JPS5839079B2 - energized recorder - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to electricity recording, and more specifically,
The present invention relates to a current-carrying recording medium used in a recording method in which a light-transmitting portion is formed in a current-carrying portion by energizing the light-impermeable recording medium.

Conventionally, for the purpose of easily and inexpensively duplicating a large amount of images, an original with a difference in light transmittance between the image and non-image areas was used, and the duplication was performed on a photosensitive sheet such as a diazo method. method is the most commonly used.

Further, there are many opportunities to use sheets having images based on differences in light transmittance in the field of information transmission, such as the spread of overhead projectors.

However, in general, most of the information sources to be reproduced or transmitted do not have a difference in light transmittance sufficient to be used for transmission reproduction, and different information is retained on both sides of the supporting substrate. In many cases, it is impossible to copy only one side of the information through light transmission, and it is necessary to separate the information.

To convert an information source into a master for transparent replication,
Although there are handwritten transfers to tracing paper, matte films, etc., these methods are not only uneconomical but also have many problems, such as the inability to faithfully transfer photographs, figures, etc.

An easy way to do this is to use tracing paper, film, thin paper, etc. in a dry plain paper copying machine, but due to the structure of the machine, it is difficult to pass sheets with significantly different surface properties, stiffness, etc. This is not commonly done as it can easily cause mechanical failure.

In addition, there is a second original paper that uses tracing paper as a supporting base for the wet copying method using zinc oxide, but in order to generate an electrostatic image, zinc oxide pigment must be applied to a thickness of 20 to 30 μm. The light transmission is not satisfactory.

The second original pattern using an organic semiconductor instead of zinc oxide has good light transmittance, but has problems in that it requires a developing process and is expensive.

In addition, methods such as silver salt are good in terms of transparency and resolution, but are complicated to operate, expensive, and
It is not common because it is difficult to obtain a positive diazo copy from a positive original.

The above-mentioned points are the reason why it is desired to develop a method for easily and immediately creating a master for light transmission reproduction from all kinds of sheet originals.

On the other hand, the need to immediately record electrical signals as images is increasing year by year with the development of facsimiles, non-impact printers, recorders, and the like.

In response to such requirements, so-called discharge breakdown records, electrolytic records, etc. have been used.

There are inconveniences in discharge breakdown recording, such as odorous perforation gas, and in electrolysis recording, there are inherent problems because it is a wet method. As such, it is not possible to record a large number of sheets.

However, the demand for making large numbers of copies of this information is increasing year by year, and there is a need for a simple, quick, and precise method for reproducing and copying original images. It would be highly desirable for recorded images such as these to serve as the second original for multiple copies.

The present invention aims to provide a current-carrying recording medium for use in effective current-carrying recording and image duplication methods that eliminates the various drawbacks seen in conventional methods and has new advantages. .

・In other words, the object of the present invention is to immediately, dryly, and directly produce an odorless and odorless recording layer by simply energizing it with a voltage applied stylus or electron beam irradiation to a very simply constructed recording layer. To provide a current-carrying recording material that forms a light-transmitting part in a current-carrying part in a favorable state of dust, and which is used as a master for immediately, simply, quickly, and inexpensively duplicating the recording sheet into a photosensitive sheet. .

The present invention will be described in detail below with reference to the drawings.The current-carrying recording medium according to the present invention comprises a thin metal layer and a zeolite or zeolite-like compound on a transparent or semitransparent support. A recording layer is provided, which is formed by stacking layers containing at least one kind of solid electrolyte and a binder. Specifically, the recording layer has a structure as shown in the attached FIG. 1.

In the figure, 1 is any transparent or translucent support such as thin wood-free paper with high DP resolution, stretched polypropylene film, polyester film, cellophane, glassine, tracing paper, resin-impregnated paper, etc., 2 is aluminum, silver,
Metals such as zinc, copper, nickel, chromium, tungsten, etc. are deposited by sputtering, vacuum deposition, or other methods.
000X, preferably a thin layer deposited with a film thickness of about 5 ooA, 3 being at least one of a zeolite-like compound, a solid electrolyte, and a binder, also described in detail below. a layer containing at least one type of agent;
The above layers 2 and 3 constitute a recording layer.

In addition, 4 is a stein 5 used for energizing the recording layer.
is an electric circuit, and 6 is a return electrode.

It should be noted that the illustrated method of installing the return path electrodes is a single row according to the present invention, and is not limited to this method.

By the way, what should be noted in the present invention is that when electricity is applied, the thin metal layer directly under the stylus 4 immediately disappears in a very sharp shape, as shown in FIG.

In the figure, 7 indicates a portion where the thin metal layer has disappeared due to energization.

Moreover, the recording layer and the conductive layer are damaged by the generation of sparks, as seen when electricity is applied directly to a recording layer made of a combination of discharge destruction paper and a general semiconductor material and a binder, or to a thin metal film. Instead of being repelled and perforated in an irregular shape, the recording layer on top of the thin metal layer is not perforated or roughened, and only the thin metal layer responds to electrical signals. It has a very sharp shape and disappears.

The reason for this phenomenon will be explained in detail below.

That is, the stylus is in contact with the layer 3 composed of at least one of zeolite, zeolite-like compound, and solid electrolyte, and at least one of the binders described below (preferably organic polymer electrolyte type binder). When a negative voltage is applied to 4, the cations in the electrolyte, which are charge carriers in the recording layer, move toward the stylus, while the hydroxyl groups generated by dissociation of the water contained move toward the thin metal layer.

However, the hydroxyl groups that have reached the surface of the thin metal layer are thought to cover the surface of the thin metal layer or react with the metal, forming a barrier layer that is thinner than the thin metal layer and has high electrical resistance.

The extremely thin barrier layer is destroyed one after another by repeated tiny sparks that are difficult to observe from outside the recording layer due to the energy generated by the potential difference between the stylus and the thin metal layer.

Since the thermal energy of this minute spark concentrates on the thin metal layer, it is thought that only the thin metal layer is effectively eliminated without damaging the upper layer 3 at all.

Therefore, no odor, dust, etc. are generated during recording.

However, a thin layer of 5-10 μm consisting of zeolite, zeolite-like compound, solid electrolyte, and a large amount of binder is not originally very large and can only achieve high whiteness when coated on a thin metal layer. As shown, the portion where the thin metal layer disappears due to energization forms a sharp light-transmitting portion, in contrast to the extremely high opacity of the non-energized portion.

It goes without saying that the light-transmitting areas present in the pure white opaque areas formed in this way have sufficient contrast as reflective images, so they can also be used as ordinary recording paper. The recording paper constructed in this way has a light transmittance of 0 in the non-current-carrying part, but a light transmittance of 60 to 70 in the conductive part. When a photosensitive sheet such as a photographic photosensitive resin is brought into close contact with an electrically sensitive sheet and exposed to light from the electrically sensitive sheet side, the parts corresponding to the energized parts are regenerated on the photosensitive sheet, making duplication very easy. .

Devices for energizing electrically sensitive sheets, such as electric mimeograph machines, facsimile receivers, printer recorders, etc. By electrically reversing the electrical signals corresponding to the black and white levels of the original, it is possible to create a negative or a negative from the same original. Since you can create any positive second original, you can always
It is possible to obtain a positive final image.

This light transmittance contrast is sufficient for the purpose of ordinary diazo copying, etc., but if you want to further increase the contrast, it is necessary to add a layer in the layer 3 that softens or melts at a low temperature to cause the light scattering of the recording layer itself. paraffin, softening point 5
Phenols having a temperature of about 0 to 180° C. and having low crystallinity, low polymers thereof, and resins may be pulverized and mixed.

Furthermore, when Layer 3 of the recording medium is washed with water after being energized, a metal pattern sheet is obtained in which a mirror-like thin metal layer remains in the non-energized areas and the transparent support base is exposed in a very sharp shape in the energized areas. .

If this is lined up, use Mylar film as a support base.
-4 The light transmittance of the energized part is 95 to 100%, and the light transmittance of the non-energized part is 0 to 2%, so it is possible to obtain a sheet with a high transmittance contrast and a very sharp image. It can also be used as a trap pen.

The image reproduction of this metal pattern is extremely faithful to the original,
Since even minute halftone dots can be reproduced, the conventional method of creating metal pattern sheets using the etchlang method using harmful chemicals can be replaced with a simpler method.

In other words, by utilizing the difference in hydrophilicity between the supporting substrate and the thin metal layer, it can be used to create masters for offset printing, electrical wiring materials such as printed circuit boards for electrical wiring, or decorative materials such as labels that utilize metal mirror patterns. Can be used as a metal pattern sheet.

Here, the materials constituting the illustrated example 3 will be described in more detail.

First, the compound containing 6-water used in the present invention is:
It is defined as having the following items:

■ The compound has a 1' gap in its structure, in which loosely bound water (hereinafter commonly referred to as 6 water) is present.
deliquescence, which is caused by sodium chloride, etc., even when it contains enough water in its spaces.
There is no stickiness seen in efflorescence, and the surface remains apparently dry.

(2) Even if the water contained in the compound is completely removed by means such as heating or reduced pressure, its crystal structure will not be destroyed.

(6) The compound from which water has been completely removed immediately re-adsorbs water even in low humidity conditions and immediately returns to its original saturated state.

(2) Water coexists with various ions contained in the compound, thereby exhibiting good electrical conductivity.

As mentioned above, this compound exhibits very characteristic physical properties, and the present invention focuses on and applies these physical properties.

That is, it has been found that a system in which the compound is uniformly dispersed in a medium also exhibits the characteristic physical properties described above.

The list of compounds that can be applied to the present invention is as follows.

First, there are various condensed acids, of which natural zeolite minerals are representative.

Natural zeolite mineral is called aluminosilicate (M2
+, 2M+)C-A1203・m5iO2・nH2O(
3! m! 10).

M2+. M+ generates divalent and monovalent metal ions, respectively, but most of them are Ca2+ and Na1→1
→1 +・ contains Sr pBa #K and can be exchanged with other cations.

These zeolite minerals have unique ``gaps'' in their 93-dimensional framework structure, and exchangeable cations are located in the ``gaps'' along with water molecules.

In addition to water, other common solvents can also be adsorbed in the gaps, but the more polar they are, the more selectively they can be adsorbed.

There are also many synthetic zeolites that have a three-dimensional framework structure similar to natural zeolites and have the same basic properties as natural zeolites.

Furthermore, there are natural and synthetic minerals that have the same basic properties as zeolite minerals, that is, they have a gap and their crystal structure does not change during the desorption phenomenon of water molecules, but their chemical composition is completely different from that of zeolite minerals. It exists as a product.

This is called a zeolite-like mineral and can be applied to the present invention.

The zeolite minerals used in the present invention can be structurally classified into the following six types, both natural and synthetic.

Any of the above-mentioned compounds can be applied to the present invention, but it is preferable that the compound has a large "open space" volume, has a large water content, and therefore exhibits a good amount of current flow.

Hollandite, β-spodumene, and cuprous halides-copper halides having structures such as halogenated N,N'-dialkyl-triethylenediamine, cuprous chloride monochloride N-alkyl-hexamolenetetramine, etc. Organic copper halide, soda silicate glass such as Pyrex, and general formula MAg4■3. Here M is Rb+,
ni +, NH1'''Jr9 (Z A g2 Ss Ag
25es Ag2 Te eβ-Ag3sipα-Ag
3S Engineering, Ag6E.

A silver compound having a structure such as WO4 and α-CuBr eα
-Cu S e p ct-Cu 2 Hg I 6 etc. It is a water-insoluble ionic crystalline, oxide electrolyte, etc. in which movement of ions such as silver ions, oxygen ions, alkali ions, protons, etc. brings about conductivity.

Preferably, the material exhibits conductivity of 10 Ω crn or higher near room temperature and has a white or pale color.

Binders used in the present invention include gelatin, casein, gum arabic, shellac, starch and its decomposition products or derivatives, natural polymers such as alginic acid and its derivatives, cellulose nitrate, and cellulose such as carboxymethyl cellulose. derivatives, semi-synthetic polymers such as natural rubber plastics such as chlorinated rubber and cyclized rubber, polyisobutylene, polystyrene, terpene resins, polyacrylic acid, polyacrylic ester, polymethacrylic ester, polyacrylonitrile, Polyacrylamide, polyvinyl acetate, polyvinyl alcohol, polyvinylpyrrolidone, polyacetal resin, polyvinyl chloride, polyvinylpyridine, polyvinylcarbazole, polybutadiene, polystyrene-butadiene, butyl rubber, polyoxymethylene, polyethyleneimine, polyethylene hydrochloride, poly( Polymerizable synthetic polymers such as 2-acryloxyethyldimethylsulfonium chloride), phenolic resins, amino resins, toluene resins, alkyd'fljEL unsaturated polyester resins, allyl resins, polycarbonates, polyamide resins, polyether resins, silicone resins, Examples of the present invention include condensation polymerization type synthetic polymers such as furan resin and thiol rubber, addition polymerization type resins such as polyurethane, polyurea, and epoxy resins, and poly(methyl vinyl ether/maleic acid) noalkyl monoester. Preferred examples include &L carboxymethyl cellulose, sodium alginate derivatives, polyac IJ/L/acid derivatives cation-modified starches, and high polymers having hydrophilic polar groups such as alkyl monoesters of poly(methyl vinyl ether/L//maleic acid). Molecular electrolyte type binder has good binding power.

Conductive polymers such as quaternary ammonium salts fall within the scope of this binder, but they have problems such as odor during recording and corrosion of thin metal layers.

More preferably, a binder of a type that has a low reactivity with metals having a polar group and does not tend to generate metal salts and color the recording layer when energized is preferable.

- The above two active ingredients of the present invention, namely zeolite, zeolite-like compound, solid electrolyte type P and binder B are P
/H, 5/1 to 15/1, particularly preferably 7/1
Mixed in a ratio of ~10/1 and deposited on the supporting substrate 30~5
00711fi/rr? , preferably 100-200
■ On top of the metal thin layer provided at a ratio of /-, an additional coating thickness of 5~
It is formed as a coating film by any method with a thickness of 20μ, particularly preferably 8±2μ.

The present invention will be explained in more detail below based on Examples.

Example 1 3AW molecular sieves 50 r manufactured by Showa Union ■
Polyacrylic acid sole (Toagosei Chemical Industry Co., Ltd. Aron 2
Add 0L) 201ii' and mix well, then add 50μ of the paint.
Aluminum is applied to Mylar film by vacuum evaporation method.
00ml/rr? Use a Mayer bar to coat the base to a thickness of 6 to 8μ.
It was dried with warm air around ℃.

The electrically sensitive recording paper thus produced has a very high degree of whiteness and has stable quality with no economical changes.

. Toshafax 5H-600 manufactured by Tokyo Aircraft Instrument ■
was modified to apply an applied voltage of -150 to -200 V and a constant current control value of 25 to 30 mA to the recording layer through a tungsten stylus.

The scanning speed of the stylus is 0.7 to 1.5 m/sec,
Half of the manuscript was recorded as positive, and the other half was recorded by inverting the electric signal using a negative/positive changeover switch installed in the Tosha fax machine.

A high-resolution recording surface that is extremely faithful to the original was obtained in completely odorless, smokeless, and dustless conditions.

In the front half of the recorded image, a negative image in which one image area was transparent was obtained, and in the rear half, a positive image in which the background was transparent was obtained.

This recorded image has light reflection contrast as a visible image, but it also has transparent parts 60 for transmitted light.
%% Opaque area has a transparency of 0%, so if you expose and develop with transmitted light with the diazo copy paper facing down, the front half of the white area where the area is clearly cut out will be a negative, and the rear half will be a positive. A beautiful diazocopy of the image was obtained.

Example 2 The same method as in Example 1 was carried out using the following zeolite, zeolite-like compound, and solid electrolyte instead of the 3A type molecular sieves, and the results shown in Table 1 were obtained.

Example 3 When the same method as in Example 1 was carried out using the following binder instead of polyacrylic acid Sogoo, the results shown in Table 2 were obtained.

Example 4 Zeolum (13X type combined zeolite) 402 from Tekkosha ■
' and methanol 601% 12 tons of Gantret ES-425 was added to the slurry dispersed in a 601% ball bottle for one day.
' If/lr? Apply at a film thickness of .

In the same manner as shown in Example 1, negative inversion recording is performed on the entire surface, that is, the background is used as the current-carrying portion.

The recording layer is then washed with water, and when rinsed away, a metal pattern is created that is extremely faithful to the original image.

This has the light transmittance of the metal button part Oφ and the bank ground 95.

When this was used as a trap pen in an overhead projector, a screen with extremely high resolution was obtained.

Implementation row 5 A facsimile image of the electric shock recording paper made in the same manner as in Example 4 is received and recorded using a Toko fax machine manufactured by Tokyo Aviation Keiki.

This recorded image can be used as it is as a recording medium having a visible image, but if duplication is required, Example 1. However, when a larger number of copies are required, the recording layer can be washed away by washing with water.
By treating it with etching solution and passing it through a baby offset rotary press, we were able to make approximately 500 beautiful copies at even lower cost.

This is an extremely convenient method when distributing information from a remote location to a large number of receiving areas.

[Brief explanation of drawings]

FIGS. 1 and 2 are explanatory diagrams schematically showing an example of the current-carrying recording body of the present invention. DESCRIPTION OF SYMBOLS 1... Light-transmitting support body, 2... Metal thin layer, 3...
A layer comprising at least one type selected from a compound containing water, a solid electrolyte, and a binder. 4... Stylus, 5... Electric circuit, 6... Return path electrode, 7... Metal thin layer disappearance site.

Claims (1)

[Claims] 1 A thin metal layer is provided on a light-transparent support, and a composition comprising at least one of a compound or a solid electrolyte and a binder is laminated on top of the thin metal layer. Characteristic energized recording material.