JPS5845263A - Electrically conductive high molecular molded product and its production - Google Patents

Abstract

PURPOSE:Copper sulfide is contained in a molded polymer product bearing cyano groups, thus giving electric conductivity to the molded product. CONSTITUTION:Copper sulfide is dispersed in a molded polymer product bearing cyano groups. The molded polymer product is dipped in a bath containing cupprous ion and a compound releasing both of sulfur atoms and sulfur ions or either of them or dipped in the first bath to effect the adsorption of cupprous ions and treated with a liquid or gas containing a compound releasing both or either of sulfur atoms and sulfur ions to effect the adsorption of copper sulfide dispersed in the molded product. In both treating processes, the suitable temperature is 40-120 deg.C, however, higher than 60 deg.C is economical in the latter.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides nine conductive polymer noodle products containing agglomerated steel and 70 l! Regarding the fibrous molded product, which is a type of polymer molded product, related to the manufacturing method, patent application No. 55-124598, A855-028
686. 1974-074752, 1984-097128
However, the present invention builds on this idea and proposes the application of a variety of molded objects such as film, book, rod, and plate shapes.

As proposed earlier, cyanide groups and '1m pot ions show a strong affinity, so it is possible to apply this method not only to polymer molded products that have cyanide groups in their molecular structure, but also to already molded polymer products. This production becomes possible by introducing a cyan group by means such as graft polymerization.

That is, for polymer molded products having cyan groups or polymer compounds not having cyan groups, in which cyanide/groups have been introduced at any stage, (g) divalent copper ions and reducing agents or A method of treating in a bath containing a compound capable of releasing either one of the steel ions and/or the red yellow ion and optionally an enemy for Pkl14, salt, etc. @ First, as the first step, heat treatment is performed in a bath containing 2III copper ions and a reducing agent, or monovalent steel ions, and if necessary IJI for pH adjustment, and a salt solution.
After the monovalent steel ions are absorbed into the molded product, as a second step, the monovalent copper ions and/or sulfur ions can be released from the molded product. Compound, and optionally pHg! The steel ions can be dispersed and adsorbed into the molded product as sulfurized steel using either method (a) or (b), which is a method of heat treatment in a bath containing rice, salt, etc. for i. , This made it possible to impart tetraelectricity to this molded product.

As the above-mentioned 211flltI) 11m ion, Kenpo Daini Steel, cupric chloride, Nitrate Nisteel II, Nagiba Daini 2j14, etc. can be used. As the reducing agent, metal steel, hydroxyl acene, ferrous sulfate, panadinoic acid anhydride, fur72-ol, sodium hyposunate, or dextrose could be used.

As the first copper ion, cuprous chloride and its ammoem complex salt could be used.

In front of the sulfur fence, compounds that can release either or both of sulfur ions include sodium sulfide, sulfite,
Nithionite, sodium dithionite, sodium thiosulfate, acidic sodium sulfite, sodium bitetrasulfite, sulfur dioxide, hydrogen sulfide, rongaric acid) can be used; It can also be used as a reducing agent to reduce the above-mentioned divalent copper ions to monovalent copper ions, and can also be used as an acid or salt for pH adjustment when necessary. , 4Ilktl&, inorganic acids such as hydrochloric acid, #1 acid, organic ranges such as enoic acid, #1 acid, or their salts, or combinations of acid and salts, such as the combination of enoic acid and disodium phosphate. I was able to use it in many ways.

(4), (11) In either method, the treatment temperature when adsorbing monovalent monovalent ions and converting monovalent copper ions into sulfide steel is high; If the temperature is too high, the molded product may become deformed, and at low temperatures, the reaction takes time, so there is a temperature range in which the reaction is difficult.

That is, the temperature range is approximately 40"C to 120"C, but in the case of the method (b) above, in which the absorption of copper and its conversion into copper sulfide are carried out in separate baths, neither step Even in this case, it was more economical to conduct the test at 6 G''C or higher because it would save time.

The conductive molded product thus obtained is xll! When analyzed with I, guidienite (Cu985) chalcosite (
Cu28) Sperite (Cu8) diffraction-1
It became clear that it was contained in the form of sulfide.

The diffraction gap V4 peak is shown as follows.The present invention will be described in detail with reference to Examples below.

Example 1 Approximately 2 f of acrylic fiber (Bonnell 2 denier, 51 cod, cut type 17B manufactured by Mitsubishi Lane) was coated with dimethylformamide (M, M-]) 1 methyl/arma
mid@D, M, ? , abbreviated as )) while heating to about 100mj, the melted pot was left for a while (after leaving it to degas, transfer it to a jar of about 5cc#tV and remove the solvent with hot air).
M and F were volatilized to obtain a film containing acrylonitrile as the main component. The size of the film is electrolytic corrosion 7.5a, thickness @Hiro α02m111, weight company approximately α14, 9, ζ? The film was immersed in 10 [Jml] of a solution containing 60 f disodium phosphate, 12 citric acid, 20 f sulfuric acid, 20 f sodium thiosulfate, and 20 f sodium acid sulfite per liter and heated at 6 oc for 3 hours. Upon treatment, a light brown transparent film with conductivity was obtained. The surface resistance of this material was 500Ω.

X@Digienite was the main component, and a small amount of chalcosite diffraction lines were observed.

Example 2 Approximately 5 Qml of the same acrylic fiber DVv solution as described in Example 1 was poured into a petri dish, heated from below and at the same time hot air was blown to vaporize and remove fiDMF. Electrolytic corrosion γ51 thickness α
This film, which was 16U and weighed approximately 0.65F, contained 209G of sulfuric acid and 10-hydroxylamine hydrochloride to the film lid. The temperature was raised steadily from a low temperature in a bath of 80° C. for 2 hours. After thoroughly washing with water, the temperature was gradually raised from low temperature to 70"C for 11 hours in a 200snj bath containing 8F sodium dinitionite, 60F disodium phosphate, and 8F sodium citrate. The surface resistivity (/4.) of the obtained film was 160Ω.

X- was mainly composed of digenite, and diffraction of copelite was observed.

Example 6 10 for the weight of the film made in the same manner as Example 1
After treatment at 90C for 2 hours in 200 mJ of a solution containing copper chloride of 1 liter, 8 f sodium thiosulfate, 10 f hydroxyluaquine hydrochloride, 2
10 containing 0f disodium phosphate, 8f citric acid
Treated at 45'C in a cold bath for 10 hours.

The surface resistivity (Pl) of the obtained film was 220Ω.

Example 4 Nylon 711m (BOφ15 manufactured by Toshi) Sf was immersed in 20Qm/liter containing 10 Da perMU ammonium and 10F per liter sodium for 60 minutes in a 'filter', and then pulled up. Water droplets on both sides of the rear film
Put it in a stainless steel container, put it in a vacuum bottle 1 at 19, reduce the pressure of the container with mercury at 1611st, introduce acrylonitrile vapor, and add 68 to 40'.
The graft polymerization reaction was carried out at c for 3 hours, and the thickness of the film increased by 66 cm due to the graft polymerization, and the grade increased by 62.8%. This product was treated in the same treatment bath as in Example 1 at 47'C for 5 hours.

The obtained conductive film was completely brown and transparent, and had a surface resistivity (/S) of 200Ω.

In xiM, it was observed that digenite and chalconite have almost the same diffraction.

5. 60'11 with 2 board thickness and 51 pieces! (6λ5%
)'f/ is saturated with Mukron Koshiki potassium and 9 liquids 2
After soaking in 00 IK and chemically etching at 6ΩC for 6Ω and thoroughly rinsing with water, 1 liter contains 201 disodium phosphate, 8f citric acid, 20f copper elvicate, and 201 sodium dithionite. The board was immersed in solution 20011/, well stirred, and then treated at 40"C for 10 hours. The plate obtained by thoroughly washing with water and sintering exhibited a gray-black color and a surface resistivity of
4/,) was 240Ω.

Example 6 Polyester film (Maituna 12 made by Toshi > 51) in 1 liter of water, 11001F acrylonitrile, 2
1m area of f and 10f of 21
7mc (emulsifier, manufactured by Oh Kogyo ll1i series) containing liquid 20
Graph of acrylic double chloride for 90 minutes at 105υ in a bath with a low temperature of 100 ml. p
When treated at 70V for 2 hours in a 200m bath containing 60f of disodium phosphate, 15f of citric acid, 10f of copper sulfate, 10C of sodium sulfite, and 10f of sodium sulfite, a brown conductive material was obtained. A polyester film was obtained. The surface resistance (p,) of this material was 420Ω.

Example 7 Approximately 1 f of nine acrylic films made by the method shown in Example @2
Y s 2 pieces of constant # against film electric t! copper and 10
Excellent hydroxylamide hydrochloride.

The temperature was gradually raised from low temperature in a bath of 200 m/m containing
．． The well-rinsed well was placed in a sealed Tanahata with a gas inlet, and sulfuric acid gas was injected until the pressure inside the container reached 0.5 - 0.5 °C in gauge pressure, and then heated at 105 °C for 2 hours.
When the fine water is drawn, the pressure inside the container of fk air is LOq/ by gauge pressure.
es21C)'i, press-fitted with 6 t, once 105
I embroidered for 90 minutes at ~110″C.

Take out the cold i4 copy, wash thoroughly with water, and dry.The soft brown resistor 4 (door) has a conductive film with a resistance of 600 ohms.

Claims (1)

[Scope of Claims] L A conductive polymer molded product containing sulfide steel in a polymer molded product containing cyan groups. A conductive polymer characterized in that a polymer molded product containing a λ cyan group is treated in a bath containing a copper ion and a compound capable of releasing both or either of a sensitive yellow atom or a sulfur ion. Method of manufacturing molded products. & Monovalent southern ions are applied to the supramolecular molded article containing cyan groups in the first bath! A waxy woven molecule jell product characterized by treating the dried bales in a liquid phase or a gas phase containing a compound capable of releasing either or both of sulfur ions and sulfur ions. 〇 Loading force method・