JPS5833497A - Current passing transfer recording material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a recording material for electrical transfer, and more specifically, it is useful for printing on noiseless typewriters, electronic meters, J1 machines, computer outputs, and in some cases, printing records for copying electronic transmissions. The present invention relates to a recording material for electrical transfer.

As electronic computers and facsimile machines gradually become more sophisticated, printers, which serve as their terminal devices, also come to occupy the position of high cost. This terminal device can be roughly divided into impact printers (mechanical printers)
The recording methods of the latter are (5) electrophotography, (2) thermal recording, and (2) thermal recording.
3) discharge recording, (4) heat-sensitive fr-= (5) current transfer, etc. are known. However, the former impact printer has a mechanical defect in that it cannot avoid the noise it generates.

On the other hand, the recording method used in the rear # (horn impact printer) is advantageous in that it does not generate noise, but it has various problems.

In other words, the electrophotographic method requires 5 steps: obi-sashimi, shoyuan, #4m, transfer, and cleaning, making the process complicated, as well as the reliability of having a high-quality transcriptionist available at all times, and the miniaturization of the equipment. has its drawbacks.

The heat-sensitive recording method still has problems with the storage stability of the heat-sensitive recording paper used therein, and also has the disadvantage that the heat-sensitive recording paper itself is processed paper and plain paper cannot be used. The discharge recording method is advantageous in that discharge transfer to plain paper is very easy, but it has the disadvantage that odor and burnt residue are generated due to discharge breakdown. However, since the thermal transfer method uses a thermal head, it is difficult to obtain high-density full images.
The recording speed is slow (the maximum is about a parrot), and the recording speed is slow (
There are disadvantages such as the sea/dot angle is the limit).

Even for the same non-impact printer method, the number above is 14, and the current transfer method (current transfer recording method) is 14.
A high-density image can be obtained once the IR-sheet is passed through.

It has the advantage that the recording speed is fast, and the equipment used in this method can be made compact. For this reason, several proposals have been made regarding the current transfer paper (recording material for current transfer) used in this method and further improvements to the method.

(1) As a type (electrification #% transfer method) in which the ink is heat-conducted by energizing the base l-, USP 2713822 and USP 374
4611 uses an insulating layer (or resistance +1
) / 4 m + - / ink 1 - 3 + - m iv is used, but this layer structure is complicated. As for this type of paper, Japanese Patent Application Laid-Open No. 54-58511 uses an electric transfer paper having a two-layer interpolation.

The M construction of this current transfer paper involves considerable difficulty. (11) Regarding ink 1 - of the type in which electricity is applied to itself (current transfer method), there are various publications such as JP-A-49-38629, JP-A-53-7246, and JP-A-58-8276. conductive ink on conductive paste)
An electrically conductive transfer paper with a 21-structure is described, but the anisotropic conductive paste here is made using special materials and genetics, so the cost is high! Moreover, these electrically conductive transfer papers still have some problems in terms of performance.

For example, (a) the method described in JP-A-49-38629 adopts a method of blending ferromagnetic gold fIY under a perpendicular magnetic field, so that a homogeneous anisotropic conductive paste with a large area is produced. It's difficult to create. (a) Japanese Patent Publication No. 53-724
In the method described in Publication No. 6, an anisotropic conductive paste is created by dividing the metal powder into a binder, but the uniform fraction of the metal at this time is irregular and aggregates are formed in some parts. A short circuit occurs partially, making it impossible to conduct electricity faithfully to the stylus, causing the dot shape to become distorted and reducing resolution. We have proposed an anisotropically conductive paste in which a conductive material 8 such as carbon is buried in a columnar manner in the thickness direction, but this currently has only 2
The first prize is that the decomposition limit is 4 pieces per piece at a pitch of 50 μm.

In any case, in the case of (1) above, the thermal effect increases because the heat is indirectly conducted to the ink layer.

Also, defects such as dot quality finishing due to thermal diffusion? Furthermore, in the above (11), since the anisotropic conductive pace is a requirement for #l formation, it has disadvantages in terms of employment, and also has the disadvantage that t
P! It has drawbacks such as high cost due to the special materials and manufacturing methods involved.

The present inventors took these circumstances into consideration.

Advantages of the current transfer recording method (16 lines/tm <ra^! degree recording is 0.5 m6.
c/dot (The recording speed K is fast up to 100%, the Sat is small because it can transfer fjLm only with the stylus, and it can record on plain paper, etc.). Recording material for transfer (electrified transfer paper)
In order to overcome the disadvantages of yt's printing, we have already proposed a recording material for electrical transfer consisting of only one layer of conductive transfer 1. However, when trying to achieve a high sensitivity fY with this single-layer electrical transfer recording material (conductive ink sheet), does the strength of the ink sheet decrease? However, it cannot be denied that there are limits to increasing sensitivity.

Further, the present inventors have conducted research and examination.

By combining pace j- and ink t- with appropriate physical properties, high It has been found that high-density recording with S image power is not sufficient.

The present invention has been completely revised based on this knowledge.

Therefore, one object of the present invention is to solve the disadvantages of using a special base layer Y as in the above-mentioned prior art - distortion of the dot shape due to variations in quality, decrease in mechanical strength, and high cost due to special manufacturing methods using special materials. An object of the present invention is to provide a recording material Y for electrical transfer that eliminates the problems of -. Another object of the invention is.

It is an object of the present invention to provide a recording material for electric transfer that has further improved next gradation properties and high sensitivity 1f' than the ink sheet having the one-shot structure shown in #, and also has a good strong f'Y.

That is, in the present invention, a recording medium and a recording material for electrical transfer are placed one on top of the other, a return electrode is brought into contact with the recording material, and a recording electrode needle r is brought into contact with the surface of the recording material, and a voltage r is applied to the recording material. The recording material used in the current transfer recording method in which dandruff is transferred onto the recording medium by applying electricity is cellulose acetate and carmen blank with an acetylation degree of 45 or more.
A base layer having a structure of 1 = 1 and a melting point or softening point of 50
~150°C binder JBI and curl blank r
It is characterized in that it consists of a main layer and a secondary ink 1-, and the electrical resistance value of these layers is lower in the ink layer than in the base layer.

Hereinafter, the button of the present invention will be explained in more detail based on the accompanying drawings. Figure 1 shows the conventional anisotropic conductive paste #11'
Outline of recording using the recording material XLR for electrical transfer, which is composed of conductive ink I@l 12' and conductive ink I@l 12';
FIG. 2 is a diagram showing an overview of recording using the recording material IY for electrical transfer according to the present invention, and FIG.
Diagram showing the current flowing through the au electrode and current density K
(J)′lk: Represented graph, #! FIG. 4 is a cut-away perspective view of I@I in which actual current transfer recording is performed using a multi-stylus, and FIG. 5 is a multi-stylus R in which electrode needles are arranged in a staggered manner.

Please refer to the numbers given in these drawings.

2 is a recording body (usually 411. resin sheet, 3-dimensional object may be used), 3 is a recording needle (recording electrode needle), 3' is a multi-stylus, 4 is a return electrode, 5 is an 8-pin recording mark 7711111
6 (represented by an arrow) is the recording current, 7 (represented by a broken line) is the heat transfer ink transferred from the ink sheet l to the recording medium 2, 8 is the support a-a, 11 2 represents a pace layer, 12 represents an ink density, and as shown in FIG.
) and I/IJ2 (#n on the side of the recording medium).

The recording material l for electrical transfer of the present invention is as described above, r/c,
Base layer 11 and ink 1-12! It is shaped from the first bite.

In order to carry out electrical transfer recording, as shown in FIG.
Ma? From the recording needle 3 to the base I 11 of the C recording material, conduction is made to the ZERUS signal voltage 5R in the recording material 1 and the return electrode 4 is energized. At this time, as shown in Figure 3 ft) (a) K, the current density directly below the recording needle 3 (the maximum is the current density), and the HI circuit electrode is below the recording needle 3 (or multi-stylus 3'). Since it has a wide contact area, the current spreads and the current density becomes smaller.The ink #12 (carmen black particles and its (binder components, etc.) present in the periphery are softened or melted and transferred to the recording medium 2.

The range of the resistance value (4m(2)) of the ink layer 12 is
Commercially available tester (Yokogawa Electric a##%TYPE3201)k
Width 1 cm, 1lnlllll (
It has been confirmed from numerous experiments conducted by the present inventors that the f-direction suppressed in step 7) is 10''% Ω, preferably 10 8 to J g 4 Ω.

If it is lower than 10ζ, the current value per dot recording is iO
Even when vH is applied, it becomes larger than lOOmA, and it becomes difficult to record simultaneous application using multiple styluses. Also, 1
If the current density is 0 sΩ, it becomes necessary to apply a high voltage χ of 3 oov or more in order to obtain the current density tL necessary for recording, which is inconvenient.

In order to maintain the above-mentioned appropriate resistance value range Y, the content of Carmen Black in Ink 1-12 is suitably 5 to 40 weights. This resistance value is 111 of Carmen Black.
Although it varies depending on the MK, a material that satisfies the resistance value while maintaining #'s strong tLY is a so-called conductive carbon, such as a furnace type carmen blank.

Acetylene black, lamp black, etc. are preferable.
Among them, Ryo-nes type carmen blanks with a large surface area and high oil absorption are preferred.

Similar to this ink 11112, PACE ml IK also contains carmen black (preferably called conductive carmen, of which a furnace type carmen blank is effective), and its resistance is 11 (4 m(1) ).
The resistance value (ρ10) of Pace 1711 is I
If the current is lower than O'Ω, the current will flow laterally from the pace 1 directly below the electrode needle, and the current will flow in the opposite direction (1 cl O'Ω) (and if you try to record it, it will be quite high. A voltage will have to be applied.

Here, it should be noted that the resistance value ρI(1) of the paste layer 1- is always larger than the resistance value ρ5(2) of the ink layer (4 m
(1) > ρ1 (2)) If not, the pace layer 11
The resin (Tsuminder component) constituting is cellulose acetate with an acetylation degree of 45 or more. Cellulose acetate with a degree of acetylation of 45% or more includes cellulose diacetate, cellulose triacetate, and cellulose polymers with a degree of acetylation intermediate therebetween. Cellulose acetate with an acetylation degree of 45 or higher is
Because it has a softening point of 180-280'C, a melting point of 280-310'C and a high heat deformation temperature fr, the softening bath is used for melting. Base film easily by law? You can make it. The use of rO-acid cellulose with an acetylation degree of 45 or less is unsuitable because it becomes water-soluble and its resistance becomes temperature-dependent, causing stickiness due to moisture.

Furthermore, as a binder for PACE 1111, the acetylated I
Part of cellulose acetate with f451 or higher.

Polymers co-bathed with this, such as polyethylene terephthalate, phenol m8F1. It is possible to substitute vinylidene i-chloride resin, vinyl chloride-vinyl acetate copolymer resin, etc.,
, *, g, o, , zno.

T10. , MgC0,, C1C0, Y: It may be considered to add a splint.

The resin (binder component) constituting the ink 412t' is a thermoplastic material with a softening point or melting point of 50 to 150°C. Typical examples of such thermoplastic substances include waxes (Nocera Fine Wax, Carnauba Wax,
polyvinyl butyral resin, which also has a low softening point (low degree of polymerization) , Eboshi resin, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, phenolic resin, ethyl cellulose, acrylic resin, ethylene glycol,
Examples include polypropylene glycol.

Incidentally, these thermoplastic substances may be used alone or in combination of two or more, and furthermore, the above-mentioned non-flk yield may be appropriately added to the ink layer 12. @lz is energizing Pace 1i1111? [The resin used there is the binder component of the paste layer 11 because it has the role of faithfully forming the shape of the pole needle (diameter and round m) and at the same time melting it in a bath with low energy and transferring it to the recording medium 2. Taking into account the melting point or softening point Y of cellulose acetate having a certain acetylation #: 45 or higher, the softening point or melting point must be 50 to 150° C. as described above. If the temperature is lower than 50℃, scumming will occur during transportation or during pressure contact, and if the temperature is higher than 150℃, it will melt with low energy and will not change its structure along with Carmen Black (coloring component). For both the base layer 11 and the ink 12, a plasticizer such as hinoki cypress may be used as a flexibility imparting substance, if necessary.
J5 plasticizers include heptalate esters (diptylphthalate, dioctyl phthalate, etc.), nisal phosphates (triethyl phosphate, tricresyl phosphate, triphenyl phosphate, etc.), and fatty acid esters (diptylphthalate, dibutyl phosphate, etc.). ), glycol-based (polyethylene glycol, polypropylene glycol, triethylene glycol, etc.)
, glycol ester type (diethylene glycol dibenzoate, etc.), wax type (animal and vegetable wax, mineral wax, etc.), fatty acid metal Jl! (stearin Il)
l! (zinc, magnesium oleate, etc.).

The addition density of these flexibility-imparting substances is suitably in the range of 5 to 200 parts by weight per 100 parts by weight of the resin (binder component). Among them, Base-11 and a small amount of polyethylene glycol (substance that imparts transmissibility)? Additives give good results.

9. In order to obtain color copies, the ink layer 12 may contain known organic or inorganic dyes, such as 7-lycyanine, alkaline del, spirit black, benzidine yellow, first trend, crystal violet, etc.
iron oxide.

A coloring component such as cadmium sulfide may be added.

In order to actually produce the second recording material of the present invention, cellulose acetate with an acetylation degree of 45 or more and a conductive material (carbon plank) are dissolved or fractionated in a solvent and placed on a glass plate, metal plate, etc. Apply and dry base 1 of 5-30.g1B thickness
111%: form a L, in addition to which a binder base e (preferably polyvinyl butyral resin) and carmen black (herein, a polyvinyl butyral resin) having a softening point to melting point of 50 to 150'C.

This carmen black serves as both a conductive material and a coloring component) or a binder component, a coloring component, and a carmen blank (here, this carmen black is used as a conductive material)Ytetrahydrofuran, 1,2-dichloroethane, A solution or fraction dissolved in a solvent such as methyl ethyl ketone, toluene, petroleum ether, ethyl acetate, dimethylformamide, methanol, etc. is applied and dried to form an ink layer J21:r' with a thickness of 1 to 30 μm7c.
The paste layer 11 and the ink layer 12'Ik can be peeled off as one body from a glass plate, metal plate, etc.

If the thickness of the base 1il11 is thinner than 5μrn, the film strength will be low. ．． This is not desirable because a 1m garage requires a large storage area.

Furthermore, if the thickness of the ink 1112 is less than 1 μm, the tot hardness will be low, and if it is thicker than 30 μm, the recording energy must be increased, which is not desirable.

In order to perform transfer recording on the pass 1 using the recording material left in this way, as shown in FIG. 2 or FIG. Recording applied voltage 5 to the electrode 4r eyelid and the base 1 11. Current m, Y recording needle 3 or multi-stylus 3.
Just turn on the power and turn on the power.

The conditions for energization, scanning 48iei, etc. are arIJl! The formation is thick (there is an influence, but generally the darkness is 0.5 to 2 m5 ec when the current is applied, and the distance is 3 to 20 lam). Recording material 1 and recording body 2 are completely separated from each other. The recording material of the present invention removes all coloring components (Carmen Black of Ink-12, etc.) even when a relatively strong electric current is applied.
Since it will not be transferred to the recording body 2, 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. Although a detailed study has not been made as to why such a high recording speed Wt'Y is obtained, it is widely believed that by separating the roles and functions of the base layer 11 and the ink layer 12, This is thought to be due to the fact that the overall thickness of the recording material could be made thinner.

Furthermore, the base d11 in the recording material of the present invention has a structure Y different from the conventional special and expensive anisotropic conductive base layer, and is essentially a conductive material used in ink #12. For example, since it contains a smaller proportion than Carmen Black Ink@12, it is more uniform and dispersible.As long as the surface resistivity and thickness are kept within the appropriate range, it is more uniform than a special anisotropic conductive paste layer. This has the effect of allowing high-quality dot recording that is faithful to the shape of the recording stylus.

Example Carmen Black A mixture consisting of 1001 parts of methylene and 1 part of carmen black was left in a glass 6z-luminium for 5 hours. , using a blade with a gap of 100 μm, apply a Kfi cloth on a glass substrate, dry it, and prepare a base i with a resistance of 10Ω and a thickness of about 6 μm.
I released the shape to l'. Further, on this base layer, a mixture of the following formulation, which had been mixed in a KFJ Russ #Gale mill, was coated with a blade having a gap of 200 μm and dried to form an ink of 1 #. The base f and the ink layer which had been horizontally bent were then peeled off from the glass substrate to obtain a recording material for electrical transfer.

Note that this recording material had a total thickness of 14 μm.

The total resistance is 1.8Ω and 6 pieces.

Polyvinyl butyral (softening point 80'C) 71 Ayabe Carmen Black 31 Sumire 1203iii parts of ethyl alcohol Next, as shown in FIG. , Under that condition, between the multi-stylus 3' (a multi-stylus with a pole needle diameter of about 130 μm and a recording needle density of 8 dots/■) and the return electrode 4 where it was attached [50V-Inlm].
When a pulse voltage of ee was applied, a current of 80mA was generated! ! The dot diameter was approximately 150 μm and the dot density was 1.
．． A clear transfer image of round donts of No. 3 was recorded on plain paper. After the recording was completed, the electrode needle V* was inspected to find that there was no adhesion from the recording material at all, and no melting traces were observed on the surface of the paste layer or paste layer.

[Brief explanation of the drawing]

FIG. 1 shows an outline of recording using a conventional electrically conductive transfer recording material composed of an anisotropic conductive paste I and a conductive ink layer. Fig. 2 is a diagram showing yx, and Fig. 2 is a diagram showing viscosity of recording using the recording material for electrical transfer according to the present invention, @3.
The figure shows the state of the current flowing from the stylus to the return electrode, and shows the graph in the following colors and current density: 1f1. Figure 4 shows a part of the state in which actual current transfer recording is performed using a multi-stylus. The cutaway perspective view of FIG. 5 is a schematic diagram of an example of a multi-stylus. 1... Recording material for current transfer 2... Recording body 3... Recording needle 3'... Multi-stylus 4... Return electrode 5... Recording applied voltage 6...
- Recording current 7... Heat transfer ink 8... Support roller 11... Base layer 12... Ink -

Claims (1)

[Claims] 1. Lay out the recording material and the recording material for electrical transfer,
The recording material KH# path electrode V* is touched, and the recording material surface is touched by the recording electrode needle tW! The recording material used in electrical transfer recording@, in which the recording material is energized by applying a voltage to the recording material and the ink is transferred onto the recording medium, mainly contains heptylulose acetate and carmen black with an acetylation degree of 45 or higher. The base layer has a melting point or softening point of 50-150'C.
79 Ing as a main component and an ink layer mainly composed of Carzeno Black, and the electric resistance value of the ink layer is lower than the electric resistance value of the base layer. Recording material for electrical transfer 0