JP3402658B2 - Electric discharge breakdown printing type recording medium - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a discharge breakdown printing type recording medium. More specifically, the present invention relates to a discharge breakdown printing type recording medium having a protective layer capable of reducing or preventing a fusion phenomenon caused by the adhesion of resin or metal debris to discharge pins during discharge breakdown printing.

[0002]

2. Description of the Related Art A discharge breakdown printing type recording medium is initially used as a recording sheet for a facsimile and then a printer, and in recent years, is also used for recording a magnetic card such as a prepaid card. In principle, a conductive metal layer (discharge recording layer) on the base material is kept in contact with the ground roller to make it conductive, and a discharge pin is caused to discharge to another part of this metal layer, whereby the metal layer Part of the metal layer is melted and destroyed to expose the lower layer of the metal layer to form a print record.

However, this discharge breakdown printing method has a problem of the following fusion phenomenon. That is, since the discharge pin immediately after the discharge is charged, the scraps of the metal layer such as the molten and scattered aluminum are easily attached to the discharge pin. In addition, usually above and below the metal layer, a protective layer, an anchor layer,
Since there is a resin layer such as a barrier layer, the resin melted by the discharge easily adheres to the discharge pin. The metal or resin debris attached to the discharge pin gradually accumulates near the tip of the discharge pin, and if the amount of deposition increases, the discharge pin with the debris will short-circuit. May not be discharged. In addition, when the amount of adhesion is large, two or more discharge pins to which dust has adhered may become conductive, and the discharge at the correct position may not occur.

Further, in addition to the above-mentioned problem caused by metal or resin residue attached to the discharge pin, the discharge pin immediately after discharge operates while having residual heat due to discharge, so that the resin layer such as the protective layer melts. However, the traces of the discharge pins are attached to the surface, which causes deterioration of print quality. further,
The molten resin may adhere to the discharge pin and cause the same problem as described above. The same problem occurs when the protective layer is soft.

In order to prevent the deterioration of printing quality due to the above-mentioned fusion phenomenon, the distance between the discharge pins is widened. However, if the interval between the discharge pins is widened, there is a drawback that it is difficult to perform fine printing, and it is preferable that the interval between the discharge pins is not too wide.

[0006]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to adhere to the discharge pin even if the discharge recording layer or the like melts and scatters by the discharge or the residual heat of the discharge pin melts the protective layer or the like. Another object of the present invention is to provide a discharge breakdown printing type recording medium in which a fusion phenomenon does not easily occur and a running mark is hardly formed on the surface even when the discharge pin is rubbed.

[0007]

The present invention is a recording medium having a discharge breakdown printing layer and a protective layer, the protective layer comprising:
The present invention relates to a discharge breakdown printing type recording medium containing Teflon wax and containing one or two kinds selected from a resin lubricant and talc.

The present invention is a discharge breakdown printing type recording medium having a discharge breakdown printing layer and a protective layer. More specifically, as shown in FIG. 1, the recording medium has a discharge breakdown printing layer 2 and a protective layer 3 on a base material 1 in this order. An anchor layer 4 (not shown) may be provided between the discharge breakdown printing layer and the protective layer for the purpose of improving the adhesion between the discharge breakdown printing layer 2 and the protective layer 3.

The discharge breakdown printing type recording medium of the present invention may further have a magnetic recording layer in addition to the discharge breakdown printing layer. For example, as shown in FIG. 2, a recording medium having a magnetic recording layer 5, a discharge breakdown printing layer 2 and a protective layer 3 on a base material 1 in this order can be mentioned.
A barrier layer 6 may be provided between the magnetic recording layer 5 and the discharge breakdown printing layer 2 for the purpose of preventing the discharge breakdown printing layer 2 from being deteriorated by the components of the magnetic recording layer 5. Further, an anchor layer 4 may be provided between the discharge breakdown printing layer and the protective layer for the purpose of improving the adhesion between the discharge breakdown printing layer 2 and the protective layer 3.

In the present invention, the substrate 1 has a sheet shape, a film shape, a plate shape or the like, and the material is PE.
Plastics such as T (polyethylene terephthalate), nylon, cellulose diacetate, polystyrene, polyethylene, polypropylene, polyester, polyimide and polycarbonate; metals such as copper and aluminum;
Paper, impregnated paper and the like can be used alone or in combination of two or more kinds. The thickness of the base material is not particularly limited and may be appropriately selected depending on the intended use.
It is about 5 mm.

The discharge breakdown printing layer 2 is composed of a thin film of a single metal, alloy or compound, and is composed of a layer capable of destroying a recording portion by utilizing a discharge phenomenon. Specifically, Al, Ni, Sn,
It is made of a metal such as Zn, Ti, Te, In, Bi or Pb, or an alloy or compound thereof. The discharge breakdown printing layer can be formed by a method such as a vacuum vapor deposition method, a sputtering method, or a plating method. The film thickness of the discharge breakdown printing layer is 100 Å to 1 μm, preferably 300 to 1000 Å.

The protective layer 3 is generally intended to protect the discharge breakdown printing layer 2, which is a recording layer, or the discharge breakdown printing layer 2 and the magnetic recording layer 5, in order to secure the physical properties and durability of the recording medium. Is formed as. Furthermore, in the present invention, by selecting the material of the protective layer, the fusion phenomenon is prevented and the running trace of the discharge pin is hard to be formed. From such a viewpoint, in the present invention, the protective layer contains Teflon wax in the binder resin and contains one or two kinds selected from a resin lubricant and talc. Of these substances, one type does not provide a sufficient effect, and preferably three types of Teflon wax, a resin lubricant and talc are contained. By including these components,
Appropriate hardness, slipperiness and heat resistance can be imparted,
As a result, the fusion phenomenon can be prevented. Further, by using an electron beam or ultraviolet ray curable resin as the binder resin, the hardness is increased, and the running trace of the discharge pin is hardly attached.

In the present invention, the Teflon wax is a finely pulverized fluoroethylene resin (PTFE), which is also called Teflon powder wax. In order to perform stable discharge breakdown recording, Teflon wax has an average particle size in the range of 1 to 2 μm.
In order to prevent thermal dissolution due to the discharge pin, it is suitable that the melting point is 300 ° C or higher. Such Teflon wax is commercially available (for example, SST-1MG, SST-3T manufactured by Shamrock).
G, Hoechst HOSTAFLON TF-9205, Daikin Industries Lubron L-2, Lubron L-5) are easily available.

The resin-based lubricant is generally known as a modifier for plastic materials, and is used for the purpose of improving fluidity in injection molding. It is relatively suitable from the viewpoint of dispersion in a binder or coating suitability. Oligomers having a low molecular weight are suitable. Such resin-based lubricants are commercially available products (for example, ADEKA STAB FC manufactured by Asahi Denka Co., Ltd.
-112, FC-113, FC-117, FC-400, AX-38) can be easily obtained.

Talc is a hydrous silicate mineral of magnesium, has a composition represented by Mg ₃ Si ₄ O ₁₀ (OH) ₂ , has excellent heat resistance, and is a filler having a strong affinity for organic substances. is there. Although the composition varies slightly depending on the production area, it contains silicon oxide (about 60 to 65%) and magnesium oxide (about 30 to 35%) as main components, and as a trace component,
Includes ferric oxide (Fe ₂ O ₃ ), aluminum oxide, calcium oxide and the like. In many cases, the protective layer is transparent and is required to have the same characteristics as those of the above waxes. Therefore, it is preferable that the protective layer has a small particle size, for example, an average particle size of 1 to 2 μm.
A range of m is suitable. As for talc, commercially available products (for example, Micro-ace L-1, Micro-ace P-3 manufactured by Nippon Talc, Hytron, Hytron A, Microlite, US-100, US-150S manufactured by Takehara Chemical Industry) can be easily obtained. it can.

If the added amounts of Teflon wax, resin lubricant and talc are too small, sufficient effects cannot be obtained.
If the amount is too large, the coating suitability and the glossiness of the protective layer are reduced.
0% However, when three types are contained, it is appropriate that the upper limit of the total of the three types is 20%.

Further, the binder resin of the protective layer is preferably an ultraviolet ray or electron beam curable resin from the viewpoint that the traces of discharge pins are less likely to run, and in particular, a polyfunctional resin is suitable. . Examples of the polyfunctional resin include polyfunctional acrylic resins. Examples of the polyfunctional acrylic resin include dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 7,11-octadecadiene-1,18-dicarboxylic acid bis (3-acryloyloxy-2-hydroxypropyl), 11- Vinyl-7-hexadecene-
1,16-dicarboxylic acid bis (3-acryloyloxy-2-hydroxypropyl), acrylic acid esterified product of 1,2-epoxypropane adduct of propyridine trimethanol, 6-hexanolide adduct of dipentaerythritol and acrylic acid An esterification product with 2,2-bis [3,5-dibromo-4- (2-methacryloyloxyethoxy) phenyl] propane, 2,2-bis [4-
(2-Acryloyloxyethoxy) -3,5-dibromophenyl] propane, 5-ethyl-2- (2-hydroxy-1,1-dimethylethyl) -5- (hydroxymethyl) -1,3-dioxane mono Or diacrylate ester, 3,9-bis (2-acryloyloxy-1,
1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 3-hydroxy-2,
2-Dimethylpropyl = 3-hydroxy-2,2-dimethylpropionate 6-hexanolide addition polymer <degree of polymerization 1 to 7> and an esterification product of acrylic acid, 2-hydroxyethyl = 6-hexanolide of methacrylate Examples thereof include reaction products of an addition polymer <degree of polymerization 0 to 6> and phosphoric anhydride.

If necessary, the binder resin contains a photopolymerization initiator such as acetophenones, benzophenones, Michler benzoyl benzoate, α-amyloxime ester, tetramethylmeuram monosulfide and thioxanthone, and n. It goes without saying that a photosensitizer such as -butylamine, triethylamine, tri-n-butylphosphine and N-vinylpyrrolidone can be contained.

As a coating method for forming the protective layer, for example, an offset coating method, a silk screen coating method, a roll coating method, a reverse coating method, a gravure coating method, a gravure reverse coating method, a kiss coating method, a comma coating method and the like are used. . The ultraviolet curable resin is cured by irradiating ultraviolet rays having an energy of 100 to 1000 kev, preferably 100 to 300 kev with a light source such as a carbon arc, a xenon lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp or various electron beam accelerators. Can be done by. The electron beam curable resin can be cured by irradiating it with an electron beam using a non-scanning electron beam curing device, a scanning electron beam curing device, or the like.

The thickness of the protective layer is 2 μm or less, preferably 0.5, from the viewpoint that good electrical continuity between the discharge breakdown printing layer 2 and the earth roller 10 can be maintained and, as a result, good printing characteristics can be obtained. It is suitable that the thickness is ˜1.5 μm.

The anchor layer 4 is used for the purpose of improving the adhesion between the discharge breakdown printing layer 2 and the protective layer 3. Therefore, it has excellent adhesiveness such as polyester resin, urethane resin, vinyl chloride / vinyl acetate copolymer, ethylene /
A vinyl acetate copolymer, an ionomer resin, a polyolefin-based copolymer or the like can be used as the anchor layer. The total thickness of the anchor layer and the protective layer is 2
When the thickness is less than or equal to μm, the electrical continuity between the discharge breakdown printing layer 2 and the earth roller 10 is kept good, and as a result,
It is preferable from the viewpoint that good printing characteristics can be obtained.

The magnetic recording layer 5 can be formed by applying a coating material in which conventionally known magnetic fine particles are dispersed in a suitable resin or ink vehicle to the base material 1 by a known method. As the magnetic fine particles, for example, γ-Fe ₂ O
₃ , Fe ₃ O ₄ , CrO ₂ , Fe, Fe-Cr, Fe-
Co, Co-Cr, Co-Ni, MnAl, Ba ferrite, Sr ferrite, etc. can be mentioned. The resin or ink vehicle includes butyral resin, vinyl chloride / vinyl acetate copolymer resin, urethane resin, polyester resin, cellulose resin, acrylic resin, styrene /
A maleic acid copolymer resin or the like is used, and if necessary,
A rubber resin such as nitrile rubber or a urethane elastomer may be added. In addition to magnetic materials and the like, additives such as surfactants, silane coupling agents, plasticizers, waxes, silicone oils and carbon can be appropriately added as needed. Examples of the coating method of the coating material containing the magnetic fine particles include a gravure method, a roll method, a knife edge method and the like. The thickness of the magnetic recording layer is about 1 to 100 μm, preferably 5 to 20 μm.

In addition to using the coating material containing the above-mentioned magnetic fine particles, the magnetic recording layer is made of Fe, Fe--Cr, Fe--Co,
A metal or alloy such as Co—Cr or Co—Ni can also be formed on the base material by a method such as a vacuum vapor deposition method, a sputtering method, or a plating method. In this case, the thickness of the magnetic recording layer is about 100 Å to 1 μm, preferably 5 Å.
It is from 00 to 2000 angstroms.

The barrier layer 6 prevents the discharge breakdown printing layer 2 from deteriorating due to the leaching of water from the magnetic recording layer.
That is, a pigment may be added to the magnetic recording layer in order to control the surface electric resistance value of the magnetic recording layer within a specific range, and the pigment and the magnetic fine particles or impurities contained in these pigments may be present in the presence of water. The metal such as aluminum may be corroded to deteriorate the discharge breakdown printing layer 2.

The barrier layer is composed of a cured layer containing a binder resin as a main component and curing the binder resin. As the binder resin, vinyl chloride resin, vinyl chloride / vinyl acetate copolymer resin, vinyl acetate resin, ethylene / vinyl acetate copolymer, rubber resin, acrylic resin or methacrylic resin homopolymer or copolymer, polyurethane Resins, polyester resins, cellulose resins, polyolefin resins, alkyd resins, styrene resins, phenol resins, ionomer resins and the like are used. Additives such as a plasticizer, a stabilizer, and a curing agent can be appropriately added to these binder resins, if necessary.

The barrier layer is formed by appropriately adding additives to the above binder resin, and then sufficiently kneading the mixture with a solvent or a diluent to prepare a coating composition, which is applied onto the magnetic recording layer by a gravure method or a roll method. Method, knife edge method or the like can be used. The film thickness after curing of the barrier layer is appropriately about 5 μm, preferably 1 μm.

When information is recorded on the discharge breakdown print layer 2 of the discharge breakdown print type recording medium of the present invention, as shown in FIG. 1, a ground roller 10 is brought into contact with the surface of the medium and further discharge (recording) pins. This is performed by causing discharge according to the recorded information by 11 to form the discharge breakdown site 12 in the protective layer 3 and the discharge breakdown print layer 2.

On the other hand, in the case of a discharge breakdown printing type recording medium further having a magnetic recording layer, the information can be recorded on the magnetic recording layer and reproduced if necessary in addition to the recording of the information by the discharge breakdown printing. . In a recording medium having a magnetic recording layer and a discharge breakdown printing layer, it is possible to double-check magnetic information and visible information in a single recording medium, and
It is effective in preventing counterfeiting.

[0029]

EFFECTS OF THE INVENTION The discharge breakdown printing type recording medium of the present invention is unlikely to adhere to the discharge pin and cause a fusion phenomenon even if it is melted and scattered by the discharge or melted by the residual heat of the discharge pin. Even if the pin rubs, it is difficult for the surface to leave a running mark.

[0030]

EXAMPLES The present invention will be further described below with reference to examples.

Example 1 188 μm polyerylene terephthalate film (P
A coating composition having the following composition was applied onto the ET film) by a gravure coating method to form a magnetic recording layer with a thickness of 10 μm. Paint for magnetic recording layer Barium ferrite 36 parts by weight Urethane resin 12 parts by weight Carbon 2 parts by weight Toluene 20 parts by weight Methyl ethyl ketone 15 parts by weight Methyl isobutyl ketone 15 parts by weight Isocyanate curing agent 2 parts by weight

A coating for barrier layer having the following composition was applied on the above magnetic recording layer by a gravure coating method to a thickness of 0.5 μm to form a barrier layer. Barrier layer paint Acrylic resin 40 parts by weight Toluene 30 parts by weight Methyl ethyl ketone 30 parts by weight Isocyanate curing agent 2 parts by weight

Aluminum was formed on the barrier layer to a thickness of 400 angstroms by a vacuum deposition method, and this was used as a discharge breakdown print recording layer. An anchor layer coating material having the following composition was applied onto the above discharge breakdown print recording layer by a gravure coating method to form an anchor layer having a thickness of 0.5 μm. Paint for anchor layer Polyester resin 10 parts by weight Vinyl chloride / vinyl acetate copolymer 10 parts by weight Toluene 50 parts by weight Methyl ethyl ketone 50 parts by weight Isocyanate curing agent 5 parts by weight

On the anchor layer, a protective layer coating composition having the following composition was applied by a gravure coating method to form a protective layer having a thickness of 0.5 μm. Paint for protective layer Dipentaerythritol hexaacrylate (DPHA) 100 parts by weight Lubron L-5 (manufactured by Daikin Industries) 3 parts by weight ADEKA STAB FC-117 (manufactured by Asahi Denka Kogyo) 3 parts by weight Microace P-3 (manufactured by Nippon Talc) 3 parts by weight N-vinylpyrrolidone 20 parts by weight Benzophenone 15 parts by weight

The discharge breakdown printing type recording medium of the present invention obtained as described above was printed with an applied voltage of 50 V, 24 dots, and 48 mm / line continuously for a maximum of 20,000 lines, so that a pin due to the fusion phenomenon occurred. A printing test was performed to see if the running traces were observed. The results are shown in Table 1.

Examples 2 to 4 The same as Example 1 except that the coating composition for the protective layer used any two of Teflon wax (PTFE), a resin lubricant and talc, as shown in Table 1. Then, a discharge breakdown printing type recording medium of the present invention was prepared, and a printing test was conducted in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 1 to 5 In Table 1, the coating material for the protective layer was selected from one of Teflon wax (PTFE), resin lubricant, talc, silicone oil (silicon) and paraffin wax (paraffin). A discharge breakdown printing type recording medium of the present invention was prepared in the same manner as in Example 1 except that the composition was changed as shown, and a printing test was conducted in the same manner as in Example 1. The results are shown in Table 1.

[0038]

[Table 1]

◯: A running trace of the pin was observed, but 10,
Good printing was possible for 000 lines or more. Δ: A trace of running of the pin was observed, 1,000 rows to 10,0
A printing failure occurred during the 00th line. X: A running trace was conspicuous from the 1st line, and a printing defect occurred in less than 1,000 lines.

From the results shown in Table 1, Teflon wax (PTFE) and a resin lubricant, or Teflon Wack was used for the protective layer.
By containing at least two kinds of slag (PTFE) and talc, the fusion phenomenon can be effectively prevented and good printing can be obtained.

[Brief description of drawings]

FIG. 1 is a sectional view showing the basic structure of a discharge breakdown printing type recording medium of the present invention.

FIG. 2 is a cross-sectional view showing a discharge breakdown printing type recording medium according to an embodiment of the present invention.

[Explanation of symbols]

1 base material 2 Discharge breakdown printing layer 3 protective layer 4 anchor layer 5 Magnetic recording layer 6 barrier layers 10 Earth roller 11 discharge pins 12 Discharge destruction part

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) B42D 5/00-15/10 B41M 5/24

Claims (3)

(57) [Claims] 1. A recording medium having a discharge breakdown printing layer and a protective layer, the protective layer containing Teflon wax ,
And discharge breakdown printing type recording medium characterized in that it contains one or two elements selected from a resin-based lubricants, and talc. 2. The protective layer contains Teflon wax ,
One resin-based lubricants and one or an ultraviolet or electron beam-curable resin containing claim 1 discharge breakdown printing type recording medium according selected from talc. 3. The discharge breakdown printing type recording medium according to claim 1, further comprising a magnetic recording layer.