JPS59132508A - Conductive highly molecular material and method of producingsame - 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 conductive polymer material and a method for producing the same. More specifically, the present invention relates to a method for manufacturing a robust and highly conductive polymer material at low cost.

2) A polymeric material containing an IJ group is treated with a copper salt and reducible (
It is known that by processing in an aqueous solution containing a yellow compound, a strongly dense cuprous sulfide thin film is formed on the surface of the day molecular phase interaction, and a polymeric material with high conductivity can be obtained. (Japanese Patent Publication No. 7-J/!; No. 70, No. 70, No. st-qogiq, /jt9'19
No. 9). This method can be applied to other conductive polymer materials, such as those in which a conductive film is formed on the surface of the polymer by vacuum evaporation, sputtering, plating, etc., or conductive fillers are dispersed and mixed into the polymer to create a composite material. It is better than . For example, it is superior to the former in terms of price, adhesion, and the ability to choose the size and shape of the material more freely.
Moreover, it is superior to the latter in terms of strength, moldability retention, transparency, etc. of molded products. However, when used for calculator contacts, connector gas wood, printed circuits, electrode extraction, etc., the conductivity is still insufficient, and when using films, attempts to make them highly conductive result in loss of transparency. or the surface smoothness is lost. If the nitrile group content is low, the adhesion, uniformity, and properties of the conductive layer will be insufficient. Furthermore, it has drawbacks such as insufficient resistance to some organic solvents and acids.

The present inventors have conducted extensive research in order to improve these shortcomings and obtain conductive materials that are more robust, stable, highly conductive, and highly transparent in the case of films and sheets.
As a result of the incubation, the nitrile group-containing 1t47 molecules were treated in a water bath solution containing a copper salt and a reducing ω(C yellow compound) to firmly adhere to the surface or surface and interior of this polymeric material. Substantially ω1 is composed of cupric oxide.
It has been discovered that by forming /-, an extremely excellent conductive material can be obtained in which several of the problems observed in the case of cuprous sulfide are significantly improved, and based on this knowledge, the present invention was completed. I ended up doing it.

The present invention will now be described in more detail.

The nitrile group-containing polymer used in the present invention may be of any type as long as it contains a nitrile group. For example, acrylonitrile, methacrylonitrile, vinylidene cyanide, single or copolymers of α-cyanoacrylic esters, cyanoethyl cellulose, and the like are conveniently used. In the case of a copolymer, the copolymerization type may be a random copolymer, a block copolymer, a graft copolymer, or the like. Furthermore, blends of these nitrile group-containing polymers and other polymers can also be used. Also used are polymers that do not contain nitrile groups or molded products thereof into which nitrile groups are introduced by chemical treatment, plasma treatment, surface graft polymerization, or other treatments.

2) The higher the IJ group content, the higher the m conductivity and the more uniform.
Although a product with good conductivity can be obtained, in cases where high conductivity is not required, such as in antistatic applications, a product in which the weight ratio of the functional group in the offshore body is about 1% can also be used.

The shape of the polymeric material used in the present invention does not matter. It can be applied to powders, fibers, films, porous membranes, sheets, coatings, and other molded products of various shapes.

Furthermore, the method of molding the polymer material is not limited. For example, if the film is delicate, it may be made by any known method such as a melting method, dry method, wet method, etc., and a thin film of a nitrile group-containing polymer is formed on another base material by plasma polymerization. It may also be something that has been done.

In order to improve mechanical and thermal properties, it is also preferable to perform stretching, heat setting, etc.

In the case of porous membranes, any method suitable for the polymer among known porous membrane manufacturing methods such as wet casting, elution, and blowing agent methods may be used.

In the case of fallen film, the coating method can be a coating method using a known coating pattern such as a bar coater, gravure roll coater, curtain coater, knife coater, or spinner, depending on the properties and shape of the polymer, a spray method, A method such as immersion is used.

Even in the case of various other molded products, those made by any known method such as injection molding, extrusion molding, etc. can be applied.

The copper salts used in the present invention include cupric chloride,
Divalent copper salts such as copper sulfate, nitrate, cupric acetate, silver oxalate, heptavalent copper salts such as cuprous chloride, cupric iodide, cupric cyanide, fM thiocyanate, etc. used. When using a heptavalent copper salt, hydrochloric acid, potassium iodide, ammonia, etc. may be added to increase solubility.

As the reducing sulfur compound, sulboformic acid salt, dithionite, thiosulfate, sulfite, bisulfite, pyromite (Ml, acid salt, thiourea, etc.) can be used.

In the present invention, the conductive layer consisting essentially of cupric sulfide is formed by treating these nitrile group-containing polymeric materials in an aqueous solution containing a copper salt and a reducing sulfur compound. The most typical conditions for forming a layer are the molar ratio and concentration of the copper salt and the reducing sulfur compound in the reaction aqueous solution.

In general, it is necessary that the concentration be within a certain range, and that the ratio of the lending sulfur compound to the copper salt be high to a certain extent. Concentrations and ratios suitable for forming a conductive layer consisting essentially of cupric sulfide vary depending on the type of copper salt or reducible sulfur compound and the type and shape of the polymer. Moreover, these are influenced by temperature, reaction time, pH of the reaction solution, etc. In some cases, it may also change by adding oxidizing agents, reducing agents, etc. If the sum of the copper PA concentration and the sulfur compound U degree is too low, or if the ratio of the reducing sulfur compound concentration to the copper salt 8 degree is too low, a conductive layer consisting essentially of cupric sulfide may be formed. doesn't happen. For example, when the amount of copper salt is increased relative to the reducing sulfur compound, a conductive layer consisting essentially of (1,1f di-copper) is formed in a range larger than a certain daughterness ratio. ,5-72,2/,5-
'/No. 0, Tokuhan Shoj Kugg Otsusa No. 0, left 7-70
1:/No.7,/! ;9'199'').Also, if the sum of copper salt concentration and reducing property (61r yellow compound concentration) is gradually lowered, it will not become conductive below a certain concentration, but even if it becomes conductive, it will peel off extremely. Cheap.

As described above, in order to provide uniform and robust conductivity in the present invention, Mtg is determined by adjusting the copper salt concentration and the reducing sulfur compound concentration to appropriate ranges.

For example, using copper sulfate as the Qil salt and sodium thiosulfate as the reducing sulfur compound (polyacryloni) IJ
The conditions for forming a cupric sulfide layer on the film are as follows: reaction time is 70 minutes, reaction temperature is 91I'C.
The ratio of copper salt to L-based sulfur compound is λ, s near,! r to θθ/: tatata, and the rotation of both is 0. /
! ; mol/l or more. Preferably, the ratio is!
,! ; Near 5 to 03: 93, and the combined density of both is o,, 2omovl! 0.95 mol from
/l. When the ratio exceeds 5 and the copper salt concentration becomes 0, either a conductive layer consisting essentially of cuprous sulfide or no conductive layer is formed. In addition, even if the ratio is from Yusnias to θθ/:999, the sum of the sensitivities is C
1/! ; It is not conductive below moV1.

(6:i: if copper nitrate, copper acetate, copper chloride, etc. are used instead of copper, the range where conductive J<2' consisting essentially of cupric sulfide is formed is ω11 of copper oxide. The results were the same as in the case.

The 'zQ' polymer material obtained in this way can be conveniently used as it is, but after being treated to make it conductive,
Conductivity decreases by 70% when dry heat treatment is performed at a humidity higher than 10°C or when friction is applied with a load of about 10θ/cJ.
This will improve by about 300%.

The conductive polymer material obtained by the present invention is colored from light green to green, and a cupric sulfide layer is formed.It can also be used for X-ray diffraction, fluorescent X-ray, opercular analysis, ESCA, etc. It was confirmed. (
The interplanar spacing of the main diffraction lines by X-ray diffraction is ko, 79A, ig
gA,,3. θ/A indicates that it is cupric sulfide,
Daigenite (sulfurized No.-IM>) is clearly different.

) The adhesion and uniformity of the conductive layer of the isoelectric polymer material obtained by such treatment vary depending on the type and shape of the polymer. Regarding the shape of the material, when using the same polymer under the same processing conditions, porous membranes and fibers tend to have better uniformity and adhesion than films and pellets.

The electrically conductive material of the cupric sulfide-2) IJ group-containing subassembly obtained by the present invention has a higher conductive material than the conventional cupric-2) IJ group-containing polymer conductive material. Conductivity when the weight of copper deposited is the same, (2) Especially for polymeric materials, Uniformity of conductive layer formation when the IJ group-containing layer is small, ■Especially for polymeric materials (2) When the IJ group-containing layer is small Adhesion strength between the conductive layer and polymer material, ■Resistance to inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, organic acids such as acetic acid, formic acid, and succinic acid, and some organic solvents, and ■Transparency when applied to transparent films. It is excellent in terms of conductivity, etc. Also, since the active species have a long lifespan, they are a control item for continuous processing. For example, when copper sulfate is used as the copper salt and sodium thiosulfate is used as the reducing sulfur compound, the molar ratio of the two is l;/, and the sum of their concentrations is θsrn o
A treatment solution consisting of a 1/l aqueous solution loses its activity within 20 seconds at 90°C, whereas the molar ratio of the two is /:
? In this case, the activity lasts for 20 minutes or more.

The conductive polymer material of the present invention can be used in various ways depending on its shape. For example, conductive films and sheets include /I
Potential applications include transparent electrodes for light emitters, electrophotography, and antistatic films. Conceivable applications of the conductive powder include conductive fillers for conductive rubber and conductive plastic materials, 41 conductive paints, and conductive adhesives. Conductive porous membranes are expected to have applications such as gas diffusion electrodes, other electrodes, and charged particle separation filters.

Conductive fine fibers can be used to produce antistatic fiber products in all fields such as yarn, woven fabrics, knitted fabrics, felts, and nonwoven fabrics by blending, etc., and can be applied to carpets, antistatic products, women's underwear, etc.

Hereinafter, the present invention will be explained in more detail using Example F1.

Example / ASi fat (acrylonitrile-containing Htxo-B amount %) 30
A molten blend of paraffin 70 parts with a melting point of 70"C was extruded into cold water through a clearance 02TH The membrane was further washed with petroleum ether to obtain a porous membrane having a thickness of 71 and a porosity of 65%.

This porous membrane was coated with Na25204 (θ+mol/l.

qOCC') and aqueous hydrochloric acid solution of CuC1 (CuC1O,e
4f//% hydrochloric acid water bath g! (adjusted by adding i/θ nod) (the ratio of the moisture content of cuprous chloride to the concentration of sodium thiosulfate is /near?), and gradually raised the temperature from room temperature to qOoC, and at qOoC of 50 Process for minutes. After washing with water, this film was fixed on a frame and dried at 0° C. for 10 minutes.

Porous yF thus obtained! vGreen, surface resistance is 7.
It was 2oW mouth. Note that it was confirmed by X-ray diffraction that the conductive layer was substantially made of cupric sulfide.

Example 70 wt% nitric acid solution of a copolymer containing λ acronitrile (1-ht%) and methyl acrylate (Ω0 wt%).
2 m kn %) was formed into a wet film, and then biaxially stretched by a factor of 2.5 in both length and width using a biaxial stretching machine to obtain a transparent stretched film with a thickness of 25 μm. Copper sulfate (0θ, ?
mol/l) and sodium thiosulfate (0.27 mol/l)
Aqueous solution containing (copper sulfate concentration and thiosulfate) IJ
The ratio of the concentration of
The temperature was gradually increased to 5°C and treated at 5°C for ttS.

This film was fixed on a frame and dry heat fixed for 3 minutes at /A 0°C. The obtained film was green, had a visible light transmittance of 5.2%, and a surface resistance of 7(1) Q10. It was confirmed by X-ray diffraction that the conductive layer was essentially cupric sulfide.

Comparative Example 1 The reaction of Example 1 was carried out with the sum of the concentrations of silver sulfate and thiosulfate being 0.03 mol// (other conditions being constant), but the film could not be made conductive.

Comparative Example A transparent stretched film obtained by wet film forming and stretching in the same manner as in Example was mixed with copper sulfate (θ04LOmol/l) and thio(Af kll sodium (θ0'I Omol/j).
) was immersed in an aqueous solution (ratio of copper sulfate concentration and sodium thiosulfate concentration is /:/), heated from room temperature to g-s"C, and treated at gsoC for 93 minutes. This film was fixed on a frame. Then, it was fixed by dry heat for 3 minutes at /30''C. The obtained film was golden in color, had a visible light transmittance of 37%, and a surface resistance of 70Ω. In addition, it was confirmed by X-ray diffraction that the conductive layer was essentially copper sulfide.

Example 3 The conductive film (7007 openings) obtained in Example λ,
Comparing the chemical resistance of the conductive film (?0Ω10) obtained in Comparative Example C, the results are as shown in Table 1. The conductive film of Example C is more eroded by any chemical. I understand.

Example q A copolymer pellet containing acrylonitrile, S% by weight, and styrene by S% was molded into a sheet having a thickness of 270 μm using a compression molding machine. This sheet was agglomerated into an aqueous solution containing cupric chloride (ooza mol/l) and sodium thiosulfate (0.60 mol/l) (cupric chloride concentration and thiosulfate concentration). 1) The water was immersed in water, heated gradually from room temperature to 3°C, and treated with gs"c for tits.
After washing the sheet with water, it was fixed on a frame and dried at O''C for 70 minutes.The obtained sheet was green, had a visible light transmittance of 73%, and a surface resistance of 2 g×/θ4Ω. Diffraction confirmed that the conductive layer was essentially cupric sulfide.

Comparison) ν1] The reaction of Example 3 was carried out at a cupric chloride concentration of 0. J mol
/l % Sodium thiosulfate concentration 0. Jmol/l(
(other conditions being constant), conductivity could not be achieved.

Example S Slurry
0,2? ) to an aqueous solution of 50Ω and heated at 93° while stirring.
Raise the temperature from room temperature to C. There to Na2S2・5H2
0 (<z3r) aqueous solution (50 cc) was added and reacted at 93°C for 60 minutes (copper sulfate concentration and thiosulfate concentration)
The ratio of IJum concentration is /:1As). After the reaction, it was filtered, washed with water, and thoroughly dried to obtain an is:by black-rimmed powder. This powder was molded into a disk with a diameter of 2 ctn at a pressure of J for S minutes/50 kg/r), and its conductivity was measured to be /4 tΩ. Furthermore, it was confirmed by X-ray diffraction that the conductive material was essentially cupric sulfide.

In addition, 70 parts of copolymer powder and 5x parts of sulfurized No.
Although a similar disk was molded by thoroughly mixing the 1 powder, conductivity could not be imparted.

70% by weight of acrylonitrile and methyl acrylate, 70
Weight percent of comonomer powder and polypropylene powder were uniformly mixed at a weight ratio of 7=3.

Using the mixture, a sheet having a thickness of 00μ was produced using a compression molding machine. This sheet was mixed with cupric bromide (Oθqmol/
7), Na2S20J (0,,? / mol/j
') (ratio of cupric bromide concentration and sodium thiosulfate concentration is /':'Zg), and the temperature was gradually raised from room temperature to S'C, and at gs'C for lIs minutes. Processed. After washing this sheet with water, it was dried at a constant temperature of 70 minutes at 0°C. The resulting sheet was green in color and had a visible light transmittance of 67.
%, the surface resistance was l g X/030 cold. Note that it was confirmed by X-ray diffraction that the conductive layer was substantially made of cupric sulfide.

Example 7 Acrylic 1. j Nitrile q & Jumon%, Methyl acrylate 6
70% by weight nitric acid solution of the copolymer containing t% (/5
lb) was wet-spun to obtain an S denier acrylic fiber. Copper nitrate (0,0Q mo
l/7) and Na2 S20'3 (θλmol/l
) was immersed in an aqueous solution (ratio of copper nitrate opening to sodium thiosulfate concentration: 5°C), and the temperature was gradually raised from room temperature to 5°C for 95 minutes at 5°C. Processed. After washing the yarn with water, it was dried with tio'c for 75 minutes.

The thread obtained is green in color and has a monofilament size of 3 an
The resistance between the two points was g/×/θ4Ω.

Furthermore, X-ray diffraction reveals that the conductive layer is essentially cupric sulfide? I confirmed it.

Example g Polyethylene terephthalate film (IFXII-x
sμ ) to Ce(SO4)2 (,?mmol),
Acry T'1. = tolyl/θml, dioctyl sodium succinate/θOl+19, water, +00
ml of the mixed solution and treated with go''c for 7 hours.The film was soaked in sodium thiosulfate (03 mol/l).
and copper nitrate (00 g mo1/l) (61
'Ratio of 1m copper concentration to sodium sulfate concentration +f/:lI
4') immersed in water and gradually raised to gO'C from Ningtan,
The film was washed with water and then dried for 10 minutes at a constant temperature of 50°C.The resulting sheet was green in color with a visible light transmittance of 79% and a surface resistance of 2900.
It was a pleasure. Note that it was confirmed by X-ray diffraction that the conductive layer was substantially made of cupric sulfide.

Patent Applicant: Asahi Kasei Koshiba Co., Ltd. Representative Patent Attorney Toru Hoshino Procedural Amendment (Voluntary) Commissioner of the Japan Patent Office Kazuo Wakasugi 1. Indication of the case 1988! Samurai Permit No. 773352 Title of the invention Conductivity = 14+- Polymer material and its manufacturing method 3,
Relationship with the 41 amendments Patent applicant 4, agent address: 3-7 Yotsuya, Shinjuku-ku, Tokyo, 5B6 Shin Hill
, Number of inventions increased by amendment None 7. The statement in the description of the contents of the amendment subject to amendment shall be amended as follows.

(1) Page 15, line 14 Correct "CaSO4" to rCu5O+J.

(2) Page 17, line 8 Correct "copper nitrate" to "copper acetate".

(3) On page 18, line 3, "sodium thiosulfate" is corrected to "sodium sulfite."

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (2)

[Claims] (1) A conductive polymer material comprising a conductive layer consisting essentially of cupric sulfide formed on or inside a polymer material having a nitrile group a. (2) By treating a polymeric material containing a nitrile group in an aqueous solution containing a copper salt, a restoring agent, and a yellow compound, the surface or surface and interior of the polymeric material is substantially freed from secondary sulfide steel. 1. A method for producing a heme-conductive high-conductivity material, which comprises forming a conductive layer consisting of: