JPH07137312A - Electrothermal transfer ink medium - Google Patents

Abstract

PURPOSE:To provide an electrothermal transfer ink medium easy in the reduc tion of thickness or the simplification of production by simple constitution without damaging recording capacity due to an electrophermal transfer recording system and more inexpensive than a conventional product. CONSTITUTION:A conductive layer 3 and a heat generating layer 4 are laminated to the single surface of an insulating polymer film support material and a thermal transfer ink layer 5 is laminated to the other surface thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric transfer ink medium used in an electric transfer recording system.

[0002]

2. Description of the Related Art Generally, an electrically conductive transfer ink medium has a heat generating layer which generates heat when energized, a conductive layer for supplying an image signal current from a current recording head to the heat generating layer, and a transfer property due to heat generation of the heat generating layer. And a heat-sensitive transferable ink layer composed of the ink composition shown in FIG.

In conducting energization transfer recording using such an energization transfer ink medium, first, energization in which a plurality of independent recording electrodes are provided in parallel at the tip of the heating layer surface of the energization transfer ink medium. Touch the recording head. At the same time, the return electrode is brought into contact with the conductive layer of the ink medium. Then, the current corresponding to the image information is applied from the energization recording head through each recording electrode to selectively heat only the heat generating layer of the energized portion, and the ink of the heat-sensitive transferable ink layer portion corresponding to the heat generating portion. Is melted, and the ink is transferred to a recording paper which is arranged so as to face the ink layer, whereby an image is formed by an electric transfer recording method.

By the way, as a conventional electric transfer ink medium, specifically, a conductive resin film, which is made by dispersing carbon particles or the like in a resin material, also serves as a heat generating layer, so that the supporting material also functions as a heat generating layer. A material in which a conductive layer and an ink layer are sequentially laminated on one side of a conductive resin film is known (see Journal of Image Electronics Engineers, No. 16, No. 1 (1987), page 27, and Sawai et al. "Development of Electric Transfer Recording Head", Proceedings of 102nd Research Meeting of the Institute of Image Electronics Engineers of Japan (1988), page 25). In addition, a heat-generating layer, a conductive layer, and an ink layer are sequentially laminated on a support material having anisotropic conductive characteristics (US Pat. No. 4,897,6).
No. 69, etc.) are known.

[0005]

However, in many of the conventional electro-transfer ink media as described above, as a supporting material thereof, a resin film in which a conductive substance is dispersed to impart conductivity is used. However, since the conductive resin film is relatively expensive, the cost of the ink medium itself is high.

Further, the conductive resin film has a constraint that the film thickness must be increased to a certain degree (at least 15 to 20 μm or more) in order to compensate for the strength lowered by the dispersion of the conductive substance, which also results in the cost reduction. I was invited up. Moreover, since the support material has a high ratio of the thickness to the entire ink medium, when the ink medium is wound, the winding diameter is always a certain size or more, and it is impossible to reduce the diameter, for example. There were some problems.

In order to simplify the structure of this kind of ink medium, a resin film in which a conductive substance is dispersed is applied to one surface of a resin film to provide a heat generating layer, and an ink layer is provided to the other surface to form an ink. There has been provided a method of using a recording head which constitutes a medium and causes heat generation by energizing between recording electrodes of the recording head which is in contact with a heat generating layer at the time of electric transfer recording. However, since such a technique causes a heat generation phenomenon between the recording electrodes of the recording head, the pulse driving method at the time of recording is complicated, the cost of the recording system is high, and the heat generating layer is coated with a resin liquid. It was difficult to obtain a high-quality image because it was a work film and had a thick dispersion of conductive materials and the like, and the obtained transfer image had low recording performance such as variations in printing rate and dot diameter.

An object of the present invention is to enable high-quality image recording without deteriorating the recording performance of the electric transfer recording system, and also to reduce the thickness and simplify the manufacturing with a simple structure. An object of the present invention is to provide an electrically conductive transfer ink medium that is cheaper than a commercial product.

[0009]

That is, in the electrotransfer ink medium of the present invention, a conductive layer and a heat generating layer, both of which are thinned, are laminated in this order on one surface of an insulating polymer film support, and the other surface is formed. It is characterized by having a layered structure in which heat-sensitive transferable ink layers are laminated.

In the electrotransfer ink medium of the present invention, preferably, the insulating polymer film support has a thickness of 0.5 to 20 μm or the conductive layer has a thickness of 0 according to the above technical means. .6 μm or less, the thickness of the heat generating layer is 0.8 μm or less, or the conductive layer and the heat generating layer are thin film layers made of a material mainly containing a metal material and a ceramic material. To do.

The insulating polymer film support material is composed of a flexible polymer film having an insulating property with a volume resistance value of 5 × 10 ¹¹ Ω · cm or more. When the volume resistance value is smaller than the above value, there is a problem such as a print pulse current leak phenomenon. As such an insulating polymer film supporting material, for example, a synthetic resin film made of polyaramid, polyimide, polyester, polysulfone or the like is used, and preferably for preventing deformation due to high heat at the time of manufacturing or printing / recording. A material having heat resistance is used. Among the above synthetic resin films, the polyaramid film is most preferable because it has excellent uniformity of volume resistance value in the whole film.

The thickness of the insulating polymer film support material is 0.5 to 20 μm, preferably 2 to 6 μm.
If the thickness is less than 0.5 μm, sufficient strength cannot be obtained, and there is a problem that it is difficult to handle at the time of manufacturing the ink medium, and wrinkles occur at the transporting step at the time of energization recording. On the other hand, if the thickness is more than 20 μm, the winding diameter at the time of winding becomes large, or the efficiency of heat transfer from the heat generating layer to the ink layer at the time of recording is lowered, and more printing energy is required. However, there is a problem in that the printing efficiency dots are blurred and the dot diameters vary, leading to deterioration in image quality. Further, if the thickness is in the range of 2 to 6 μm, sufficient strength is ensured, the degree of freedom in selecting printing conditions such as printing pressure is expanded, and the winding diameter of the ink medium when wound is more improved. The size can be reduced, the optimum heat transfer efficiency can be obtained, and the printed dots can be made clear and uniform, which enables higher quality printing and recording.

The conductive layer has a volume resistance value of 5 × 10.^-7~ 2x
10 Ω · cm, preferably 1 × 10 ^-6~ 6 × 10^-3Ω ・
A thin film made of a conductive material in the cm range.
It If the volume resistance value exceeds the above numerical range,
The resistance value of the energizing circuit at the time of character recording becomes high and the printing energy
The ratio of the space increases. The thickness of the conductive layer is 0.6μ
m or less, more preferably in the range of 0.05 to 0.3 μm
is there. If this thickness is thicker than 0.6 μm, the heat generation energy
Printing energy efficiency
Is reduced. Also, ensure the uniformity of the volume resistance of the conductive layer.
Therefore, the layer thickness must be 0.05 μm or more.
It

This conductive layer contains a metal material such as gold, silver, copper, platinum, aluminum, chromium, tin, nickel, tungsten, millibutene, or a conductive ceramic material such as ruthenium oxide or boron carbide. It is made of the material. The means for forming the conductive layer is not particularly limited as long as it can be formed into a thin film, but from the viewpoint of ensuring the uniformity of the layer thickness and thus the uniformity of the resistance value and the manufacturing efficiency, a vacuum deposition method, a high frequency sputtering method, electrolysis or no electroless method. Electrolytic plating, cluster ion beam method, ion plating method, etc. are preferable.

The heating layer has a volume resistance value of 2 × 10 ⁻³ to 8 ×.
10 ³ Ω · cm, preferably 2 × 10 ^{−2 to} 5 × 10 Ω ·
It is a thin film in the range of cm. If this volume resistance value is smaller than the above lower limit value, efficient heat generation required for printing and recording cannot be obtained, and in order to obtain the optimum drive resistance value for the heat generation, it is necessary to make the layer thickness extremely thin. Thin film formation becomes difficult. On the contrary, if the volume resistance value is larger than the above upper limit value,
Since the heat generation resistance is too large, proper heat generation cannot be obtained during printing and recording, resulting in image quality deterioration. The thickness of the heat generating layer is 0.8 μm or less, preferably 0.05 to 0.4 μm. If this thickness exceeds 0.8 μm, the amount of heat leakage increases and the printing energy efficiency decreases. Also,
If the thickness is less than 0.05 μm, it is difficult to obtain the uniformity of the heat generating layer, and uneven heat generation easily occurs.

The heat generating layer is formed of a metal material, a conductive or insulating ceramic material, or the like, which is used alone or in combination. As the metal material,
C, Ni, Au, Ag, Fe, Al, Ti, Pd, C
r, Cu, Co, Pt, Mo, W, Rb, Ru, InR
h etc. can be used. The conductive ceramic materials include VO ₂ , Ru ₂ O, TaN, SiC, ZrN, Zr.
O ₂ , InO, Ta ₂ N, VN, TiB ₂ , ZrB ₂ , Hf
_{B 2, TaB 2, MoB 2} , CrB 2, B 4 C, MoB, Z
rC, VC, TiC or the like or a compound containing them can be used, and as the insulating ceramic material, AlN, SiN
₄ S, SiO ₂ , Al ₂ O ₃ , MgO, VO ₂ , ZrO ₂ , B
_{i 2 O 3, MO 2,} TiO 2, MoO 2, WO 2, ReO 3 , etc., or these containing compounds. Further, as a means for forming the heat generating layer, a single or multi-source type vacuum deposition method, a high frequency sputtering method, a DC sputtering method, an electrolytic or electroless plating method, a cluster ion beam method, an ion plating method and the like are preferable.

Further, the heat generating layer is presumed to reach a high temperature of 200 ° C. or higher due to the heat generated during printing and recording, and is therefore 300 ° C.
It is necessary to configure so as to have heat resistance of C or higher. Therefore, in order to ensure such heat resistance, the heat generating layer is preferably formed of an inorganic material containing a metal or a ceramic material as a main component. By using such a material, the heat generating layer can be easily thinned, has excellent heat resistance, has less variation in volume resistance value in the layer, and can be efficiently formed.

The heat transferable ink layer is composed of an ink material which is melted or sublimated by heating and transferred to the recording paper. Specifically, an ink material in which a coloring material such as carbon black is dispersed in a thermoplastic resin, or an ink material containing a binder and a sublimable dye as main components is used.

In the electrically conductive recording ink medium of the present invention, in addition to the above-mentioned layers, if necessary, the ink may include a peeling layer (for example, a low surface energy layer), an offset prevention layer, an image gloss layer (for example, a matte surface layer) and the like. These functional layers can be appropriately laminated.

The production of this electrically conductive recording ink medium is
Basically, a conductive layer and a heat generating layer are laminated in this order on one surface of the insulating polymer film support material, and then an ink layer is laminated on the other surface side of the film support material. In this case, if both the conductive layer and the heat generating layer are formed by the above-mentioned thin film forming means, it is possible to form a layer with a uniform layer thickness and high accuracy, and moreover, since the same vacuum system production line can be used in combination, the efficiency can be improved. Good manufacturing is possible.

In conducting electric transfer recording using the electric recording ink medium of the present invention, the surface of the heat-sensitive transfer ink layer is pressed against the recording paper and the surface of the heat generating layer is pressed against the electric recording head. Then, when the image information signal emitted from the drive circuit is applied to the ink medium via each recording electrode of the energization recording head, the applied heat generating layer portion generates heat by energization, and the heat is generated in the conductive layer and the polymer film. The ink material is transferred to the ink layer through the support material, and the ink material corresponding to the heat generating portion is melted or sublimated to form recording paper, and recording is performed.

[0022]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 A polyaramid film having a thickness of 1.5 μm (volume resistance value:
10 ¹³ to 10 ¹⁵ Ω · cm) reached vacuum degree 2 × 10 ⁻⁶ To
In a state of being installed in a vacuum system set to rr and controlled to be heated to 200 ° C., an aluminum film is deposited on one surface thereof by an electron beam heating evaporation method to form a conductive layer having a thickness of 0.2 μm (volume resistance value: 10 ⁶ Ω · cm). Then, S is deposited on the conductive layer by an electron beam heating evaporation method using a dual evaporation source.
iO ₂ and Au were simultaneously evaporated from different evaporation sources and deposited to form a heat generating layer having a thickness of 0.4 μm. At this time, the volume resistance value of the heat generating layer was 7 × 10 ⁻¹ Ω · cm.

Next, after taking out from the vacuum system, an ink material composed of a polyester resin (melting point 96 ° C.) solution containing 10% by weight of pigment is applied to a film surface opposite to the heat generating layer surface by a roll coater and dried. Then, an ink layer having a thickness of 2 μm was formed. As a result, an electrically conductive recording ink medium 1 having a layer structure as shown in FIG. 1 was obtained. In the figure, 2 is an insulating polymer film support material, 3 is a conductive layer, 4 is a heat generating layer,
Reference numeral 5 represents a heat transferable ink layer.

Using the electrically conductive recording ink medium 1 thus obtained, as shown in FIG. 2, the electrically conductive recording head 6 of 200 DPI was pressed against the surface of the heat generating layer 4 at a linear pressure of 300 g / cm and applied to the recording paper 7. Voltage 17V, pulse width 400μsec
The image (dot) signal was applied to perform printing and recording, and the variations in printing energy, printing rate, and printing dot diameter at that time were measured. The results are shown in Table 1. In FIG. 2, 8 is a recording electrode, 9 is a return electrode integrally provided on the head, and 10 is a back pressure roll.

Here, the printing energy indicates the amount of printing heat per dot printing, and is calculated by measuring the input voltage, current and pulse width required for printing,
Generally, 0.5 mJ / dot or less is considered to be the best. The print ratio indicates the print ratio of dots in which the average dot diameter in the vertical and horizontal directions of one dot printed for an image input signal is 50 μm or more. The variation in the print dot diameter is indicated by the standard deviation σ _n (n = 100) when 100 print dots are sampled at random.

Example 2 Polyester film having a thickness of 3 μm (volume resistance value: about 1
(0 ¹⁴ Ω · cm) is installed in a vacuum system having an ultimate vacuum of 2 × 10 ⁻⁶ Torr and heated at 100 ° C.,
An aluminum film was formed on one surface of the conductive layer by electron beam heating evaporation method to form a conductive layer having a thickness of 0.1 μm (volume resistance value: 5 ×).
10 ⁻⁶ Ω · cm). Then, a small amount of argon gas was introduced into the vacuum system, and the vacuum degree was 3 × 10 ⁻³ T.
In the state of orr, a sputtering film made of a composite material of SiO ₂ and Ta in a volume ratio of 65:35 was deposited on the conductive layer by a high frequency sputtering method to form a 0.2 μm thick film. An exothermic layer was provided. At this time, the volume resistance value of the heat generating layer was 3 × 10 ⁻¹ Ω · cm.

Then, after being taken out from the vacuum system, an ink layer having a thickness of 3 μm after drying and made of the same ink material as in Example 1 was formed on the film surface opposite to the heat generating layer surface to obtain an electrically conductive recording ink medium.

Using the obtained ink medium, a linear pressure of 40
0g / cm, applied voltage 5V, pulse width 800μsec
After printing and recording under the same printing conditions as in Example 1 except for the above, the same measurement as in Example 1 was performed, and the results are also shown in Table 1.

Example 3 Polyimide film having a thickness of 3 μm (volume resistance value: about 10
⁽¹⁵ Ω · cm) is installed in a vacuum system with an ultimate vacuum of 1 × 10 ⁻⁶ Torr and heated to 250 ° C., and nickel is deposited on one side by electron beam heating type vapor deposition. 0.3 μm thick conductive layer (volume resistance value: 3 × 10 ⁻⁵
Ω · cm).

Next, after taking out from the vacuum system and applying a paste of ruthenium / chromium on the conductive layer by a spin coating method, it is heated and baked at 350 ° C. in a vacuum system to have a thickness of 0.4 μm. Of the heat generation layer. At this time, the volume resistance value of the heat generating layer was 3 × 10 Ω · cm.

Then, after taking out from the vacuum system, an ink material comprising a solution of a polyvinyl alcohol resin containing 70% by weight of a sublimable dye is applied to the film surface opposite to the heat generating layer surface by the same method as in Example 1. And dried to form an ink layer having a thickness of 1.5 μm, which was used as an electrically conductive recording ink medium.

Using the obtained ink medium, the linear pressure was set to 50.
After recording and recording under the same printing conditions as in Example 1 except that the applied voltage was 0 g / cm, the applied voltage was 18 V, and the pulse width was 1 msec, the same measurement as in Example 1 was performed (however, measurement of variations in print dot diameter). Is not performed), and the results are also shown in Table 1.

Comparative Example 1 A 25 μm thick polyaramid film (volume resistance value: about 10 ¹⁵ Ω · cm) was placed in a vacuum system having an ultimate vacuum of 2 × 10 ⁻⁶ Torr and heated to 80 ° C. With the
An aluminum film was deposited on one surface of the conductive film by an electron beam heating evaporation method to form a conductive layer having a thickness of 0.3 μm (volume resistance value: 5 ×
10 ⁻⁶ Ω · cm). Then, on the conductive layer, SiO ₂ and Au were simultaneously evaporated from different evaporation sources by an electron beam heating evaporation method using a _dual evaporation source as in Example 1 to form a film having a thickness of 0. A heating layer of 5 μm was provided. At this time, the volume resistance value of the heat generating layer was 1 × 10 Ω · cm.

Next, after being taken out from the vacuum system, an ink layer having a thickness of 2 μm after drying and made of the same ink material as in Example 1 was formed on the film surface opposite to the heat generating layer surface to obtain an electrically conductive recording ink medium.

Using the obtained ink medium, the applied voltage was set to 2
After printing and recording under the same printing conditions as in Example 1 except that the voltage was 6 V and the pulse width was 1.2 msec, the same measurement as in Example 1 was performed, and the results are also shown in Table 1.

Comparative Example 2 A polyimide film having a thickness of 5 μm (volume resistance value: about 10
⁽¹⁵ Ω · cm) is installed in a vacuum system with an ultimate vacuum of 1 × 10 ⁻⁶ Torr and heated to 250 ° C., and nickel is deposited on one side by electron beam heating type vapor deposition. 0.3 μm thick conductive layer (volume resistance value: 3 × 10 ⁻⁵
Ω · cm).

Next, after taking out from the vacuum system, a polyimide precursor in which carbon black is dispersed is applied on the conductive layer by a spin coating method and dried by heating at 200 ° C., and then 350 ° C. in the vacuum system. Heat cured to a thickness of 7
A heating layer of μm was provided. At this time, the volume resistance value of the heat generating layer was 6 × 10 Ω · cm. Next, after taking out from the vacuum system, an ink layer having a thickness of 2 μm after drying and made of the same ink material as in Example 1 was formed on the film surface opposite to the heat generating layer surface to obtain an electrically conductive recording ink medium.

Using the obtained ink medium, the linear pressure was set to 50.
0g / cm, applied voltage 34V, pulse width 0.5mse
After printing and recording were performed under the same printing conditions as in Example 1 except that c was used, the same measurement as in Example 1 was performed, and the results are shown in Table 1.
It is shown together with.

Comparative Example 3 A carbon black-dispersed polycarbonate film having a thickness of 15 μm (volume resistance value: 2.3) serving as a heating layer and a supporting material.
Ω · cm) is installed in a vacuum system having an ultimate vacuum of 4 × 10 ⁻⁶ Torr and is heated to 30 ° C., and aluminum is deposited on one surface thereof by an electron beam heating type vapor deposition method. 0.2 μm thick conductive layer (volume resistance value: 5 × 10
^-6 Ω · cm).

Next, after taking out from the vacuum system, an ink layer having a thickness of 3 μm after drying and made of the same ink material as in Example 1 was formed on the film surface opposite to the conductive layer surface. As a result, the conventional electrically conductive recording ink medium 10 having the conventional layer structure as shown in FIG. 3 was obtained. In the figure, 11 is a heat generating layer / supporting material film, 12 is a conductive layer, and 13 is a heat transferable ink layer.

Using the obtained ink medium, the linear pressure was set to 50.
0g / cm, applied voltage 14V, pulse width 0.5mse
After printing and recording under the same printing conditions as in Example 1 except that the result was c, the same measurement as in Example 1 was performed, and the results are shown in Table 1.
It is shown together with.

Comparative Example 4 A polyester resin solution in which metal powder and carbon black were dispersed was applied to one side of a polycarbonate film having a thickness of 6 μm and dried, and then a heating layer having a thickness of 3 μm (volume resistance value: 5 × 10 ^{−2) was used.} Ω · cm), and then, on the other side of the film, a thickness of 3 consisting of a material in which a pigment is dispersed in a wax material.
An electric recording ink medium was provided by providing an ink layer of μm.

By using the ink medium and applying a pair of applied voltage pulses of +10 V and -10 V to the recording electrodes of the recording head corresponding to the portion to be printed, the recording and recording are performed between the electrodes. Example 1 except that
After printing and recording under the same printing conditions as above, the same measurement as in Example 1 was performed. The results are also shown in Table 1.

[0045]

[Table 1]

[0046]

As described above, the electrically conductive transfer ink medium of the present invention does not use a conductive film as a supporting material but uses an insulating polymer film supporting material, and has a conductive surface on one side. It has a unique layered structure in which a layer and a heat generating layer are laminated and an ink layer is laminated on the other surface. Therefore, it has a simple structure and is easy to manufacture, and can be provided at a lower cost than the conventional product using the conductive film. Further, also in the case of print recording, it is not the method of generating heat by energizing between the recording electrodes of the recording head, and it is possible to perform good print recording with high image quality as in the conventional product.

The insulating polymer film support material has excellent strength because it does not contain a conductive substance such as a conductive film. Even if the thickness is thin, sufficient strength can be obtained. The thickness of the entire ink medium can be reduced more easily than in the past. As a result, when wound, the winding diameter can be reduced and the handling becomes extremely convenient. In the present invention, sufficient strength is secured even when the thickness of the film support material is 0.5 to 20 μm, and the effect of reducing the winding diameter is more remarkably obtained.

Further, since the conductive layer and the heat generating layer are thin film layers made of a material containing a metal material and a ceramic material as main components, any layer can be formed by a thin film forming means such as a vapor deposition method. It is possible to simplify and improve production efficiency. Further, since a conductive layer and a heat generating layer having excellent heat resistance can be obtained, and a layer having a uniform film thickness and a uniform volume resistance value can be obtained by forming by a thin film forming means such as a vapor deposition method, high quality printing can be achieved. Records can be made.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an electric transfer ink medium according to one embodiment (Example 1) of the present invention.

FIG. 2 is a schematic cross-sectional view showing a recording method using the electric transfer ink medium of the present invention.

FIG. 3 is a cross-sectional view showing an example of a conventional energization transfer ink medium (Comparative example 3).

[Explanation of symbols]

1 ... Electric transfer ink medium, 2 ... Insulating polymer support material, 3
... current-carrying layer, 4 ... heat-generating layer, 5 ... heat-sensitive transferable ink layer.

Claims (5)

[Claims] 1. An electric transfer ink comprising a layer structure in which a conductive layer and a heat generating layer are laminated in this order on one surface of an insulating polymer film support material, and a heat-sensitive transfer ink layer is laminated on the other surface. Medium. 2. The electric transfer ink medium according to claim 1, wherein the insulating polymer film support material has a thickness of 0.5 to 20 μm. 3. The electrotransfer ink medium according to claim 1, wherein the conductive layer has a thickness of 0.6 μm or less. 4. The electric transfer ink medium according to claim 1, wherein the heat generating layer has a thickness of 0.8 μm or less. 5. The electric transfer ink medium according to claim 1, wherein the conductive layer and the heat generating layer are thin film layers made of a material containing a metal material and a ceramic material as main components.