JPS6317638B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a discharge recording material capable of recording images such as characters, figures, symbols, etc. in multiple colors in correspondence with electrical information signals, and more specifically, the present invention relates to a discharge recording material that can record images such as characters, figures, symbols, etc. in multiple colors in response to electrical information signals, and more specifically, the present invention relates to a discharge recording material in which a colored material layer and a metal vapor deposition layer are laminated on a base material. The present invention relates to a discharge recording material characterized in that the colored substance in the colored substance layer is a microcapsule with a coating thickness different for each colored substance. Discharge recording has features such as a simple recording mechanism, a fast recording response speed, and no need for development or fixing because primary color is developed.
For example, vapor-deposited recording paper (manufactured by Honshu Paper Industries Co., Ltd., trade name: Silvero) has a base material 1, as shown in FIG.
A colored layer 2 and a metal vapor deposition layer 3 are sequentially provided on the . The colored layer 2 is made of carbon black, dye, paint, and binder, and the metal vapor deposited layer 3 is melted and scattered by discharge breakdown to record images such as letters, figures, symbols, etc. Recording paper (manufactured by Honshu Paper Co., Ltd., trade name: Silverno RA type) with excellent heat resistance, light resistance, and moisture resistance has also been developed, and is being considered for various uses. However, since the above-mentioned conventional discharge recording paper has a monochromatic colored layer, the range of application is currently extremely limited despite having the above-mentioned excellent characteristics. An object of the present invention is to provide a novel discharge recording material that can perform multicolor recording using a discharge recording method and has a wide range of applications. Conventionally, discharge recording materials that produce two colors using a discharge recording method are known. These manufacturing methods include a method in which colored layers of different colors are laminated on a base material and then a metal vapor deposited layer is laminated, and a method in which colored substances of different colors are created in stripes on the base material and a metal vapor deposited layer is laminated. There is a way to do it. In the former method, in order for the colored substance serving as the upper layer to maintain the necessary color density, the layer must be approximately several microns thick;
As a result, the discharge breakdown voltage becomes high, the sharpness of coloring is poor, a large amount of printing sludge occurs, and multicolor development of three or more colors is practically impossible. On the other hand, the latter method has the drawback that it lacks printing flexibility and its range of application is extremely limited. The present inventors have determined that the breaking strength of microcapsules is determined by the multiplicative product of the coating thickness and the voltage applied during recording, and that the coating thickness is determined by the blending ratio of coating material and coloring substance during microcapsule production. Focusing on this, different colored substances are individually microencapsulated with different film thicknesses, and the resulting different colored substances and two or more types of microcapsules with different film thicknesses are blended in appropriate proportions and placed on a substrate. The discharge recording material of the present invention was completed by coating and further laminating a metal vapor deposited film. The discharge recording material of the present invention having the above structure is
Since two or more colored substances are microencapsulated with different film thicknesses, if the appropriate discharge breakdown voltage is increased continuously or stepwise, the capsules with the smallest film thickness will be destroyed one after another. I'm going to go. Therefore, by appropriately selecting the discharge breakdown voltage, multicolor development of two or more colors can be achieved extremely easily. According to the present invention, it is possible to perform multicolor recording at a discharge breakdown voltage of 20 to 100 V, and clear multicolor recording is possible without impairing print flexibility. Coloring substances used in the present invention include oxides,
Application materials such as sulfides, chromates, ferrocyanic compounds, dyes such as direct dyes, basic dyes, acid dyes, sulfur dyes, disperse dyes, vat dyes, naphthol dyes, etc., and any hydrophobic coloring substance. But it's okay. The most preferred coloring substances include chrome red, molybdenum red, molybdenum orange, and Seritrin orange R for red colors, Bourchien blue, ultramarine, and centrin first blue B for blue colors, and chrome green, sink green, and sink green for green colors. Centrin First Green 5B, yellow colors include sink yellow, Naples yellow, nickel titanium yellow, and other dyes or pigments. These dyes or application materials are commercially available and can be easily obtained. In order to actually produce the discharge recording material of the present invention, for example, a paint in which the colored substance is microencapsulated and coated by a complex coacervation method is applied onto a base material and dried to form a colored layer. After that, a metal vapor deposition layer may be provided by a conventional method. The encapsulated material is an insulator with a surface resistance of 10 ¹² Ωcm or more, and may generate discharge noise. In order to prevent this, conductive metal fine particles such as copper or silver may be appropriately added to the microcapsule suspension as a current conduction aid to improve the recording characteristics. Encapsulants are microparticles with an average particle size of several microns or less, and have the role of a roughening agent, and are usually used as roughening agents such as silica, aluminum hydroxide,
It has the characteristic that it does not require magnesium carbonate, titanium oxide, zinc oxide, barium sulfate, etc. The metal vapor deposited layer is generally made of aluminum, zinc, magnesium, etc., but when used in the present invention, zinc,
Aluminum is most preferable since the magnesium vapor deposited layer has extremely poor storage stability. For the microencapsulation method of the colored substance of the present invention, ordinary microencapsulation methods can be used as appropriate;
Microencapsulation by complex coacervation is the most preferred method. The complex coacervation method is a method in which two types of aqueous solutions, a polycation colloid and a polyanionic colloid, are mixed, interlaced, phase separated, and encapsulated. Gelatin is used as the polycation, and examples of the polyanion include gum arabic, alginate sorta, agar, carboxymethyl cellulose, polyvinyl methyl ether, maleic anhydride copolymer,
Although polyvinylbenzenesulfonic acid and the like can be used, gum arabic is most suitable. The breakdown voltage strength of the encapsulated material is determined by the ratio of the amount of the coating material made of polyanion and polycation to the colored substance that becomes the inclusion. If the encapsulated material is spherical, the film thickness is expressed by the following formula. r ₂ − r ₁ = [(Ww・dw/Wn・dn+1) ^1/3 −1] r ₁ , where r ₁ = radius of core material, r ₂ = radius of encapsulated material, Ww = weight of coating material, Wn = coloring The weight of the substance, dw = specific gravity of the coating material, dn = specific gravity of the coloring substance. The size of the encapsulated material is related to print quality and naturalness after vapor deposition, and it is desirable to adjust the size to about 25 μm or less, preferably about 10 μm or less in the encapsulation process. As mentioned above, since the discharge recording material of the present invention encapsulates the colored substance in microcapsules with different film thicknesses, the colored substance-containing microcapsules with different discharge breakdown strengths exist completely independently within the layer. A colored layer is formed. Moreover, since the capsule coating material has high insulating properties, electrical contact between the capsule and the deposited film is prevented, and a discharge recording material with high shelf life can be obtained. Next, the present invention will be explained in more detail with reference to Examples. Example Colored substance microencapsulated paints having the formulations shown in Tables 1 and 2 below were prepared.

[Table] 1% acetic acid and 5% Na ₂ CO ₃ were used to adjust the pH, and glyoxal was used as a curing agent.

[Table] 1% acetic acid and 5% Na ₂ CO ₃ were used to adjust the pH, and glyoxal was used as a curing agent. The thickness of the film of the microcapsules thus obtained was 1-1 and 2-1: approximately 1.40μ, respectively.
1-2 and 2-2: about 0.60μ, 1-3 and 2-
3: about 0.34μ, 1-4 and 2-4: about 0.24μ. Moreover, the average particle size of the encapsulated product was about 10μ. These microcapsule paints containing colored substances are combined and applied at a weight ratio of 50/50 to a thickness of 3 to 8 g/m ² on high-quality paper of 50 g/m ² to form a colored substance layer. A discharge recording material was created by vacuum-depositing aluminum on the material. This discharge recording material has an impedance of 51Ω, an applied voltage of 30V and 60V, an application time of 0.5 milliseconds, and a stylus pressure of 6g.
Discharge recording was performed under the following recording conditions. Table the results.
It is shown in conjunction with 3.

[Table] In sample Nos. 1, 2, 5 and 6, the film thickness of each microcapsule is about 1.40μ or about 0.60μ, so
When 30V is applied, both capsules are not destroyed and no color develops, but when 60V is applied, both capsules are destroyed and the orange and blue are mixed and colored green. or,
In sample Nos. 11, 12, 15 and 16, the film thickness of each microcapsule was about 0.34μ or about 0.24μ, so
Both capsules are destroyed by applying 30V and colored green. Therefore, in any of the above cases, it is not possible to separate and develop two colors. On the other hand, in samples No. 3, 4, 7, and 8, the film thickness of the blue capsule was about 0.34μ or about 0.24μ.
On the other hand, since the film thickness of the orange capsule is about 1.40μ or about 0.60μ, only the blue capsule is destroyed and colored blue in the 30V application section, and both capsules are destroyed in the 60V application section. Orange and blue are mixed and colored green, producing a clear two-color image of blue and green. Similarly, for samples No. 9, 10, 13 and 14, 30V
The application section is colored orange, and the 60V application section is colored green, resulting in a two-color image of orange and green. It goes without saying that in the above operation, a multicolor image of three or more colors can be formed by appropriately changing the discharge breakdown voltage, the film thickness and blending ratio of the microcapsules, the mixing ratio of the coloring substances, and the like. As is clear from the above results, the discharge recording material of the present invention is capable of developing multiple colors, and therefore has an extremely wide range of uses such as recording materials for facsimiles, registers, and various recorders.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing the structure of a conventional discharge recording paper, and FIG. 2 is a sectional view of the discharge recording paper of the present invention. 1... Base material, 2... Colored layer, 2'... Microencapsulated colored substance layer (○● indicates microcapsules containing different colored substances), 3... Metal vapor deposited layer.

Claims (1)

[Claims] 1. In a discharge recording material formed by laminating a colored substance layer and a metal vapor deposited layer on a base material, the colored substance in the colored substance layer is formed into a microcapsule with a film thickness different for each colored substance. The discharge recording material is characterized by: