JPS5812790A - Recording material for electric current sensitized transfer - Google Patents

Abstract

PURPOSE:To provide the titled material free from strength problems and capable of recording with a high resolution and a high density without using a special base layer, by a method wherein a double-layer construction consisting of a base layer and an ink layer is provided, and the surface resistivities of the layers are set in a specified relationship. CONSTITUTION:The surface resistivity of the base layer 11 is set to be 1X10<3>- 1X10<6>OMEGA while the surface resistivity rhos2 is set to be 1X10<2>-1X10<5>OMEGA, with the relationship of rhos1>rhos2. The base layer 11 is laminated with the ink layer 12 to provide strength for the recording material 1, and a resin used for the layer 11 must have a softening point of not lower than 150 deg.C, since an electric current is passed therein. A resin used for the ink layer 12 has a softening point of 50-150 deg.C, inclusive, and constitute a favorable heat transfer ink 7 together with coloring components 121.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a recording material for electrical transfer, and more particularly for printing with a noiseless typewriter and two electronic meters.

The present invention relates to a recording material for electrical transfer that is useful for printed records such as computer output or copies of electronic transmission records.

As electronic computers and facsimile machines have become increasingly sophisticated, printers, which serve as terminal devices, have also come to occupy an important position. This terminal device can be roughly divided into impact printers (mechanical printers) and non-impact printers, and the recording methods of the latter include (1) child photo printing, (2) thermal printing, and (3) radiation printing. (4) thermal transfer, (5) electrical transfer, etc. However, the former impact printer has a defect in that it cannot avoid the noise generated over the mm.

Some of the latter (non-impact printers) have the advantage of not producing noise, but have a number of problems. For example, electrophotography uses charging
The process is complicated, requiring five steps of exposure, development, transfer, and cleaning, and has disadvantages such as difficulty in obtaining high-quality transferred images in a timely manner, and miniaturization of the apparatus. In the heat-sensitive recording method, there are still problems with the storage stability of the heat-sensitive recording paper used therein, and the heat-sensitive recording paper itself has the disadvantage that it is processed paper and plain paper cannot be used. The discharge recording method is advantageous in that discharge transfer can be performed on plain paper, but there is a problem with it!
The drawback is that the destruction generates odors and combustion fumes.

In addition, since the thermal transfer method uses a thermal head, it is difficult to obtain high-density images. is achieved].

Similarly, /Nin Zect Glinter one type, but different from the above, energized transfer arrangement method C type transfer recording method)
can produce high-density images on plain paper and has a fast recording speed.
Furthermore, the device employed in this method also has the advantage of being miniaturized. For this reason, several proposals have been made regarding improvements to the IIE transfer paper (recording material for electrical transfer) used in this method, as well as further improvements to the eU method itself.

II) USP 2713822
Or, in USP 3,744,611, a three-layer structure of an insulating layer (or resistance layer)/conductive layer/ink layer is used as a current transfer paper, but this layer structure is complicated. In addition, in (H)% Publication No. 55-124 (No. 94, Japanese Patent Application Laid-open No. 53-7246, Percentage Publication No. 56-8276, Japanese Patent Publication No. 55-12393, etc.), all have an anisotropically conductive base layer. Alternatively, a two-layer conductive transfer paper with a metal dispersed conductive 1fdl conductive ink layer is described, but the anisotropically conductive base layer here is made of special materials and manufacturing methods. In addition, these energized transfer papers still have some problems in terms of performance.

For example, in the method described in (a) Japanese Patent Publication No. 55-12394, a method of orienting a ferromagnetic metal under a perpendicular magnetic field is adopted, so that a homogeneous anisotropically conductive base layer with a large area is formed. Please create it.

(b) In the method described in JP-A-53-7246, an anisotropically conductive base layer (metal dispersion side 1) is manufactured by dispersing metal powder in a binder. It is difficult to uniformly disperse the metal, and agglomerates form in some parts, creating a local short circuit, making it impossible to conduct electricity faithfully to the stylus, causing the Q-dot shape to collapse, and reducing the mowing force. (C) JP-A-56-8276 discloses an anisotropic conductive paste Rti in which a conductive material such as metal or carton is embedded in silicone rubber in a columnar manner in the direction of its entire thickness. At present, the resolution is limited to 4 lines/a < 250 μm at a pitch of 250 μm.Furthermore, the method described in Japanese Patent Publication No. 55-12393 (G) requires the creation of an anisotropically conductive base layer. Moreover, since conductive paper is used, the cost is high.
In addition, there are large variations in quality.

The present inventors (G) took all of these circumstances into consideration and proposed three advantages of the C1 current transfer recording arrangement (capable of high-density recording up to 16 lines/fence; The speed is fast, the stylus can do the marking and transfer, so the A position is 5 - small, and it can record on plain paper, etc.)
In order to eliminate the drawbacks of the conventional electrical transfer paper (C) while taking full advantage of this, we proposed a recording material for electrical transfer consisting of only one conductive transfer layer (R). However, with this single-layer recording material for electrical transfer (conductive ink), attempts to achieve high density result in a decrease in the strength of the ink, and it cannot be denied that there is a limit to increasing the density.

Further, as a result of research and consideration, the present inventors found that by combining a base layer and an ink layer with appropriate physical properties t, the above-mentioned
f) Special base layer (anisotropically conductive base layer) like P → No. 5: Recording is possible without using Xtlr'' It was discovered that high-resolution, high-density recording is not sufficient.The present invention was completed based on this knowledge.

Therefore, the object of the present invention is to solve the disadvantages of using a special base layer like the above-mentioned prior art - deformation of the dot shape due to variations in quality, and to solve the problem of reduced strength and using a special base layer using a special material. The object of the present invention is to provide a complete recording material for electrical transfer that eliminates the high cost caused by the manufacturing method. Another object of the present invention is to provide a recording material for electrical transfer that has a high sensitivity comparable to that of the single-layer ink sheet described above and also has good strength t.

That is, the recording material according to the present invention and the recording material for electrical transfer are placed one on top of the other, the return polarization is brought into contact with the recording material, and the recording magnetic pole wire is brought into contact with the surface of the recording material, and a voltage is applied to the recording material. 2. The recording material used in the continuous transfer recording method in which the ink is transferred onto the recording medium by energizing the recording material has a surface specific resistance value (ρ!1 (1) ) 1 x 10M~lXl0'Ω base layer, a coloring component, and a surface resistivity value (ρB (20l
Consisting of a multi-layer with an ink layer of Xl0” to lXl0IΩ,
And all the conditions of ρm (1) > 4g (2) are satisfied 't-1? It is a sign.

Hereinafter, the present invention will be explained in more detail based on the accompanying drawings. FIG. 1 is a diagram showing an outline of the current transfer recording method C method, FIG. 2 is a view of the M side of the recording material for continuous transfer according to the present invention, and FIG. 3 is a diagram showing the current transfer recording method actually performed. FIG. 4 is a diagram of a multi-stylus in which the recording needles are arranged in a staggered manner, and FIG. 5 is a diagram of a multi-stylus in which the recording needles are integrated with the return electrode. ing. 2. In the numbers attached to these drawings, 1 is the recording material for transfer, and 2 is the recording material f, which may be plain paper, resin sheet, cloth, or other tactile material.)
3 is the recording needle (recording electrode needle), 3'9 and f are the multi-stylus, 4, 4' and/or return path Ill poles, 5 is the recording applied voltage, and 6 (the ratio indicated by the arrow) is the recording current. ,7(
(represented by broken lines) are heat transfer ink transferred from recording material 1 to recording body 2, support rollers 8p and 9, 11
1 represents the base layer, 12 represents the ink layer, and 121 represents the coloring component. As shown in FIG. It represents a lever.

Δ As described above, the recording material for electrical transfer of the present invention is formed from a multilayer structure including the base layer 11 and the ink layer 12. Examples of resins constituting the base layer 11 include styrene resin, acrylic resin (methyl methacrylate-1, ethyl acrylate, n-butyl methacrylate, etc.), vinyl chloride resin (vinyl chloride-vinyl acetate copolymer, etc.), and styrene resin. , polycarbonate resin, polyester resin, polyazed resin, polyvinyl butyral resin, and the like.

However, since this base layer 11 is laminated on the ink 1-12 and has the role of providing full strength and conducting electricity to the recording material, the resin needs to have a softening point of 150°C or higher, and the surface of the base layer 11 The specific resistance value ρ5(1) is lX10
It needs to be in the range of 3 to lXl0'Ω. Softening point is 1
If a resin with a temperature lower than 50°C is used, the film-forming ability will be low, and even if the sheet is not strong enough, the heat generated during energization will soften the paste 11 or cause it to melt in the bath. becomes unable to fulfill its full role.

In addition, the surface specific resistance value of pace l-11 is I x 10
If it is lower than 8Ω, the direct current will flow laterally from the base layer directly under the polarization needle, and if it is higher than lXl0'Ω, the direct current will become a current, and if you try to record it, you will end up applying a high voltage. You will have to apply voltage.

On the other hand, examples of the resin C binder that constitutes the entire ink layer 12 include low softening point acrylic resins such as 2-ethylhexyfluor acrylate and lauryl methacrylate, and polyvinyl butyral resins having a low softening point C (low degree of polymerization). In addition to these resins, waxes such as niparaffin wax, polyethylene wax, and carnauba wax; oils and fats such as 772 oils; glycols such as polyethylene glycol and polypropylene glycol; It was recognized that the performance was considerably inferior compared to that used.

The ink layer 12 has the role of passing through the base layer 11 faithfully to the diameter and round shape of the needle, and at the same time melting with low energy and transferring to the recording medium 2. Therefore, the resin used there has a softening point of 50
The temperature must be between 150'C and 150'C. If the softening point is lower than 50°C, it will cause stains during transportation or during pressure contact, whereas if it is higher than 150°C, it will melt with low energy and will not form a good thermal transfer ink 7 together with the coloring component 121. . Surface specific resistance value ρ of the ink layer 12
(2) must be in the range of lXl0'' to 1x10'Ω, but if it is lower than 10θΩ, the current value per dot recording will be large, 100 mA or more even when IOV is applied, and simultaneous application recording with multiple styluses will be difficult. On the other hand, if it is higher than 100Ω, it becomes necessary to apply a high pressure of 300V or more in order to obtain the current density necessary for recording.

Further, a coloring component 121 is added and dispersed in the ink layer 12, and this coloring component (coloring pigment, coloring dye) 121
constitutes the heat transfer ink 7 together with a part of the resin (binder) existing around it.These coloring components 121 include carzen black (particularly furnace type carzen black, acetylene black, lamp black, etc.) In addition, examples of organic or inorganic color dyes/pigments include phthalocyanine, alkali blue, spirit black, benzidine yellow, fast red, crystal iolet, iron oxide, and cadium sulfide.

What are the physical properties of the recording material for electrical transfer of the present invention without using a support material? Since it is composed of a base layer 11 and an ink layer 12 which are different from each other, it is necessary that either the resin of the base layer 11 or the ink layer 12 or the resins of both layers have film-forming ability. According to the experiments conducted by the present inventors, it is preferable to use a polycarbonate resin having a softening point of 200°C or more as the resin that makes up the entire base layer 11, and the resin (binder) that makes up the ink layer 12 has a softening point of 80°C. More than 20
It has been found that the use of polyvinyl phthyral resins at temperatures below 0° C. is advantageous and that significantly better results can be obtained by doing so. Of course, it may be considered that these resins may be appropriately blended with the above-mentioned resins or binders.

In fact, when preparing the recording material of the present invention, the surface specific resistance value f of each of the pace layer 11 and the ink layer 12 is
Various organic or inorganic conductive materials are added to each of the layers in appropriate amounts in order to meet the above specified ranges. Typical examples of such conductive materials include conductive carzen black (J, which is also suitable as the coloring component 121), ordinary carzen black, graphite, and oil black.

However, what should be noted about the relationship between the surface resistivity values of the base layer 11 and the ink layer 12 is that the surface resistivity value ρ1(1) of the base layer 11 is that of the ink Ii #12 ρI(
2) is always larger than (ρ8(1) >4m (2)
) 1! This is something we must keep up with.

If this relationship does not hold, conduct energized transfer alignment 13- It will no longer be possible.

For both the base layer 11 and the ink layer 12, various plasticizers may be used in combination as flexibility-imparting substances, if necessary. Such 7,1'' plasticizers include phthalate esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphate esters (phosphor triethyl, tricresyl phosphate, triphenyl phosphate, etc.), fatty acid esters C dizotyl sepacate, etc. J, glycol type (polyethylene glycol, polypropylene glycol, triethylene glycol f!
g), glycol ester type C diethylene glycol dibenzoate) rj g).

Wax-based (animal and vegetable waxes, mineral waxes, etc.)
, fatty acid metal #1 (zinc stearate, magnesium oleate, etc.).

The appropriate amount of these flexibility-imparting substances added is in the range of 5 to 200 parts by weight per 100 parts by weight of the resin (binder component).

Among these, the base layer 11 has a film-forming ability, i(I
It is more desirable to use J carbonate resin and add a small amount of 14-polyethylene glycol (OT flexibility imparting substance) to this resin because it gives good results.

As a means for producing the recording material of the present invention, first, a resin having a softening point of at least 150°C or higher (a polycarbonate resin, a conductive material, and a glass plate dissolved or dispersed in a suitable solvent) is first used. , apply it on a metal plate, etc. and dry it to form a base layer with a thickness of 5 to 30 μm,
The above four resins have a softening point of at least 50 to 150°C (
Preferably, a mixture of J containing polyvinyl butyral resin as a main component, a conductive material, and a coloring component, all dissolved or dispersed in a suitable solution, is coated and dried to form an entire ink layer with a thickness of 0.5 to 10' μm. It is sufficient to remove the stripper from all of these glass plates, metal plates, etc. Here, the amount of the colored portion in the total weight of the ink layer 12 is suitably about 5 to 30% by weight. Examples of the solvent include tetrahydrofuran, 1,2-dichloroethane, methyl ethyl ketone, toluene, petroleum ether, ethyl acetate, dimethylformamide, and methanol.

The recording material for electrical transfer produced in this way is used for electrical transfer recording in Figure 1. Similar to the conventional method shown above, the ink layer 12 (+- is brought into close contact with the recording body 2,
The return path of the base layer 11i is connected and disconnected, and the current signal from the recording mark IJ voltage 5 is passed through the recording needle 3 to the pace 1-11 of the base layer 11i. Recording material 11
When this energization reaches l and c, the current density directly below the recording needle is maximum, and since the return path 1 pole 4 has a larger contact area than the recording needle 3, the current spreads as it approaches the return path electrode 4. Current density becomes smaller. The Joule heat generated by this energization softens or melts the recording material 2-
This metastasizes. Here, an image corresponding to the spill current signal is formed on the recording medium 2.

The conditions of energization, number of strokes, etc. greatly affect the image type JJ5C, but in general, 1O~200V, energization time 05~2
m (8), and the number of set meal lines is about 3 to 20 pieces/pan. The recording material 1 and the recording body 2 are brought into complete contact with each other. In the recording material VX of the present invention, even when a relatively strong current is applied, all the coloring components 121 are not transferred onto the recording medium 2, so that it can be used repeatedly.

As described above, by using the recording material of the present invention, a high quality image can be quickly formed on a recording medium such as plain paper with low recording energy. A detailed study of why high-density images can be obtained at a high velocity by using this recording material has not been done, but the roles of the base layer 11 and the layer 12 are completely separated. In particular, this is thought to be due to the fact that the material of the recording material can be selected from a wide range, and the total thickness of the recording material can be made thinner.

Furthermore, it is understood that the base layer 11 of the recording material of the present invention is completely different in structure from the conventional special and expensive anisotropic conductive paste layer; Since a uniformly dispersed layer containing a smaller proportion than the Zenblack gold ink layer 12 is sufficient, as long as the surface resistivity value 2 and the thickness are kept within an appropriate range 2,
17- Since it is more uniform than a special anisotropic conductive paste layer, it has the effect of allowing high-quality dot recording that is more faithful to the shape of the recording needle.

Next, examples and comparative examples will be shown. Note that all parts are parts by weight.

Example 1 Polycarbonate resin [softening point 230°C]
95 part dedicated carbon black
5 parts Tetrahydrofuran 9
A mixture consisting of 0.00 parts was dispersed for 5 hours in an I-ru, and then it was spread on a glass substrate using a blade with a gap of 150 μm.
Apply this coating and dry for 1 minute at 60℃ to determine the surface specific resistance value ρ.
1 (1) is 50 Ω and the thickness is about 8 μm Pace I! f'
c Completed Y3. Furthermore, on this paste layer, a mixture of the following formulation was dispersed for 5 hours using a ball spatula, and then applied using a blade with a gap of 100 μm, dried at 60°C for 1 minute, and the surface resistivity value ρB (2) was obtained. is 30Ω and the thickness is F
J4μm ink 1*gold formed. The laminated base layer and ink layer were integrated and peeled off from the glass substrate to prepare a recording material for electrical transfer.

Polyvinyl butyral resin (softening point 80″C)
70! conductive carbon black
30 parts ethyl alcohol
11001B Example 2 The polycarbonate resin of the base layer had a total softening point of 210°C, the V content of the conductive carbon black was 7% by weight, and the polyvinyl butyral resin of the ink layer had a total softening point of 150°C. A recording material for electrical transfer was prepared in exactly the same manner as in Example 1, except that the total content of evaporative carzen black was 40% (however, the thickness of the base layer was approximately 101 tm, and ρ5(1) = 20). KΩ; The thickness of the ink layer is about 4 μm1ρm(2)=]5Ω.

Example 3 The polycarbonate resin of the base layer has a total softening point of 210°C, the conductive cardan black content is 5% by weight, the high resistance carbon black content is 5% by weight, and the polyvinyl butyral resin of the ink layer is made of polyvinyl butyral resin. A recording material for electrical transfer was prepared in exactly the same manner as in Example 1, except that the material had a softening point of 200° C., and the 1130i1i weight percent containing conductive carzen black was combined with the 1150 weight percent high resistance carzeno black (with the exception that , the thickness of the base layer is about 10.!1m,
ρI (1) = 120Ω: Ink layer (r) thickness is 2
ti m, ρm (2) = 30 KΩ.

Comparative example 1 Polycarbonate cod? Nate Nanpo (softening point 230℃1
Part 90 Dedicated Carzen Black
10 parts tetrahydrofuran
A mixture consisting of 900 parts of gold was dispersed for 5 hours in a Knoll mill. It was applied onto a glass substrate using a blade with a gap of 150 μm, dried at 60°C for 1 minute, and then peeled off. A 12 μm single-layer recording material for electrical transfer (conductive ink sheet) was prepared.

Comparative Example 2 An ink layer similar to that of Example 2 was provided on an anisotropically conductive base material to prepare a recording material for electrical transfer. Na3,
The anisotropic conductive paste layer here contains 50% by weight of 1C copper powder in polyvinyl chloride resin with a softening point of 220°C, and the surface specific resistance (ρml is calculated as follows: ) (V=10VJ.

12 m = 0 (VA = 20 v) It has the performance advantage of being immediately shorted by %.

Comparative Example 3 Example 11 A mixture of the following formulation was dispersed in a ball for 5 hours at a gap of 10.
Apply with a 0 μm blade, dry at 60°C for 1 minute,
Ink no. with a thickness of about 4 μm (ρg(2) = 30Ω)
? A recording sheet 41 for electrical transfer was formed.

Paraffin wax (melting point 60℃J'
70dJl conductive carbon black
30 parts cyclohexane
1100 copies of these 64n [recording materials? , As shown in Fig. 3, in the cases of C Examples 1 to 3 and Comparative Examples 2 to 3, the ink layer and the plain paper were placed in close contact with plain paper. The edge polarization needle - all multi-stylus used, its diameter is 130 μm21 - and the distance between adjacent recording needles is 1 - is brought into contact with the base layer, and between the multi-stylus and the return path' electrode, a thick pressure is applied ( In Comparative Example 1, the lower surface of the recording material was in close contact with the plain paper and the upper surface was in contact with the multi-stylus, and the application λ was applied.
The results obtained on plain paper were also rated as n-scanning images. At the same time, the recording material was conveyed through the production facility shown in FIG. 3, and the strength of the needle sheet was evaluated, including the occurrence of tears and wrinkles. Results table-1
It was 2nd place.

Margin below 22-

[Brief explanation of the drawing]

Figure 1 is a diagram showing an overview of the IT transfer recording method, Figure 2
The figure is a sectional view of a recording material for electrical transfer according to the present invention, FIG. 3 is a schematic perspective view of an example of a state in which 1iIc transfer recording is actually performed, and FIG. 4 is an enlarged view of an example of a multi-stylus. , FIG. 5 is an enlarged view of an example of a multi-stylus in which the recording needle is integrated with the return electrode. l...Recording material for transfer transfer 2...Recording body 3...
-Recording electrode needle 4...Return electrode 5...Recording applied voltage 8, 9...Skinned roller 11...Pace layer 12
... Ink layer 121 ... Coloring component fan 1 Figure fan 3 Figure 463 4th evil

Claims (1)

[Claims] 1. Recording bodies and recording materials for electrical transfer? Place them one on top of the other,
This is used in the current transfer recording method, in which the return electrode is brought into contact with the surface of the recording material, and the recording electrode wire is brought into contact with the surface of the recording material, and the recording material is energized by applying a full voltage to transfer ink onto the recording medium. Recording material has a softening point of 150℃
Surface specific resistance value (ρ1(1)
Surface specific resistance value (pmf2) JIXIO with a pace m of J I
1 &: A recording material for electrical transfer characterized by comprising a multilayer ink layer with an ink layer of ~I x 1.01 Ω and satisfying the condition ρg (1) > ρ1 (2).