JPH04290786A - Discharge breakdown recording medium - Google Patents

Abstract

PURPOSE:To improve the corrosion inhibitive properties of a recording layer and thereby enhance its durability and reliability by forming an aluminum film containing a mixture of manganese, copper and magnesium or either one of these ingredients in the recording layer. CONSTITUTION:This discharge breakdown recording medium, consisting of a recording layer 3 of metal film provided on a base 1 through a background layer 2, has holes opened by breaking down part of the recording layer 3 using electric discharge for printing process. The recording layer 3 is formed with a thin film of aluminum containing a mixture of manganese, copper and magnesium or either one of these ingredients. Further, the background layer 2 is formed with a coat containing color pigment or is constituted with a two-tier coated film of a coat 21 containing color pigment and a transparent film 22 laminated on the coat 21. The color pigment is a magnetic powder. If manganese, copper and magnesium are added to aluminum, an oxide film formed on the surface of aluminum becomes rigid and passive, so that the recording layer is more highly corrosion-inhibitive.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a discharge destruction recording material that prints by destroying a part of a recording layer made of a thin metal film provided on a substrate through an underlayer by electric discharge and making holes. More specifically, the present invention relates to a discharge breakdown recording medium having good durability and excellent reliability.

0002

[Prior Art] Printing and recording methods using metal thin films have conventionally been known as heat-sensitive recording methods in which printing is performed by heating a part of a heat-sensitive recording layer made of a thin film of a low-melting point metal to create melt holes, and metal thin films. There are discharge destruction recording methods that print by destroying a part of the recording layer made of a thin film by electric discharge and making holes.The recording medium used in these recording methods is disclosed in Japanese Patent Application Laid-Open No. 59-199284. A heat-sensitive recording material disclosed in Japanese Patent Publication No. 54-15416 and a discharge destruction recording material disclosed in Japanese Patent Publication No. 54-15416 have been proposed.

0003

[Problem to be solved by the invention] However, the thermal recording method cannot be rewritten and has excellent durability and stability over time, so it can be used when printing and displaying amounts, counts, dates, etc. Although it is used in various ways, the printing method is basically a thermal head method, which requires time for the head to cool down, so there is a limit to the printing speed, and it is difficult to perform high-speed processing at stations and supermarkets. Its use is severely restricted in fields that require it. In addition, the discharge destruction recording method is superior in that it cannot be rewritten and can print at higher speeds than the heat-sensitive recording method, but in principle, electricity is applied to the recording layer made of a thin metal film to melt it. Since printing is performed by scattering, it is not possible to form a thick protective layer made of an insulating resin layer on the recording layer. For this reason, it is difficult to obtain sufficient barrier properties against the intrusion of moisture, etc., and for example, it is made of aluminum, which has good conductivity, high whiteness and good appearance, and is easy to form a thin film and has good mass production. When the printed recording layer is not sufficiently protected and is exposed to a high humidity environment, it corrodes, causing changes in appearance or falling off, or the printed area disappears or becomes unclear, making it impossible to record. However, compared to thermal recording methods, this method has disadvantages in that it is inferior in durability and lacks reliability.

0004

[Means for Solving the Problems] The present invention was made as a result of various studies in view of the current situation, and it is possible to replace the recording layer made of a thin metal film formed on the underlayer of a discharge breakdown recording material with manganese, copper or copper. By forming a thin film of aluminum containing magnesium alone or in combination, the recording layer has improved corrosion resistance and improved durability and reliability.

[0005] In the present invention, the recording layer made of a thin metal film formed on the underlayer preferably contains manganese, copper, and magnesium in aluminum, singly or in combination. When these elements are added, the oxide film formed on the aluminum surface becomes tough and becomes a passivation material. Therefore, a recording layer formed of aluminum containing manganese, copper, and magnesium alone or in combination has sufficiently improved corrosion resistance.

[0006] Therefore, even if the thickness of the protective layer formed on the recording layer is thinner than that in the heat-sensitive recording method and does not provide sufficient barrier properties against the intrusion of moisture, etc., corrosion will not occur. Corrosion resistance is improved even under corrosive atmospheres such as high humidity. As a result, the thickness of the protective layer can be reduced and the electrical resistance does not increase, making it easy to conduct electricity to the recording layer and preventing deterioration in print quality.

[0007] In order to sufficiently improve the corrosion resistance of the recording layer, manganese, copper, and magnesium are contained singly or in combination in the range of 0.5 to 5% with respect to aluminum in the recording layer. It is preferable that these contents are too small, and sufficient corrosion resistance cannot be obtained.

[0008] The recording layer made of such a thin metal film is
Using an alloy of aluminum and manganese, copper, magnesium, etc., vacuum evaporation,
It is formed by applying methods such as plating and sputtering.

Here, as the substrate, conventionally used nylon, cellulose diacetate, cellulose triacetate, polystyrene, polyethylene, polypropylene, polyester, polyimide, polycarbonate can be used.
Plastic substrates such as polyester, polyethylene terephthalate, polyethylene naphthalate, etc. are preferably used.

The base layer formed on the substrate may be made of acrylic resin, vinyl chloride-vinyl acetate copolymer, acrylic silicone resin, polyvinyl butyral resin, polyurethane resin, or phenol resin. Resin, epoxy resin, and various other thermoplastic resins and thermosetting resins are dissolved in an organic solvent, either alone or as a mixture of two or more, and the base layer paint obtained by this dissolution is applied onto the substrate. , formed by drying.

At this time, in order to obtain high-contrast printing, the base layer should contain a colored pigment, or the base layer should consist of a coating film containing a colored pigment and a transparent resin layer laminated thereon. It is desirable to have a two-layer base layer.

[0012] In order to incorporate a colored pigment into the base layer, the colored pigment can be mixed with an acrylic resin, a vinyl chloride-vinyl acetate copolymer, a cellulose resin, a polyvinyl butyral resin, a polyurethane resin, or a polyester. A base layer paint containing a colored pigment is prepared by mixing and dispersing it with a binder resin such as a base resin, a phenol resin, or an isocyanate compound, and an organic solvent, and this base layer paint is applied onto a substrate. This is done by drying to form a base layer. In particular, binder resins used in combination with this colored pigment include polyurethane resins, vinyl chloride-vinyl acetate copolymers, and vinyl chloride resins having acrylic hydroxyl groups. is preferably used.

The colored pigment must have a color that can be visually recognized between the recording layer made of a thin metal film, but from the viewpoint of contrast, black pigments are preferably used, and carbon black and other pigments are preferred. is preferably used. Further, a magnetic powder may be used as the colored pigment, and the underlayer may also serve as the magnetic recording layer.If the pigment is used also as the magnetic recording layer, not only coloring but also magnetic recording can be performed at the same time.

[0014] The thickness of such an underlayer varies depending on the type of material and forming method, but it is usually preferably 5 μm or less. However, in general, if the thickness is less than 0.2 μm, it is difficult to function as an underlayer, so 0.2 μm or less is less effective.
The thickness is preferably 2 μm or more.

Furthermore, a transparent protective layer that sufficiently transmits light is usually formed on the recording layer made of a thin metal film.
This protective layer can be made of acrylic resin, vinyl chloride-vinyl acetate copolymer, acrylic silicone resin, polyvinyl butyral resin, polyurethane resin, phenol resin, epoxy resin, and various other resins. The protective layer is formed by dissolving a thermoplastic resin and a thermosetting resin alone or in combination of two or more in an organic solvent, and coating the resulting protective layer coating on the recording layer and drying it.

[0016] Such a discharge destruction recording medium of the present invention is as follows:
As shown in FIG. 1, a base layer 2, a recording layer 3 made of a thin metal film, and a protective layer 4 are sequentially laminated on a substrate 1, and a ground electrode 5 and a printing electrode are in contact with the protective layer 4. Using a discharge rupture printer equipped with 6, the metal of the recording layer 4 is melted and scattered to form the holes 7, and printing is performed at a high speed about three times that of a normal thermal recording method.

[0017]

[Example] Next, an example of the present invention will be described. Example 1 Barium ferrite magnetic powder (average particle size 0
．． 8 μm) 80 parts by weight Acrylic hydroxyl group-containing vinyl chloride-vinyl acetate copolymer
10 〃 (U.C.C.
manufactured by VAGH) Polyurethane resin (manufactured by Dainippon Ink & Chemicals Co., Ltd.; Pande 7
〃X T5201) Trifunctional polyisocyanate compound (Japan Polyurethane 1〃 Kogyo Co., Ltd.; Coronate L) Carbon black

4 〃
toluene

260 Cyclohexanone

260 This composition was mixed and dispersed in a ball mill for 100 hours to prepare a magnetic paint, and this magnetic paint was applied to a polyethylene terephthalate film with a thickness of 188 μm.
A black magnetic layer having a thickness of 15 μm was formed by coating and drying on a sheet by a gravure method.

Next, on the black magnetic layer, an acrylic silicone resin (which is made by copolymerizing an acrylic resin with a silane compound) is applied.
A base layer paint prepared by dissolving Silacoat (manufactured by Chisso Corporation) in xylene was applied to a thickness of 2.5 μm by a gravure method and dried to form a base layer.

Next, using an EBX-6 type resistance heating vapor deposition apparatus manufactured by ULBAC, the base layer was coated without heating.
Vacuum level: 1 x 105 Torr, deposition rate: 50 Å/sec
Then, an aluminum-manganese alloy (manganese content: 1% by weight) was vacuum-deposited to form a recording layer with a thickness of 500 Å consisting of a metal thin film of aluminum-manganese alloy (manganese content: 1% by weight) on the underlayer.

Next, a paint having the same composition as that of the base layer was applied onto the recording layer and dried to form a protective layer made of acrylic silicone resin with a thickness of 0.4 μm, as shown in FIG. On polyethylene terephthalate sheet 1,
A discharge breakdown recording body was produced in which a magnetic layer 21, an underlayer 22, a recording layer 3, and a protective layer 4 were laminated in this order.

Example 2 In forming the recording layer in Example 1, aluminum-copper-manganese alloy (copper content 0.1% by weight, manganese content) was used instead of aluminum-manganese alloy (manganese content 1% by weight). A recording layer with a thickness of 500 Å made of an aluminum-copper-manganese alloy (copper content: 0.1% by weight, manganese content: 1% by weight) was formed in the same manner as in Example 1, except that 1% by weight of aluminum was used. We then created a discharge breakdown record.

Example 3 In the formation of the recording layer in Example 1, an aluminum-copper alloy (copper content: 2.5% by weight) was used instead of an aluminum-manganese alloy (manganese content: 1% by weight). A recording layer having a thickness of 500 Å made of an aluminum-copper alloy (copper content: 2.5% by weight) was formed in the same manner as in Example 1 to produce a discharge breakdown recording medium.

Example 4 In forming the recording layer in Example 1, aluminum-copper-magnesium alloy (copper content 0.3% by weight, magnesium content) was used instead of aluminum-manganese alloy (manganese content 1% by weight). An aluminum-copper-magnesium alloy (copper content: 0.3% by weight, magnesium content: 1% by weight) was prepared in the same manner as in Example 1, except that 1% by weight) was used.
A recording layer with a thickness of 500 Å was formed, and a discharge breakdown recording medium was prepared.

Comparative Example 1 A 500 Å thick layer made of aluminum was prepared in the same manner as in Example 1, except that aluminum was used instead of the aluminum-manganese alloy (manganese content: 1% by weight) in forming the recording layer in Example 1. A recording layer was formed to create a discharge breakdown recording medium.

[0025] The discharge breakdown recording materials obtained in each example and comparative example were printed at a printing speed of 150 mm/sec using a discharge breakdown printer head with a dot density of 8 lines/mm and a dot size of 120 x 120 μm. The print density and the shape of the font were investigated. Print density is measured by so-called reflection density measurement, and reflection density is determined by Macbeth
This was carried out using a RD915 type densitometer on a 5 mm square printing area, and the average density including the unfused area between each dot was determined. In addition, the shape of the font was observed using a 100x optical microscope. As a result, there was no difference in print density or font shape between the discharge breakdown recording materials obtained in each Example and Comparative Example, and the print characteristics were the same.

[0026] Furthermore, the durability of the discharge breakdown recording bodies obtained in each of the Examples and Comparative Examples was tested. The durability test was carried out by leaving each of the obtained discharge breakdown recording bodies in an atmosphere of 60° C. and 90% RH for 10 days, and observing changes in appearance, fading of printed parts, etc. For comparison, a heat-sensitive melt printing type recording medium using Sn was simultaneously tested and designated as Comparative Example 2. Table 1 below shows the results.

[0027]

[0028]

[Effects of the Invention] As is clear from Table 1 above, the discharge breakdown recording material obtained by the present invention has less change in appearance than the conventional discharge breakdown recording material and heat-sensitive recording material, and the printed portion has been improved. There is no discoloration, and in particular, the discharge breakdown recording bodies obtained in Examples 2 and 4 do not change their appearance at all even in a high temperature and high humidity atmosphere. Therefore, the discharge breakdown recording bodies obtained by the present invention have excellent durability. It can be seen that the corrosion resistance is sufficiently improved, and the durability and reliability are sufficiently improved.

[0029]

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram illustrating the principle of printing on a discharge destruction recording medium using a discharge destruction printer.

FIG. 2 is an enlarged sectional view of a main part of an embodiment of the discharge destruction recording material obtained by the present invention.

[Explanation of symbols]

1 Base 2 Base layer 21 Magnetic layer (colored base layer) 22 Base layer (transparent base layer) 3 Recording layer 4 Protective layer 7 holes

Claims (1)

[Scope of Claims] [Claim 1] A discharge destruction record in which a recording layer made of a thin metal film is provided on a substrate via an underlayer, and a part of the recording layer is destroyed by discharge to form a hole to print. A discharge breakdown recording material characterized in that the recording layer is formed of a thin film of aluminum containing manganese, copper, and magnesium alone or in combination.Claim 2: The underlayer is formed of a coating film containing a colored pigment. 3. The discharge breakdown recording material according to claim 1, wherein the underlayer is a two-layer paint film, a paint film containing a colored pigment and a transparent paint film laminated thereon. [Claim 4] The discharge breakdown recording material according to claim 1, wherein the colored pigment is a magnetic powder.Claim 2:
and discharge breakdown recording material according to 3.