JPH0347789A - Resistant composition film and recording material - Google Patents

Abstract

PURPOSE:To extremely lower the friction force between an electrifying head and a resistant composition film by providing a conductive heat-resistant smooth layer containing at least any one of an aromatic polyamide resin, an aromatic polyamideimide resin and a polyimide resin and a conductive material to at least one surface of a composition prepared by mixing a resin and a conductive material. CONSTITUTION:A conductive heat-resistant sliding layer 4 is laminated to a composition 3 prepared by mixing a resin 1 and a conductive material 2 to obtain a resistant composition film 5. As the resin 1, for example, a polyimide resin, a polyamide resin and a polyamideimide resin are adapted and, as the conductive material 2, carbon is general. Generally, the conductive heat-resistant smooth layer contains the conductive material and a resin and, as this resin, one having heat deformation temp. higher than that of the resin of the composition 3 is pref. and, for example, an aromatic polyamide resin, an aromatic polyamideimide resin and an aromatic polyimide resin are designated. A metal electrode layer may be laminated to the composition. However, when the conductive heat-resistant smooth layer 4 is laminated only to one surface of the composition 3, said metal electrode layer is laminated to the other surface of the composition 3.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a resistive composition film and a recording medium using this resistive composition film, and particularly relates to a resistive composition film and a recording medium using the resistive composition film, and in particular, to generate Joule heat by applying current from an external electrode (hereinafter referred to as a current-carrying head). The present invention relates to a resistive composition film that generates the above-mentioned Joule heat, and a recording medium that uses the Joule heat to thermally transfer a dye or a coloring material layer, for example.

2. Prior Art Conventionally, as a resistive composition film in this field and a recording medium using a resistive composition film (for example, Japanese Patent Publication No. 59-21790
As described in the publication, a low resistance layer (RL) of polyimide containing conductive carbon and 5iO-Cr
A printed ribbon has been proposed in which a high resistance layer (R,) of cermet and a conductor layer of stainless steel are laminated in this order.

Furthermore, as described in JP-A-62-135392, 4Q Cr-N, S n-8n O, IT
Thermal transfer printed resistive ribbons have been proposed with layers of O, AI-N or AI-AIpOs.

Conventionally proposed resistive composition films and recording bodies using resistive composition films (compositions in which a conductive material is kneaded into resin have a surface that is the same as the bulk state). The contact resistance with an object is large (for example, Japanese Patent Publication No. 59-21790), and the contact resistance with the current-carrying head is reduced by using a resistive electrode layer such as Cr-N. For example, when a resistive composition film is run in contact with a current-carrying bed, the frictional force at the interface between the electrode and the resistive composition film is large and the run does not run well.The electrode is scraped and deformed. However, recording media using a resistive composition film have the disadvantage that the resistive composition film is scraped off and contaminates the electrode parts. (hereinafter referred to as head jam) or head jam, which may cause poor contact of the energized head, causing disturbances in the recorded image, causing ground force blur or sticking, significantly contaminating the recorded image, and deteriorating the image quality of the recorded image. Disadvantages (for example, the running speed of the resistive composition film is 1 /
The recording method that reduces the amount of wear of the resistive composition film by slowing down the recording speed to n (hereinafter referred to as n-time mode recording method) is making it even more difficult to put the current technology into practical use.

The present invention has been proposed to overcome the above-mentioned drawbacks, namely, it is possible to extremely reduce the frictional force between the current-carrying head and the resistive composition film, prevent head clogging, and further reduce the frictional force by a factor of n. It is an object of the present invention to provide a resistive composition film and a recording medium using the resistive composition film, which can be applied to a mode recording method and has almost no contact failure between the current-carrying head and the resistive composition film.

Means for Solving the Problems The present invention; Aromatic polyamide resin on at least one side of a composition prepared by mixing a resin and a conductive material.
Aromatic polyamide-imide resin A conductive heat-resistant slippery layer containing at least one of polyimide resins and a conductive material is provided.

Function: A conductive, heat-resistant, slippery layer laminated on at least one side of a composition prepared by mixing a resin and a conductive material, has an extremely low frictional force, suppresses head clogging, and prevents poor contact with the current-carrying head. It also reduces

Embodiment FIG. 1 is a cross-sectional conceptual diagram illustrating the structure of a resistive composition film in an embodiment of the present invention.

Composition 3 prepared by mixing resin 1 and conductive material 2
This is a resistive composition film 5 on which a conductive heat-resistant slippery layer 4 is laminated.

As materials for resin l (for example, polyimide resin, polyamide resin, polyamide-imide resin, polyester resin, polycarbonate resin, polyether resin)
Common resins such as polyurethane resin, epoxy resin, melamine resin, and phenol resin are applicable. Polyurethane resins, epoxy resins, melamine resins, phenolic resins, etc. (for example, polyimide, polyester, polycarbonate, polyamide, etc.) are commonly used by coating on various films. Group polyamide resin is preferable in terms of high heat resistance and tensile strength. The material for the conductive material 2 is ζ. Any conductive material such as carbon, graphite, or metal may be used as a force support. Finished composition Although carbon is commonly used in terms of cost and ease of handling, these conductive materials can be used singly or in combination.

The composition 3 may contain additives such as a dispersing agent or a leveling agent added to the resin 1 and the conductive material 2. It is located at the interface with Composition 3, and plays the role of an electrode for supplying current from the current-carrying head to Composition 3, as well as the role of improving abrasion resistance and contact with the current-carrying head.

Furthermore, since the resistive composition film 51 of the present invention is applied to a device that generates Joule heat by passing electricity from a current-carrying head, the conductive heat-resistant slipping layer 4 is also required to have heat resistance, and to improve the lubricity with the current-carrying head. It is preferable that the conductive heat-resistant slipping layer 4 has a higher surface resistivity and a higher volume resistivity than the composition 3. is formed to be low. On the other hand, the conductive heat-resistant slippery layer 4 is mainly caused by the current-carrying head.
The conductive heat-resistant slipping layer 4 is formed to have a lower surface resistivity than the composition 3.

In general, the conductive heat-resistant slippery layer 4 (contains a conductive material and a resin) has the same structure as composition 3.

The conductive heat-resistant slippery layer 4 can be formed without containing a resin component. It is a wear body for the electrode of the current-carrying head. It is a material that adjusts the surface resistivity. It has good adhesion with the composition 3 and facilitates industrial use. A configuration including a conductive material and a conductive material is preferable.

The resin of the conductive heat-resistant slipping layer 4 (preferably a resin that has flexibility, heat resistance, and adhesiveness with the composition 3, and has a higher heat distortion temperature than the resin of the composition 3) Examples of the resin include aromatic polyamide resin, aromatic polyamideimide resin, and polyimide resin, and it is preferable to use these resins singly or in combination.Also, resin 1 of composition 3 is an aromatic polyamide resin. When the group polyamide-imide resin or the polyimide resin is used, conductive heat-resistant slippery layer 4 and composition 3
1. is preferable because it provides good adhesion. X.

The conductive heat-resistant slippery layer 4 is coated with conductive paint using a bar coater, for example.
It is preferably formed by coating with a gravure coater, a reverse coater, etc. Aromatic polyamide-imide resin or polyimide resin having an imide skeleton is particularly preferable because it exhibits heat resistance by imidizing the resin after coating. When carrying out imidization at °C, the reaction can be carried out at low temperatures using a conventional method, for example, using an aromatic amine catalyst such as pyridine, αcoβ-2T-picoline, 2,4- or 2,6-lutidine, or quinoline.Composition It is preferable that the resin of Product 3 has poor heat resistance.

Conductive material of conductive heat-resistant lubricant layer 4 (conductive material 2 of composition 3)
Among these materials, natural graphite is preferred because it can provide lubricity as a conductive material itself.The content of the conductive material in the resin of the conductive heat-resistant slipping layer 4 is Type Specific gravity Force that cannot be generalized as it varies depending on the resistivity, resin type, flexibility, etc. To (melon resin 1
The maximum ratio of the conductive material to 00 parts by weight is about 50 parts by weight. This method can be applied even when the heat-resistant slipping layer 4 does not have a film-forming ability. Therefore, taking the above-mentioned example, the conductive material can be contained in an amount of about 100 parts by weight per 100 parts by weight of the resin.

The surface resistivity of the conductive heat-resistant slippery layer 4 is as follows:
form (which layer mainly generates Joule heat)
, the applied device varies depending on the form of the current-carrying head and the surface resistivity of the composition 3 (according to experiments, when the composition 3 mainly generates heat due to the current-carrying
It is desirable that the surface resistivity is at least twice as high as the surface resistivity of the composition 3 used, preferably about one order of magnitude higher.On the other hand, when the conductive heat-resistant slippery layer 4 mainly generates heat when energized, the composition 3 used is used.
It is desired that the surface resistivity is about 1/2 or less, preferably about an order of magnitude lower than the surface resistivity. The lower the volume resistivity of the conductive, heat-resistant, slippery layer 4, the better. Generally, it is determined in relation to the surface resistivity.

Therefore, it is necessary to adjust the surface resistivity of the conductive heat-resistant slippery layer 4 (power to change the ratio of the conductive material and resin), force that can be done by controlling the film thickness of the conductive heat-resistant slippery layer 4 (volume resistance The latter is more useful for the request to keep the ratio as low as possible.

The reason is that the resistive composition film 5 has better contact with the current-carrying head than the composition 3 used. and the amount of conductive material contained in the conductive heat-resistant slippery layer 4 is
This may be because the amount of the conductive material is larger than that of the conductive material inside, but the conductive heat-resistant slippery layer 4 contains a material other than the conductive material and resin described above.
Silicone oil/k such as dimethylpolysiloxane, alkylaryl modification, etc. Epoxy modification Carboxyl modification
Reactive silicone oils (such as amino-modified) are: Polyether modification of dimethyl silicone Carboxy modification of dimethyl silicone Before silicone surface activation such as amide modification of dimethyl silicone Perfluoroalkyl sulfonate Perfluoroalkyl carboxylate Perfluoroalkyl ethylene oxide adduct Oligomer containing perfluoroalkyl group/hydrophilic group/lipophilic group Urethane containing perfluoroalkyl group/lipophilic group.

Fluorinated surfactants such as perfluoroalkyl phosphate esters, lubricants such as fatty acid amide, etc. may be included, and these lubricants may be used singly or in combination of two or more; A silicone-based or fluorine-based surfactant such as reactive silicone oil/lz or a silicone surfactant is preferable because the effect is significant even if the amount of the lubricant added is small. The content of the lubricant is 0.1 to 1 O of the resin in the conductive heat-resistant lubricant layer 4.
A weight percent range is preferred. When the conductive heat-resistant lubricant layer 4 contains a lubricant, the frictional force with the current-carrying head is further reduced, which is preferable. It goes without saying that the electrically conductive, heat-resistant, slippery layer 4 may be applied to both sides of the composition 3.

In addition, as shown in Figure 1, the case where only the conductive, heat-resistant, slippery layer 4 is laminated on the composition 3. However, a metal electrode layer may be laminated on the composition 3. When the slippery layer 4 is laminated only on one side of the composition 3 (
It goes without saying that a metal electrode layer can be laminated on the other side of the composition 3.Also, when the conductive heat-resistant slippery layer 4 is laminated on both sides of the composition 3, the metal electrode layer can be laminated on one side. It is only layered.

Resistive composition film 5 provided with a metal electrode layer (friend) The current passed from the current-carrying head can be concentrated in the thickness direction of the resistive composition film 5 near the top of the electrode portion of the current-carrying head.
When the conductive heat-resistant slippery layer 4 is laminated on both sides of the composition 3, and when the metal electrode layer is laminated on one side of the composition 3, the conductive heat-resistant slippery layer 4 immediately below the metal electrode layer Ka-length
The current on the electrode of the current-carrying head can be concentrated in the thickness direction of the resistive composition M5.
-3iOa, Cr-8i02. TiC-5iC, Ti-
Even if AI-N or the like is formed by sputtering or vacuum evaporation, the material of the metal electrode layer may be low resistance metal such as aluminum (or other metal material with a relatively high resistance component). The current on the electrode of the current-carrying head can be concentrated more in the thickness direction of the resistive composition film 5 than in the case where the resistive composition film 5 includes a slipping layer. As shown, conductive heat-resistant slipping layer 4
is formed only on one side of the composition 3 (of course, the lateral lubricant layer is laminated on the other side of the composition 3. Also, conductive heat-resistant lubricant layers are formed on both sides of the composition 3). If the resistive composition film 5 includes a lubricant layer (for example, if the lubricant layer is laminated only on one side) (for example, if the resistive composition film 5 includes a lubricant layer) Electricity is applied to generate Joule heat in the resistive composition film 5, and this Joule heat is used to record by applying heat to a commercially available thermal transfer recording ribbon or thermal recording paper. It is possible to make the thermal transfer recording ribbon or thermal recording paper and the resistive composition film 5 slide while being in close contact with each other. The metal electrode layer and the lubricant layer are laminated on the resistive composition film 5 (
It goes without saying that both the effects of providing a metal electrode layer and the effect of providing a lubricant layer can be obtained. A heat-resistant resin similar to the resin in the conductive heat-resistant slipping layer 4 is preferable, and the same resin material as the conductive heat-resistant slipping layer 4 is provided.

The lubricant of the lubricant layer (the material mentioned above for the lubricant in the conductive heat-resistant lubricant layer 4 is provided. Also, the addition of the lubricant into the resin is the same as that of the conductive heat-resistant lubricant layer 4). 1-10% by weight
is preferred.

Furthermore, FIG. 1 shows a case where a conductive heat-resistant slippery layer 4 is laminated on a single molded article of composition 3. For example, one side of a plastic base material (hereinafter referred to as the main base material) that does not contain a conductive material It is also possible to laminate a coating material of composition 3 on the surface (-in this case, the conductive heat-resistant slipping layer 4 is laminated on top of the composition 3).

In addition, a metal electrode layer (formed at the interface between the main base material and composition 3) is formed on the interface between the main base material and composition 3. ＼ Alternatively, the main base material itself may contain a lubricant.

In addition, in this case, generation of Joule heat (mainly due to composition 3).On the contrary, generation of Joule heat is mainly due to the conductive heat-resistant slipping layer
In this case, the layer of composition 3 is not particularly necessary, and it is sufficient to laminate the conductive heat-resistant slippery layer 4 directly on the main substrate. One in which composition 3 and conductive heat-resistant slippery layer 4 are formed on the base material, one in which only conductive heat-resistant slippery layer 4 is laminated on the main base material, and one in which composition 3 is formed alone as shown in FIG. When comparing a molded product with a conductive heat-resistant slippery layer 4 laminated thereon, the total thickness of the finished resistive composition film 5, the thickness of the conductive heat-resistant slippery layer 4, and various physical properties such as surface resistivity are At the same time, the Joule heat transfer efficiency (since the conductive material 2 in the composition 3 contributes to heat conduction), the latter is better.

FIG. 2 shows a conceptual cross-sectional diagram illustrating the structure of a recording medium in an embodiment of the present invention.

On the opposite side of the conductive heat-resistant slippery layer 4 of the resistive composition film 5
A color material layer 8 containing a dye 6 and a binder 7 is laminated.

The material of the binder 7 (varies depending on the nature of the dye 6 used): If the dye 6 is a disperse dye that sublimes or vaporizes when heated, a basic dye or a color former, for example, acrylonitrile styrene copolymer, polyvinyl butyral, polysulfone, etc. A highly heat-resistant resin is used as the binder 7, and in this case only the dye 6 is transferred.

In this case, when using a dye 6 that is not like this, a resin with a low melting point or softening point such as wax, vinyl acetate resin or its copolymer, low molecular weight polystyrene, xylene resin, rosin resin, etc. is used as the binder 7. is transferred together with the coloring material layer 8. When using the coloring material layer 8 of the type in which only the coloring matter 6 is transferred, it goes without saying that an image receptor having a dyeing substance for dyeing the coloring matter 6 is used.

FIG. 2 shows a case where the resistive composition film 5 does not contain a metal electrode layer. layered on top. When the resistive composition film 5 includes a metal electrode layer (as described in FIG.
Of course, the resistive composition film 5! can be concentrated in the thickness direction of the resistive composition film 5! in FIG. J<, the force that is when laminated on a single molded product of composition 3 containing a resin and a conductive material (the main base material may be used (-in this case, the coloring material layer 8 is formed on the raw base material) However, if it also has a metal electrode layer,
The metal electrode layer is formed at the interface between the composition 3 and the main substrate, and the coloring material layer 8 is of course formed on the raw substrate.Also, the coloring material layer 8 may contain a lubricant (- When the coloring material layer 8 contains a lubricant, it slides between the coloring material layer 8 of the recording medium and the image receptor, and the speed of the recording medium is 1/n with respect to the speed of the image receptor.
By slowing down the speed, it is possible to perform an n-times mode recording method that reduces wear on the recording medium, which reduces running costs, which is preferable in 1. X.

Method 41 of incorporating a lubricant into the coloring material layer 8 L A method of dissolving or dispersing the lubricant in the binder 7 of the coloring material layer 8 L A method of laminating a lubricant layer on the surface of the coloring material layer 8 may also be used. The material of the lubricant of the layer 8 is the lubricant listed in the conductive heat-resistant lubricant layer 4, particles of alumina, guanamine resin, melamine resin, etc.A recording body using the resistive composition film of the present invention is Not limited to the thermal transfer type listed in the diagram,
For example, it can be applied to transferring Joule heat generated in the resistive composition film 5 to a foaming agent and applying the pressure generated by the foaming agent to cause liquid ink to fly.

Hereinafter, the present invention will be explained in more detail with reference to specific examples.Example-1 Carbon-containing aromatic polyamide film (CAPA) (
(manufactured by Toshiku Co., Ltd.)) with a thickness of 10 μm and a surface resistivity of 1.
．． Prepare IKΩ as a composition, apply the following paint to one side of this CAPA as a conductive heat-resistant slippery layer using a bar coater, and after drying the solvent, 2
The resistive composition film of this example was obtained by heating at 00°C for 15 minutes to imidize.The film thickness of this conductive heat-resistant slipping layer was 1
．． To 1μ, the surface resistivity is 33Ω/[L, the volume resistivity is 3.5Ω’CrrL, the surface resistivity of the resistive composition film is 1.3Ω/[L], and the conductive heat-resistant slippery layer paint Composition> ○Carbon-containing polyimide conductive paint Electropack Z-278 (manufactured by Taitai Kako Co., Ltd., the same hereinafter)
・ 100 parts by weight ○ Cyclohexanone ・
- 300 parts by weight Example-2 Conductive heat-resistant slipping layer paint No. 2 of Example-1 0.5 parts by weight of silicone oil L-45 (1000) (manufactured by Nippon Unicar Co., Ltd.) as a lubricant (based on the resin) 5 PHR) was added to the CAPA of Example-1 in the same manner as in Example-1, dried and imidized to obtain the resistive composition film of this example. is 0.9 μ Surface resistivity is 72 Ω/[1 Volume resistivity is 4 Ω・C The surface resistivity of the resistive composition film is 1.5 Ω/[9 Example-3 Example- Aluminum was vapor-deposited on the CAPA side of the resistive composition film of 1 to form the resistive composition film of this example. The surface resistivity from the side is 2.
Example-4 Ti-8 was applied to the CAPA side of the resistive composition film of Example-1.
The film was formed using iOat-200 Angstrom sputtering.
To obtain the resistive composition film of this example, the surface resistivity of the resistive composition film was 4.5Ω/mouth.
ζ Disperse the lubricant layer paint with the following composition in a ball mill for 2 hours,
The film was coated with wiren and cured by irradiating it with a thick IKW high-pressure mercury lamp for 2 minutes after drying the solvent to obtain the resistive composition film of this example. The surface resistivity of the resistive composition film was the same as that of the resistive composition film of Example-1, 1.3 Ω/g. 30 parts by weight O Darocure-1173 (manufactured by Merck & Co.) 1.5 parts by weight O anhydrous silica Aerosil R972 (Nippon Aerosil (Japan Aerosil)
Co., Ltd.) 3 parts by weight O-fluorinated carbon G
F (manufactured by Daikin Industries, Ltd.) 3 parts by weight ○Silicone oil L-7602 (manufactured by Nihon Uniriki Co., Ltd.) 5 parts by weight ○Ethyl acetate
70 overlapping part Example-6 Aluminum electrode surface C of the resistive composition film of Example-3
The lubricant layer paint of Example-5 was applied in the same manner as in Example-5, dried, and cured to obtain the resistant composition film of this example. The thickness of the lubricant layer was 3 μm, which was the same as in Example-5, and the The surface resistivity of the composition film was the same as that of the resistive composition film of Example-3, and was 2.
．． Example 7 A composition of CAPA with a thickness of 6 μm and a surface resistivity of 6.5 and a resistance of Ω/hole was prepared, and the conductive heat-resistant slipping layer of Example-1 was applied to this composition. −
The resistive composition film of this example was coated in the same manner as in 1. After drying and imidization, the film thickness of this conductive heat-resistant and slippery layer was 9 μm. The volume resistivity was 9Ω/crrg. The surface resistivity of the resistive composition film was 1.3Ω/mouth. Example-8 The conductive heat-resistant film of Example-1 was applied on both sides of the composition of Example-1 The slippery layer was coated, dried and imidized in the same manner as in Example 1. The resistive composition film of this example was obtained.The thickness of both conductive heat-resistant slippery layers was 09μ.The surface resistivity was 7.
The volume resistivity is both 4Ω/crr4, and the surface resistivity of the resistive composition film is 1.2Ω/mouth. IKΩ/mouth Example 9 200 angstroms of aluminum was vapor-deposited on one side of the resistive composition film of Example 8 to obtain the resistive composition film of this example. The surface resistivity of the film is 2.4
Ω/9 Example-10 On one side of the resistive composition film of Example-8 Example-5
The lubricant layer paint was applied and dried and cured in the same manner as in Example-5.
The thickness of the lubricant layer is 3 μm, which is the same as in Example-5, and the surface resistivity of the resistive composition film of this example is the same as that of the resistive composition film of Example-8. 1. Example-11 Prepare the CAPA of Example-1 as a composition, apply the following paint as a conductive heat-resistant slippery layer to one side of this composition using a bar coater, and dry the solvent. The film thickness of this conductive heat-resistant slippery layer was 1.1 μm.
8 Surface resistivity is 34Ω/[1 volume resistivity is 3.6Ω
・Go to C The surface resistivity of the resistive composition film is 1.3 Ω/mm Conductive heat-resistant slippery layer coating composition> ○Aromatic polyamide (PA) (manufactured by Toshiku Co., Ltd.)... 1
00 parts by weight ON, N-dimethylformamide (DMF)...
100 parts by weight ○ Xylene 300 parts by weight ○ Conductive parts - Conductive parts by weight 60 parts by weight First, the above PA and D
Melt MF at 100℃ and add conductive carbon.
Xylene heated to 100°C was gradually added, and the mixture was ground and dispersed in a sand mill for 1 hour to form a paint.9 Example-12 Carbon-containing polycarbonate film (CPC) (manufactured by Bayer AG, hereinafter the same) with a thickness of 10 μm and a surface resistivity of 64
Prepare a composition of 0 Ω/mouth, apply a paint with the following composition as a conductive heat-resistant slippery layer to one side of this CPC using a bar coater, dry the solvent, and then heat it at 100°C for 15 minutes to imidize it. The resistive composition film of this example was prepared by heating and drying to remove pyridine.
/The volume resistivity is 3.9Ω・C nail The surface resistivity of the resistive composition film is 630Ω/9〈Electropack Z-278 100 layers〉 Hexanone 20 parts by weight ○Xylene... 240 parts by weight ○Pyridine
... 40 parts by weight Example-13 The CPC of Example-12 was prepared as a composition and nine CPs were prepared.
Coat a paint with the following composition as a conductive heat-resistant slippery layer on one side of C using a bar coater, and after drying the solvent,
The resistive composition film of this example was obtained by heating at ℃ for 15 minutes to imidize it and drying it by degassing and heating to remove pyridine. is 49Ω/[1 volume resistivity is 4.2Ω・CrrK
The surface resistivity of the resistive composition film is 660 Ω/mm. Conductive heat-resistant slippery layer paint composition> ○Carbon-containing aromatic polyamide-imide conductive paint Electropack Z-282 (manufactured by Ohmaki Kako Co., Ltd.) )
... 100 parts by weight ○ Cyclohexanone
50 parts by weight xylene... 24
0 parts by weight ○Pyridine 11 parts by weight Comparative Example-A The CAPA of the composition of Example-1 was used as it was as a resistive composition film of this comparative example.9 Comparative Example-B The CAPA of the composition of Example-1 was used as the film. The lubricant layer of Example-5 was coated on one side in the same manner as in Example-5, dried, and cured to form a resistant composition film of this comparative example.9 Comparative Example-〇 A fragrance that does not contain carbon and has a thickness of 6 μm. Using a group polyamide film as a base material, apply the conductive heat-resistant slippery layer of Example-7 in the same manner as in Example-7, dry and imidize to obtain the resistive composition film of this comparative example. The thickness of the slipping layer is 9μR, and the surface resistivity of the resistive composition film is 1.3Ω.
9 Comparative Example-D The CPC of the composition of Example-12 was used as the resistive composition film of this comparative example, and the resistive composition films of 9 or more (Examples 1 to 13 and Comparative Example-A
-D) were energized under the following energization conditions, and a commercially available thermal recording paper and each resistive composition film were stacked and run at the same speed to record (100% mode recording). -1, 5, 6, 10 and Comparative Examples - Resistive composition film C of A and B Recording where the running speed of the resistive composition film was 1/3 of the running speed of the thermal recording paper (3x mode recording ) After recording 10,000 solid lines for each of the nine, the current-carrying head was visually inspected under a microscope to check for head clogging, and to evaluate poor contact by looking at white spots on the recorded heat-sensitive recording paper. A copper plate, which is an electrode material, was placed on the conductive heat-resistant slippery layer of the membrane, and the results were evaluated using the coefficient of dynamic friction at 25° C., and the results are shown in Table 1.

Note that the QQ Δ X marks for head jams indicate the following conditions.

◎: After recording, there is no head clogging in any of the dots on the head, and there is no change in the electrodes of the head.

○: After recording, there are traces of head jamming in several places among the dots on the head.

△: After recording, some head jams clearly occurred in some of the dots on the head.

×: After recording, a head jam occurs in the dot direction part of the head.

Table 1 (The * mark in the table indicates that there was damage to the thermal paper side of the resistive composition film.) Current application conditions> ○ Current-carrying head separation electrode density...6 dots/mm (separation electrode and ○Recording period ・・0.4ms ○Applied pulse width ・・80μs ○Applied energy ・・3.5J/am2 As shown in Table 1, the resistance of the present invention is Sexual composition film (Example-
1 to 13) are conventional resistive composition films (Comparative Examples-A-D)
The coefficient of friction is smaller than that of the conventional head, and there is no head clogging, and there are almost no contact failures.

That is, resistant composition A of Example-1 and Comparative Examples-A and B
Furthermore, when comparing the resistive composition films of Examples 12 and 13 and Comparative Example, the film of the present invention has a better coefficient of friction, head clogging, and poor contact, even though they each use the same composition. Comparing the resistive composition films of Examples 1 and 12, there was a slight difference in the friction coefficient and poor contact despite using the same conductive heat-resistant slipping layer. The reason for this is Example-1
This is because CPC, which has poor heat resistance, was used in the composition of the resistive composition film No. 2, and the imidization was incomplete.

Examples-1 and 11. There was a slight difference in head clogging between the resistive composition films of Examples 12 and 13. This is thought to be due to the difference in heat resistance of the resins used in the conductive heat-resistant slipping layer.

Furthermore, in the 3x mode recording, the resistive composition film of Comparative Example-A did not run, and the resistive composition film 1 of Example-1 had damage on the thermal recording paper side. This is the force to apply pack tension to slow down the speed of the resistive composition film relative to the speed of the thermal paper for recording in the 3x mode (comparative example - the resistive composition film of A This is because the tensile strength of the resistive composition film does not exceed the pack tension.For this reason, the conductive heat-resistant slipping layer of the present invention also has the effect of imparting thermomechanical strength to the composition.

Comparing the resistive composition films of Examples 1 and 2, it was found that the friction coefficient of the resistive composition film of Example 2 was lower due to the effect of the lubricant mixed in the conductive heat-resistant slipping layer. ing. However, head clogging and poor contact of the resistive composition film of Example-2 are slightly inferior to those of the resistive composition film of Example-1.
The reason for this is that the heat resistance of the resin of the conductive heat-resistant lubricant layer was slightly reduced by mixing the lubricant.

Examples-3 and 1. Comparing the resolution of the thermal recording paper on which the resistive composition films of Examples 9 and 8 were recorded, the resistive composition films of Example 2 and Comparative Example-A were compared, and in both cases, the one with vapor-deposited aluminum had better resolution. 9. This is because the current was concentrated in the thickness direction of the resistive composition film near the electrode of the current-carrying head.a Comparing the resistive composition films of Examples 9 and 3 in the same manner,
The resistive composition film 9 of Example 9, in which a conductive heat-resistant slippery layer was laminated directly under the metal electrode layer, had better image resolution.
This is to concentrate the current near the electrode of the current-carrying head from the mid-length of the conductive heat-resistant slippery layer directly below the metal electrode layer.

Furthermore, when comparing the resistive composition films of Examples 3 and 4, Example 4 in which TiC-3i02 having a resistive component was formed
The resistive composition film fills the space between the separate electrode and the common electrode of the current-carrying head, increasing the recording density. This is because the metal electrode layer having a resistive component contributes to heat generation.

Comparing the resistive composition films of Example-1 and 5.6.10, there was no difference in Koshin mode recording. In 3x mode recording, a lubricant layer was coated in Example-5, 6, and 10. When comparing the resistive composition films of Example-7 and Comparative Example-C, the interface between the current-carrying head and the resistive composition film is The same electrically conductive, heat-resistant, slippery layer had a friction coefficient of 1.7 (recording density of heat-sensitive recording paper), but there was no difference in friction coefficient for head clogging or contact failure. The resistive composition film of Comparative Example-〇 was 1.4, which was slightly higher than that of the resistive composition film of Example-7.The reason for this is that Conductive material force (this is because it contributes to heat transfer).

Example-14 Heat melt transfer ink having the following composition was used in Examples-1 to 4.7 to
9.11-13. and Comparative Examples-A, C.

Resistor composition film No. D Hot-melt coating was carried out so that the ink thickness was 5 μm, and the resistive composition film was formed (u
L Added "-1" to the comparative example number to set the recording body number (for example, the resistive composition film of Example-1 was recorded as recording body 1-1).
).

Hot melt ink composition> ○NPS-6115 (manufactured by Nippon Seiro Co., Ltd.) ioo parts by weight ○YS resin px-too (manufactured by Yasushi Oil Industries Co., Ltd.)
30 parts by weight ○ Carbon black 30 parts by weight These recording media (Using commercially available plain paper as the image receptor, the speed of the image receptor and the recording body are the same for C equal magnification mode recording), and the energization conditions described above were applied. Example 15 A thermal dye transfer ink using a sublimable or vaporizable dye having the following composition was applied to Example 1 to 4, 7 to 9° 11 to l 3.
Comparative Examples - Wire bar coating was applied to the resistive composition films of A, C, and D so that the dry ink thickness was 5 μm, and "-2" was added to the comparative example number of the resistive composition film. The number is the number of the recording body (for example, the resistive composition film of Example-1 is recording body 1-2).

Thermal dye transfer ink composition> 1. Sublimable or vaporizable dye. 5-bis(ethylamino)-4,8-naphthoquinone... 10 parts by weight Titanium oxide 6 parts by weight Silicone lubricant L-7001 (manufactured by Nihon Uniriki Co., Ltd.)
・0.2 parts by weight ○Polyvinyl butyral ・
... 4 parts by weight ○Toluene ...10
0 parts by weight These recording bodies have a polyester-based dyeing layer that sufficiently dyes the dye.The speed of the recording body is set to 1/10 of the speed of the image receptor (10 times recording) Table 2 shows the results of recording density, head clogging, contact failure, and runnability of these recording bodies that were energized under the above-mentioned energization conditions and recorded 10,000 lines solidly.

Note that the symbols for head jam in Table 2 are the same as in Table 1, and the symbols for runnability are as follows.

◎: Both the recording medium and the image receptor run extremely well.

○: Both the recording medium and the image receptor run almost well.

△: There is unevenness in the running of the recording medium.

×: The recording medium is torn into pieces.

(Recording body D-2 traveled only about 3 lines) As is clear from Table 2 Example-I~4, 7~9.1
Recording bodies using resistive composition films of Nos. 1 to 13 (Top Comparative Example - Compared to conventional recording bodies using resistive composition films of A and D, exhibiting better characteristics regardless of the recording mode) .

Below in Table 2, the present invention will be described in detail, mainly with respect to points that differ from the results obtained only with the resistive composition film.

First, the results of recording in the same magnification mode on the recording medium will be compared.

Recording body 1-1. 2-1 and 3-1. 4-1, and when recording bodies 8-1 and 9-1 are compared, recording body 3-
1. 4-1 and 9-1 have low recording density; for example, when recording characters, they have excellent resolution and sharp print. This tendency is sharper in the k recording body 9-1 when comparing the recording bodies 1-1 and 9-1. This effect is much more effective than when only a resistive composition is used.The reason for this is that unlike thermal paper, the coloring material that is directly thermally transferred is on the resistive composition, so the heat does not spread. This is because the recording material 4-11 has the highest recording density, unlike a low-resistance metal electrode layer such as aluminum.
This is because heat was generated in the metal electrode layer having a resistance component.

When the recording bodies 7-1 and 1-1 are compared, there is almost no difference in color. When the recording bodies 7-1 and C-1 are compared, there is a marked difference in recording density. This is because the recording material C-1 uses the main base material, so it is difficult for heat to be transferred into the raw base material.Even though it is recorded in the same magnification mode, it is C-1. This is because the same resistive composition is not subjected to electric heating pulses and the recording medium is not forced to bend.aAlso, although the same results as in Table 1 are obtained regarding head clogging and poor contact, this is due to the fact that the resistive composition Composition force (which shows that it has a large effect on the recording properties of the recording medium) Next, we will compare the results of recording in the 10x mode of the recording medium.As is clear from Table 2, using recording bodies with the same color material layer. Despite this, the recording characteristics of the present invention and the prior art are significantly different. The contribution is large, and when the recording medium of the present invention is used, all recording characteristics can be satisfied, but only recording medium C-2 has no problems with head clogging, poor contact, and running performance.
There are extremely few problems compared to .

This is due to the same reason as in the same magnification mode recording, as the resin of the resistive composition film used in the recording medium D-2 lacks heat resistance.
In recording bodies 11-1 and 12-1 using the same composition, the recording bodies 11-1 and 12-1 of the present invention ran very well. When used, there is less head clogging.Therefore, for example, the life of the current-carrying head can be extended.

The reason why head clogging is lower than the results in Table 1 is the difference between 3x mode recording and 10x mode recording. Although it takes 3 pulses in Table 2, it takes 10 pulses, but it goes without saying that the effect is the same even if other conductive materials such as carbon are used in the examples cited here. Effects of the Invention A Friend of the Invention A resistive composition is provided with at least one conductive heat-resistant slippery layer of a composition prepared by mixing a resin and a conductive material. The frictional force between the recording medium used, the energized head, and the resistive composition can be extremely low, the head does not get jammed, and it can also be applied to the n-times mode recording method, and it is compatible with the energized head. The effect is that there is almost no contact failure with the resistant composition.

[BRIEF DESCRIPTION OF THE DRAWINGS] FIG. 1 is a cross-sectional conceptual diagram illustrating the structure of a resistive composition film in an embodiment of the present invention. FIG. 2 is a cross-sectional diagram illustrating the structure of a recording medium in an embodiment of the present invention. In the conceptual diagram...Resin 2...Conductive edge 3...Composition 4.
...Conductive heat-resistant slippery layer 5...Resistance composition 4K 6
・・・Black color 7...Binder, 8...Color material style

Claims (10)

[Claims] (1) At least one of aromatic polyamide resins, aromatic polyamideimide resins, and polyimide resins is applied to at least one surface of a composition prepared by mixing a resin and a conductive material, 1. A resistive composition film comprising a conductive heat-resistant slippery layer containing a conductive material. (2) The resistive composition film according to claim 1, characterized in that an electrically conductive, heat-resistant, slippery layer is provided on one side of the composition, and a metal electrode layer is provided on the other side of the composition. (3) The resistive composition film according to claim 1, characterized in that conductive heat-resistant slipping layers are provided on both sides of the composition, and one side of the composition is provided with a metal electrode layer. (4) The resistive composition film according to claim 1, wherein an electrically conductive heat-resistant lubricant layer is provided on one side of the composition, and a lubricant layer is provided on the other side of the composition. (5) The resistive composition film according to claim 1, wherein conductive heat-resistant lubricant layers are provided on both sides of the composition, and a lubricant layer is provided on one side of the composition. (6) The resistive composition film according to claim 2 or 3, characterized in that a lubricant layer is laminated on the metal electrode layer. (7) The resistive composition film according to claim 1, 2, 3, 4, or 5, wherein the resin of the composition is any one of aromatic polyamide, aromatic polyamideimide, and polyimide. (8) The resistive composition film according to claim 1, 2, 3, 4, or 5, wherein the conductive heat-resistant lubricant layer contains at least one type of lubricant selected from silicone-based and fluorine-based lubricants. (9) A recording medium, characterized in that a coloring material layer containing a dye and a binder is provided on the other surface of the resistive composition film according to claim 1. (10) The recording medium according to claim 9, characterized in that a metal electrode layer is provided at the interface between the composition and the coloring material layer.