JPH0675993B2 - Discharge thermal transfer recording material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a discharge thermal transfer recording material.

[Conventional technology]

In recent years, information has become remarkably 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. The discharge thermal transfer recording system is also a typical example.

As a recording material used in the recording system, a recording material (USP3744611) has been proposed in which a conductive layer is laminated on one surface of an insulating substrate and a thermal transfer ink layer is laminated on the other surface. Since this recording material uses an insulating base material, it has high strength and is easy to handle, and when recording, electricity can be supplied from the recording needle and there is no need to use an expensive thermal head. is doing.

However, since the ink layer is transferred by applying heat to the conductive layer to generate heat in the layer, the amount of heat generated is small, and the insulating base material is interposed between the ink layer and the image density of transfer recording. Has a small size and a small resolution. Further, when the recording voltage is increased in order to increase the image density, the discharge is destroyed and the resolution is further lowered.

[Problems to be solved by the invention]

In view of the above-mentioned drawbacks, an object of the present invention is to obtain a recorded image with high mechanical strength, easy handling without breaking even with a long body, and high speed image density and resolution by discharging from a recording needle. Another object of the present invention is to provide a discharge thermal transfer recording material capable of

[Means for solving problems]

The resin matrix used in the present invention only needs to have a film forming ability and an electrical insulating property, and a thermoplastic resin is preferably used. The thermoplastic resin has a large binding force to the conductivity-imparting agent, a large mechanical strength when formed into a sheet or a film, and is preferably flexible and strong, for example, polyethylene, polypropylene, Polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polystyrene, polyacrylonitrile, polyvinyl acetal, polyacrylic ester,
Polymethacrylic acid ester, polyester, cellulose acetate, polyurethane, polyvinyl alcohol, carboxymethyl cellulose, gelatin, polyamide, polyarylate, polycarbonate, polysulfone and the like, vinyl chloride-ethylene copolymer, ethylene-vinyl acetate copolymer, polyvinyl. Acetal, polyamide and polyarylate are preferably used.

The conductivity-imparting agent used in the present invention is selected from the group consisting of metal powder, carbon black and graphite.

Examples of the metal powder include copper, aluminum, iron,
Examples include powders of tin, zinc, nickel, molybdenum, silver, bronze, brass and the like, and metal powders coated with metals such as copper powder coated with silver, and powders of copper, zinc and iron are preferably used. .

The metal powder preferably has a small shape and a uniform particle size, and the particle size is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm.

Further, it is preferable that the carbon black and graphite have small shapes and uniform particle diameters, and the particle diameter is preferably 10 microns or less.

The heat generating resistance layer (A) in the present invention is a layer which is composed of the above resin matrix and a conductivity-imparting agent, and generates heat by being discharged and destroyed together with the conductive layer (B) during discharge recording.

If the amount of the conductivity-imparting agent added to the resin matrix increases, the conductivity becomes too good and the current given from the recording needle diffuses, making it difficult to transmit to the conductive layer (B) immediately below the recording needle. When the amount is less, the conductivity becomes smaller and the calorific value becomes smaller. Therefore, 5 to 400 parts by weight of the conductivity-imparting agent is added to 100 parts by weight of the resin matrix, and the surface resistance is 0.5 × 10 ² to 10 ⁷ Ω Of.

Although the thickness of the layer is not particularly limited, it is preferably 0.3 to 5 μm so as to be easily destroyed by discharge.

The method for forming the heat generating resistance layer (A) is not limited at all, and any known method such as a solution casting method, an emulsion casting method, a calendering method, or an extrusion method may be adopted.

In the present invention, the conductive layer (B) is a layer that is destroyed by discharge during discharge recording and is laminated on the heating resistance layer (A). If the surface resistance is too small or conversely increases, the heating resistance layer ( 0.1 ~ 5 because A) will not be destroyed by discharge
Made to 0 Ω. Also, the heating resistance layer (A) and the conductive layer (B)
If the difference in surface resistance between the two is small, the amount of heat generated when discharge recording is performed, so the ratio of the surface resistance of the heating resistance layer (A) to the surface resistance of the conductive layer (B) is 10 to 10 ³ . Is preferred. Further, the conductive layer (B) is formed of a metal thin film, but the surface resistance becomes larger than 50 Ω when the thickness becomes thin, and the surface resistance becomes smaller than 0.1 Ω when the thickness becomes thicker, so that it is 400 to 5000 angstrom. Well, preferably 500-3
000 angstroms, more preferably 600-2000
Angstrom. Examples of the metal include aluminum, silver, gold, copper, zinc, tin, nickel and molybdenum, and aluminum is preferably used.

Any method may be adopted as the method for forming the conductive layer (B), and examples thereof include a vacuum deposition method, an ion plating method, and an electroless plating method. In addition, if there is a minute defect or pinhole in the metal thin film, the current concentrates on that part during energization and causes a large discharge breakdown. Therefore, in order to eliminate the above defect or pinhole, two or more layers are formed by the above method. It is preferable to form the conductive layer (B) by laminating the metal thin films of.

The insulating base material layer (C) in the present invention is a layer that is not destroyed by discharge during discharge recording, and is laminated on the conductive layer (B). The insulating resin layer prevents transfer of the heating resistance layer (A) and the conductive layer (B) that are destroyed by discharge during discharge recording, and the heating resistance layer (A) and the conductive layer that are destroyed by discharge. It is a layer that conducts the heat generated in (B) to the heat-sensitive transfer layer.

Examples of the base material for forming the layer (C) include films and sheets of the above resin matrix, paper, non-woven fabric and the like. The layer (C) preferably has excellent heat resistance, for example, polyester. Polyamide, polyamide-imide, polyimide, polycarbonate, urethane acrylic type, acrylic ester type, and acrylic ester type of epoxy resin, such as a photosensitive resin obtained by ultraviolet curing, are preferably used.

The thickness of the layer (C) is preferably thin because it conducts heat as described above, but it is preferably 2 to 10 microns because it is not necessary to prevent discharge breakdown.

Further, in order to improve the thermal conductivity to the layer, a metal powder may be added, and the metal powder may be the above-mentioned metal powder, but the thermal conductivity is excellent, the particle size is uniform, and it is small and bulky. Those having a low specific gravity are preferable, and examples thereof include scaly aluminum powder and dendritic copper powder.
When the metal powder is added, if the surface resistance becomes small, the recorded image becomes unclear and discharge breakdown occurs together with the conductive layer (B).

The heat-sensitive transfer layer (D) in the present invention is a layer that is transferred by heat during discharge recording, and is preferably formed of a thermoplastic binder and is laminated on the insulating base material layer (C). It

Any resin matrix can be used as the binder, but since the layer is thermally transferred, the melting point is 50%.
Those having a temperature of up to 110 ° C. are preferable, for example, paraffin wax, carnauba wax, polyethylene wax, low molecular weight polystyrene and its derivatives, polyvinyl butyral, vinyl chloride-vinyl acetate copolymer, polyamide,
Examples thereof include polyurethane, ketone resin, ethylene-vinyl acetate copolymer, petroleum resin and the like.

If it is desired to obtain a colored record, a colorant may be added, and any known pigment or dye may be used as the colorant, for example, nickel yellow, titanium yellow, cadmium red, naphthol yellow, permanent orange, Crystal violet, malachite green,
Examples thereof include phthalocyanine blue and brilliant carmine 6B, and the addition amount thereof may be arbitrarily determined depending on the color, density, etc. at the time of recording. To obtain a black recorded image, carbon black, aniline black, iron tetroxide, etc. may be added. In addition, it is preferable to add an inorganic filler such as calcium carbonate, magnesium carbonate, barium sulfate, clay or lithopone in order to improve transferability and wear resistance of the obtained recorded image.

Further, when the heat-sensitive transfer layer (D) contains a large amount of a coloring agent, the recording material may be contaminated with the coloring agent when the recording material of the present invention is laminated on the recording paper and discharge recording is performed. Because there is
The heat-sensitive transfer layer is preferably formed of two or more layers, and the outermost layer preferably contains a small amount of a colorant.

The thickness of the layer (D) is preferably 0.5 to 20 .mu., More preferably 1 to 6 .mu., Because the thicker the layer, the harder it is to transfer heat.

The method for forming the heat-sensitive transfer layer (D) is not particularly limited, and examples thereof include a solution casting method, an emulsion casting method, a calendar method, an extrusion method, and a gravure printing method.

The constitution of each layer of the recording material of the present invention is as described above, and the heating resistance layer (A), the conductive layer (B), and the insulating base material layer (C).
Then, the heat-sensitive transfer layer (D) is sequentially laminated to form a discharge heat-sensitive transfer recording material having a four-layer structure.

Another recording material of the present invention is a heating high resistance layer (E) between the heating resistance layer (A) and the conductive layer (B) of the above recording material.
Are laminated.

The heat-generating high-resistance layer (E) is a layer made of a resin matrix and an inorganic filler, which is destroyed by discharge at the end of discharge recording and generates heat.

As the inorganic filler, any known one can be used,
For example, calcium carbonate, magnesium carbonate, barium sulfate, titanium oxide, zinc oxide, clay, talc, lithopone, etc. are listed. 5 to 400 parts by weight is added to 100 parts by weight of the matrix.

If the surface resistance also becomes smaller, it becomes more difficult to cause discharge breakdown and the amount of heat generation decreases, so it is made 10 ⁹ Ω or more.

Further, the thickness of the heating resistance layer (E) is preferably 0.3 to 3 [mu] so as to be easily destroyed by discharge.

The method for forming the heat-generating high-resistance layer (E) is not limited in any way, and any known method such as a solution casting method, an emulsion casting method, a calender method, an extrusion method may be adopted.

[Work]

The structure of the discharge thermal transfer recording material of the present invention is as described above, and the recording material is supplied to a discharge or discharge recording apparatus,
When a recording meter is brought into contact with the surface layer and recording paper such as paper or plastic film is brought into contact with the underside of the heat-sensitive transfer layer to perform discharge recording, the heat-generating resistance layer (A), conductivity (B) and heat-generating high resistance immediately below the recording are recorded. The layer (E) is destroyed by electric discharge and generates heat, and this heat transfers the heat-sensitive transfer layer to a recording sheet for recording.

〔The invention's effect〕

The constitution of the electrically-conductive heat-sensitive transfer recording material of the present invention is as described above, and the heat generating resistance layer (A), the heat generating high resistance layer (E) and the conductive layer (B) are destroyed by discharge and generate a large amount of heat. A large recorded image can be obtained, and a high-density recorded image can be obtained by adding a colorant to the heat-sensitive transfer layer (D). Since the heat generating resistance layer (A), the heat generating high resistance layer (E) and the conductive layer (B) can be made very thin, the manufacturing cost is low, and soot and malodor are hardly generated even if the discharge breakdown occurs. Since the debris hardly adheres to the recording needle, maintenance of the recording device is easy.

Further, since the insulating base material layer is laminated, the mechanical strength is large, and even a long wound body does not break during recording.

Therefore, the recording material of the present invention is used for facsimiles, various measuring instruments,
It is preferably used for printing out of recorders and recording displays on computers.

Moreover, the recording material of the present invention is not limited to black recording,
Since it does not cause turbidity in color recording, it is extremely effective for high-speed printout of color recording display.

〔Example〕

Next, examples of the present invention will be described. Below, simply “part”
"Parts by weight" means "parts by weight".

Example 1 A vacuum-deposited film was obtained by vacuum-depositing aluminum twice on a surface of a 6-μm-thick polyester film under the condition of 10 ⁻⁵ Torr to form a conductive layer having a thickness of 800 Å and a surface resistance of 0.8Ω.

Polyamide (manufactured by Sanyo Chemical Industries, trade name Polymide S-
40A) 100 parts Furnace Black (Lion Akzo, trade name Ketjen Black EC) 30 parts Menunol 300 parts Toluene 300 parts Dissolve and disperse the composition having the above composition, apply it on the conductive layer and dry it. A heat generating resistance layer having a thickness of 2 μ and a surface resistance of 0.7 × 10 ⁴ Ω was formed to obtain a three-layer laminated sheet.

Ketone resin (Honshu Chemical Co., Ltd., product name Halon 80) 100 parts Synthetic metal dye (Hodogaya Chemical Co., product Spiron Black BN
H) 25 parts Beeswax 15 parts Carnauba wax 15 parts Ethyl acetate 50 parts Toluene 50 parts Next, the compounding composition having the above composition is dissolved and dispersed, coated on the other surface of the polyester film and dried to form a thermal transfer layer having a thickness of 3 μm. An electric discharge thermal transfer recording material having a thickness of 11 μm was obtained.

The obtained recording material is cut into a width of 7 mm, supplied to a copy-making base paper plate making machine (made by Gestettner Co., Ltd., which is an improved version of Guest Fax 1100), and a high-quality paper is contacted under the heat-sensitive transfer layer to make it on the surface sheet. Touch the recording needle to, DC 25V, 30mA
Of electricity, scanning line density 12 / mm, recording speed L2m
When discharge recording was performed under the condition of / sec, soot and carbon black were scarcely scattered, no bad odor was observed, and a clear black image was obtained on the high-quality paper without cutting during recording. The density of the obtained image was L15 and the resolution was 12 / mm.

Example 2 Polyamide (manufactured by Sanyo Chemical Industry Co., Ltd., trade name Polyamide S-
40A) 100 parts Light calcium carbonate (manufactured by Shiraishi Calcium Co., trade name Silver W) 100 parts Methanol 300 parts Toluene 300 parts The composition of the above composition was dissolved and dispersed, and the conductivity of the vapor deposition film obtained in Example 1 was measured. It is applied on the layer and dried to form a heating high resistance layer with a thickness of 1μ and a surface resistance of 0.5 × 10 ¹¹ Ω.
A three-layer laminated sheet was obtained.

Then, a heating resistance layer and a thermal transfer layer were formed in the same manner as in Example 1 to obtain a discharge thermal transfer recording material having a thickness of 12 μm.

When recording was performed in the same manner as in Example 1 using the obtained recording material, soot and carbon black were scarcely scattered, and a clear black image was obtained on high-quality paper without an offensive odor. The density of the obtained image is L30 and the resolution is 12 / mm.
Met.

Example 3 Polyamide (manufactured by Sanyo Chemical Industry Co., Ltd., trade name Polymide S-
40A) 100 parts graphite (Nippon Graphite Co., Ltd., trade name Soil Graphite ASP) 250 parts methanol 300 parts toluene 300 parts The compound having the above composition was dissolved and dispersed, and Example 1 was placed on the conductive layer of the vapor deposition film. Apply and dry to a thickness of 3
A heating resistance layer having a surface resistance of 0.5 × 10 ³ Ω was formed.

Then, in the same manner as in Example 1, a thermal transfer layer having a thickness of 3 μm was formed to obtain a discharge thermal transfer recording material having a thickness of 12 μm.

When discharge recording was performed using the obtained recording material in the same manner as in Example 1, there was almost no scattering of soot or graphite, no bad odor, and a clear black image was obtained on high-quality paper. The density of the obtained image was L10 and the resolution was 12 / mm.

Example 4 A heating resistance layer was formed on the heating high resistance layer of the three-layer sheet obtained in Example 2 in the same manner as in Example 3, and then a heat-sensitive transfer layer was formed in the same manner as in Example 1. Formed and thickness 13
A discharge thermal transfer recording material having a thickness of μ was obtained.

When discharge recording was performed in the same manner as in Example 1 using the obtained recording material, soot and graphite were scarcely scattered, no bad odor was generated, and a clear black image was obtained on the high-quality paper. The resulting image has a density of L25 and a resolution of 12 / mm
Met.

Claims (7)

[Claims] 1. A laminate having a four-layer structure, comprising: (A) 100 parts by weight of a resin matrix, and one or more conductivity imparting agents selected from the group consisting of metal powder, carbon black and graphite. 400 parts by weight, surface resistance of 0.5 × 10 ² to 10 ⁷ Ω, and a heating resistance layer that is destroyed by discharge during discharge recording; (B) Discharge consisting of a metal thin film, surface resistance of 0.1 to 50 Ω A conductive layer that is destroyed by discharge during recording; (C) An insulating substrate layer that is not destroyed by discharge during discharge recording; and (D) a heat-sensitive transfer layer, which are laminated in the order given above. Thermal transfer recording material. 2. A discharge heat-sensitive transfer recording material according to claim 1, wherein the heating resistance layer (A) has a thickness of 0.3 to 5 .mu.m. 3. The discharge thermal transfer recording material according to claim 1, wherein the ratio of the surface resistance of the heat generating resistance layer (A) to the surface resistance of the conductive layer (B) is 10 to 10 ³ . 4. A laminate having a five-layer structure, comprising (A) 100 parts by weight of a resin matrix, and one or more conductivity-imparting agents selected from the group consisting of metal powder, carbon black and graphite. 400 parts by weight, a surface resistance of 0.5 × 10 ² to 10 ⁷ Ω, and a heating resistance layer which is destroyed by discharge during discharge recording; (E) 100 parts by weight of resin matrix and 5 to 200 inorganic fillers.
A heat-generating high-resistance layer consisting of parts by weight and having a surface resistance of 10 ⁹ Ω or more and being destroyed by discharge during discharge recording; (B) A discharge thin film made of a metal thin film having a surface resistance of 0.1 to 50 Ω A conductive layer which is destroyed by discharge; (C) an insulating base material layer which is not destroyed by discharge during discharge recording; and (D) a heat-sensitive transfer layer, which are laminated in the above-mentioned order. 5. A discharge heat-sensitive transfer recording material according to claim 4, wherein the heating resistance layer (A) has a thickness of 0.3 to 5 .mu.m. 6. The discharge heat-sensitive transfer recording material according to claim 4, wherein the heat-generating high-resistance layer (E) has a thickness of 0.3 to 3 μm. 7. The fourth and fifth claims, wherein the ratio of the surface resistances of the heating resistance layer (A) and the conductive layer (B) is 10 to 10 ³ .
And the heat-sensitive transfer recording material according to item 6.