JPS61250038A - Production of conductive composite - Google Patents

Abstract

PURPOSE:To readily obtain the plastic conductive composite of high durability, by ringing a material to be subjected to electrical conductivity treatment into contact with a gaseous phase atmosphere of monomer capable of forming electron conjugated polymer followed by irradiation of active energy rays. CONSTITUTION:A solution prepared by dissolving, in an appropriate solvent, such a monomer having in its molecular structure conjugated double bond capable of inducing polymerization by light energy as five-membered heterocyclic compound (pref. pyrrole, thiophene, furan, indole or a derivative therefrom) is heated to generate a monomer gas, which is then brought into contact with a material to be subjected to electrical conductivity treatment consisting of plastic film, molded product, etc. to infiltrate said monomer gas into the material followed by irradiation of active energy rays, pref. ultraviolet light to polymerize the monomer, thus obtaining the objective composite. Preferably, additional doping is performed either as pretreatment, post-treatment or during the photopolymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for manufacturing a conductive composite of a plastic ring used, for example, as an IC packaging material.

(Prior Art) It has been conventional practice to manufacture conductive composites by using plastic as a base material and subjecting it to conductivity imparting treatment. Such conductive composites have high conductivity and Taking advantage of the characteristics of plastic materials, it is used as a material for preventing static electricity damage, such as in IC packaging materials.

Conventional methods for producing conductive composites include methods for thinly vapor-depositing metal oxides on plastic films, etc., methods for thinly coating conductive paints containing metal oxides on plastic films, etc., and methods for forming transparent films. A method of coating a plastic film or the like with a pigment, a method of electrolytically oxidizing polymerization of virol onto polyvinyl chloride, etc. are known.

(Problem that the invention seeks to solve).

The above-mentioned conventional method forms a conductive film on the surface of plastic, so it is generally classified as K.

It is not possible to obtain a conductive composite with excellent durability, which has disadvantages such as poor bonding stability of the conductive film to the plastic substrate and the conductive film peeling off or being scratched by external force. There wasn't. According to the electrolytic oxidation polymerization method of pyrrole, conductive polypyrrole can be formed in a plastic base material, but the manufacturing cost is high due to electrolysis, it requires complicated manufacturing equipment, and the shape of KH It can only be applied to film-like and sheet-like glass substrates, and it can only be applied to relatively small-sized items, such as molded products, long-sized products, and large-sized products. The disadvantage is that it is difficult to apply to products.

(Means for Solving the Problems) The method for producing a conductive composite of the present invention involves contacting a conductive treated material made of glass with a 7-mer gas phase atmosphere capable of forming an electronically conjugated polymer. .

The method is characterized by obtaining a conductive composite by irradiating it with active energy rays.

The base resin of the electrically conductive treated material used in the present invention is as follows.

Polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyethylene, polybutadiene, polystyrene,
Examples include polycarbonate, nylon, polyetherimide, polyether sulfone, cellophane, polyethylene terephthalate, etc., and in general, materials with poor gas barrier properties are advantageously applied in the present invention. The material to be electrically conductively treated may be a plastic film using the above-mentioned resin as a base resin or a plastic molded product (injection molded product, pressure-pressure vacuum molded product, etc.).9 The present invention can be advantageously applied to either case. Although the thickness of the material to be electrically conductively treated is not particularly limited, it is preferably 5 μWL to 1000 μWL.

In the present invention, the material to be electrically conductively treated is brought into contact with a gas phase atmosphere of a monomer capable of forming an electronically conjugated polymer. It refers to a substance that has bonds and undergoes polymerization when exposed to light energy.2 Representative examples include 5.
Examples include membered heterocyclic compounds. The 5-membered heterocyclic compounds preferably used in the present invention are pyrrole, thiophene, 75ene, indole, or derivatives thereof 9 For example, 3-methylpyrrole, 3-)f-ruthio7ene, 3-
Examples include methylfuran, 3-methylindole, etc., but are not limited to these.

The above monomers are dissolved in a suitable solvent.

This monomer solution is heated to generate 7-mer gas. Alternatively, the monomer gas may be generated from the solid itself. As the above-mentioned solvent, any commonly used organic solvent can be used. For example, alcohols such as methanol, ethanol, and butanol, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

Ethers such as ethyl ether and tetrahydrofuran 1)
．． Nohalohydrocarbons such as methylene chloride and chloroform, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene, benzene and xylene, and aliphatic hydrocarbons such as hexane.

Examples include nitrogen-containing compounds such as acetonitrile and benzonitrile. In implementing the present invention.

Among the above-mentioned solvents, a solvent suitable for the base resin of the material to be electrically conductively treated may be selected, but among the above-mentioned solvents, those with a low boiling point are more advantageous in terms of manufacturing conditions.

In the present invention, irradiation with active energy rays is used as a means for photopolymerizing the gaseous monomer.

Ultraviolet rays are preferred as the active energy rays, and the irradiation time varies depending on the thickness of the material to be electrically conductively treated, the degree of electrical conductivity to be imparted, etc., but is generally preferably 2 to 24 hours. When irradiating, the material to be electrically conductively treated may be irradiated directly or may be irradiated through a transparent body such as a transparent plate or a transparent container.

The concentration of the monomer gas with which the material to be electrically conductive is in contact can be arbitrarily adjusted by adjusting the irradiation time of active energy rays, etc., but it is usually desirable to set the concentration to 1000 F or more.

Photopolymerization of the monomers imparts electrical conductivity to the material to be electrically conductively treated, but it is preferable to carry out doping treatment in order to impart greater electrical conductivity.

Doping treatment methods include 1) applying a dopant to the surface of the material to be electrically conductively treated as a pretreatment, and 2) adding a gaseous dopant together with monomer gas into the resin of the material to be electrically conductively treated during photopolymerization. 3) Method 9 of doping treatment as post-treatment For example, after photopolymerization, there are methods of immersing a material to be conductively treated to which conductivity has been imparted in a dopant solution (for example, an aqueous hydrochloric acid solution).

As the dopant, any commonly used acceptor dopant can be used. Acceptor dopants include halogens such as chlorine, bromine, and iodine, Lewis acids such as phosphorus pentafluoride and arsenic pentafluoride, protonic acids such as hydrogen fluoride, hydrogen chloride, and sulfuric acid, and transitions such as ferric chloride. Transition metal compounds such as metal chlorides, silver perchlorate, silver boron fluoride,
Examples include organic compounds such as 7.7.8.8-tetracyanoquinodimethane.

In carrying out the present invention, an apparatus such as that shown in FIG. 1, for example, is used. This device consists of a monomer gas contact tank 1, a monomer gas supply device 2, a dopant supply device 3, and an active energy ray source 4.

The monomer gas contact tank 1 has an open upper surface, and is configured such that a conductive treatment target material 5 made of a plastic film is placed on the upper surface of the opening. The monomer gas supply device 2 consists of a monomer solution tank 6 and a heating device 7, and the monomer solution (for example, an acetonitrile solution of pyrrole) 8 in the monomer solution tank 6 is heated to generate a monomer gas (for example, pyrrole gas), This monomer gas is supplied to the nitrogen blowing pipe 9
The nitrogen gas supplied through the monomer gas contact tank 1 is fed into the monomer gas contact tank 1 via the supply pipe 10.

On the other hand, the dopant supply device 3 consists of a dopant tank 1) and a heating device 12, and the dopant (for example, iodine) 13 in the dopant tank 1) is heated to generate a dopant gas (for example, iodine gas). , the nitrogen gas supplied through the nitrogen blowing pipe 14 is sent into the monomer gas contact tank 1 via the supply pipe 15.

The monomer gas and dopant gas thus fed into the contact tank 1 come into contact with the surface of the material 5 to be electrically conductively treated and penetrate into the resin of the material 5 to be treated. Active energy rays (for example, ultraviolet light) are irradiated onto the conductive material 5 from an active energy ray source (for example, an ultraviolet lamp) 4 installed above the conductive material 5, thereby causing the resin of the conductive material to be heated. The penetrating hexamer is photopolymerized to produce an electronically conjugated polymer (for example, pyrrole is photopolymerized to produce polypyrrole). The generation of this electronically conjugated polymer imparts electrical conductivity to the material 5 to be electrically conductively treated. Further, since dopants are mixed as impurities in the resin of the material to be electrically conductively treated, the electrical conductivity is improved due to the doping effect, and even higher electrical conductivity can be obtained. Note that 16 is a discharge pipe for discharging the condensed liquefied top and liquefied solvent to the outside of the tank.

In this way, a conductive composite in which the electronically conjugated polymer is impregnated into the resin of the material to be electrically conductively treated is obtained. However, since the base resin of the material to be electrically conductively treated and the electronically conjugated polymer have a so-called hybrid structure, for example, heating is required. However, the electronically conjugated polymer will not escape from the base resin, and the conductivity will not decrease or disappear due to thermal factors.

If the material to be electrically conductively treated is a plastic molded product, a separate device from the above device is prepared. In this apparatus, although not particularly shown, the monomer gas contact tank is configured as a closed container, and a plastic molded product is set in this tank. The means for supplying hemotsmer gas in the closed contact tank may be the same as in the case of the above device, but it is also possible to put a monomer solution below the ia and heat it to generate hemotomer gas in the tank. . Alternatively, the dopant may be placed in a suitable container below the contact tank without contacting the monomer solution. In either case, it is necessary to set the plastic molded article in a contact tank using appropriate means so as to bring it into sufficient pressure contact with the monomer gas and dopant gas.

(Function) In the present invention, a monomer capable of forming an electronically conjugated polymer permeates into the resin of the material to be electrically conductively treated.

It is photopolymerized by active energy rays to form a polymer in the resin.

It is highly unlikely that photopolymerization occurs before the monomer penetrates into the resin, and the polymer penetrates into the resin, but if such a phenomenon were to occur, the present invention would This also includes cases where

(Effects of the Invention) According to the present invention, a material to be electrically conductively treated is brought into contact with a gas phase atmosphere of a monomer capable of forming an electronically conjugated polymer.

Since polymerization is caused by irradiation with active energy rays, and K imparts conductivity to the material to be treated, it is easier to produce a conductive composite compared to conventional methods.

Furthermore, since the base resin of the material to be conductively treated and the electronically conjugated polymer impregnated in the resin have a so-called hybrid structure, the conductive composite obtained according to the present invention is immersed in a heated chemical. The conductivity does not decrease or disappear even when exposed to heat, and it has excellent heat resistance and chemical resistance.Furthermore, the conductivity is not impaired by external force, and it has extremely high durability as a conductive composite. .

According to the present invention, the manufacturing apparatus used for carrying out the invention has a simple structure and the manufacturing cost is low. Furthermore, the material to be conductively treated can be applied not only to plastic films or sheets, but also to complex-shaped products such as plastic molded products, long-sized products, and Oya products, and can handle a wide variety of conductive composites of various types. It has the effect of being manufacturable.

Furthermore, in the present invention, when a transparent material is used as the material to be electrically conductively treated, its transparency is not impaired;
It is possible to produce composites with excellent conductivity.

The conductive composite produced according to the present invention can be used for IC packaging,
In addition to being useful as a material for preventing static electricity damage in materials such as IC magazines and IC magazines, it can also be used in a wide range of other applications.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 A methanol solution of virol with a molar concentration of 5'Oa/k was placed in the glass container K of 1) with an open top.

A small glass container with an open top and a height sufficient to prevent the pyrrole solution from entering was immersed in this solution, and 0.5.9 iodine was placed in the glass container. 1m
'A 20 μm thick polychloride and nylidene film was placed on the top opening of the glass container.

1) While heating the inside of the glass container for 40'CK, the above film is exposed to ultraviolet rays with a wavelength of around 254 nm for 10 minutes from above.
After irradiation for several hours, a brown transparent film was obtained.

After washing this film with methanol and drying it at 100° C. for 1 hour, its electrical conductivity was measured, and it was found that it had the desired electrical conductivity.

Furthermore, as a result of measuring the total light transmittance, it was found that the film had desired transparency. These results are shown in Table 1.

Example 2 Using the apparatus shown in FIG. 1, a nylon-6 film with a thickness of 30μ was placed in the upper opening of the monomer gas contact tank 1, and 0.5 molar concentration of virol was introduced into the monomer solution. An acetonitrile solution was added, the monomer solution tank was heated to 40° C., and pyrrole gas was supplied into the contact tank 1. Also, put iodine in the dopant tank 1) and
iodine gas was supplied into the contact tank 1. Ultraviolet light having a wavelength of around 254 nm was irradiated from above the nylon-6 film for 16.5 hours to obtain a pale yellow transparent film. This film was subjected to the same post-treatment as in Example 1, and its electrical conductivity and total light transmittance were measured after death, and it was found to have desired electrical conductivity and transparency. The results are shown in Table 1.

Example 3 0, O1) A soft polyvinyl chloride film with a thickness of 300 μm was immersed for 24 hours in a molar concentration of ferric chloride methanol solution and placed in the top opening of a glass container containing the same pyrrole solution as in Example IK. A brown transparent film was obtained by heating and irradiating with ultraviolet rays under the same conditions as in Example 1 except that iodine was not used as a dopant.

After washing this film with methanol and drying it at room temperature, its electrical conductivity and total light transmittance were measured, and it was found to have desired electrical conductivity and transparency. The results are shown in Table 1.

Example 4 In a completely sealed container of 1) that transmits ultraviolet rays, 50 rnl of an acetonitrile solution of virol with a concentration of 0.5 molar,
Place the 0.5.9% iodine in another small glass container, and place a hard polyvinyl chloride molded product for automatic IC mounting (
500 μm thick) and heated the inside of the above airtight container to 40°C.
At the same time, ultraviolet rays with a wavelength of around 254 nm were irradiated from the outside of the sealed container for 16.5 hours to obtain a brown transparent molded product.

After washing this molded article with methanol and drying it at room temperature, its electrical conductivity and total light transmittance were measured, and it was found that it had desired electrical conductivity and transparency. The results are shown in Table 1.

Example 5 In a III vessel similar to Example 1, 50 #tl of a molarity thiophene solution in O,OS in acetonitrile.

Place the 0, 5, and p iodine in another small glass container, 1) place a 20 μ thick polyvinylidene chloride film on the top opening of the container, and 1) heat the inside of the container to 40°C. The film was then irradiated with ultraviolet light having a wavelength of around 254 nm for 10 hours to obtain a brown transparent film.

After washing this film with methanol and drying it at 100° C. for 1 hour, its electrical conductivity and total light transmittance were measured, and it was found that it had desired electrical conductivity and transparency. The results are shown in Table 1.

Table 1 *1--Measured using a high resistance meter.

*2 --- Measured using a spectrophotometer (light source: tungsten lamp).

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing a manufacturing apparatus used for carrying out the present invention. 1 =----monomer gas contact tank 2・-1---
Monomer gas supply device 3 --- Dono(tont supply device 4. --- Active energy ray source 5 ---
Patent applicant for electrically conductive treated materials: Isamu Hosoi, agent, patent attorney, Axis Co., Ltd. Figure 1 □ Procedure (Hoshosho (self-proposal) May 19, 1985 Patent Application No. 92913, 1985) 2. Name of the invention Method for manufacturing a conductive composite 3. Relationship with the case of the person making the amendment Patent applicant address 5 name (007), 22 Daikyo-cho, Shinjuku-ku, Tokyo
Achilles Co., Ltd. Representative Masao Oka 4, Agent 101 Address 2-75 Kanda Sakuma-cho, Chiyoda-ku, Tokyo, Date of amendment order Voluntary amendment 6, Column 7 for detailed explanation of the invention in the specification subject to amendment, Details of the amendment As shown in Attachment 1, Detailed explanation of the invention in the specification (1) "Polyvinylidene fluoride" in the last line of page 3 to the first line of page 4 of the specification is changed to "polyvinylidene fluoride." to correct. (21, page 7, lines 9 to 12, "Lewis acids such as phosphorus pentafluoride and arsenic pentafluoride, hydrogen fluoride, and hydrogen chloride. Protonic acids such as sulfuric acid, transition metal chlorides such as ferric chloride, etc.") thing,
"Transition metal compounds such as silver perchlorate and silver boron fluoride" will be corrected as follows. "Lewis acids such as phosphorus chloride and arsenic oxide; protic acids such as hydrogen fluoride, hydrogen chloride, and sulfuric acid; transition metal chlorides such as ferric chloride; silver perchlorate, silver boron fluoride, etc.""Transition metal compounds"

Claims (3)

[Claims] (1) A conductive material made of plastic is brought into contact with a gas phase atmosphere of a monomer capable of forming an electronically conjugated polymer, and is irradiated with active energy rays to obtain a composite material imparted with conductivity. A method for producing a conductive composite. (2) The method for producing a conductive composite according to claim 1, wherein the material to be conductively treated is a plastic film or a plastic molded product. (3) The method for producing a conductive composite according to claim 1, wherein the monomer capable of forming an electronically conjugated polymer is one selected from pyrrole, thiophene, furan, indole, and derivatives thereof. .