JPH0746533B2 - Polymer sheet with conductive path - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polymer sheet in which a conductive path is formed.

[Conventional technology]

Currently, in order to pass an electric current between arbitrary points on an insulator, a method of connecting the two points with a metal or a conductive paint is used. However, such a method requires a lot of time and labor.

Furthermore, a substrate such as a copper clad circuit substrate on which a predetermined conductive path is formed is used.

However, in this case, the path is fixed in advance, the operation is complicated, and it is impossible to form a conductive path between arbitrary points on the insulator.

[Problems to be solved by the invention]

An object of the present invention is to provide a novel polymer sheet which is an insulating polymer sheet and which can easily conduct electric conduction between arbitrary points on the sheet surface.

[Means for solving problems]

The present inventors finally arrived at the present invention as a result of various studies in order to achieve the above objects.

That is, the present invention is a polymer sheet having one or more layers containing a conductive polymer inside an insulating polymer sheet, and a conductive path is formed through the conductive polymer by heating or light irradiation. It is a polymer sheet that has been put.

The insulating polymer used in the present invention is a polymer that is electrically insulating, can be formed into a sheet, and becomes conductive when heated or irradiated with light, and examples thereof include polyethylene, polypropylene, and ethylene-vinyl acetate. Copolymer,
Polyvinyl chloride, polystyrene, polyacrylonitrile, styrene-acrylonitrile copolymer, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride,
Polyvinylidene cyanide, polycarbonate, polyamide, polyimide, polyethylene terephthalate, polybutylene terephthalate, polyvinyl alcohol, polyvinyl carbazole, polyvinyl butyral, polyvinyl acetal, polymethyl methacrylate, polymethyl pentene, acetyl cellulose, thermoplastic polymers such as polysulfone, co- Examples thereof include polymers and thermosetting resins such as phenol resins, epoxy resins and unsaturated polyester resins.

As the conductive polymer in the present invention, various known ones are used, but preferred are five-membered heterocyclic compounds such as pyrrole, furan, thiophene, selenophene, and tellurophene and derivatives thereof, aniline and derivatives thereof, and the like. Polymers may be mentioned. These compounds can be used alone or in combination of two or more kinds.

The polymer sheet having one or more layers containing a conductive polymer in the insulating polymer sheet of the present invention can be obtained by various methods.

For example, after the acid or the oxidant is contained in these insulating polymer sheets, the surface is washed to remove the acid or the oxidant from the surface and the vicinity of the surface, and then the hetero five-membered cyclic compound or aniline or A polymer sheet in which a layer containing a conductive polymer is easily formed in an insulating polymer sheet by contacting a monomer such as a derivative thereof in a gas phase or a liquid phase and chemically polymerizing the same is obtained. can get.

As the acid or oxidizing agent used here, an inorganic acid, a compound of a metal, or an inorganic or organic oxide or peroxide is used, and for example, an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid or chlorosulfonic acid. As a Lewis acid, halides of metals such as titanium, zirconium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, palladium, platinum, copper, aluminum and tin, inorganic acid salts, organic acid salts and compounds of these metals can also be used. Known compounds are used as suitable oxidizing agents. Furthermore, salts of peroxyacids such as peroxodisulfuric acid and percarbonate, benzoquinone and organic peroxides are also used.

There are various methods for incorporating these acids and oxidizing agents into the insulating polymer compound. For example, as a method for adding them during sheet formation, a method in which a sheet is prepared by kneading and dispersing with a ball mill, roll, or the like, polymer. Examples include a method in which an acid or an oxidizing agent is dissolved in a solution in which materials are dissolved and then cast to form a sheet. Further, the insulating polymer sheet containing an acid or an oxidizing agent can be obtained by immersing or exposing the insulating polymer sheet in a solution containing an acid or an oxidizing agent or in a gas phase. After that, the surface may be washed with a solvent that dissolves an acid or an oxidizing agent, and the monomers may be brought into contact with each other to polymerize. The simplest method is, for example, a method in which a polymer sheet is immersed in a solution containing an acid or an oxidant, then pulled up, the surface is washed, dried, and then contacted with a monomer vapor for polymerization. Is mentioned.

As the solvent used at this time, alcohol other than water,
Benzene, toluene, hexane, tetrahydrofuran,
Examples thereof include organic solvents such as dioxane, acetonitrile, benzonitrile, nitromethane, nitribenzene, chloroform, dichloromethane, chlorobenzene and dimethylformamide.

Further, in order to allow two or more layers containing a conductive polymer to exist, the oxidizer may be permeated into the front and back surfaces by changing the immersion time of the insulating polymer in the oxidant solution, or the obtained conductive Repeat the same operation again on the polymer sheet with the layer containing the polymer, or apply the insulating polymer solution to the polymer sheet with the layer containing the conductive polymer, and perform the same operation after removing the solvent. Is a preferred method.

The polymer sheet in the present invention is, for example, a polymer sheet in which a layer containing a conductive polymer is present inside the insulating polymer sheet obtained as described above, and the surface is covered with an insulating layer. is there. The conductive path is formed in the polymer sheet by heating or irradiating light.

That is, the insulating polymer becomes electrically conductive by being carbonized, graphitized, or a conjugated system developed by being heated or irradiated with light. Therefore, by using an appropriate heat source or a light source, at any position on the surface of the composite type sheet, the position of the terminal where the conductive path is to be formed is heated, or the position is irradiated by irradiating the position. It can be electrically conductive. As the heating or irradiation used for such a purpose, various industrially used heating or irradiation methods such as high-frequency heating, hot plate, and laser processing can be used. However, particularly by using a laser, the power density and the exposure time can be easily controlled, so that good conductivity can be obtained. The conductive portion in the insulating polymer thus formed is connected to the conductive polymer layer in the insulating layer to form a conductive path in the polymer sheet.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to examples.

Example-1 Polyvinyl chloride sheet (length 10 cm x width 10 cm x thickness 1 mm)
Was immersed in a saturated solution (500 ml) of iron (III) chloride dissolved in chloroform for 15 minutes as an oxidant, taken out, and the excess oxidant on the surface and in the vicinity of the surface was washed with chloroform and then dried. The polyvinyl chloride sheet containing the oxidizing agent was placed in a desiccator containing a pyrrole aqueous solution in the lower stage, and the pyrrole was brought into contact with the vapor phase to chemically polymerize the pyrrole. After 24 hours, the sheet was taken out, thoroughly washed with methanol, and sufficiently dried under reduced pressure.

10mm in diameter facing the front and back of this sheet
When gold was vapor-deposited on to form an electrode and the resistance in the direction perpendicular to the surface was measured, it was found to have an insulating property of 10 ¹⁴ Ω or more. Also, a part of this sheet was cut into a size of 5 mm square, silver paste was applied to the opposing cross sections to form electrodes, and the electrical conductivity between cross sections perpendicular to the surface and parallel to each other was measured to be 2 × 10 ^-4. S /
It was cm.

A 1 mm diameter CO ₂ laser was vertically applied to the two places at a distance of 1 cm on the surface of this sheet. The electrode was attached to the place where the laser was irradiated, and the resistance between two points was measured and found to be 6 MΩ.

In the above examples, as the insulating polymer compound,
An example of using polyvinyl chloride was shown, but the same effect was obtained when other insulating polymer materials were used.

Example-2 On the surface of a polyvinyl chloride sheet (10 cm x 10 cm x 1 mm),
Cellophane tape with a width of 10 mm was vertically attached at intervals of 5 mm, and cellophane tape with a width of 10 mm was affixed to the back surface at intervals of 5 mm so as to be perpendicular to the direction of the front surface.
Using this sheet, pyrrole was polymerized in the same manner as in Example 1 except that the time of immersion in the oxidizing agent solution was 10 minutes. When the electrical resistance in the direction perpendicular to the surface of this sheet was measured, it had an insulating property of 10 ¹⁴ Ω or more.

Hereinafter, the details of the present invention will be specifically described with reference to the drawings.

FIG. 1 is an enlarged perspective perspective view showing a polymer sheet having a conductive path according to the present invention obtained in Example 2 above.
2 is a sectional view taken along the line AA showing the conductive path formed from the front surface shown in FIG. 1, and FIG. 3 is a sectional view taken along the line BB showing the conductive path formed from the back surface shown in FIG. is there.

1 to 3, 1 is a polymer sheet having conductive paths according to the present invention, 2 is a polyvinyl chloride sheet (10 cm × 10 cm × 1 mm), 2a, 2b, 2c and 2d are The four sides, 2e and 2f are the front and back sides, and 3 and 3 are a plurality of conductive paths (5 m) formed with a layer in the polyvinyl chloride sheet 2 below the portion excluding the vinyl tape from the surface 2e by the above method.
m × 6 pieces) 4 and 4 are a plurality of conductive layers formed in the polyvinyl chloride sheet 2 from the back surface 2f by the same method so as not to intersect the conductive paths 3 and 3 and at right angles. It is a sex path (5 mm x 6).

Conductive paths 3, 3 and 4, 4 are polyvinyl chloride sheet 2
Two layers each containing polypyrrole are formed in orthogonal directions without intersecting each other. That is, this layer is formed on the same surface with a width of 6 mm and 6 lines at equal intervals, and further both layers are formed so as to be perpendicular to each other with a space between them.

Next, the results of measuring the electrical conductivity or insulation resistance of the polymer sheet 1 having the conductive paths formed between the four sides or by the method at points g, h and i shown in FIGS. And explain.

The electric conductivity in the cross-sectional direction between 2a-2c and 2b-2d among the four sides of the sheet 1 was 10 ^-6 S / cm, but 2a-2b, and
Between 2c and 2d, the insulation was 10 ^-15 S / cm or more. This is due to the three-dimensional structure of the sheet 1 as described above, and when the cross section of this composition was examined, it was found that the composition shown in FIGS.
This is because, as shown in the figure, the layer containing polypyrrole was divided into an upper layer portion and a lower layer portion, and they were orthogonal to each other with a gap.

In this sheet 1, g point (upper pyrrole layer), h point (portion where the upper and lower pyrrole layers intersect), and i point (lower pyrrole layer), g point and h point are the surface 2e. From
At point i, a CO ₂ laser having a diameter of 1 mm was vertically applied from the back surface 2f. Attach the electrode where the laser was radiated, and g
-I The resistance between two points was measured and found to be 18 MΩ.

Incidentally, the structure of the present invention is not limited to the above examples, for example, the pyrrole layer was formed in one layer or two layers, but at least one layer, the width of the layer is the purpose of the present invention. Within the scope of the object of the present invention, the present invention covers all modified embodiments which can be easily conceived by those skilled in the art from the above description.

〔The invention's effect〕

According to the method of the present invention, the composite sheet is heated,
Alternatively, by irradiating light, it is possible to easily form a conductive path between arbitrary points and three-dimensionally, which is industrially valuable.

[Brief description of drawings]

FIG. 1 is an enlarged perspective perspective view showing a polymer sheet having a conductive path according to the present invention obtained in Example 2 above.
2 is a sectional view taken along the line AA showing the conductive path formed from the front surface shown in FIG. 1, and FIG. 3 is a sectional view taken along the line BB showing the conductive path formed from the back surface shown in FIG. is there. 1 ... Polymer sheet with conductive path formed 2 ... Polyvinyl chloride sheet 3, 3 ... Conductive path 4, 4 ... Conductive path

Claims (1)

[Claims] 1. A polymer sheet having one or more layers containing a conductive polymer inside an insulating polymer sheet, wherein a conductive path is formed through the conductive polymer by heating or light irradiation. A polymer sheet