JPH01613A - Manufacturing method of conductive polymer material - 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 (Field of Industrial Application) The present invention relates to a method of imparting conductivity to a polymer material, and more particularly to a method of producing a conductive polymer material 1a with little coloring.

(Prior Art) Conventionally, a method for producing a white conductive polymer material involves reacting copper-plated fibers with iodine to convert them into a white coating made of cuprous iodide (Japanese Patent Laid-Open No. 54-5499). ), a method for obtaining a white conductive polymer material by treating a polymer material with an aqueous solution containing an FLK cuprous compound in which iodine is adsorbed to form a film made of cuprous iodide (Japanese Patent Application Laid-Open No. Publication No. 55-148279, JP-A-56-99
No. 255) is known.

However, when attempting to implement these methods industrially, there are problems such as a large increase in cost and deterioration of the polymer material due to iodine treatment.

That is, the method of reacting steel-plated fibers with iodine has the disadvantage that the manufacturing cost of copper-plated fibers is high and the resulting conductive fibers are also expensive fibers.

In addition, the method of adsorbing iodine onto a polymeric material and then treating it with an aqueous solution containing a cuprous compound causes various problems as the iodine adsorption behavior varies greatly depending on the type of polymeric material. .

That is, acrylic fibers and polyamide fibers that relatively easily adsorb iodine from an aqueous iodine-X/potassium iodide solution have the disadvantage that the fiber structure relaxes in proportion to the increase in the amount of iodine adsorbed, resulting in a decrease in strength.

In addition, iodine is difficult to adsorb to polymer molded products such as polyester fibers, polyvinyl chloride boards, polymethyl methacrylate boards, and polycarbonate boards, so high concentrations of iodine/potassium iodide are required to adsorb iodine to polymer molded products. It is necessary to use an aqueous solution and to process at high temperature, which has the drawback of significantly increasing costs when carried out industrially.

On the other hand, as another method of imparting conductivity to polymer materials,
The present inventors first performed a heat treatment in an aqueous solution containing a polymer material gold copper salt, a reducing sulfur compound, and a water-soluble basic salt of a nitrogen-containing organic compound having 12 or more carbon atoms. A method for imparting conductivity to all polymeric materials at low cost has been clarified (Japanese Patent Application No. 155813/1982).

However, the conductive polymer material obtained by this method is colored because a black copper sulfide coating is formed on the surface layer of the polymer material, and only a highly conductive polymer material can be obtained. There is a strong demand for the development of low-cost conductive technology.

(Problems to be Solved by the Invention) The present invention solves the major problems of making polymer materials electrically conductive using conventional techniques (1) Increased cost (2) Problems of deterioration of polymer materials related to iodine adsorption treatment The purpose of this research is to provide a technology for imparting conductivity to various polymer materials with low coloration and low density.

(Means for Solving the Problems) The present invention involves treating a colored conductive polymer material with a copper sulfide coating formed on the surface layer of the polymer material with gaseous iodine to remove at least a portion of the copper sulfide. A method for producing a conductive polymer material characterized by converting it into copper iodide.

The conductive polymer material used in the present invention, in which a copper sulfide coating is formed on the surface layer of the polymer material, is a polymer material gold copper salt, a reducing sulfur compound, and a water-soluble base of a nitrogen-containing organic compound having carbon number +2 or more. It is obtained by heat treatment in an aqueous solution containing a chemical salt.

The polymer material may be either a thermoplastic resin or a thermosetting resin, but examples include poly(meth)acrylate resin, polyolefin resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyester resin, polyester resin, polycarbonate resin, and polyphenylene. sulfide resin,
Polymers such as polyacetal resins, phenol resins, and epoxy resins are preferably used, and the forms of polymer materials include powders, linear objects, rods, films, plates, etc., as well as extrusion molding from intermediate materials, pressure molding, It is applied to molded products in various product forms obtained by various molding methods such as injection molding.

The copper salt used to form copper sulfide is one that reacts with sulfur from a reducing sulfur compound to produce copper sulfide, and for example, cupric sulfate, cupric chloride, cupric nitrate, etc. are preferably used. .

Examples of the reducing sulfur compound include sodium thiosulfate, acidic sodium sulfite, sodium biosulfite, sodium sulfide, sodium hydrogen sulfide, etc., and sodium thiosulfate is particularly preferably used.

Also, during the copper sulfide formation process, KtF! Preferred water-soluble basic salts of nitrogen-containing organic compounds having 12 or more carbon atoms include lacrylamine hydrochloride, dodecylmethylamine hydrochloride, octadecyltrimethylammonium chloride,
Hexadecyltrimethylammonium chloride, Tetradecyltrimethylammonium chloride 0, Benzyldimethyldodecylammonium chloride, 0.1.
Basic Blue 1, O, 1, Basic Blue S, O
, X, Basic proof J/-5, Q, Engineering, Basic proof, 0.1. Basic Violet 1.0.1. Examples include compounds such as Basic Green 4. In addition, O
,X, is the color index (+30LOURINDE
X). For forming a copper sulfide film on the surface layer of a polymer material, a copper salt, a reducing sulfur compound, and a carbon number 1 are used.
Preferably used is a method in which the polymeric material is immersed in an aqueous solution of about 25C containing water-soluble salt salts of two or more nitrogen-containing organic compounds in which no copper sulfide is produced, and then this aqueous solution is heated to raise the temperature. It will be done. The temperature should preferably be raised at a rate of about 1 to 10 C/min to avoid rapid heating, and the upper limit temperature must be set to a temperature that does not cause plasticity of the polymeric material. The concentration of the copper salt in the aqueous solution used as the treatment liquid is 0.01 to 5% by weight, the concentration of the reducing sulfur compound is approximately equimolar to the copper salt, and the amount of the water-soluble basic salt of the nitrogen-containing organic compound used is 0.1-10% by weight of the amount of copper salt used
By using the above method, it is preferable to obtain a conductive polymer material in which a conductive layer made of copper sulfide is formed on the surface layer of the polymer material.

subsequently placing the conductive polymer material in a gaseous iodine-containing atmosphere to convert at least a portion of the copper sulfide to copper iodide;
Use a conductive polymer material with low coloration. The gaseous iodine used in this case is obtained by placing solid iodine in a sealed container and sublimating it.

Although the concentration of gaseous iodine is determined by the weight of solid iodine to be sublimated, treatment at room temperature in an atmosphere with a saturated gaseous iodine concentration is preferably used. Furthermore, the treatment temperature and time can be within the range of several minutes to several tens of minutes at room temperature. That is, since the concentration of iodine used is low and the treatment can be carried out at relatively low temperatures and in a short time, it is greatly useful for reducing costs and preventing deterioration of polymeric materials due to iodine treatment, which is the objective of the present invention. .

(Effects of the Invention) The present invention provides a technology for industrially manufacturing a conductive polymer material with little coloration at low cost, and will greatly contribute to the development of the electronic field in particular.

(Example) The present invention will be explained below with reference to Examples.

Example 1 A polyethylene terephthalate film with a thickness of 100 μm was coated with 0.2% by weight of cupric sulfate (5H20), 0.2% by weight of sodium thiosulfate (5H20), and 0.002% of hexade, tartrimethylammonium chloride.
% by weight, and heated to 70C at a rate of IC'/min while stirring, and at the same temperature 0 to 2
After being treated for 0 minutes, it was washed with running water and dried to obtain a colored transparent conductive film (Comparative Examples 1 to 3) in which a dark brown copper sulfide thin film was formed on the surface layer of the film.

Among these, the film f25C of Comparative Example 3 was placed in a saturated gaseous iodine-containing atmosphere at normal pressure, treated with gaseous iodine for 10 to 15 minutes, and then washed with alcohol, washed with running water, and dried to remove some of the copper sulfide. A transparent conductive film (inventions 1 and 2) with little coloring was obtained by converting to iodide mainly consisting of copperide.

These are the results of determining the light transmittance and electrical resistance of the transparent conductive film obtained by the following company.

Examples 1 to 3 are transparent conductive films coated with p-copper sulfide using conventional techniques, and have an electrical resistance of t o2Ω/
If you try to give a low level of conductivity, the light transmittance will be 4.
0% or less, the coloring is large and the transparency is poor.

On the other hand, the transparent conductive film obtained by the method of the present invention has little coloring, good transparency, 5 L, and excellent electrical conductivity.

Patent applicant: Mitsubishi Rayon Co., Ltd.

Claims (1)

[Claims] Conductive material characterized by treating a colored conductive polymer material with a copper sulfide coating formed on the surface layer of the polymer material with gaseous iodine to convert at least a portion of the copper sulfide into copper iodide. Manufacturing method for polymeric materials.