JPS6079604A - Method of producing polyacrylonitrile conductive film - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a manufacturing method for imparting electrical conductivity to a polyacrylonitrile film.

Polymer materials generally have a large inspiratory resistance value, which varies from 10 to 10 Ω, and are used as quasi-insulating materials.

On the other hand, attempts have been made to use C as a C-conducting material by mixing sensitive powders such as gold 4 and carbon with this polymeric material.

For example, this is a mixture of materials such as polyethylene, polypropylene, nylon, and epoxy with powders such as aluminum, iron, silver, and carbon.
U~IL111. Arashi's things are obtained. In this pond,
With the emergence of polymeric materials that have conductivity themselves, C
There is.

For example, there is a material made by thermally decomposing polyacrylonitrile to give it semiconductivity, and there is also a material made by thermally decomposing a heat-resistant polyimide film, which has a resistance of 10Ω and 1. An object of the present invention is to provide a novel method for producing a conductive film incorporating a polyacrylonitrile polymer material.

Another object of the present invention is to provide a method for producing a polymeric conductive film made of polyacrylonitrile whose conductivity can be easily adjusted.

] - The gist of Narichi and Honmima is that the polyacrylonitrile film is given C conductivity by complexing cuprous ions and then polishing. This is a method for producing a conductive film of polyacrylic 1conitrile.C is a method for producing a conductive film of polyacrylic nitrile obtained by the method of the present invention. be done.

Hereinafter, the present invention will be described in detail according to examples. EXAMPLES First, the first step, the process for producing a polyacrylonitrile film, will be explained.

A 14% N,N dimethylformamide solution of polyacrylonitrile (hereinafter referred to as PAN) polymerized by a known method was cast onto a glass plate with a clean and flat surface, and the mixture was heated at room temperature under reduced pressure for 2.5 hours. Dry at uH9 for 48 hours. PA used
The average molecular weight of N was 70,000-120,000. Furthermore, it was dried at a temperature of 45C115ruIQ for 24 hours and slowly peeled off from the glass plate to obtain a CPAN film.

The obtained PAN film is clear and has a thickness of 50~1001
1 mm Glass transition temperature (Tg) = a 2-92'c.

The cold crystallization temperature (rac) was 12 tr.

Next, the second step of introducing cuprous ions as a complex into the PAN film will be described.

0.3-2% CuCe in water, 15-3%
A Cu net of the same amount as Na(1) and CuC1ff1 was added together with water at a predetermined ratio and boiled at 1C.

When the aqueous solution becomes transparent, the P obtained in the above step
Put 20 sheets of AN film (approximately 8.5 g) into the water solution,
React in a boiling state for 1 to 8 hours, take out 4 sheets of boiled PAN film at each time, and add to water at 15℃.
It was washed in an ultrasonic cleaner for 5 minutes and then in running water for 1 hour. After that, it was vacuum dried at a temperature of 4 ohms, and cuprous ions (hereinafter referred to as CLL) were applied to the PAN film.
Introduced.

Figure 1 shows the PAN film obtained in this second step.
c, The results of measuring the weight increase with respect to the complexation reaction time when the Cu Cl 3 concentration was changed are shown. Weight increase per unit area W (mg/d
) was calculated from the following formula.

W=:Wc-N.

However, the weight of the PAN film (mg/cm) before the complexation of ilo:Cu and the weight of the PAN film (mg/d) after the complexation of wC:C1,l. Q, 3% CuCl, aqueous solution/1 scale with 1 mark, 5% CuCg, water, J solution, ◎
The one marked is 1.04 CuCl! , aqueous solution, and those marked O correspond to 2.0% CuCl, water a night.

Next, in the first and fifth step, a method for obtaining a PAN conductive film (Cu is reduced to an aged PAN film) will be explained.

+ The PAN-Cu 4-body film obtained in the above step was boiled for 5 hours in an aqueous solution of 1-tihydrosulfite sodium salt [CLI f (reduced) in the film.

After the reduction reaction, thoroughly wash with water and dry as in the above step.
It was stored in a desiccator to obtain a conductive film.

Figures 2 and 3 show various amounts of P in the Steel Authority after the complexation reaction.
This figure shows the relationship between the reduction time of C% in AN film, surface conductivity, and volume conductivity. The copper content in the PAN films shown in FIGS. 2 and 5 was measured according to a conventional atomic absorption method.

In Figures 2 and 3, the ones marked with * are those with a copper content of 17 Chi, the ones marked with () are those with a copper content of 22 Chi, and the ones with ◎ are those with a copper content of 28 Chi. correspond to something. Further, the surface conductivity and volume conductivity of the obtained PAN conductive film were measured according to J-Technical Engineering 5-C2525. Moreover, all measurements were performed at 30t.

As is clear from FIGS. 2 to 5, the PAN films obtained in the examples of the present invention had sufficient electrical conductivity.

In addition, the mechanical properties of the PAN film on which Cu was adsorbed by the complexation reaction were measured, and the results are shown in Table 1. Sara KJ! The mechanical properties of the pre-processed PAN conductive 1 raw film 1'C were measured and the results are shown in Table 2. Incidentally, the PAN film showing the results in Table 1 was one in which the complexation reaction time was 8 hours. Further, the PAN conductive films showing the results in Table 2 were subjected to reduction treatment using a 1% aqueous solution of sodium hydrosulfide salt.

As is clear from Table 2, in the examples of the present invention, no deterioration of the quality was observed in the raw film. It exhibits characteristics that pose no problems in use.

Next, preferred specific implementations of C1 for the method for producing a polyacrylonitrile conductive film according to the present invention are as follows.

PAN film [was treated in boiling water for 10 hours,
l? A ladle of 8 g of Al (from which dimethylformamide in the film had been completely removed) was used.

Next, in a second step, C'3.5% of CuC1, water-soluble, was reacted with Ccu+ overnight. The processing conditions are as follows.

CuC1: 6.53g Cu steel: :S, 09g Mace: 17.069H! O: 1300m1 Reaction temperature: Boiling Reaction time: 5.1.2. After the complexation reaction for 4 hours, it was washed under running water overnight, and then washed with a Goshinsaka purifier for about 1 hour.
It was washed for 5 minutes, then washed under running water for 6 hours, and vacuum dried at 50°C.

The PAN film obtained in the third process was subjected to a reduction treatment. This one! The initial treatment was carried out with 1 part of sodium hydrosulfite of 2.0. The processing conditions are as follows.
Ridechiru.

Hydrosulfide sodium salt: 26.09 (
After 10 hours of reaction, wash in an ultrasonic washer for about 30 minutes, then wash under running water overnight, and wash at 50'C. in! 'C, air dried.

The obtained PAN4 conductive film exhibited good magnetic conductivity and shallow strength as in the above-mentioned examples.

In addition, this 75ζ in which the C1 reduction treatment was performed using hydronalphite sodium salt in Example ii above.
・Yokabudo Tong, Kin) Shinden, 5-ferric iron, acidic sodium succinate, hydroxylamine, glucose, furfural, etc. can be used.

Furthermore, the surface conductivity (C1 at room temperature to 160C) of the PAN conductive film obtained by the production method of the present invention (
When the temperature dependence of σ8) was measured, as shown in FIG. 4, a transition appeared near I Q Q 'c when 5 V was applied.

As is clear from the above examples, according to the method for producing a polyacrylonitrile conductive film according to the present invention, Cu is complexed into a polyacrylonitrile film.
C conductivity is imparted to the polyacrylonitrile film by introducing C into a complex and then reducing it. It is possible to fabricate a magnetically conductive film with a conductivity of
A conductive film can be easily obtained, and a manufacturing method useful in fields requiring such a conductive film can be provided.

[Brief explanation of drawings]

Figure 1 shows the measurement results of the weight increase with respect to the complexation reaction time when the CuCe2 concentration was changed for PAN films. Figure 4 shows the relationship between C1 reduction time, surface conductivity, and volume conductivity for the film.
The figure shows the temperature dependence of surface conductivity (σ8). For Patent Applicant Murayama Seisakusho Co., Ltd. 1. Time [hrl. Total + VJrn 594 December 20th 2, Title of invention Method for producing polyacrylonitrile conductive film 3,
January 61, 159th Meisho era (shipment date)

Claims (1)

[Claims] 1. A method for producing a polyacrylonitrile conductive film, which comprises introducing tK1 copper-f-one as a complex into the polyacrylonitrile film, and then reducing the film to impart C conductivity.