JPS5921316B2 - Current recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a recording material that can be transferred and recorded by energization.

In recent years, information has become extremely abundant, and the need for prompt transmission and recording of that information has increased, and various developments have been made regarding information management systems such as information processing systems, information transmission systems, and information recording systems. .

Heat-sensitive recording materials, discharge recording materials, and the like are provided as recording materials compatible with the above-mentioned system. However, heat-sensitive recording materials contain both a coloring agent and a coloring aid in the sheet of recording material, so there is a risk of coloring if shock or pressure is applied carelessly, and if stored for a long time. It has the disadvantage of gradually developing color. Furthermore, discharge recording materials have the disadvantage that they produce bad odors and soot during recording because the binder is destroyed by discharge.
The purpose of the present invention is to provide an electrically conductive recording material that does not develop color even when stored for a long period of time or when subjected to impact or pressure during storage, and that can record without producing bad odor or soot during recording. It is about providing.

That is, the gist of the present invention is (4) a resin matrix in which a conductivity imparting agent and a fine powder of a low melting point resin are dispersed, the surface resistance is greater than 1 Ω and less than 10 5 Ω, and the material is energized when recording electricity. The semiconductive resin layer that is destroyed and transferred, (B
It consists of a resin matrix and metal powder, which are laminated on one side of a semi-conductive resin layer, and the metal powder has a density of 5 to 60
A metal-containing resin layer that occupies a volume % and has a surface resistance of 10 5 to 10 16 Ω and is not destroyed by discharge during electrical recording; It exists in a current-carrying recording material consisting of a conductive layer that has a surface resistance that is higher than the surface resistance of the semiconductive resin layer, and is destroyed and transferred during current-carrying recording.

The resin matrix used in the present invention only needs to have film-forming ability and electrical insulation properties, and thermoplastic resins are preferably used.

The above-mentioned thermoplastic resin is desirably one that has a high binding power to metal powder, a conductivity imparting agent, etc., has high mechanical strength when molded into a sheet or film, is flexible, and has strong stiffness, such as Polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, ethylene monovinyl acetate copolymer, vinyl chloride monovinyl acetate copolymer, polystyrene, polyacrylonitrile, polyvinyl acetal, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, polyester , acetic acid cellulose, polyvinyl alcohol, carboxymethyl cellulose, gelatin, etc., and polyethylene, polyvinyl chloride, vinyl chloride-ethylene copolymer, vinyl chloride monovinyl acetate copolymer, polyvinyl acetal, and cellulose acetate are preferably used. . The resin matrices forming each of the metal-containing resin layer, semiconductive resin layer, and conductive layer may be of the same kind or of different kinds.

The conductivity imparting agent used in the present invention may have conductivity, such as carbon black, graphite, zeolite, zinc oxide, stannic oxide, metastannic acid, cuprous iodide, reduced oxidation Titanium, ferric oxide, silicon carbide, etc. are preferably used.

Metal powders such as copper, aluminum, tin, molybdenum, and silver are also preferably used. The particle size of the conductivity imparting agent is preferably small and uniform, and preferably has an average particle size of 10 microns or less. The low melting point resin used in the present invention has a low melting point and is used as a current recording material, and when energized, it is heated and melted by the resistance heat of the energized electricity, and the surrounding conductivity imparting agent and coloring material are It is preferable to use a resin which is destroyed by electric current and transferred to recording paper and has a melting point of 30 to 100°C.

Further, the particle size of the fine powder is preferably small, preferably 50 μm or less. Examples of the low melting point resin include low molecular weight polypropylene, polyethylene, ethylene monovinyl acetate copolymer, polyethylene glycol, polypropylene glycol, wax, microcrystal wax, and the like.

In the present invention, the semiconductive resin layer is a layer that is destroyed and transferred by electrical current during recording, and is formed by dispersing the conductivity imparting agent and the fine powder of the low melting point resin in the resin matrix. .

The amount of the conductivity imparting agent and low melting point resin added is not particularly limited, and the surface resistance of the semiconductive resin layer is 1Ω.
The conductivity imparting agent may be added in an amount of 1 to 1000 parts by weight, and the low melting point resin may be added in an amount of 100 to 500 parts by weight to 100 parts by weight of the resin matrix. It is preferable to The thickness of the semiconductive resin layer is not particularly limited, but
The method for forming the semiconductive resin layer is not particularly limited, and any known method may be adopted, but the resin matrix is soluble but has a low melting point. It is preferable that the resin matrix, the conductivity imparting agent, and the fine powder of the low melting point resin are dissolved and dispersed in a solvent in which the resin does not dissolve or hardly dissolves, and is formed by a casting method.

Furthermore, the low melting point resin of the semiconductive resin layer is used as the current recording material of the present invention, and is dissolved during current recording, and is transferred to the recording paper together with the surrounding conductivity imparting agent, etc. Therefore, it is a coloring material. may be added. In other words, if you want to obtain a black image, you can use carbon black as a conductivity imparting agent, or you can use a non-dark colored conductivity imparting agent such as zinc oxide or stannic oxide, and add a coloring agent to create a colored image. images are obtained. Any known colorant can be used as the colorant, such as nickel yellow, titanium yellow, cadmium red, naphthol yellow, permanet orange, crystal violet, malachite green, etc., and the amount added is recorded. It may be arbitrarily determined based on the color, density, etc.

Note that when the coloring material has conductivity, it is necessary to pay attention to the surface resistance of the semiconductive resin layer. Further, an inorganic filler may be further added to the semiconductive resin layer. Examples of the above-mentioned inorganic fillers include calcium oxide, magnesium oxide, potassium carbonate, sodium carbonate, calcium carbonate, strontium carbonate, titanium oxide, barium sulfate,
Examples include litobone, basic magnesium carbonate, silica, and clay.

Further, the particle size of the inorganic filler is uniform, and the average particle size is 0.
05 to 10μ is preferable, more preferably 0.1
~3.0μ, and the amount added is 10μ
It is preferable to add 10 to 1000 parts by weight per 0 parts by weight. When the inorganic filler has conductivity, the surface resistance of the semiconductive resin layer is greater than 1Ω.
Care must be taken to ensure that the resistance is less than 6Ω. In the present invention, the metal-containing resin layer is laminated on one surface of the semiconductive resin layer and is made of the resin matrix and metal powder, and is a layer that is not destroyed by electrical current during recording.

The above-mentioned metal powder means a metal made into powder, and the powder needs to have electrical conductivity.

It is preferable to use a powder of a highly conductive metal, and specific examples of suitable metal powders include powders of copper, aluminum, iron, tin, zinc, nickel, molybdenum, silver, bronze, brass, and the like. Further, metal powder coated with other metals can also be used, such as copper powder coated with silver. Among the metal powders mentioned above, copper, zinc, and iron are more preferably used. The particle shape of the metal powder is preferably resin-like, spherical or lumpy, and the particle size is preferably small and uniform, with an average particle size of 0.2 to 20 microns being preferred, and more preferably It is 0.5 to 10 mikukan. In the present invention, one or more kinds of metal powders may be selected and used from among the above-mentioned metal powders as necessary.

Also, if the amount added is too small, the conductivity will be low, and conversely, if the amount added is too large, the conductivity will be too good and the current applied from the recording needle will be diffused, causing it to drop directly below the recording needle. Since it becomes difficult to bend and the accuracy of recording decreases, the surface resistance is determined to be 5 to 60% by volume of the metal-containing resin layer and to be 10 6 to 10 16 Q, preferably 10 9 to 10 14 Ω. The thickness of the metal-containing resin layer is not particularly limited, but 5
It is preferable that it is 50μ. Further, any known method may be used to form the metal-containing resin layer, such as a solution casting method, a calender method, an extrusion method, etc. The above-mentioned metal-containing resin layer is used as a current-carrying recording material, and when conducting current-carrying recording, it is brought into contact with a current-carrying recording needle to record the current-carrying data, so the metal-containing resin layer eliminates the risk of cracking, etc., and improves storage stability. However, plasticizers, fillers, lubricants, stabilizers, antioxidants, flame retardants, etc. may be added to prevent the constituent substances from adhering to the recording needle and further improve the formability of the layer. .

In the present invention, the conductive layer is a layer laminated on the other surface of the semiconductive resin layer, and has a surface resistance of 104 Ω or less and smaller than the surface resistance of the semiconductive resin layer, and is capable of recording electricity. When it is energized, it is destroyed and transferred.

If the difference in surface resistance between the semiconductive resin layer and the conductive resin layer is small, recording performance tends to decrease when current is applied. The ratio is preferably 10 to 104. The conductive layer may be formed by dispersing the conductivity imparting agent in the resin matrix, or may be formed from a metal thin film, but a metal thin film is more preferred since it can be made very thin. If the thickness of the metal thin film is too thin, the surface resistance will be 104Ω.
On the other hand, if it is too thick, current recording will not be possible, so it is best to have a thickness of 40 to 5000 angstroms.
Preferably it is 100 to 3000 angstroms,
More preferably, it is 200 to 2000 angstroms. Examples of metals used include aluminum, silver, gold, copper, zinc, tin, nickel, and molybdenum.
Aluminum, silver and gold are preferred. Any known method may be used to form the conductive layer as a metal thin film, such as a vacuum evaporation method, an ion sputtering method, or the like. Further, when the conductivity imparting agent is dispersed in the resin matrix and formed, it may be formed by any known method, and the layer thickness is preferably 2 to 30 microns. Further, the above-mentioned inorganic filler, low melting point resin, coloring material, etc. may be added to the layer. The structure of the current-carrying recording material of the present invention is as described above. The current-carrying recording material is supplied to a current-carrying recording device, a current-carrying recording needle is brought into contact with the metal-containing resin layer, and paper or plastic film is placed under the conductive layer. When a recording paper such as the like is brought into contact with electricity and recorded, heat is generated in the metal-containing resin layer and the semiconductive resin layer directly under the electricity-carrying recording needle, and the generated heat melts the low melting point resin, and the surrounding conductivity imparting agent, etc. At the same time, it is destroyed by electricity, and is transferred and recorded on recording paper. At this time, it is possible to record at a low voltage of several volts to several + volts. Furthermore, since the structure of the energization recording material of the present invention is as described above, there is no fear of color development during storage or transportation, and no foul odor or soot is generated during energization recording.

Therefore, the current-carrying recording material of the present invention is suitably used for recording and displaying in facsimiles, various measuring instruments, recorders, computers, and the like. Next, examples of the present invention will be described.

Hereinafter, the term "parts" simply means "parts by weight." Example - VVHS A blend having the above composition was dissolved and dispersed, cast on a glass plate, and dried to obtain a metal-containing resin sheet with a thickness of 20 μm.

The electrolytic copper powder was 16.9% by volume in the sheet. Moreover, the surface resistance of the sheet was 0.8×10 13 Ω. Next, a compound having the above composition is dissolved and dispersed, applied and dried on the above sheet to form a semiconductive resin layer with a thickness of 10 μm,
A composite sheet with a thickness of 30μ was obtained.

The surface resistance of the semiconductive resin layer was 1.0×10 3 Ω. Next, apply 3X104 to the semiconductive resin layer of the composite sheet.
Gold was vacuum-deposited under conditions of T0rr to form a conductive layer with a thickness of 400 angstroms to obtain a current-carrying recording material.

Claims (1)

[Claims] 1 (A) A resin matrix in which a conductivity imparting agent and a fine powder of a low melting point resin are dispersed, a surface resistance of more than 1Ω and less than 10^5Ω, and capable of recording electricity. (B) A semiconductive resin layer that is destroyed and transferred when electrically applied; (C) a metal-containing resin layer having a surface resistance of 10^5 to 10^1^6 Ω and not being destroyed by electrical current during electrical recording; and (C) a metal-containing resin layer laminated on the other surface of the semiconductive resin layer. A current-carrying recording material comprising a conductive layer having a surface resistance of 10^4 Ω or less and smaller than the surface resistance of the semiconductive resin layer, which is destroyed and transferred during current-carrying recording. 2. The electrically conductive recording material according to claim 1, wherein the conductivity imparting agent is carbon black. 3. The electrically conductive recording material according to claim 1, wherein the low melting point resin has a melting point of 30 to 100°C. 4. The electrically conductive recording material according to claim 1, wherein the amount of the low melting point resin added is 100 to 500 parts by weight based on 100 parts by weight of the resin matrix. 5. The electrically conductive recording material according to claim 1, wherein the metal powder has an average particle size of 0.2 to 20 μm. 6 The surface resistance of the metal-containing resin layer is 10^9 to 10^1^
The current-carrying recording material according to claim 1, which has a resistance of 4Ω. 7. The electrically conductive recording material according to claim 1, wherein the conductive layer is a metal vapor deposited film. 8. The current-carrying recording material according to claim 1, wherein the ratio of the surface resistance of the semiconductive resin layer to the surface resistance of the conductive layer is 10 to 10^4.