JPH0785365B2 - Method for producing conductive polymer pattern - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a conductive polymer pattern (including a conductive polymer image having a shade, hereinafter "pattern" includes "image"), and more specifically, it is described. The present invention relates to a method for producing a large area or a complex conductive polymer pattern on various substrates by a simple method. INDUSTRIAL APPLICABILITY The present invention is used for low current electric circuits, switches, electronic materials such as photoelectric devices, electronic substrates and the like.

[0002]

2. Description of the Related Art Conductive polymers have attracted attention as conductors to replace conventional metals, and various conductive polymers have been synthesized and studied. There are problems and limited uses. These conductive polymers are generally produced by an electrolytic polymerization method (first method) (Japanese Patent Laid-Open No. 63-231884 and Japanese Patent Laid-Open No. 61-84884).
No. 138414).

However, there is also known a method of producing a conductive film by vapor-phase polymerizing pyrroles on a predetermined substrate. For example, a method in which a crosslinkable polyvinyl alcohol to which an oxidant is added is applied, crosslinked by irradiation with light, and then pyrrole is vapor-phase polymerized on the crosslinked polymer layer (Japanese Patent Laid-Open No. Sho 6-62).
No. 2-188394, second method), a method in which a polymer layer containing pyrroles and an electrolyte is immersed in a photosensitizer solution and polymerized by light irradiation (JP-A-2-160314, third method), A method of coating a resist material to which a polymerization catalyst is added onto a substrate, irradiating it with light to cure it, then removing the non-irradiated portion, and then polymerizing the monomer (JP-A-2-27).
No. 3926, fourth method), a method of forming a polypyrrole film having a predetermined shape using photolithography (JP-A-2-216127, fifth method), and a polymer compound containing a polymerization catalyst is printed in a desired pattern. Method of forming and forming a conductive film on this pattern (JP-A-62-334)
No. 92, sixth method) and the like are known. Other reference methods include those disclosed in JP-A-60-257011 and JP-A-60-262182.

[0004]

However, the above first electrolytic polymerization method is limited to those which can be used for a substrate such as an electrode, and it is difficult to produce a large area or a complicated pattern.
In addition, although the above-mentioned second to fifth methods all perform light irradiation, in the second method, only light irradiation is carried out for crosslinking of polyvinyl alcohol. In the third method, an oxidation polymerization catalyst of pyrroles (eg FeCl ₃ etc.)
No. is used, but a photosensitizer is used to photopolymerize by this action.

In the fourth and fifth methods, since a desired pattern is formed by using photolithography, a series of steps such as resist coating, light irradiation, uncured portion removal, and cured film removal are required. In addition to being very complex, light irradiation is only used to cure the resist. In the above method of forming a conductive film having a desired pattern by using light irradiation, the oxidation catalyst (FeCl ₃
There is no one paying attention to or suggesting that the catalytic performance of (1) etc. is reduced. Further, although these methods can form a conductive polymer film having a constant thickness, they cannot form a shaded image. Furthermore, the sixth
In the method (1), a pattern is formed by printing, so it is difficult to form a fine and accurate pattern.

The present invention overcomes the above-mentioned drawbacks, and an object of the present invention is to provide a method for producing an arbitrary conductive pattern simply, quickly and accurately.

[0007]

The inventors of the present invention have found that among oxidizing agents that can be used for oxidative polymerization of conductive polymers, the oxidizability is reduced or disappears by light irradiation, and high conductivity is achieved in the light irradiated portion. The present inventors have completed the present invention by finding that there is an oxidizer having a property that the molecular monomer does not polymerize or the degree of reduction of its oxidizability changes depending on the degree of irradiation. That is, the method for producing a conductive polymer pattern of the present invention is capable of oxidatively polymerizing a monomer and oxidatively polymerizing by light irradiation.
Iron compounds, copper compounds whose ability is reduced or eliminated
, Nickel compounds, cobalt compounds and chromium compounds
At least an oxidizing agent ing from singly to is disposed on the substrate surface, or an oxidizing agent layer is formed on the substrate surface made of oxidant and other matrix polymers, optionally to the substrate surface of the Light irradiation to form a desired latent pattern that can be polymerized by reducing or eliminating the oxidative polymerization ability of the light-irradiated portion, and then forming a desired latent latent pattern on the polymerizable latent pattern portion. The above-mentioned monomer is vapor-phase polymerized to form a desired conductive polymer pattern layer.

[0008] As "oxidizing agent" as used in the present invention, iron, copper, an effective nickel, cobalt, the metal compound of chromium, a particularly preferred compound, iron chloride (III), iron (III) sulfate, etc. And a compound of copper (II) such as copper (II) chloride and copper (II) bromide. These metal compounds may be used alone or in combination of two or more.

The oxidizer is used alone in various solvents such as water, alcohols such as methanol, ketones such as acetone, halogenated hydrocarbons such as chloroform and 1,2-dichloroethane, and hydrocarbons such as benzene. It can be used by being applied to various base materials as a dissolved solution. Further, a solution using various solvents capable of dissolving the oxidizing agent and the matrix polymer can be used as a composite film containing the oxidizing agent by a method such as a casting method or a bar coating method. The composite with the matrix polymer can also be used as a film or the like prepared by another general film forming method, for example, kneading and extrusion with a base polymer. Further, the oxidizing agent may be applied together with a conductive salt serving as a doping agent.

As the above-mentioned "matrix polymer",
Any polymer compatible with the above oxidizing agents can be used. For example, especially polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, polymethyl methacrylate,
Polyacrylonitrile and the like are good. In addition, natural polymers such as gelatin can also be used.

The "monomer" used in the present invention includes pyrroles, thiophenes, furans and the like. Since the polymers such as pyrroles and thiophenes are black, a shaded mask (that is, positive,
A negative or the like) can be used to create a desired polymer image.
Examples of the pyrroles include unsubstituted pyrrole, N-substituted pyrrole, ring-substituted pyrrole and the like. It should be noted that the thiophenes and furans are also unsubstituted,
Substitution types can be used. It is also possible to copolymerize with two or more kinds of the exemplified 5-membered ring compounds or other copolymerizable monomers.

As the above-mentioned "light irradiation" means, sunlight, visible light, ultraviolet light or the like can be selected according to the purpose.
A device for generating light including these is used. Further, in order to form a predetermined light irradiation pattern, a known method, for example, a method of irradiating light with a predetermined mask, negative, positive or the like arranged on the surface of a predetermined substrate can be used. Incidentally, as described above, if a shaded mask (that is, positive, negative, etc.) is used, a desired polymer image can be produced. The "polymerizable latent pattern" means a pattern composed of a portion or layer containing an oxidizing agent having an oxidative polymerization ability, that is, a pattern in which the difference in the degree of polymerization does not matter. For example, the latent pattern also includes a portion where light irradiation is completely blocked and the polymerization ability is large, and a portion where the light irradiation is slightly blocked and the polymerization ability is reduced but still can be polymerized. Then, the vapor of the monomer is brought into contact with the latent pattern portion capable of being polymerized, and vapor phase polymerization is carried out. The conductive polymer obtained by this gas phase polymerization includes metal salt (oxidizing agent) content, irradiation light type, light irradiation wavelength, light irradiation intensity (that is, strength of oxidative polymerization ability), light irradiation time, matrix polymer It is possible to freely change the film thickness, the electric conductivity, the shading, etc. by selecting the kind and the like.

It is also possible to make the mask portion conductive so that the pattern has a difference in conductivity between the light irradiation portion and the mask portion. Furthermore, a thick film can be used to make a material having different conductivity on the front and back of the film. Further, the conductivity may be inclined depending on the shade of the mask, or a plurality of materials having different conductivity may be manufactured at the same time. Furthermore, since it is easy to apply an oxidizing agent to the surface of the base material by coating or other general thin film forming method, etc., the "base material" used in the present invention
As for all solid materials (not only sheets, plates,
(Cloth, non-woven fabric, paper, etc.) can be used, and the material thereof is not particularly limited.

[0014]

The oxidant used in the present invention has a reduced or eliminated oxidative polymerization ability upon irradiation with light. Therefore, when a layer such as this oxidant is irradiated with light such as ultraviolet light through a mask in a desired pattern, and a conductive polymer monomer vapor is brought into contact with it, a polymer is generated in the light-irradiated portion. Not (or almost never),
Since the conductive polymer is generated in the non-light-irradiated portion, a desired conductive pattern or a pattern having different conductivity can be obtained.

When the oxidant layer or the like is irradiated with light so as to obtain a desired light irradiation image pattern by using a shaded mask (negative, positive, etc.), the oxidative polymerization ability of the light irradiated portion is reduced. Since it is reduced depending on the light and shade, the degree of gas phase polymerization of the monomer can be changed according to this degree. Since this polymer has a black color, a portion having a large oxidative polymerization ability becomes darker, a portion having a small oxidative polymerization ability becomes a lighter color, and a portion having no oxidative polymerization ability becomes white. Polymer images can be formed.

According to the present invention, the degree of polymerization of the monomer can be freely and extremely easily adjusted by changing the concentration of the oxidant, the light irradiation time, the density of the negative, and the conductivity can be changed. it can. In addition, it is easy to form patterns on large areas, curved surfaces, uneven parts, etc.
It is also possible to fabricate a pattern of m. Further, it is not necessary to remove the insoluble portion as in the case of the resist, and the operation can be performed easily.

[0017]

As described above, according to the present invention, it is possible to easily and quickly produce an arbitrary conductive polymer pattern with high accuracy. Moreover, since the oxidizing agent is applied by applying a single solution of the oxidizing agent or a mixed solution with the matrix polymer, the applicable range of the usable substrate is extremely wide.
Furthermore, according to the present invention, all surfaces that can be irradiated with light can be applied, for example, even if the base material has a spherical shape, has various irregularities and curved surfaces, or even inside a container or the like,
Furthermore, the conductive polymer pattern can be formed extremely easily not only in the form of sheet, plate, etc. but also in the form of fiber (woven fabric, nonwoven fabric, filter paper, etc.). Further, in the above method of forming a polymer image, since the density of the monomer can be easily expressed by the degree of polymerization of the monomer, it is useful as a method for producing a black and white photograph without using silver salt.

[0018]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 5 parts of polyvinyl alcohol (polymerization degree: 500) was dissolved in 50 parts of water, and iron (III) chloride 1 was added to this solution so that the weight ratio to polyvinyl alcohol was 30%, and completely dissolved. To do. As shown in FIG. 1, this solution is cast on the surface of a polyester film 3 to form a thin film 2 having an appropriate thickness. The thin film 2 was covered with a mask 4 and irradiated with a 2 KW jet light for 10 minutes from a distance of 1 m. The polyester film after light irradiation was placed in a closed container containing a pyrrole monomer at the bottom,
The conductive polypyrrole pattern layer 5 was formed on the non-irradiated portion 22 by vapor-phase polymerization at 1 ° C. for 1 hour. The polypyrrole layer is not formed on the light irradiation portion 21. The surface resistance measured by a tester is
The light-irradiated portion 21 was insulative, while the non-light-irradiated portion 22 by the mask had a resistance of 1 KΩ.

Example 2 Polyvinyl acetate (5 parts) was dissolved in ethyl acetate (50 parts), and iron (III) chloride was added to this solution so that the weight ratio was 30% as in the case of Example 1, and the mixture was thoroughly added. Dissolve. This solution is cast in a Teflon dish to form a thin film having an appropriate thickness. A mask is placed on this thin film and 2 cm
Light was irradiated for 5 minutes using a 100 watt high-pressure mercury lamp at intervals. After the light irradiation, gas phase polymerization was carried out at 20 ° C. for 2 hours in a closed container having a pyrrole monomer in the lower part. The light-irradiated portion is insulating, and the non-light-irradiated portion by the mask is 250
A KΩ pattern was obtained.

Example 3 Polyvinyl alcohol (polymerization degree: 500) (5 parts) was dissolved in water (50 parts), and copper (II) bromide was added to the solution in the same manner as in Example 1 so that the weight ratio was 30%. Completely dissolve. This solution is applied on a polyester film by a bar coating method and dried to form a thin film having an appropriate thickness. The thin film was covered with a mask and irradiated with light from a 100 watt high pressure mercury lamp for 5 minutes. After irradiation with light, gas phase polymerization was carried out at 20 ° C. for 1 hour in a closed container containing a pyrrole monomer at the bottom. The light-irradiated portion showed 1 MΩ, and the non-light-irradiated portion by the mask had a pattern of 4.4 KΩ.

Example 4 In place of the mask used in Example 1, light irradiation was performed using a positive and negative image, and a black and white photographic image with a different image was obtained.

Example 5 A 10% solution of iron (III) chloride in methanol was passed through a filter paper (N
o. 2) is impregnated and dried at room temperature. The filter paper was irradiated with light under the same conditions as in Example 1, and then the pyrrole monomer was vapor-phase polymerized at 20 ° C. for 5 minutes. The light irradiation part is 2.
4 MΩ was shown, and a pattern of 830Ω was obtained in the non-light-irradiated portion by the mask. The present invention is not limited to the specific examples described above, and various modifications may be made within the scope of the present invention depending on the purpose and application.

[Brief description of drawings]

FIG. 1 is a partial explanatory cross-sectional view of performing light irradiation using a mask in Example 1.

FIG. 2 is an explanatory cross-sectional view showing a state after polymerizing pyrrole in Example 1.

[Explanation of symbols]

1; oxidizer, 2; thin film, 21; light irradiation part, 22; non-light irradiation part, 3; polyester film, 4; mask,
5: Conductive polypyrrole pattern layer.

Claims (1)

[Claims] 1. A monomer capable of being oxidatively polymerized and exposed to light.
Iron compound that reduces or eliminates the ability of oxidative polymerization
Materials, copper compounds, nickel compounds, cobalt compounds and
Alone it is disposed on the substrate surface Ru oxidant name from at least one of chromium compound, or oxidizing agent layer is formed on the substrate surface made of oxidant and other matrix polymer, the substrate surface To a desired light irradiation pattern to reduce or eliminate the oxidative polymerization ability of the light-irradiated portion to form a desired polymerizable latent pattern, and then the polymerizable latent pattern. A method for producing a conductive polymer pattern, comprising forming a desired conductive polymer pattern layer by vapor-phase polymerizing the above-mentioned monomer on a part.