JPS5830155B2 - discharge recording material - Google Patents

Description

[Detailed description of the invention] The present invention relates to a discharge recording material.

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. A typical example is a discharge recording system.

The discharge recording system applies several hundred volts to the recording needle in the form of voltage,
By applying an electric signal of several watts and destroying the semiconductive recording layer on the surface of the recording material by the discharge generated, an image is formed on the recording layer itself or on the substrate laminated with the recording layer. This method is widely used as a simple pitching method that does not require operations such as development and fixing, and is used, for example, in facsimile machines, various measuring instruments, recorders, pitching displays in computers, and electrical recording transcription. It is used for plate making of base paper, etc.

As mentioned above, in discharge recording, an image is formed by bringing a discharge recording needle into direct contact with the recording side surface of a discharge recording material and destroying the recording layer by discharging discharge from the recording needle. During discharge breakdown, a foul odor or soot is generated, or colored substances such as carbon black dispersed in the recording layer are scattered.

These and carbon black adhere to the recording material and contaminate it, or adhere to the discharge recording needle and impede accurate discharge, causing a decrease in recording reliability.

In addition, in discharge recording, since the discharge recording needle is scanned by directly contacting the recording material, it has the disadvantage that the recording material is scratched or hardened, impairing the naturalness of the recording material.

An object of the present invention is to provide an electrical discharge recording material that does not have the above-mentioned drawbacks, such as the generation of bad odors and the contamination of the recording material itself or the electrical discharge recording device due to the scattering of colored substances such as soot and carbon black. To provide a discharge recording material that can provide clear, natural-looking, and soft recorded images without problems such as deterioration of discharge recording accuracy due to adhesion of colored substances such as soot and carbon black to the discharge recording needle. be.

That is, the gist of the present invention is that (4) it is composed of a conductivity imparting agent and a resin matrix, and has a surface resistance of 1080 to 101 for dogs.
A semiconductive resin layer that is destroyed by discharge during discharge recording with a resistance of 6 Ω or less: (2) The above-mentioned material is laminated on one surface of the semiconductive resin layer and is composed of a conductivity imparting agent other than metal powder and a resin matrix. A conductive resin layer in which the conductivity imparting agent accounts for 4 to 70% by volume and has a surface resistance of 104 to 108 Ω, which is not destroyed by discharge during discharge recording; and (0) laminated on the other surface of the semiconductive resin layer. The present invention relates to a discharge recording material comprising a conductive layer which is destroyed by discharge during discharge recording and has a surface resistance of 10@4 Ω or less.

The resin matrix used in the present invention may be any polymer resin that has film-forming ability and electrical insulation, and any polymer resin can be used.
In general, it is desirable to use a material that has a high binding strength to metal powder, conductivity imparting agent, inorganic filler, etc., has high mechanical strength when formed into a sheet or film, is flexible, and has strong stiffness, such as polyethylene, Polypropylene, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polystyrene, polyacrylonitrile, polyvinyl acetal, polyacrylic acid alkyl ester, polymethacrylic acid alkyl ester, cellulose acetate, Polymer resins such as polyvinyl alcohol, carboxymethyl cellulose, and gelatin are mentioned, and polyethylene, polypropylene, polyvinyl chloride, vinyl chloride-ethylene copolymer, polyvinyl acetal, and cellulose acetate are preferably used.

The resin matrices of the conductive resin layer, semiconductive resin layer, and conductive layer may be of the same type or different types.

In the present invention, the semiconductive resin layer is formed by dispersing a conductivity imparting agent in the resin matrix,
The surface resistance of the dog is 1016Ω or less compared to 108Ω.

The above-mentioned conductivity imparting agent only needs to have conductivity,
For example, carbon black, graphite, zeolite, zinc oxide, stannic oxide, metastannic acid, cuprous iodide, reduced titanium oxide, ferric oxide, and the like are preferably used.

Metal powders such as copper, aluminum, tin, molybdenum, and silver are also preferably used.

The conductivity imparting agent preferably has a small particle size and a uniform particle size, preferably an average particle size of 10 microns or less.

The addition Jt of the conductivity imparting agent may be determined so that the surface resistance of the semiconductive resin layer when dispersed in a resin matrix to form a semiconductive resin layer is 1080 to 1016 Ω or less. , typically a resin matrix 10
It is added in an amount of 1 to 1000 parts by weight per 0 parts by weight.

The semiconductive resin layer is used as the discharge recording material of the present invention,
When electrical discharge recording is performed, the electrically conductive layer described later is destroyed by electrical discharge and adheres to the recording paper for recording. Therefore, a coloring agent may be added to the semiconductive resin layer, and in particular, a coloring agent may be added to the semiconductive resin layer as a conductivity imparting agent. When using a material that is not dark (not black like carbon black, but zinc oxide, stannic oxide, etc.), a colored recording other than black can be obtained by adding a coloring agent.

Any known colorant can be used as the colorant, such as nickel yellow, titanium yellow cadmium red, naphthol yellow permanent orange, crystal bionet, malachite green, etc. The amount added is the color when recorded, It may be arbitrarily determined depending on the concentration, etc.

Note that when the coloring material has conductivity, it is necessary to pay attention to the surface resistance of the semiconductive resin layer.

An inorganic filler may be added to the above semiconductive resin layer, and by adding the inorganic filler, when discharge recording is performed, the discharge recorded image becomes clearer.

Examples of the inorganic fillers include calcium oxide, magnesium oxide, potassium carbonate, sodium carbonate, calcium carbonate, strontium carbonate, titanium oxide, barium sulfate, lithopone, basic magnesium carbonate, silica, and clay.

Further, the particle size of the inorganic filler is uniform, and the average particle size is 0.
Preferably 1 to 10μ, more preferably 0.1 to 10μ
3.0μ, and the amount added is 100μ
It is preferable to add 10 to 1000 parts by weight based on the weight part.

In the present invention, the conductive resin layer is formed by dispersing a conductivity imparting agent other than metal powder in the resin matrix, and the conductivity imparting agent accounts for 4 to 70% by volume and has a surface resistance of 104. ~108Ω and is laminated on one surface of the semiconductive resin layer.

As the conductivity imparting agent, all conductivity imparting agents except metal powder among the conductivity imparting agents used in the semiconductive resin layer can be used.

The amount of the conductivity imparting agent to be added may be determined so that the volume fraction with the resin matrix is 4 to 70% and the surface resistance of the conductive resin layer is 10' to lo8Ω.

The conductive resin layer is used as a discharge recording material, and when recording a discharge, it is brought into contact with a discharge recording needle and the discharge is recorded.
Plasticizers, fillers, Lubricants, stabilizers, antioxidants, flame retardants, etc. may be added.

In the present invention, the conductive layer is laminated on the other surface of the semiconductive resin layer, and has a surface resistance of 104Ω or less, and is formed by dispersing a conductivity imparting agent in a resin matrix. Alternatively, it may be a metal thin film, and a metal thin film is more preferable because it can be made very thin.

As the conductivity imparting agent, the conductivity imparting agent used to form the semiconductive resin layer is used, and the amount added is determined so that the surface resistance of the conductive layer is 104Ω or less. Generally, it is preferable to add 10 to 1000 parts by weight per 100 parts by weight of the resin matrix.

When a metal thin film is used as a conductive layer, its surface resistance must be 104Ω or less; if the thickness is too thin, the surface resistance will be greater than 1040Ω, and if it is too thick, it will be difficult to break down due to discharge. Therefore, the thickness is preferably 40 to 5000 angstroms, preferably 100 to 30 angstroms.
00 angstroms, more preferably 200 to 200 angstroms.
It is 2000 angstroms.

And metals include aluminum, silver, gold, copper, zinc,
Nickel, molybdenum, etc. are used, and aluminum, silver, and gold are preferred.

The structures of the semiconductive resin layer, the conductive resin layer, and the conductive layer in the present invention are as described above, and the thickness of each layer is not limited in any way, but the thickness of the semiconductive resin layer is 2 to 30 mm.
μ, the conductive resin layer preferably has a value of 5 to 50 μ, and when the conductive layer is other than the metal thin film, it is preferably 2 to 30 μ.

Further, the method for forming each layer is not limited in any way, and any known method such as a laminar liquid casting method, an emulsion casting method, a calendering method, an extrusion method, etc. may be employed.

Further, when forming the conductive layer with a metal thin film, any known method may be employed, such as vacuum evaporation, ion sputtering, etc., and vacuum evaporation is preferred.

In the present invention, a conductive resin layer is laminated on one side of the semiconductive resin layer, and a conductive layer is laminated on the other side of the semiconductive resin layer to produce the discharge recording material of the present invention. ,
Any known method may be used for laminating each layer.
For example, a method in which a semiconductive resin layer is formed by a liquid casting method on a conductive resin layer formed by a solution casting method, and a conductive layer is further formed thereon by a solution casting method.
A method is adopted in which each layer is laminated while being extruded using an extruder.

In addition, when forming a conductive layer using a metal thin film, a conductive layer is formed on the surface of the semiconductive resin layer of the laminate of the conductive resin layer and the semiconductive resin layer obtained as described above by the method described above. Alternatively, a conductive layer may be laminated on the semiconductive resin layer by the method described above, and then a conductive resin layer may be formed on the other surface of the conductive resin layer.

The structure of the discharge recording material of the present invention is as described above. The discharge recording material is supplied to a discharge recording device, a discharge recording needle is brought into contact with the conductive resin layer, and a recording paper is brought under the conductive layer. When discharge recording is performed in contact with the discharge recording needle, the semiconductive resin layer and the conductive layer directly under the discharge recording needle are destroyed by discharge, and recording is performed on the recording paper.

Since the conductive resin layer does not change in any way, it prevents soot and carbon black from scattering or adhering to the discharge recording needle during discharge recording, reducing the hassle of maintaining the discharge recording needle. .

Therefore, since soot and carbon black do not adhere to the discharge recorder, highly reliable and clear records can be obtained.

Further, since the conductivity imparting agent of the conductive resin layer is a conductive substance other than metal powder, the layer has approximately electrical isotropy, so that no electricity is accumulated on the layer.

Therefore, since no dust or dust is attached to the layer, no dust or dust is attached to the recording needle during discharge recording.
Highly reliable and clear records can be obtained.

Furthermore, if the conductive layer is formed by vacuum evaporation or ion sputtering, it is very easy to manufacture and can be made very thin, which makes it easy to break down due to electrical discharge and provides clear records with high sensitivity and reliability. It is.

In the discharge recording material of the present invention, when discharge recording is performed, the semiconductive resin layer and the conductive layer are destroyed by discharge, and the destroyed material is transferred and recorded on the recording paper. By changing the composition of the conductive layer (conductivity imparting agent, coloring material, etc.), it is possible to record various colors.

That is, for example, if a semiconductive resin layer is formed with a resin matrix and carbon black, a black recording can be obtained, and if a semiconductive resin layer is formed with a resin matrix and a colored material such as conductive zinc oxide or stannic oxide, a black recording can be obtained. If the conductive layer is formed using a non-dense conductivity imparting agent and a coloring agent, and the conductive layer is formed from a metal thin film, a color record of the above-mentioned coloring agent can be obtained.

Furthermore, by adding a filler to the semiconductive resin layer, the resulting recording becomes clearer and the resolution is improved.

In addition, since the conductive resin layer does not change in any way, it can be used like carbon paper, and if the discharge recording material is brought into contact with the surface of the recording paper and discharge recording is performed while sending both in the same direction, it is easy to record discharge continuously. If discharge recording is performed by increasing the feeding speed of the recording paper than the discharge recording material, more economical recording can be achieved.

It is also possible to make the discharge recording material into a ribbon shape and set it up like a typewriter for discharge recording.

Therefore, the discharge 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, parts simply mean parts by weight.

Example 1 100 parts of polyvinyl acetal (degree of polymerization 1
750. Acetalization degree 67%) Conductive zinc oxide (average particle size 1μ) 300 parts ethyl alcohol
Dissolving and dispersing 100 parts of a blend consisting of the above composition,
It was cast onto a glass plate and dried to obtain a conductive resin sheet with a thickness of 25 μm.

The conductive zinc oxide powder was 37% by volume in the sheet.

The sheet had a volume resistivity of 2.0×10 5 Ω and a surface resistance of 2.2×10 6 Ω.

Polyvinyl acecool 100 parts (degree of polymerization 1
750, degree of acetalization 67%) Thermal black
60 parts rutile titanium oxide (average particle size 0
．． 3μ) 100 parts ethyl alcohol 1o
The oo part is then dissolved and dispersed with a formulation having the above composition,
A semiconductive resin layer with a thickness of 8 μm was formed by coating and drying on the above sheet to obtain a composite sheet with a thickness of 33 μm.

The surface resistance of the semiconductive resin layer was 0.6×10”Ω.

Polyvinyl acetal 100 (degree of polymerization 1)
750, degree of acetalization 67%) Acetylene black
60 parts ethyl alcohol
Further, 1000 parts of the compound having the above composition was dissolved and dispersed, applied and dried on the semiconductive resin layer of the composite sheet to form a conductive layer with a thickness of 8 μm, and a discharge recording material with a thickness of 41 μm was obtained. Ta.

The surface resistance of the conductive layer was 1.8×10”Ω.

The obtained discharge recording material was supplied to a facsimile receiver (manufactured by Matsushita Denshu Co., Ltd., trade name: Panafax 1000D), and high-quality paper was brought into contact with the bottom of the conductive resin layer to determine the scanning line density, B7/i.
When discharge recording was performed under the conditions of 1.m, there was no scattering of soot or carbon black, almost no odor, and no through holes were formed in the conductive resin layer, and a clear black image was obtained on high-quality paper.

The image density was 0.51 and the resolution was 4 e/mm.

Example 2 100 parts of polyvinyl acetal (degree of polymerization 1
7501 Degree of acetalization 67%) Conductive zinc oxide (average particle size 1μ) 50 parts zinc oxide (No. 1 zinc white)
300 parts ethyl alcohol 1000
Example 1 A formulation having the above composition was dissolved and dispersed.
A semiconductive resin layer with a thickness of 10 μm was formed by coating and drying on the conductive resin sheet obtained in step 1 to obtain a composite sheet with a thickness of 35 μm.

The surface resistance of the semiconductive resin layer was 0.9×10”Ω.

Next, Example 1 was applied onto the semiconductive resin layer of the composite sheet.
Form a conductive layer with a thickness of 8μ in the same manner as in
A discharge recording material with a thickness of 43 μm was obtained.

When the obtained discharge recording material was used for discharge recording in the same manner as in Example 1, there was no scattering of soot or carbon black, almost no bad odor, and no through holes were formed in the conductive resin layer. , a clear black image was obtained on high-quality paper.

The image density was 0.30 and the resolution was between 4e1.

Claims (1)

[Claims] 1(A) Consisting of a conductivity imparting agent and a resin matrix,
A semiconductive resin layer that is destroyed by electrical discharge during discharge recording and has a surface resistance of 1080 to 1010 Ω or less; (2) A conductivity imparting agent other than metal powder that is laminated on one surface of the semiconductive resin layer; and a resin matrix, the conductivity imparting agent accounts for 4 to 70% by volume, and the surface resistance is 10' to 108 Ω, a conductive resin layer that is not destroyed by discharge during discharge recording; and (0) the above-mentioned half. A discharge recording material comprising a conductive layer laminated on the other side of the conductive resin layer and having a surface resistance of 10@4 Ω or less and which is destroyed by discharge during discharge recording. 2. The discharge recording material according to claim 1, wherein a colorant is added to the semiconductive resin layer. 3. The discharge recording material according to claim 1 or 2, wherein an inorganic filler is added to the semiconductive resin layer. 4. The discharge recording material according to claim 1, wherein the conductive layer is a metal vapor deposited film. 5. The discharge recording material according to claim 4, wherein the metal vapor deposited film is an aluminum vapor deposited film. 6. The discharge recording material according to claim 1, wherein the conductive layer comprises a conductivity imparting agent and a resin matrix.