JPH01122486A - Electro-transferring recording material - Google Patents

Abstract

PURPOSE:To obtain superior mechanical strength, heat resistance, and image fixing properties, by a method wherein, a metal film layer is provided on a surface of a conductive resin film, thereon a far infrared radiation film layer is provided, and further thereon a thermally transferring ink layer is provided through a hot-melt release layer. CONSTITUTION:A substrate 1 consists of two layers of a resistant layer (a conductive resin film) 11 and a metal film layer 12. An ink layer 3 consists of at least two layers, i.e. a hot-melt release layer 31 and a transfer layer 32 (a thermally transferring ink layer). A far infrared radiation film layer 2 is provided between the substrate 1 and the ink layer 3. On the transfer layer 32, an adhesive layer may be formed, as necessary. In this case, it is desirable that a release paper is applied to the surface of the adhesive layer when an electro-transferring recording material is unused. The resistant layer 11 requires high heat resistance and mechanical strength, but on the other hand it is important for the resistant layer to be thin for thermal efficiency, handling characteristics, and profitability.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a recording material for electrical transfer, and more specifically,
Noiseless Typewriter - 1 This invention relates to a recording material for electrical transfer that is useful for printing records such as computer printing, computer output, and records of photocopying and transmission.

[Prior Art] Various recording materials for electrical transfer have been proposed so far. To give some examples, JP-A-54-58511 discloses a recording material (non-impact printing ribbon) consisting of a two-layer structure of a transfer layer and a resistance layer containing polycarbonate resin and conductive carbon black. is proposed. However, the heat distortion temperature of the polycarbonate resin used as a component of the resistance layer is 120 to 130°C.
Because of the low viscosity of the stylus, some of it adheres to the stylus during recording, reducing print quality and, in turn, shortening the life of the stylus.

In JP-A-56-93585, the resistive layer is composed of a polyimide carbon layer and a SiC layer, but these resistive layers alone do not form a film with sufficient strength, making it expensive to use as a carrier that also serves as a conductive layer. Although stainless steel with a thickness of approximately 5 μl is used, the dot quality is poor.

Also, JP-A-59-120494 and JP-A-59
The recording material for electrical transfer disclosed in Publication No. 120495 includes a resistance layer (base layer), an intermediate layer, and a transfer M! J(
However, since the intermediate layer contains a resin component and carbon, the resistance cannot be made sufficiently low, resulting in a high recording voltage of 100 to 200 V.

In addition, these known techniques almost commonly have the defect that they are easily affected by the surface smoothness of the recording medium (transfer paper, etc.), making it difficult to obtain a sufficiently good dot shape.

[Purpose] The present invention has been made in view of the above problems, and its main purpose is to provide a product with excellent mechanical strength, heat resistance and image fixing properties,
It is possible to record with lower recording energy than before, and it is not affected by the smoothness of the surface of the paper being transferred, and a sufficient dot shape can be obtained even if the surface smoothness is low, extending the life of the stylus. Another object of the present invention is to provide a recording material for electrical transfer that enables low-voltage driving.

[Structure] The recording material for electrical transfer of the present invention has a metal thin film layer provided on one side of a conductive resin film, a far infrared emitting film layer on the metal thin film layer, and a far infrared emitting film layer on the far infrared emitting film layer. It is characterized in that a thermally transferable ink layer is provided through a thermally meltable peeling layer.

Incidentally, the present inventors have been conducting various studies regarding recording materials for electrical transfer.

By adopting the above structure, recording can be performed with lower recording energy than before, and it is not affected by the smoothness of the surface of the transfer paper, and a sufficient dot shape can be obtained even if the surface smoothness is low. Furthermore, it was confirmed that the image did not fall off. This is because during recording, the far-infrared emitting film layer absorbs heat generated at the interface with the metal thin film layer,
This is thought to be because the heat is efficiently conducted to the heat-melting release layer and the heat-transferable ink layer, and recording energy is effectively utilized. The present invention has been made based on such knowledge.

As before, the recording material of the present invention is placed overlapping a recording medium, a return electrode is brought into contact with the recording material, and a recording electrode (i.e., 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. FIG. 1 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 resistive layer (conductive resin film) 11 and a metal thin film layer 12, and the ink layer 3 includes at least a heat-melting peeling layer 31 and a transfer layer 32 (
A far-infrared emitting film layer 2 is provided between the base material 1 and the ink layer 3. As will be described later, an adhesive layer may be provided on the transfer layer 32 if necessary, and in that case, when the recording material for electrical transfer is not used, a release paper is provided on the surface of the adhesive layer. is desirable.

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. Resistance layer (conductive resin film) 11 (1)
(2) A resin film with a conductive agent coated on its surface, (2) a resin film with a conductive agent dispersed in it, etc. can be used.

However, in order to satisfy heat resistance and mechanical strength with a thin film, the present invention uses a conductive resin film of the type (2) above, and in particular, a film in which conductive carbon black is dispersed in aromatic polyamide. The use of is advantageous.

For aromatic polyamides, for example, Japanese Patent Application Laid-Open No. 53-35797
Those described in the above publication can be used. That is, the aromatic polyamide used in the present invention has the general formula % (however, Ar1. Ar, , Ar are all divalent aromatic groups, and they may be the same or different). (Also, it may be a compound in which a halogen atom or the like is substituted into an aromatic group in order to improve solvent solubility and processability.) Specifically, poly(,
-phenylene isophthalamide), poly(m-phenylene terephthalamide), poly(p-phenylene isophthalamide), poly(p-phenylene terephthalamide)
, poly(4,4'-oxydiphenylene terephthalamide), poly(4,4'-oxydiphenylene isophthalamide), poly(m-benzamide), poly(p-benzamide), and the like. Among them, poly(+a-me phenylene isophthalamide, poly(m-
Phenylene terephthalamide) is useful when forming a film using a wet method (casting method) because it is soluble in many solvents and can be dissolved at high temperatures.

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

The metal thin film layer 12 has the function of lowering the resistance level of the recording material and prolonging the concentration of current, thereby reducing crosstalk, and is useful for enabling sharp recording with low voltage and low recording energy. be. There are methods such as ion sputtering and ion blasting to provide the metal thin film layer 12 on the conductive resin film 11.

Industrially, the most excellent method is a vacuum deposition method under a vacuum of 10-4 to 10-' Torr. As the metal thin film layer 12, an aluminum vapor deposition layer is suitable.

The far infrared emitting film layer 2 is made of, for example, Sin, Tie, 5
iZrO, 14nO, CuO1Cr, 0. , Fe
, O3lMn, O, Ag2O3, ZrO□ (among them, it is preferable to use Sin) as a main component.

These are dispersed in a resin solution to a content of 2 to 13% by weight, and formed by coating. Examples of the resin (binder) include polyester resin and vinyl acetate resin, and examples of the solvent include isopropyl alcohol, toluene, and methyl ethyl ketone.

As described above, the ink layer 3 includes at least the release layer 31,
It consists of two layers: a transfer layer 32. Release layer (heat-melting release layer)
Reference numeral 31 is a layer that melts due to heat and loses its mechanical strength, making it easy to peel off the transfer layer 32. Also, the transfer layer (thermal transferable ink layer) 32 contains a coloring material and is softened by heat to cause unevenness of the recording medium. This is a layer that has adhesive properties (covering the concave areas during bridge transfer).

As the release layer 31, for example, natural waxes such as candela wax, carnauba wax, and rice wax; petroleum waxes such as paraffin wax and microcrystalline wax; and synthetic waxes such as polyethylene wax and polypropylene wax are used at temperatures below 120°C. A substance that melts at a relatively low temperature, preferably from 60°C to 110°C, to become a low-viscosity liquid, an adhesion modifier, and a metal thin film layer 12.
Ethylene-vinyl acetate copolymer that is compatible with these low melt viscosity substances to improve adhesion to.

It is formed by mixing resins such as styrene-butadiene copolymer, ethylene-(meth)acrylic copolymer, xylene resin, and ketone resin. In addition to this, the release layer 31 may be formed of a substance that is difficult to mix with the transfer layer 32 in order to improve storage stability at high temperatures, or may have supercooling properties to meet the recording conditions. substances (e.g. 1,3
It is also effective to add diphetoxy 2-propatool).

For the transfer layer 32, a well-known heat-melting transfer 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 rather than the conventional formulation. , and does not become a very low viscosity liquid when heated,
It is desirable to have a certain degree of mechanical strength.
The transfer layer 32 that meets these requirements is made of a coloring material and a styrene resin, an ethylene-vinyl acetate copolymer, an ethylene-(meth)acrylic copolymer, or a polyamide resin, which is used as a main ingredient for conventional hot melt adhesives. A material whose main component is a heat-softening resin that has been widely used is used. A suitable amount of wax, polyethylene wax, etc. may be added to this transfer layer 32 in order to further improve thermal sensitivity and fixation of prints on the recording medium.

As mentioned above, an adhesive layer 4 is preferably provided on top of the thermally transferable ink layer 32 (FIG. 2).

The adhesive layer 4 is a useful layer because it facilitates the peeling of the transfer layer 32 and improves image fixation on a recording medium (transfer paper, etc.).

A thermoplastic resin is used for this adhesive layer 4, and preferably has a melting point or softening point of 70 to 140°C. These include acrylic resins, methacrylic resins, styrene resins, vinyl acetate resins, vinyl chloride resins, vinylidene chloride resins, petroleum resins, novolac resins, olefin resins, polyester resins, polyacetal resins, or copolymers containing these monomers. Examples include merging.

Note that a coloring material may be added to the adhesive layer 4 with the intention of improving the print density on the recording medium.

In order to actually produce the recording material of the present invention, conductive carbon black is first wet-dispersed in a resin, particularly an aromatic polyamide, using a solvent such as dimethylformamide or dimethylacetamide, and then formed into a film by a casting method. A metal thin film layer (preferably 1
A far-infrared emitting film is formed on this metal thin film layer by a hot-melt method or a solvent coating method using toluene, xylene, alcohols, etc. as a solvent. A layer, a release layer, and a transfer layer may be provided in this order.

Further, as described above, as shown in FIG. 2, if necessary, the adhesive layer 4 may be provided on the transfer layer 32, and a release paper may be provided on the surface of the adhesive layer 4 (FIG. 2).

The thickness of each layer of the recording material to be manufactured is such that the resistance layer (conductive resin film layer) 11 has a thickness of 2 to 15 μm, preferably 4 to 10 μm.
μ+a, metal thin film layer 12 is 40 to 200n11, far infrared emitting film layer 2 is 1 to 5 μm, preferably 1.5 to 3.5.
un, the peeling layer 31 is 0.5 to 5 μn+, the transfer layer 32 is 3
The adhesive layer 4 has a thickness of about 0.5 to 5 μm.

As shown in FIG. 3, the recording material of the present invention also includes waxes on the transfer layer 32 to further improve the recording properties.
Heat-softening or heat-melting material made of resin, etc., thickness 0.5
A surface layer 5 of ~5 μm may be provided.

In order to carry out current transfer recording using the recording material for current transfer produced in this way, 1. For example, as shown in FIG. The recording electrode 71 is placed on the surface of the resistance layer 11 on the opposite side.
and the return electrode 72 are brought into pressure contact with each other, and a print signal current is passed through the recording electrode 71.

When the recording material is energized, current flows from the recording electrode 71 toward the metal thin film layer 12 at a high density, diffuses within the metal thin film layer 12, and flows toward the return electrode 72 at a low density.

The far-infrared emitting film layer 2 absorbs and conducts Joule heat from high-density current and heat generated by interfacial resistance within the recording material, and a small area of the recording material generates heat, which heats the ink layer 3 in that area and transfers it to the transfer layer 32. Alternatively, the transfer layer 32 adheres to the recording medium (transfer paper, etc.) 6 together with the adhesive layer 4 or the surface layer 5.

The release layer 31 melts and the transfer layer 32 is transferred to the recording medium 6 (
Or adhesive layer 4 and transfer layer 32 or surface layer 5 and transfer layer 3
2 and transfer to the recording medium 6), recording corresponding to the print signal current can be obtained.

The conditions of energization, the number of scanning lines, etc. greatly affect image formation, but in general, the signal voltage is 10 to 200V, and the energization time is 0.0V.
The speed is about 5 to 1 rm sec, and the number of scanning lines is about 3 to 20 lines/am. The recording material and the recording body (transferred body) are brought into complete contact with each other.

The present invention will be further explained below with reference to Examples along with Comparative Examples, but the present invention is not limited to these examples. All parts herein are parts by weight.

Example I I - A mixture consisting of 85 parts of phenylene terephthalimide, 15 parts of conductive carbon, and 900 parts of dimethylformamide was dispersed in a ball mill for 200 hours, and then cast onto a glass plate using a blade with a gear diameter of approximately 200 μm. After drying in a dryer at 110°C for 1 hour, it was immersed in cold water at about 5°C for 1 minute and peeled off from the glass plate to a thickness of about 6μ.
A base layer (resistance layer) of m was obtained. 10-'To this
At rr, aluminum was deposited to a thickness of about 1100 nm. Furthermore, on this aluminum vapor deposited layer,
8 parts polyester resin 10 parts toluene
A far-infrared emitting layer having a thickness of about 3 μm was provided by coating a resin dispersion containing 82 parts with a wire bar.

A release layer composition consisting of 85 parts of polyethylene wax (melting point: 92° C.) was applied onto this far-infrared emitting layer to a thickness of about 1 μl by a hot melt method. Polystyrene resin (MH102 manufactured by Mitsubishi Monsando Chemical Co., Ltd.: softening point 101°C, molecular weight 5500,
0) 35 parts polyethylene oxide (acid value 25. melting point 9)
8℃) 10 parts Paraffin wax (melting point 78℃) 20 parts Carbon black for coloring material 10 parts Toluene A mixture consisting of 400 parts was dispersed in a ball mill for 24 hours, applied with a wire bar, and dried for 1 minute at 80℃ with a hair dryer. An ink layer (transfer layer) having a thickness of about 5 μm was formed.

The ink ribbon made in this way has a diameter of approximately 60 μm.
When recording was carried out at an applied voltage of 12 V (resistance of 0.5 Ω) and a recording power of 0.25 W using a multi-stylus in which m recording electrodes were arranged in two rows in a staggered manner at a density of 8/a+m, one surface was recorded. A high resolution of 16 dots/mm and a dot density of 1.0 on plain paper (recording material) with a Beck smoothness of 10 seconds.
4 sharp characters were obtained.

Further, although 5 million characters were repeatedly recorded using this ink ribbon, no ribbon residue was observed on the surface of the multi-stylus. The tensile strength of this ribbon was 790 g.

Example 2 On the surface of the ink layer (transfer layer) having a thickness of about 5 μm in Example 1, a mixture consisting of 2 parts of carbon black for coloring material and 188 parts of toluene was further dispersed in a ball mill for 24 hours and coated with a wire bar. It was dried at ℃ for 1 minute to form an adhesive layer with a thickness of about 2 μm.

When the ink ribbon thus produced was subjected to recording in the same manner as in Example 1, a high resolution of 16 dots/m was obtained on plain paper (recording material) with a surface smoothness of 3 seconds in Beck smoothness. Sharp characters with a dot density of 1.4 were obtained. As a result of rubbing this image 10 times with a crockmeter (sand eraser), no image was observed to come off.

Furthermore, although 5 million characters were repeatedly recorded using this ink ribbon, no wear of the multi-stylus was observed.

Example 3 5i0 instead of 8 parts of SiO in the far infrared emitting film layer
An ink ribbon was prepared in the same manner as in Example 2 except that a mixture of 24 parts of TiO and 4 parts of TiO□ was used.

The ink ribbon made in this way has a diameter of approximately 60 μm.
When recording was performed at an applied voltage of 12 V (resistance 0.5 KQ) and a recording power of 0.27 W using a multi-stylus with two rows of Otori recording electrodes arranged in a staggered manner at a density of 8 electrodes/I1 m, the surface was smooth. A dot density of 1 with a high resolution of 16 dots/m on plain paper (recording material) with a Beck smoothness of 10 seconds.
．． 38 sharp characters were obtained.

Furthermore, although 5 million characters were repeatedly recorded using this ink ribbon, no ribbon residue was observed on the surface of the multi-stylus. The tensile strength of this ribbon was 790 g.

Example 4 A low melting point polyamide resin (
50 parts oleic acid amide (melting point 75°C)
) A release layer was provided by applying a release layer composition of 50 parts by a hot melt method to a thickness of about 0.8 μm.

On top of this, a mixture of 60 parts of paraffin wax (melting point 78°C) and 10 parts of phthalocyanine was applied in the same manner as in Example 1 to form an ink layer with a thickness of about 5 μm.
A transfer layer) was formed.

On top of this, a surface layer having the following composition was provided to a thickness of about 1.2 μm by hot melting while cooling from the base material surface.

(Surface layer composition) xylene resin (softening point 110°C) 15 parts terpene resin (
When the ink ribbon thus obtained was recorded in the same manner as in Example 1, it was clear at an applied voltage of 11.5 V (resistance 0.5 KQ) and an applied power of 0.21 W. It was found that the recording material for electric transfer of the present invention is also suitable for color recording.

Comparative Example 1 An ink ribbon was produced in exactly the same manner as in Example 1 except that the far-infrared emitting film layer was not provided.

When this comparative ink ribbon was used for printing in the same manner as in Example 1, the applied voltage was 18 V (resistance 0.35 Ω),
At a recording voltage of 0.58 W, approximately twice the recording energy as in Example 1 was required.

Comparative Example 2 Recording was carried out using an ink ribbon obtained in the same manner as in Example 1 except that no aluminum layer was provided.
Even with W, sharp characters could not be obtained.

[Effect] As described above, the recording material for electrical transfer of the present invention is thinner and more compact than conventional recording materials, and can produce clear images with less energy without being affected by the smoothness of the surface of the recording material. Records are obtained.

Furthermore, printing in colors other than black is easily possible if necessary. Furthermore, according to the recording material of the invention.

Sufficient and sharp ink transfer can be performed with a low applied voltage, and the life of the stylus can be extended to achieve highly reliable recording.

[Brief explanation of the drawing]

FIG. 1, FIG. 2, and FIG. 3 are three cross-sectional views of the recording material for electrical transfer according to the present invention. FIG. 4 is a diagram for explaining the current transfer recording method. 1... Base material 2... Far-infrared emitting film layer 3
... Ink layer 6 ... Recording material (transfer paper, etc.) 11 ... Resistance layer (conductive resin film) 12 ... Metal thin film layer 31 ... Peeling layer 32 ... Transfer layer
4... Adhesive layer 5... Surface layer 71.
...Recording electrode 72...Return electrode flame 1 closed night 2 closed 31st flU Fig. 4

Claims (1)

[Claims] 1. A metal thin film layer is provided on one side of the conductive resin film, a far infrared ray emitting film layer is provided on the metal thin film layer, and a heat-melting release layer is further provided on the far infrared ray emitting film layer. 1. A recording material for electrical transfer, characterized in that a thermally transferable ink layer is provided through an ink layer. 2. The recording material for electrical transfer according to claim 1, wherein an adhesive layer is provided on the thermal transferable ink layer. 3. The recording material for electrical transfer according to claim 2, wherein the adhesive layer is a thermoplastic resin having a melting point or softening point of 70 to 140°C. 4. The recording material for electrical transfer according to claim 1 or 2, wherein the conductive resin film contains an aromatic polyamide resin and conductive carbon black as main components. 5. The recording material for electrical transfer according to claim 1 or 2, wherein the conductive resin film has a thickness of 2 to 15 μm. 6. The recording material for electrical transfer according to claim 1 or 2, wherein the metal thin film layer has a thickness of 40 to 200 nm. 7. The recording material for electrical transfer according to claim 1, 2, or 6, wherein the metal thin film layer is an aluminum vapor-deposited layer. 8. The far-infrared emitting film layer is SiO_2, TiO_2,
SiZrO_4, MnO_4, CuO, Cr_2O_3
, Fe_2O_3, Mn_2O_3, Al_2O_3,
The recording material for electrical transfer according to claim 1 or 2, which contains at least one selected from ZrO_2 and ZrO_2 as a main component. 9. The recording material for electrical transfer according to claim 1, 2 or 8, wherein the far-infrared emitting film layer has a thickness of 1 to 15 μm.