layer 3. The second ink layer 4 may be formed in this order.

The planar shape of the thermal transfer material 6 used in the present invention is not particularly limited, but it is generally used in the form of a typewriter gun or a wide tape used in line printers.

A thermal transfer recording method for performing two-color printing using the thermal transfer material 6 according to the present invention will be described below. First, thermal transfer recording using the color of the second ink layer 4 was performed by placing the thermal transfer material 6 and the thermal head 7 facing each other and applying thermal energy to adhere the thermal transfer ink layer 5 to the paper, as shown in FIGS. 2 and 3. By immediately separating the thermal transfer material 6 and the paper 8, the heated second ink layer 4 is peeled off at the peeling layer 30 and transferred onto the recording medium 80 as a recording 3a to obtain the desired color.

In this case, the release layer 3 may be transferred together with the second ink layer 4, or may remain on the first ink layer 2 side. Also, it is separated in the release layer 3 and attached to both the first ink layer 2 and the second ink layer 4. But it's okay.

Only the case where the release layer remains on the first ink layer 2 side will be described below. In addition, thermal transfer recording by mixing the color of the first ink layer 2 or the color of the second ink layer 4 is performed by heating the thermal transfer ink layer 5 as shown in FIG. 4.5.7. After applying energy and adhering it to paper, a cooling process t of the ink of the thermal transfer material 6 is provided, and then the support 1 and the cooled thermal transfer ink layer 5 are peeled off to form the first ink layer 2, the peeling layer 3, and the second ink layer.
Both the ink layer 4 and the recording material 5a and 1. transcribe with . These two types of operations make it possible to perform two-color recording. That is, heat...Thermal energy applied from the throat 7 is used to process G [after applying the thermal transferable ink layer 5 of the thermal transfer material 6 to the recording medium 8 172 layer 5
Peeling from support 1 1. In a thermal transfer recording method in which recording is carried out using a recording medium, the timing of peeling is changed to obtain recorded images of two different colors on a recording medium.

In addition to the above-mentioned requirement of 1°, the thermal transfer temperature 6 used in this method is such that the bath melting temperature of the ink layer of the first ink layer 2 is 50°C to 50°C.
It is desirable for the II'g melt viscosity (rotational viscosity dl) at 150° C. to be 500 cps or less, as will be described later.

In the present invention, H melting temperature is 1, Flow Destar (c
b''T 500 Shimadzu +47n! Ju) under the conditions of a load of 10 kg and a temperature increase rate of 2°C/min.The appearance of the sample ink is determined as the outflow start temperature when calculating the viscosity-temperature curve. .T + as the second ink layer 4
At least 5% of the resin in the heat-melting paint
0% or more, and other oils such as the above-mentioned waxes, nT plasticizers, mineral oils, vegetable oils, etc. should be appropriately mixed in.
Melting degree (Iq1 viscosity analysis) 71' 200 (l
l) It is best to choose between 11 and 1,000,000 cps.

At this time, the effect of the peeling layer, which is a non-thermal acetic acid melting layer, and the phase 1 -C
The separation effect between the two layers is remarkable. Furthermore, in order to improve the sharpness of the printing of the second ink layer 4, the second ink layer 4 may be formed into an uneven shape.

The case where the most typical thermal head is used as a thermal head will be explained in more detail below using drawings F.

FIGS. 2 and 3 show an outline of the case where only the second ink layer 4 is transferred. FIG. 3 is a schematic cross-sectional view in the thickness direction of the thermal transfer material 6. FIG. The upper part of FIG. 2 shows the state before recording.

In FIG. 2, a thermal head 7b with 6 heat-sensitive transfer materials and a heater part 8 of the thermal head represents a platen with 9 recording materials.

A case will be described in which the combined stroke 1 ink layer 2 is black and the second ink layer 4 is red. FIG. 3 shows the state after recording [The M head 7 moves to the right and the tape is wound onto a reel (not shown)] The thermal transfer material 6 is transferred from the recording medium 8 to the heater of the thermal head 7. Immediately after passing through the section 7b, it was separated, indicating that a red record 4a was obtained on the recording medium 8.

4 and 5 show a thermal transfer material 6 schematically showing a case where the first ink layer 2, release layer 3, and second ink layer 4 are transferred together.
FIG. 2 is a schematic cross-sectional view in the thickness direction.

FIG. 4 shows the state before recording. The difference from FIG. 2 is that after the heat-sensitive transfer material 6 is heated, a member 10 is provided for peeling off the edge of the material 6, which runs idly for a certain distance t while remaining in close contact with the recording medium 8. -[
; It serves to press the thermal transfer material 6 onto the recording medium 8 at the required time and for the required time.

That is, FIGS. 2 and 3 show the case where the member 10 is separated from the platen side.

FIG. 5 shows the state after the d list. 1~ After the head is heated, it travels in the right direction, and the thermal transfer material 6 is wound up on a reel (not shown), and immediately after the member 10, the heat-sensitive transfer material 6 is transferred. The thermal transfer material 6 and the recording medium 8 are separated to form a first ink layer 2 and a release layer 3.
, indicating that both the second ink layer 4 was transferred and a black recording 5a was obtained on the recording medium 8.

FIG. 6; s'+row shows an outline of another embodiment. FIG. 3 is a schematic cross-sectional view in the thickness direction of the thermal transfer material 6. FIG.

Figure 6 shows the method for obtaining a black record, and Figures 4 and 5
The difference from the method shown in the figure is that after the thermal transfer material 6 is heated by the thermal head 7 and comes into close contact with the recording medium 8, it is moved a certain distance l in the state 11 for 1 degree and then separated. A member 1 is removably provided integrally with the thermal head 7.
1 is used, and in this case, when obtaining a red record and when obtaining a black record, the heads are replaced respectively, or only the member 11 is attached and detached to obtain a two-color record.

Next, a second process is performed in which two-color recording is performed using the thermal transfer material 6 of the present invention.
We will explain how to do this.

The second method is to obtain two-color recording by changing the voltage applied to the thermal head, and the melting temperature of the first ink layer 2 is 7.
0°C to 100°C, and the melting temperature of the second ink layer 4 is 50°C to
It is best to keep it at 60℃. At this time, in combination with the non-thermofusible peeling layer, the peeling effect between the first ink layer 2 and the second ink layer 4 is significant.

A case will be described in which the combined stroke 1 ink layer 2 is black and the second ink layer 4 is red. When the thermal transfer material 6 and the recording target 8 are stacked facing each other and a low heat energy is applied by a heat hender, only the second ink layer 4 is transferred and a red print is obtained. - In addition, when high impression heating energy is applied, the first ink layer 2, release layer 3, and second ink layer 4 are melt-transferred, and the red color of the second ink layer 4 is covered by the black color of the first ink layer 2. A black record is obtained.

〔Example〕

The present invention will be explained in more detail with reference to Examples below.

Example 1 Formulation A Terpene-phenol copolymer resin 10 parts Oil-soluble red dye 1 part MEK
89 parts The above resin was dissolved in ■K, an oil-soluble red dye was dissolved in the solution, and coating materials A' and 17 of the second ink layer were dissolved.
is.

Formulation B Carbon black 12 parts Oxidized wax 30 parts Low molecular weight oxidized polyethylene 10 parts Noah rough fin wax
After heating and dissolving 48 parts oxidized wax, low molecular weight polyethylene oxide, and paraffin wax, Car-ζ No Black was mixed and stirred, and then the Car-ζ No Black was dispersed for 30 minutes in a sand mill while heating to coat the first ink layer. Agent B' and Toshida.

The coating material B' was hot-melt coated onto a 6μ polyethylene prephthalate film using a coating bar to obtain a 4μ thick coating. Next, colloidal silica as a methanol dispersion medium (methanol silica sol, manufactured by Hidori Kagaku Kogyo ■j!) was applied on the above coating film using an applicator.
The film was dried by heating at 0° C. for 1 minute to form a release layer with a thickness of 0.3 μm.

Next, coating material A' was solvent coated on the release layer using an applicator, and then heated and dried for 1 minute at 80° C. to obtain a second ink layer having a thickness of 2 μm, thereby completing a heat-sensitive transfer material.

This was cut into a tape with a width of 8 rrV'm, loaded into a thermal printer used in a word processor (Canward 45S, manufactured by Canon ■), and printed on copy paper at a voltage of 8.5V. Printing was obtained. Next, a member that presses the thermal transfer material against the copy paper is installed adjacent to the thermal head so that the thermal transfer material to which heat is applied and the copy paper remain in close contact for a certain period of time before being separated. When printing was carried out in the same manner, a clear black print was obtained on the copy paper.

Example 2 Example 1 except that the methanol silica sol used in the release layer of Example 1 was replaced with a colloidal solution of alumina hydrate using water as a dispersion medium (Alumina Sol-200, manufactured by Nichiryo Kagaku Kogyo ■). When a thermal transfer material was prepared and evaluated in exactly the same manner as above, clear two-color printing of red and black was obtained.

Example 3 Formulation C 79-manent red 15 parts oxidized wax 27 parts low molecular weight oxidized polyethylene 9 parts paraffin wax (mp47°C)
49 parts oxidized wax, low molecular weight oxidized polyethylene,
9 Melt the rough-in wax while heating and add No. 4 to it.
- Add mane/tread and run in a sand mill for 30 minutes・9-
Ink C was prepared by dispersing Manent Red.

Formulation D Carbon black 12 parts Oxidized wax 30 parts Low molecular weight oxidized polyethylene 58 parts Oxidized wax, low molecular weight oxidized polyethylene, No. 11 Rough-in wax is dissolved while heating.
Add carbon black into it and run it in a sand mill for 30 minutes? Ink D was prepared by dispersing two pumps.

Next, Ink D was applied onto a 4μ thick polyethylene terephthalate film using a printer on a hot plate to form a 4μ thick first ink layer.

Next, after cooling the hot plate and returning it to room temperature, a methanol dispersion medium, colloidal silica (manufactured by Methanol Silica Sol Nichiryo Kagaku Kogyo ■), was applied onto the first ink layer using an applicator, and a release layer of 0.7μ was formed. Established.

Next, the hot plate is heated again and the first ink layer is melted, and ink C is coated on the release layer using a printer using a printer to form a second ink layer of 3μ. 1-1 Thermal transfer of the present invention It was used as a material.

The thermal transfer material was cut to a width of 8 m/m and printed using a thermal printer used in Ward Zorosezer (Cano Ward 458, manufactured by Canon), and copied using 3F IJ Neem (imprint heating energy) minimum and maximum. When printed on paper, clear print was obtained in red for the former and black for the latter.

Comparative Example 1 A thermal transfer material was prepared in exactly the same manner as in Example 3 except that the release layer was not provided in Example 3, and when evaluated, partial color mixing of black was observed in the red print.

〔Effect of the invention〕

As is clear from the following, according to the present invention, by providing a fine powder layer between ink layers, it is possible to provide a thermal transfer material that provides a two-color recorded image with unprecedented clarity. .

[Brief explanation of drawings]

FIG. 1 is a schematic cross-sectional view in the thickness direction of the thermal transfer material used in the present invention, and FIGS. 2 and 3 are schematic cross-sectional views in the thickness direction of the thermal transfer material showing an outline of the case where only the second ink layer is transferred. 4 and 5 are schematic cross-sectional views in the thickness direction of a heat-sensitive transfer material showing an outline of the case where both the first ink layer and the second ink layer are transferred. FIG. 6: A schematic sectional view in the thickness direction of a heat-sensitive transfer material showing an outline of another embodiment. DESCRIPTION OF SYMBOLS 1... Support body, 2... First ink layer, 3... Peeling layer. 4... Second ink layer, 41... Recording when only the first ink layer is transferred, 5... Thermal transferable ink layer, 5a.
...Record when the first ink layer, release layer, and second ink layer are transferred together, 6. Thermal transfer material, 7. Thermal head,
7b... Part of the heater of the thermal head, 8... Recorded object,
9...Platen, 10...Thermal transfer material suppression member, 1
1...Thermal transfer material pressing member. Agent Patent Attorney Sekihira Yamashita■ ■■
ψ Figure 5 Figure 6 Procedural Amendments February 1986 241

Claims (3)

[Claims] (1) A first heat-melting ink layer and a second heat-melting ink layer having mutually different tones are provided on a support from the support side, and there is a space between the layers that is not melted by thermal energy during printing. A thermal transfer material characterized by being provided with a fine powder layer. (2) The heat-sensitive transfer material according to claim 1, wherein the fine powder layer comprises one or more fine powders having a particle size of 400 mμ or less selected from silicic anhydride, alumina, and alumina hydrate. (3) The thermal transfer material according to claims 1 and 2, wherein the fine powder layer has a layer thickness of 0.01μ to 2μ.