JPH0524537Y2 - - Google Patents

Description

[Detailed description of the invention] (Technical field) The present invention relates to a recording material for electrical transfer, and more specifically, it is useful for printing records such as noiseless typewriters, computer printing, computer outputs, and records of photocopying and electronic transmission. The present invention relates to a recording material for electrical transfer.

Various types of recording materials for electrical transfer have been proposed so far. To give some examples, firstly, Japanese Patent Application Laid-Open No. 54-58511 discloses a recording material (ribbon for non-impact printing) having a two-layer structure of a transfer layer and a resistance layer containing polycarbonate resin and conductive carbon black. is proposed. However, since the polycarbonate resin used as a component of the resistive layer has a low heat deformation temperature of 120 to 130°C, a portion of it adheres to the recording electrode needle (stylus) during recording, reducing print quality. There is a problem with shortening the lifespan of

In JP-A No. 56-93585, the resistance layer is composed of a polyimide carbon layer and a SiC layer,
Since a film with sufficient strength cannot be formed with these resistive layers alone, expensive stainless steel with a thickness of about 5 μm is used as a carrier that also serves as a conductive layer, but the dot quality is poor.

Also, JP-A-59-120949 and JP-A-59-120949
The recording material for electrical transfer disclosed in Publication No. 120495 has a three-layer structure of a resistance layer (base layer), an intermediate layer, and a transfer layer (ink layer), but the intermediate layer contains a resin component and carbon. Since the resistance cannot be made low enough due to the inclusion of
There was a problem with the voltage being as high as 100-200V.

In addition, some of the recording materials for electrical transfer disclosed in JP-A-57-170796 have an insulating material such as silicone oil or liquid paraffin coated on the surface of the resistive layer (base layer); There was a problem that this was still insufficient.

(Purpose) The present invention was developed in view of the above points, and its main purpose is to have excellent mechanical strength and heat resistance, and to prevent heat fusion with the recording electrode needle, resulting in excellent running properties and It enables recording with less recording energy, is less affected by the smoothness of the surface of the transfer paper, and can obtain sufficient dot shapes even with low surface smoothness, extending the life of the stylus.
Another object of the present invention is to propose a recording material for electrical transfer that enables low-voltage driving.

(Structure) In order to achieve the above object, the present invention provides a metal thin film layer on one side of a conductive resin film, and a thermally transferable ink layer is provided on the metal thin film layer via a heat-melting peeling layer. This film is characterized by a heat-resistant slip layer provided on the other side of the film.

The inventors of the present invention have conducted various studies on recording materials for electrical transfer, and have found that by adopting the structure described above, it is possible to prevent thermal adhesion between the recording material and the recording electrode, and to improve the running of the recording material. Improved sex,
It was also confirmed that the recording energy can be reduced. The present invention is based on this.

As in the past, the recording material of the present invention is placed overlapping the recording body, the return electrode is brought into contact with the recording material, the recording electrode needle (stylus) is brought into contact with the surface of the recording material, and a voltage is applied to the recording material. It can be used in an electrical transfer recording method in which an electric current is applied to transfer ink onto the recording medium.

The present invention will be explained in more detail below.
The figure shows the basic layer structure of the recording material for electrical transfer of the present invention. The base material 1 of the recording material of the present invention consists of two layers: a resistance layer 11 made of a conductive resin film and a metal thin film layer 12. It consists of two layers: an ink layer) and an ink layer.

The heat-resistant slip layer 4 is formed of a thin film on the surface of the resistance layer 11.

While the resistance layer 11 is required to have high heat resistance and mechanical strength, it is important that it be thin from the viewpoint of thermal efficiency, ease of handling, and economic efficiency. In order to satisfy heat resistance and mechanical strength with a thin base film, a conductive resin film is used in the present invention, and it is particularly advantageous to use a film in which conductive carbon black is dispersed in aromatic polyamide.

In addition, since the resistance layer 11 is in direct contact with the recording electrode needle (stylus), it is required to have heat-resistant slip properties.In the present invention, by providing a heat-resistant slip layer 4 on the surface of the resistance layer 11, it has excellent slip properties and prevents heat from reaching the stylus. Measures to prevent fusion.

As the aromatic polyamide used in the present invention, for example, those described in JP-A-53-35797 can be used. That is, the aromatic polyamide used in the present invention has the general formula -NH-Ar ₁ -NHCO-Ar ₂ -CO- or -CO-Ar ₃ -NH- (However, Ar ₁ , Ar ₂ , Ar ₃ are all is also a divalent aromatic group, and these may be the same or different.Also, halogen atoms, etc. have been substituted into the aromatic group to improve solvent solubility and processability. There is a compound represented by Specifically, poly(m-phenylene isophthalamide),
Poly(m-phenylene terephthalamide), poly(p-phenylene isophthalamide), poly(p-
phenylene terephthalamide), poly(4,4'-
Typical examples include poly(oxydiphenylene isophthalamide), poly(4,4'-oxydiphenylene isophthalamide), poly(m-benzamide), and poly(p-benzamide). Among them, poly(m-phenylene isophthalamide) and poly(m-phenylene terephthalamide) can be dissolved in many solvents and at high concentrations when forming a film using a wet method (casting method). It is useful from

Suitable examples of the solvent include dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, and the like.

The metal thin film layer 12 as a conductive layer has the function of lowering the resistance level of the recording material, increasing current concentration and reducing crosstalk, and enables sharp recording with low voltage and low recording energy. It is useful for

There are methods such as ion sputtering and ion plating to provide a metal thin film layer on the base film 11, but industrially 10 ^-4 to ^{10 -5} _Tprr
The most excellent method is vacuum evaporation under vacuum. As the metal thin film layer, an aluminum evaporated layer formed by vacuum evaporation is suitable.

Self-condensing silicone rubber is preferably used as the heat-resistant slip layer in the present invention. Among self-condensing silicone rubbers, room temperature self-condensing silicone rubbers include TSE-370 (manufactured by Toshiba Silicone Corporation), TSE-397 (manufactured by Toshiba Silicone Corporation), and KE-41.
(manufactured by Shin-Etsu Chemical Co., Ltd.), KE-41 (manufactured by Shin-Etsu Chemical Co., Ltd.) SE-
780 (manufactured by Toray Silicone), SE-781 (manufactured by Toray Silicone), SE-5001 (manufactured by Toray Silicone),
Examples include SE-738 (manufactured by Toray Silicone Co., Ltd.).

To provide a heat-resistant slip layer on a substrate, a coating solution is prepared by dissolving self-condensing silicone rubber in a suitable solvent, such as a mixed solvent of methyl ethyl ketone, ethyl acetate, toluene, etc., and this is applied using an appropriate coating method. It can be applied onto a substrate and heated at a temperature of 30 to 100°C.

The thickness of the heat-resistant slip layer varies depending on the running properties of the printer, the applied energy, etc., but it is usually
A suitable range is 0.05 to 5 μm, preferably 0.1 to 2 μm.

As described above, the ink layer 2 of the present invention consists of at least two layers, the release layer 21 and the transfer layer 22. The release layer (heat-melting release layer) 21 is a layer that melts due to heat and loses mechanical strength, making it easier to peel off the transfer layer 22.
is a layer that contains a coloring material and has the property of being softened by heat and adhering to the recording medium.

Examples of the release layer 21 include natural waxes such as candelilla wax, carnauba wax, and rice wax; petroleum waxes such as paraffin wax and microcrystalline wax; synthetic waxes such as polyethylene wax and polypropylene wax. 120℃ or less, preferably 60℃
A substance that melts at a relatively low temperature of ~110°C and becomes a low-viscosity liquid, an adhesion modifier, and an aluminum vapor deposition layer 1
Ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, ethylene-(meth) which is compatible with these low melt viscosity substances to improve adhesion to 2.
Acrylic acid copolymer, ethylene-(meth)acrylic acid alkyl ester copolymer, xylene resin,
It is formed by mixing with resins such as ketone resin.
In addition to this, the release layer 21 may be made of a substance that is difficult to mix with the transfer layer 22 to improve storage stability at high temperatures, or may have supercooling properties to meet the recording conditions. substances (e.g. 1,3
-diphenoxy-2-propanol) is also effective.

For the transfer layer 22, a well-known heat-melting transferable ink material can be used, but in order to perform recording that is not affected by the smoothness of the surface of the recording medium, it is necessary to use a resin component more than the conventional formulation. It is desirable to have a large amount of liquid, not to become a very low viscosity liquid when heated, and to have a certain degree of mechanical strength. The transfer layer 22 that meets these requirements is made of ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic copolymer,
The main ingredient is a heat-softening resin, such as polyamide resin, which has traditionally been used as a main ingredient for hot melt adhesives, and waxes and polyethylene waxes are added to this resin with the aim of improving thermal sensitivity and fixation of printing on recording media. It is made by adding tsukusu and coloring materials.

In order to actually produce the recording material of the present invention, for example, conductive carbon black is first wet-dispersed in an aromatic polyamide resin using a solvent such as dimethylformamide or dimethylacetamide, and then a film is formed by a casting method.

Obtained film base material (conductive resin film)
Aluminum is vapor-deposited under a vacuum of 10 ^-4 to 10 ^-5 _Tprr , and a release layer and a transfer layer are sequentially applied on this aluminum vapor-deposited layer using a hot-melt method or a solvent coating method using toluene, xylene, alcohol, etc. as a solvent. After that, a heat-resistant slip layer may be provided on the surface of the resistance layer 11 by a solvent coating method using a mixed solvent of methyl ethyl ketone, ethyl acetate, toluene, or the like.

The thickness of each layer of the recording material to be manufactured is as follows: the heat-resistant slip layer 4 has a thickness of 0.05 to 5 μm, preferably 0.1 to 2 μm, the resistance layer 11 has a thickness of 2 to 15 μm, preferably 4 to 10 μm, and the metal thin film layer (aluminum vapor deposited layer) 12 has a thickness of 40 μm. ~
The thickness of the peeling layer 21 is about 0.5 to 5 μm, and the thickness of the transfer layer 22 is about 3 to 10 μm.

As shown in FIG. 2, the recording material of the present invention may be provided with a heat-softening or heat-melting surface layer 23 having a thickness of 0.5 to 5 μm and made of wax, resin or the like on the transfer layer 22 in order to further improve recording characteristics.

In order to carry out current transfer recording using the recording material for current transfer produced in this way, for example, as shown in FIG. 4 recording electrodes on the surface 4
1 and the return electrode 42 are brought into pressure contact and a print signal current is passed through the recording electrode 41. When the recording material is energized, current flows at a high density from the recording electrode 41 toward the metal thin film layer 12, diffuses within the metal thin film layer 12, and flows at a low density toward the return electrode. A small area of the recording material generates heat due to the Joule heat of high-density current in the recording material, heat generation due to interfacial resistance, etc., the ink layer 2 in that area is heated, and the transfer layer 22 is transferred to the recording medium (transferred layer) 3. It is possible to obtain a record according to the print signal current.

The conditions of energization, the number of scanning lines, etc. greatly affect image formation, but generally the signal voltage is 10 to 200 V, the energization time is 0.05 to 1 msec, and the number of scanning lines is about 3 to 20 lines/mm. The recording material 1 and the recording body 2 are brought into complete contact.

The present invention will be further explained below with reference to examples as well as comparative examples, but the present invention is not limited to these examples. In the examples, all parts are by weight.

Example 1 A mixture consisting of 85 parts of m-phenylene terephthalamide, 15 parts of conductive carbon black, and 900 parts of dimethylformamide was dispersed in a ball mill for 20 hours, and then cast onto a glass plate using a blade with a gap of 200 μm. , after drying in a dryer at 110°C for 1 hour, immersing it in cold water at about 5°C for 1 minute,
It was peeled off from the glass plate to obtain a base layer (resistance layer) with a thickness of about 6 μm. Above this, at 10 ^-5 Torr,
Aluminum was deposited to a thickness of 100 nm.

Furthermore, on top of this aluminum vapor deposited layer, ethylene-vinyl acetate copolymer (90% ethylene, melt index 480) is applied.
A release layer composition consisting of 15 parts and 85 parts of polyethylene wax (melting point 92°C) was heated to a thickness of approx.
It was applied to a thickness of 1 μm. On top of this release layer: 50 parts of ethylene-vinyl acetate copolymer (72% ethylene, melt index 80) 10 parts polyethylene oxide (oxidation 25, melting point 98°C) 30 parts paraffin wax (melting point 78°C) For coloring material A mixture of 10 parts of carbon black and 400 parts of toluene was dispersed in a ball mill for 24 hours, then applied with a wire bar and dried with a hair dryer.
It was dried at 100° C. for 1 minute to form an ink layer (transfer layer) with a thickness of about 5 μm.

Next, a heat-resistant slip liquid consisting of 2.5 parts of room temperature self-condensing silicone rubber, 47.5 parts of methyl ethyl ketone, and 50.0 parts of toluene was applied to the surface of the resistance layer to a solid content of 1 μm.
It was applied using a wire bar and dried.

The ink ribbon made in this way has a diameter of approximately
The voltage was applied using a multi-stylus with 60 μm recording electrodes arranged in two rows in a staggered manner at a density of 8 electrodes/mm.
When recording was performed at 12V (resistance 0.5KΩ) and recording power 0.3W, a sharp dot density of 1.4 was obtained with a high resolution of 16 dots/mm on plain paper (recording medium) with a surface smoothness of 10 seconds. I got a character.

Furthermore, when 5 million characters were repeatedly recorded using this ink ribbon, there was no heat fusion with the multi-stylus, and no abnormality was observed in the running performance of the ribbon even at low torque (250 g).

Example 2 On the surface of the ink layer obtained in the same manner as in Example 1, a surface layer having the following composition was provided to a thickness of about 1.2 μm by hot melting while cooling from the substrate surface.

(Surface layer composition) Microcrystalline wax (melting point 82℃)
70 parts xylene resin (softening point 110°C) 15 parts terpene resin (softening point 120°C) 15 parts When the thus obtained ink ribbon was recorded in the same manner as in Example 1, the applied voltage was 11.5V.
(resistance 0.5KΩ) and applied power of 0.26W, the surface smoothness was as high as 16 dots/mm on plain paper (recording material) with a base smoothness of 10 seconds and a sharp dot density of 1.45. characters were obtained.

Furthermore, when 5 million characters were repeatedly recorded using this ink ribbon, there was no heat fusion with the multi-stylus, and no abnormality was observed in the running performance of the ribbon even at low torque (250 g).

Furthermore, the current transfer recording material of the present invention is also suitable for color recording.

Comparative Example 1 Example 1 except that the heat-resistant slip layer was not provided.
Using an ink ribbon obtained in exactly the same manner as above, an applied voltage of 12 V (resistance 0.5 KΩ) and a recording power of 0.3 W were used to record 500
As a result of repeatedly recording 10,000 characters, the ribbon fused on the multi-stylus, and an abnormality was observed in the running performance of the ribbon.

Comparative Example 2 Example 1 except that no aluminum layer was provided
When recording was performed using an ink ribbon obtained in exactly the same manner as above, the applied voltage was 150V (resistance 4KΩ),
Even with a recording power of 5.6W, sharp characters could not be obtained.

Comparative Example 3 Recording was performed using an ink ribbon obtained in exactly the same manner as in Example 1, except that a transfer layer was provided directly on the aluminum layer without providing a release layer. When an applied voltage of 35 V (resistance 0.5 KΩ) and a recording power of
Even at 2.45W, no sharp recording was obtained, and there was a slight smell of the recording medium burning. This was due to the current concentration effect of the aluminum vapor deposition layer.
This is thought to be due to a large amount of heat being generated in a small area.

(Effects) As described above, compared to conventional recording materials, the recording material for electrical transfer of the present invention has no heat fusion on the stylus, no scum stains, low torque, excellent ribbon running performance, and is reliable. You can record high quality records. Further, according to the recording material of the present invention, clear recording can be obtained with a low applied voltage without being affected by the smoothness of the surface of the recording medium. Furthermore, printing in colors other than black is easily possible if necessary.

[Brief explanation of the drawing]

1 and 2 are cross-sectional views of two examples of the recording material for electrical transfer according to the present invention, and FIG. 3 is a diagram for explaining the recording method for electrical transfer. DESCRIPTION OF SYMBOLS 1... Base material, 2... Ink layer, 3... Recording body (transfer paper, etc.), 4... Heat-resistant slip layer, 11...
...Resistance layer, 12... Aluminum vapor deposition layer, 21...
... Peeling layer, 22 ... Transfer layer, 23 ... Surface layer, 4
1... Recording electrode, 42... Return electrode.

Claims (1)

[Claims for Utility Model Registration] (1) A metal thin film layer is provided on one side of a conductive resin film, a thermally transferable ink layer is provided on the metal thin film layer via a heat-melting peeling layer, and the other side of the film is A recording material for electrical transfer, characterized in that a heat-resistant slip layer is provided on the surface. (2) The recording material for electrical transfer according to claim 1, wherein the metal thin film layer is an aluminum vapor-deposited layer. (3) The recording material for electrical transfer according to claim 1, which uses a room temperature self-condensing silicone rubber as the main component of the heat-resistant slip layer. (4) The recording material for electrical transfer according to claim 1, wherein the conductive resin film contains aromatic polyamide resin and conductive carbon black as main components. (5) The thickness of the conductive resin film is 2 to 15 μm.
A recording material for electrical transfer according to claim 1 of the utility model registration claim. (6) The recording material for electrical transfer according to claim 1, wherein the metal thin film layer has a thickness of 40 to 200 nm.