JPS609914B2 - Current recording material - Google Patents

Description

[Detailed description of the invention] The present invention relates to an electrically conductive recording material.

In recent years, information has become incredibly abundant, and the need for rapid 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. However, although many discharge recording materials used in the conventional discharge recording system have been published, all of them are capable of recording discharge only at a high voltage of 100 to 600V.

Therefore, since recording is performed using a high voltage, if you increase the number of recording needles, the recording needles will be left between the recording needles, so you cannot increase the number of needles and the recording speed will be slow. It had the following drawback. In order to overcome the above-mentioned drawbacks, the present inventors have reported a current-carrying recording material that can be used at a low voltage of 100 V or less and is composed of three layers: a metal-containing resin layer, a semiconductive resin layer, and a conductive layer.

However, the electrically conductive recording material described above has the disadvantage that the electrically conductive layer has low mechanical strength and may be damaged during storage or transportation, and that the density of the recorded image decreases when the electrically conductive recording is performed multiple times, that is, the printing durability is poor. It had An object of the present invention is to provide a current-carrying recording material that can record at a low voltage of 100 V or less, has good printing durability, and has a conductive layer that is not likely to be damaged during storage or transportation.

Other purposes include the generation of bad odors during energization recording, the contamination of the recording material itself or the energization recording device due to scattering of conductivity imparting agents such as soot and carbon black, and the conductivity of soot and carbon black to the energization recording needle. To provide a current-carrying recording material capable of obtaining clear, natural-looking, and soft recorded images without troubles such as deterioration in the accuracy of current-carrying recording due to adhesion of a sex imparting agent. That is, the gist of the present invention is a laminate having a four-layer structure, in which the first layer is made of metal powder and a resin matrix, the metal powder accounts for 5 to 6% of the bond, and the surface resistance is 1. A metal-containing resin layer with a temperature of 1 to 60: A semiconductive resin layer in which the second layer is made of a conductivity imparting agent and a resin matrix and has a surface resistance greater than IQ and 1 to 4. The third layer is a conductive layer having a surface resistance of 1 piQ or less and smaller than the surface resistance of the semiconductive resin layer; and the fourth layer is mainly composed of a resin matrix and has a surface resistance of A protective layer having a surface resistance greater than the surface resistance of the layer and a layer thickness of 10 mm or less, which is present in an electrically conductive recording material characterized in that the protective layer is laminated in the above order.

The resin matrix used in the present invention only needs to have film-forming ability and electrical insulation, and thermoplastic resins are preferably used. The above-mentioned thermoplastic resin has a high binding power to metal powder, conductivity imparting agent, inorganic filler, etc., has high mechanical strength when molded into a sheet or film, has mirror properties, and is strong. Desirably, 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 Examples include alkyl esters, polyesters, cellulose acetate, polyvinyl alcohol, carboxymethyl cellulose, gelatin, etc., polyethylene, polypinyl chloride, pinylene chloride copolymer, vinyl chloride-vinyl acetate copolymer, polyvinyl acetal, cellulose acetate. is preferably used. and a metal-containing resin layer, a semiconductive resin layer,
The resin matrices forming each of the conductive layer and the protective layer may be of the same type or different types.

The metal-containing resin layer, which is the first layer in the present invention, is made of the resin matrix and metal powder. The above-mentioned metal powder means a metal in powder form, and the powder must 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 steel, aluminum, iron, tin, zinc, nickel, molybdenum, silver, yellow steel, and the like. Further, metal powder coated with other metals can also be used, such as copper powder coated with silver. Among the above metal powders, 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 microns. In the present invention, one or more metal powders may be selected from among the metal powders described above 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, it is determined that the surface resistance is 5 to 6% of the metal-containing resin layer and the surface resistance is 1 to 60, preferably 1 to 60%. It is 1 and 40. 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. In order to prevent the constituent substances from adhering to the recording needle and further improve the formability of the layer, plasticizers, fillers, thickeners,
Stabilizers, antioxidants, oxidizing agents, etc. may be added.

The semiconductive resin layer, which is the second layer in the present invention, is made of the resin matrix and the conductivity imparting agent and is laminated on the metal-containing resin layer.

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 amount of the conductivity imparting agent added is determined so that the surface resistance of the semiconductive resin layer when dispersed in the resin matrix to form a semiconductive resin layer is greater than IQ and less than 1 and ○. Generally, 50 to 50 parts by weight of the force-pump rack and 1 to 100 parts by weight of the conductivity imparting agent other than carbon black are added to 100 parts by weight of the resin matrix. Further, it is preferable that an inorganic filler is further added to the semiconductive resin layer because the recorded image obtained when electrical recording is performed 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.
05 to 10 Buddha is preferable, more preferably 0.1
~3.0 μm, and the amount added is 10 μm per resin matrix.
It is preferable to add 10 to 100 parts by weight per part by weight of .

When the inorganic filler has conductivity, care must be taken that the surface resistance of the semiconductive resin layer is greater than IQ and less than 1'Q. Further, the above-mentioned semiconductive resin layer is made into the current-carrying recording material of the present invention, and is destroyed together with the conductive layer and the protective layer, which will be described later, when conducting current-carrying recording, resulting in paper,
Since it adheres to recording paper such as a plastic film and is recorded, a coloring agent may be added to the semiconductive resin layer.In particular, a coloring agent that is not dark in color (not black like carbon black, but oxidized) may be added to the semiconductive resin layer. When using zinc, stannic oxide, etc., a colored record other than black can be obtained by adding a colorant.

Any known colorant can be used as the colorant, such as nickel yellow, titanium yellow, cadmium red, naphthol yellow, /ゞ-Manesoto orange,
Examples include crystal violet and malachite green, and the amount added may be arbitrarily determined depending on the color, density, etc. at the time of recording. Note that when the coloring material has conductivity, it is necessary to pay attention to the surface resistance of the semiconductive resin layer. In the present invention, the conductive layer, which is the third layer, is laminated on the semiconductive resin layer, and has a surface resistance of 1 pi or less and smaller than the surface resistance of the semiconductive resin layer. be.

In addition, if the difference in surface resistance between the semiconductive resin layer and the conductive layer is small, the coloring performance will decrease when electricity is recorded. Preferably, the surface resistance ratio is 10 to 1. The conductive layer may be formed by dispersing a conductivity imparting agent in a 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. As the conductivity imparting agent, the conductivity imparting agent used to form the semiconductive resin layer may be used, and the amount added is such that the surface resistance of the conductive layer is 1 pi or less and the conductivity imparting agent is semiconductive. The surface resistance may be determined to be smaller than the surface resistance of the resin layer, and generally 10 to 100 parts by weight per 10 parts by weight of the resin matrix.
It is preferable to add 2 parts by weight.

Furthermore, even when a metal thin film is used as the conductive layer, its surface resistance must be less than 1 pi○ and smaller than the surface resistance of the semiconductive resin layer, and its thickness is too thin. The surface resistance will be greater than 1 piQ, and if it is too thick, it will be difficult to break down due to discharge, so it is best to have a thickness of 40 to 5000 angstroms, preferably 100 to 3000 angstroms.
angstrom, more preferably 200 to 20
00 angstroms.

Examples of metals used include aluminum, silver, gold, copper, zinc, tin, nickel, and molybdenum, with aluminum, silver, and gold being preferred. The structures of the metal-containing resin layer, semiconductive resin layer, and conductive layer in the present invention are as described above, and the thickness of each layer is not limited in any way, but the semiconductive resin layer has a thickness of 2 to 40 mm. Preferably, the metal-containing resin layer has a thickness of 5 to 50 F, and the conductive layer has a thickness of 2 to 30 F, except for the metal thin film.

The protective layer, which is the fourth layer in the present invention, is laminated on the conductive layer, and is a layer mainly composed of a resin matrix whose surface resistance is higher than that of the conductive layer and whose thickness is 10 mm or less. .

The resin matrix described above is used as the resin matrix. This layer is made into a current-carrying recording material and is destroyed together with the semiconductive resin layer and the conductive layer when current-carrying recording is performed, and protects the conductive layer and improves the printing durability of the current-carrying recording material. Therefore, it is preferable that this layer is easily destroyed, and the thickness of the layer is preferably 5 mm or less, more preferably 4 mm or less. The surface resistance may be greater than the surface resistance of the conductive layer, but preferably the ratio of the surface resistance of the protective layer to the surface resistance of the conductive layer is 1 or more. In order to impart electrical conductivity to the protective layer, the electrical conductivity imparting agent or the metal powder may be added.

At this time, the average particle size of the conductivity imparting agent and the metal powder is not particularly limited, but is preferably 5 mm or less,
More preferably, it is 2 Buddhas or less. The amount added is preferably 1 to 150 parts by weight based on the weight of the resin matrix 10. Further, it is preferable that an inorganic filler is added to the protective layer. As the inorganic filler, the above-mentioned inorganic filler is suitably used, and the average particle size thereof is preferably 5 or less, more preferably 2 or less. The amount of inorganic filler added is 1 part by weight per 100 parts by weight of the resin matrix.
Preferably from 0 to 100 parts by weight. Note that when it is desired to obtain a black recorded image, carbon black is preferably used as a conductivity imparting agent in the conductive layer and the protective layer, and when it is desired to obtain a colored recorded image, carbon black is used in the conductive layer and the protective layer. It is also preferable to use a conductivity-imparting agent that does not have a dark color and to add the above-mentioned coloring agent.

The method for forming each layer is not limited in any way, and any known method such as solution casting, emulsion casting, calendaring, extrusion, etc. may be employed.

Furthermore, any known method may be used to form the conductive layer from a metal thin film, such as vacuum evaporation, ion sputtering, or the like.

The structure of the main layers of the current-carrying recording material of the present invention is as described above, and the metal-containing resin layer, the semiconductive resin layer, the tortoise-conducting layer, and the protective layer are laminated in this order to form the current-carrying recording material of the present invention. . The configuration of the current-carrying recording material of the present invention is as described above, and 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 a paper or plastic film is placed under the conductive layer. When a recording paper such as the above is brought into contact with the recording paper and recorded with electricity, the semiconductive resin layer, conductive layer, and protective layer directly under the current-carrying recording needle are destroyed, and the recording is performed on the recording paper.

At this time, the voltage of electricity to be applied is lower than 100 V, and it is possible to record with low voltage. Therefore, the number of recording needles can be increased, and the recording speed can be increased. Furthermore, since the protective layer is provided as the fourth layer, the rigidity resistance is improved, and a recorded image with high density can be obtained even when energized recording is performed multiple times. Furthermore, since the protective layer covers the conductive layer, there is no risk that the conductive layer will be damaged during storage or transportation. In addition, the metal-containing resin layer is not destroyed and does not change in any way even when energized recording is performed, and since energized recording is performed at a low voltage, less soot and carbon black are generated during energized recording, and scattering can be suppressed. This prevents soot and carbon black from adhering to the energized recording needle, and reduces the troublesome maintenance of the energized recording needle. Therefore, since soot and carbon black do not adhere to the energized recording needle, highly reliable and clear recording can be obtained. In addition, if the conductive layer is formed by vacuum evaporation or ion sputtering, it is very easy to manufacture and can be made very thin, making it easy to break down due to electrical current, resulting in high sensitivity, high reliability, and clear recording. It will be done. In the current-carrying recording material of the present invention, the semi-conductive resin layer, the conductive layer and the protective layer are destroyed when current is applied, and the destroyed material is transferred and recorded on the recording paper, so the semi-conductive resin layer , Structure of the conductive layer and protective layer (conductivity imparting agent,
Various types of recording are possible by changing the coloring material, etc.).

Furthermore, by adding an inorganic filler to the semiconductive resin layer, the records obtained become clearer and the resolution is improved.

In addition, the metal-containing resin layer does not produce through holes or change in any way even when energized recording is performed, so it can be used like carbon paper, and the energized recording material is brought into contact with the surface of the recording paper and both are sent out in the same direction. However, by carrying out energization recording, it is possible to carry out energization recording simply and continuously, and in particular, if energization recording is carried out by increasing the feeding speed of the recording paper than the energization recording material, recording can be made more economically.

Further, it is also possible to make the current recording material into a ribbon shape and install it like a typewriter to record discharge.

Therefore, the current-carrying recording material of the present invention is suitable for use in facsimile machines, various measuring instruments, recorders, recording displays in computers, and the like.

Next, examples of the present invention will be described.

Hereinafter, the term "parts" simply means "parts by weight." Examples 1 to 3, Comparative Example 1 Vinyl chloride-vinyl acetate copolymer
10$ parts (degree of polymerization 650, vinyl acetate content 13%)
Electrolytic steel powder (average particle size: 14mm) 13 parts Ethyl acetate 20 parts Toluene 20 parts A blend of the above composition was dissolved and dispersed, cast onto a glass plate, dried, and made into a 20mm thick sheet. A metal-containing resin sheet was obtained.

The electrolytic steel powder was 16.9% by volume in the sheet. Further, the surface resistance of the sheet was 0.8×1pi30. Butyral resin 10 parts (polymerization degree 17)
00 Acetalization degree 65%) Thermal black
16 anchor acetylene black
4 base ethyl alcohol
140 ml Next, a blend having the above composition was dissolved and dispersed, coated on the sheet and dried to form a semiconductive resin layer with a thickness of 10 µm to obtain a composite sheet with a thickness of 30 µm.

The surface resistance of the semiconductive resin layer was 0.7×1×0. Next, aluminum was vacuum-deposited on the semiconductive resin layer of the composite sheet under conditions of 3×10-momme to a thickness of 400 mm.
A conductive layer with a thickness of angstrom is formed and the current-carrying recording material A (
Comparative Example 1) was obtained.

The surface resistance of the conductive layer was 20. butyral resin
10 anchor parts (polymerization degree 170, butyralization degree 65%) Acetylene black
8 guo ethyl alcohol
140 Ikari A mixture having the above composition was dissolved and dispersed, and applied and dried on the conductive layer of the current-carrying recording material A to form a protective layer with a thickness of 3 mm, 5 mm, and 8 mm to form a protective layer of 3 mm thick, 5 mm thick, and 8 mm thick to form a current flowing recording material B.
(Example 1), C (Example 2) and D (Example 3) were obtained.

The surface resistance of the protective layer was 2.0×1 pi. The obtained electrically conductive recording materials A and B were supplied to a facsimile receiver (manufactured by Matsushita Denshu Co., Ltd., trade name: Panafax 100 trays), high-quality paper was placed under the conductive layer or protective layer, and an applied voltage of 60 V DC was applied. , the same image was recorded five times under the conditions of scanning line density 41/yanagi. During energization recording, there was no scattering of soot or carbon black, almost no bad odor, and a clear black image was obtained on the high-quality paper without forming any through holes in the metal-containing resin layer.

The density of the obtained image is shown in FIG. Further, when the obtained current-carrying recording materials C and D were used for one-time current-carrying recording in the same manner, the image density of the current-carrying recording material C was 0. A clear image of the path was obtained, and with the current-carrying recording material D, a partially blurred image was obtained with an image density of 0.45.

Examples 4 and 5, Comparative Examples 2 and 3 Butyral resin 10 parts (degree of polymerization: 1700, degree of butyralization: 65%) Thermal black
16 Japanese silver powder (average particle size 2 French) 25 Ikarikaku ethyl alcohol
140 eaves A compound having the above composition was dissolved and dispersed, applied and dried on the metal-containing resin sheet obtained in Example 1 to form a semiconductive resin layer with a thickness of 15 μm, and a composite layer with a thickness of 35 μm was formed. Got a sheet.

The surface resistance of the semiconductive resin layer was 2.0×1 pi○.
In the same manner as in Example 1, aluminum was vacuum-deposited to a thickness of 400 angstroms on the semiconductive resin layer of the composite sheet to form a conductive layer, and electrically conductive recording material E (
Comparative Example 2) was obtained.

The surface resistance of the turtle conductive layer was 20. butyral resin
10 Foundation (polymerization degree 170, butyralization degree 65%) Thermal black
20 anchor ethyl alcohol
140 Ikarigun A compound having the above composition was dissolved and dispersed, and applied to the conductive layer of the above-mentioned current-carrying recording material E and dried to a thickness of 3.
Electrifying recording material F by forming a protective layer of 6 mm, 6 mm and 12 mm
(Example 4), G (Example 5) and Day (Comparative Example 3) were obtained.

The surface resistance of the protective layer was 0.8 x 1 mm. Using the obtained energizing recording materials E and F, the same image was recorded by energizing five times in the same manner as in Example 1. There was no scattering of soot or carbon black, almost no bad odor, and the metal-containing resin layer A clear black image was obtained on the high-quality paper without any through-holes.

The density of the obtained image is shown in FIG. Furthermore, when the obtained current-carrying recording material G and day were used for one-time electricity-carrying recording using the same machine as in Example 1, a clear image with an image density of 0.49 was obtained with the current-carrying recording material G; however, No image could be obtained with the energized recording material.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between the number of times of energization recording and the density of the obtained image. In the figure, A, B, E and F are current-carrying recording materials A, B, respectively.
The results of E and F are shown. Figure 1

Claims (1)

[Scope of Claims] 1. A laminate having a four-layer structure, wherein (A) the first layer is made of metal powder and a resin matrix, the metal powder accounts for 5 to 60% by volume, and the surface resistance is 10 Metal-containing resin layer with a resistance of ＾5 to 10＾1＾6Ω; (
B) The second layer is a semiconductive resin layer composed of a conductivity imparting agent and a resin matrix and has a surface resistance of more than 1Ω and less than 10^5Ω; (C) The third layer has a surface resistance of 10^
A conductive layer having a surface resistance of 4 Ω or less and less than the surface resistance of the semiconductive resin layer; and (D) a fourth layer mainly composed of a resin matrix and having a surface resistance greater than the surface resistance of the conductive layer. A protective layer having a thickness of 10 μm or less; and laminated in the above order. 2. The electrically conductive recording material according to claim 1, wherein the metal powder has an average particle size of 0.2 to 20 μm. 3 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. 4. The electrically conductive recording material according to claim 1, wherein the conductivity imparting agent is carbon black. 5. 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. 6. The current-carrying recording material according to claim 1, wherein the conductive layer is a metal vapor deposited film. 7. The current-carrying recording material according to claim 6, wherein the metal vapor-deposited film is an aluminum vapor-deposited film. 8. The electrically conductive recording material according to claim 1, wherein the conductive layer comprises a conductivity imparting agent and a resin matrix. 9 The ratio of the surface resistance of the protective layer to the surface resistance of the conductive layer is 10
The current-carrying recording material according to claim 1, wherein the electrification recording material is ^2 or more. 10. The electrically conductive recording material according to claim 1 or 9, wherein the protective layer comprises a resin matrix and carbon black. 11. The electrically conductive recording material according to claim 1, 9 or 10, wherein the protective layer has a thickness of 5 μm or less.