JPH024588A - Ink recording medium - Google Patents

Abstract

PURPOSE:To enable repeated use of an ink recording medium by providing a protective layer comprising a conductive ceramics or a metal having a high melting point and a high hardness, on the ink release layer side of a conductor layer of the ink recording medium. CONSTITUTION:At the time of printing, an electric signal according to an image is applied to an anisotropic conductive part 11 of an ink recording medium 1. An electric current (i) flows through the anisotropic part 11 and a heat generating resistor layer 12 to a conductor layer 13, and thermal energy generated in the resistor layer 12 is transmitted through the conductor layer 13 and an ink release layer 14 to a heat-fusible ink layer 15, whereby a heat-fusible ink is melted according to the input signal, and the melted ink is transferred onto a recording paper. The conductor layer 13 is provided on th ink release layer side 14 thereof with a protective layer comprising a conductive ceramic or at least one high-hardness high-melting-point metal selected from the group consisting of Mo, Ta, W, Ti, Ru, Re, Rh and Zr. Therefore, oxidation of the metal constituting the conductor layer 13 will not be caused by the application of the electric signal, and the layer 13 is not changed in resistance even after repeated use thereof for a long time.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to an ink recording medium used for converting electrical signals into thermal energy and transferring an ink image to a transfer material.

BACKGROUND ART Conventionally, when recording an image corresponding to a predetermined digital image signal on a recording medium, such as plain paper, a recording method using a thermal transfer recording medium such as an ink donor film is widely known.

Such recording methods include, for example, 1) thermal head transfer method (Japanese Patent Application Laid-Open No. 53-84735), 2) electric transfer method in which the ink layer is energized (Image Electrophotography Society Journal = 198
2nd year VO1, 11, No. 1, p3-9), 3)
Electric thermal transfer recording method using a print recording medium having a heat generating layer and a return electrode on an ink support of medium resistance (Japanese Patent Application Laid-Open No.
3585 Publication), 4) An energized thermal transfer recording method, etc., in which a return electrode is provided on the same side as the needle electrode, a current path to the return electrode is formed in the heat generating layer of the print recording medium, and the heat generated in the heat generating layer is utilized. Proposed.

Among these recording methods, the electrical thermal transfer recording methods 3) and 4) have the advantage of relatively fast printing speed, no need to impart conductivity to the ink, and a high degree of freedom in selecting the ink material. Various proposals have been made. However, in these electrical thermal transfer recording methods, the ink support does not have anisotropic conductivity, so the dots spread, the leakage current is large, the energy efficiency is poor, or the applied current passes through the heat generating layer twice. This causes a lot of energy loss, and since the sliding contact is made twice with the needle electrode and the return electrode, there is also a lot of heat loss due to contact resistance. This requires a certain level of resistance in the conductive layer in the recording medium, and has drawbacks such as increased heat loss in the conductive layer.

In order to solve this problem, an anisotropic conductive layer consisting of an isolated conductive pattern is provided on the heating resistor layer, an ink recording medium with an anisotropic conductive layer as the support layer, and a conductive layer on both side edges. Using an ink recording medium with exposed side end electrodes,
It has been proposed to perform print recording by bringing a conductive sliding member or a conductive roll into contact with the side end electrode portion.

Problems to be Solved by the Invention By the way, in an ink recording medium formed by laminating an anisotropic conductive layer, a heating resistor layer that generates heat by the input of an electric signal, a conductive layer, an ink peeling layer, and a heat-melting ink layer, Al or an alloy thereof is often used as the conductive layer, but if the conductive layer is exposed on both side edges and used as side electrode portions, the above-mentioned problems in the conventional technology can be improved. However, when an electric signal corresponding to an image is input, a portion of the conductive layer to which a pulse voltage is applied is oxidized, resulting in a change in resistance value.

Furthermore, the side end electrode portions of the ink recording medium suffer from wear and oxidation due to friction and current action due to contact with the conductive contact member, causing damage such as discharge. Therefore, the life of the ink recording medium is shortened, and stable recorded images cannot be obtained.

The present invention has been made in view of the above-mentioned problems in the conventional technology.

Therefore, an object of the present invention is to provide an ink recording medium that can be used repeatedly and that can perform stable print recording.

Other objects of the present invention are to enable repeated printing and recording, to enable high-speed printing and high-density energy manual operation, to reproduce high-quality color images, and to record robust images with multiple gradations. The object of the present invention is to provide an ink recording medium that can perform printing and recording with high energy efficiency and at low running cost.

Means for Solving the Problems The ink recording medium of the present invention has an anisotropic conductive layer, a heating resistor layer that generates heat upon input of an electric signal, a conductive layer, an ink peeling layer, and a heat-melting ink layer, which are laminated in sequence. conductive ceramic or M on the ink release layer side of the conductive layer.
It is characterized by providing a protective layer made of one or more metals selected from the group consisting of OSTa, W, Tr, Ru, Re, Rh, and Zr.

The ink recording medium of the present invention will be explained with reference to the drawings. FIGS. 1(a) and 1(b) are schematic cross-sectional views of the ink recording medium of the present invention, respectively.

In the figure, 11 is an anisotropic conductive layer, in (a) it is an isolated conductor pattern, and in (b) it is a ceramic layer. 12 is a heating resistor layer;
13 is a conductive layer, 14 is a protective layer, 15 is an ink release layer, 1
6 is a heat-melting ink layer.

The anisotropic conductive layer has the function of reducing current loss due to current conduction resistance when current is applied in the thickness direction, and also reduces heat loss and heat generation damage due to contact resistance between the needle electrode and the surface of the ink recording medium. It may be a conductive isolated pattern layer made of electrodes, or it may be a layer in which conductive paths made of a conductive substance such as metal powder or conductive ceramic particles are formed in an insulating material such as ceramic or synthetic resin. You can cover it. For example, a porous ceramic layer formed by anodic oxidation or the like, in which the pores are filled with a conductive substance such as metal, is preferable.

In the ink recording medium of the present invention, when the anisotropic conductive layer is a layer consisting of conductive isolated patterns, it is sufficient that the heating resistor layer has a function as a support; In the case of a conductive layer, the anisotropic conductive layer itself may function as a support, and a thin heat generating resistor layer may be formed on its negative surface.

The heating resistor layer is a layer that generates Joule heat using a current from the anisotropic conductive layer to melt the ink and transfer it to the transfer material. Resistor layer made of dispersed heat-resistant resin (polyimide resin, polyimide amide resin, silicone resin, fluororesin, epoxy resin, etc.), ZrO2, AI203
, SI 02 and other high-resistance materials such as Ti, AI, Ta,
A thin film formed using a conductive material such as Cu, ALI, or ZR is used. It is preferable that the volume resistivity of the heating resistor layer is set in the range of 10-2 to 102 Ω·cm, and the film thickness is set in the range of 1000 to 10011 m. Those within this range have excellent properties in terms of film deposition stability, film adhesion, etc.

The conductive layer serves as an electrode that diffuses and circulates the current flowing into the heating resistor layer, and is made of A1, Cr, Cu, and Z.
r, Sn, Co, etc. or alloys containing these metals, such as Cr-Ni alloy, Co-Ni alloy, C:, o-Cr
Composed of alloy etc. This conductive layer has a volume resistivity of 1
It is 0-2 Ω·cm or less and is created by vapor deposition, sputtering, or other thin film forming methods. The film thickness is 5
It is preferable to set it in a range of 0.00 to 1 μm.

A protective layer is provided on the conductive layer, that is, on the ink release layer side. The volume resistivity of the protective layer is 10-2Ω・cm
The following are conductive ceramics or high melting point, high hardness metals: Mo, Ta, W, Ti, Ru, Re, Rh,
and Zr. Conductive ceramics that can be used in the present invention include metal oxides such as RuO2, Ta2N, T
aN1Ti N, ZrN, NbN, metal nitrides such as VN, TiB2, ZrB2, HfB2, TaB2
,M.

B, CrB2, Nb82, MOB2, NbB
, metal borides such as MO2B, 54cy'r*c.

ZrC, HfC, VC, NbC, WC.

Metal carbides such as W2 C, TaC, M63 i, TaS
! 2.WS! These include silicides such as No. 2, and these can be used alone or as a mixture. The protective layer is created by vapor deposition, sputtering or other thin film formation methods. The film thickness is preferably set in a range of 200 to 2000 people.

The ink release layer is a layer whose critical surface tension is adjusted to allow good ink transfer even at low printing energy, and is a thin film having a low surface energy function.
Basically, it has a critical surface tension lower than the surface energy of the transfer material. For example, if the transfer material is plain paper, the critical surface tension must be 43 dynes/cm or less. Further, it is preferable that the critical surface tension of the ink release layer is lower than the surface tension of the heat-fusible ink layer, since a greater effect can be obtained on the transfer phenomenon of the heat-fusible ink layer. The thickness of the ink release layer itself is 50
In terms of energy transmission efficiency, it is preferable to set the thickness as thin as possible in the range of 0 to 6 μm. As the material constituting the ink release layer, for example, thermosetting silicone resin, fluorine-containing resin, etc. can be used.

The heat-melting ink layer provided on the ink release layer is formed by dispersing known dyes and pigments such as carbon black in a thermoplastic resin having a melting point of 140° C. or lower.

The thickness of the heat-melting ink layer is preferably set in a range of 1 to 15 μm.

A method of printing and recording using the above ink recording medium of the present invention will be explained with reference to the drawings. FIG. 4 is a diagram illustrating a case where print recording is performed using the ink recording medium of the present invention, and FIG. 3 is a diagram illustrating a current path during print recording.

In FIG. 4, an electric signal is input from a stylus electrode head 2 to an ink recording medium 1 conveyed by a conveyance roll 7, and a current 1 passes from an anisotropic conductive layer to a heating resistor layer to a conductive layer to a return contact roll. Grounded from 5. The heat-melting ink melted by the heat generated by the heating resistor layer is transferred onto the transfer material 3 on the back pressure roll 4 . Note that 6 is a backup roll to ensure contact with the return contact roll. After printing is completed, hot-melt ink is supplied to the ink transfer trace on the ink recording medium, and the colored hot-melt ink layer is regenerated.

At this time, the current applied from the stylus electrode head 2 flows into the conductive layer 13 via the anisotropic conductive layer 11 and the heating resistor layer 12, as shown by the arrow in FIG. A return contact roll 5 is in contact with the edge conductive portion of the conductive layer, and the current flowing through the conductive layer is grounded from the return contact roll.

Function When performing print recording using the ink recording medium of the present invention,
The ink recording medium is conveyed with a conductive contact member such as a conductive sliding member or a conductive roll in contact with the side conductive portion, and an electric signal corresponding to the image is input to the anisotropic conductive layer.

Current flows from the anisotropic conductive layer to the conductive layer via the heat generating resistor layer. At this time, electrical-thermal energy conversion takes place in the heat generating resistor layer, and the generated thermal energy passes through the conductive layer and the ink release layer. The heat is propagated through the heat-melting ink layer to the heat-melting ink layer, melting the heat-melting ink in accordance with the input signal, and transferring the heat to the recording paper. In the present invention, since the conductive layer is made of conductive ceramic or the above-mentioned high melting point, high hardness metal on the ink release layer side, the metal of the conductive layer will not be oxidized by the application of an electric signal. , the resistance value of the conductive layer does not change even after repeated use over a long period of time. Further, in the side end conductive portion, wear and oxidation will not occur due to the action of current and friction with the conductive contact member. Therefore, a stable contact state can be maintained between the side end conductive portion and the conductive roll for a long period of time.

Examples Next, the print recording medium of the present invention will be explained with reference to examples.

Example 1 Ti was deposited on one side of a conductive polyimide film having a surface resistance of 600 Ω and a thickness of 30 Mt by a high frequency sputter deposition method to form a 5,000-layer Li layer. Next, a photoresist was formed on this Ti layer and dried at 90° C. for 8 minutes to form a resist film with a thickness of 1.6 μm. The resist 1 to film were exposed through a mask having a square pattern of 18 μm square on the entire surface with a pitch of 25,
Developed and then 110°C in an oven under N2 atmosphere.
The resist film was cured by heating for 5 minutes. Next, reactive ion etching was performed to remove the li in areas where there was no photoresist film. Next, the resist film was placed in an acetone bath and ultrasonic waves were applied to remove the resist film, completing the creation of an anisotropic conductive layer consisting of a conductive pattern.

Next, AI was deposited on the other surface of the conductive polyimide film by high frequency sputter deposition method to form a conductive layer with a thickness of 1000 layers. Next, a Ti film was deposited by the same high-frequency sputter deposition method to form a protective layer with a thickness of 800 μm.

Roughly coat the protective layer with thermosetting silicone resin except for the return electrode contact area, and heat it at 150'C for 10 minutes.
Heat cured for hours, critical surface tension 32 dynes/cm
, an ink release layer having a thickness of 0.3 μm was formed.

The obtained film-like material was connected so that the anisotropic conductive layer was on the inside to form an endless belt.

Using this ink recording medium, evaluation was performed as shown in FIG. That is, the return electrode contact portion of the conductive layer is grounded by the return contact roll, and the ink recording medium being conveyed is
The back pressure contact roll to which an electrical signal of 25 mA was input into pressure contact with a pulse width of 800 μs from a stylus head with a density of 8 pieces/flip was an insulating roll. At that time, the resistance value between the electrodes of the return contact roll and the stylus electrode head was monitored.

Repeat the above operation 5,000 times, 10,000 times and 20 times.
Table 1 shows the change in resistance value when the test was repeated 000 times.

Comparative Example 1 An ink recording medium was prepared in the same manner as in Example 1 except that the protective layer was not provided. Evaluation was performed in the same manner as in Example 1, and changes in resistance values were measured. The results are shown in Table 1.

As is clear from the results in Table 1, the changes in resistance values were much smaller in the examples of the present invention than in the comparative examples. This is because the conductive layer under the heating resistor layer and the conductive layer in contact with the return contact roll are not subject to deterioration such as oxidation due to the action of the protective layer. Note that in the examples of the present invention, the resistance value slightly changed, but this is considered to be due to oxidation and wear of the conductive pattern, not due to the conductive layer.

Example 2 An aluminum foil with a thickness of 7 CHtm was immersed in an aqueous sodium hydroxide solution with a pH of 1o, and pretreated with ultrasonic waves. The pretreated AI foil was then immersed in a 4% by weight aqueous phosphoric acid solution and connected to the anode. positive mH using platinum as the cathode
A porous aluminized substrate was obtained. Next, this substrate was immersed in a nickel plating bath, and electrolytic plating was performed to fill the holes in the substrate with nickel. Next, the aluminum layer was removed by immersion in a mixed aqueous solution of phosphoric acid and nitric acid and subjected to ultrasonic treatment to obtain an anisotropic conductive layer.

A film of 5iC-Ta-8102 with a film thickness of 1 mo was deposited on this anisotropic conductive layer by a high frequency sputtering film deposition method.
A heat-resistant resistor layer was then formed. Next, AI was deposited by high frequency sputtering to form a conductive layer with a thickness of 100 mm. Further, a TiN film was deposited by high frequency sputter deposition method to form a protective layer with a thickness of 500 μm.

A thermosetting silicone resin was applied onto this conductive layer, except for the return electrode contact area, and cured by heating at 150°C for 1 hour, resulting in a critical surface tension of 31 dynes/cm and a film thickness of 0.2 μm.
An ink release layer was formed.

The obtained film-like material was connected so that the anisotropic conductive layer was on the inside to form an endless bell.

Next, on the ink release layer, a colored thermofusible ink layer having a thickness of 6#2 and containing a thermoplastic resin having a melting point of 80° C. as a main component was provided to obtain an ink recording medium.

Evaluation was performed using this ink recording medium. The return electrode contact part of the conductive layer is grounded, a stylus head with a density of 8 pieces/M is pressed in a static state, and a pulse width of 200 μs is applied for 40 m.
The electrical signal of A was input. At that time, the resistance value between the electrodes of the return contact roll and the stylus electrode head was monitored.

Repeat the above operation io, ooo times, 50,000 times and i
oo, oo.

Table 2 shows the change in resistance value when the test was repeated several times.

Comparative Example 2 An ink recording medium was prepared in the same manner as in Example 2 except that the protective layer was not provided. Evaluation was performed in the same manner as in Example 2, and changes in resistance were measured. The results are shown in Table 2.

Table 2 Effects of the Invention In the ink recording medium of the present invention, as described above, a protective layer made of conductive ceramic or the above-mentioned high melting point, high hardness metal is provided on the ink release layer side of the conductive layer. , when an electrical signal corresponding to an image is input, the conductive layer in the part of the heating layer to which the pulse voltage is applied oxidizes due to heat.
Resistance value never changes. Furthermore, wear and oxidation are not caused at the side end electrode portions of the ink recording medium due to friction and current action caused by contact with the conductive sliding member. Additionally, when the protective layer is made of conductive ceramic, it also has the advantage of good adhesion to the ink release layer. Therefore, by using the ink recording medium of the present invention, a recorded image that is stable for a long period of time can be obtained.

Therefore, according to the present invention, repeated printing is possible, high-speed printing and high-density energy manual operation are possible, high-quality color images can be reproduced, and multi-gradation and robust images can be recorded. It is possible to perform print recording with high energy efficiency and low running cost.

[Brief explanation of the drawing]

FIGS. 1(a) and (b) are schematic cross-sectional views of the ink recording medium of the present invention, FIG. 2 is an explanatory diagram showing the state in which the ink recording medium of the present invention is evaluated, and FIG. FIG. 4 is an explanatory diagram illustrating current paths in an ink recording medium, and FIG. 4 is an explanatory diagram illustrating a state in which print recording is performed using the ink recording medium of the present invention. 1... Ink recording medium, 2... Print recording head, 3
... Transfer material, 4... Back pressure contact roll, 5... Return path contact roll, 6... Backup roll, 7... Conveyance roll, 11... Anisotropic conductive layer, 12... Heat generation Resistor layer, 13... Conductive layer, 14... Protective layer, 15...
- Ink release layer, 16... heat-melting ink layer. (o) Figure 1 Patent Applicant: Fuji Xerox Co., Ltd. Agent
Patent Attorney Seibu Gokyu 2 Figure 1゜Procedural Amendment (Voluntary)

Claims (2)

[Claims] (1) In an ink recording medium formed by sequentially laminating an anisotropic conductive layer, a heating resistor layer that generates heat upon input of an electric signal, a conductive layer, an ink release layer, and a heat-melting ink layer, the ink release of the conductive layer On the layer side, conductive ceramic or Mo, T
An ink recording medium comprising a protective layer made of one or more metals selected from the group consisting of a, W, Ti, Ru, Re, Rh, and Zr. (2) The ink recording medium according to claim 1, wherein the anisotropic conductive layer is a porous ceramic layer containing metal.