JPS6155802A - Highly conductive high molecular 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] [Industrial application field] The present invention relates to a polymeric material having electrical conductivity.

More specifically, the present invention relates to a polymer material having high conductivity.

[Conventional technology]

There are two main types of conductive polymer materials. There are two types: one in which a conductive film is formed on the surface of a polymer molded body, and the other in which a conductive filler is dispersed and mixed into a polymer to form a composite material. The former method includes vacuum evaporation, ion grating,
Examples include sputtering, metal spraying, coating, and plating.

As the latter method, there are known methods such as mixing powder of metal, carbon, etc., mixing fibers such as metal, carbon, metallized lath, etc., and mixing thin powder such as metal flakes.

However, many of the former methods have drawbacks such as being expensive, the conductive layer easily peeling off from the base material, and the size and shape of the polymer material being limited. Also, in the latter method, it is necessary to mix a large amount of filler in order to make the material conductive, and it is inefficient when the purpose is to make the surface conductive. In addition, the inclusion of filler generally causes a decrease in the strength and moldability of the molded product.

On the other hand, as disclosed in JP-A No. 56-128311, by treating a polymer compound containing a nitrile group with an aqueous solution containing a copper salt and a reducing sulfur compound, it is possible to form a strong bond on the surface of the polymer material. It is known that a coherent copper sulfide layer can be formed, resulting in a polymeric material with high electrical conductivity. Although this technique is superior to the aforementioned methods in terms of cost, adhesion, stability, transparency, and conductivity, it cannot be applied to polymeric materials that do not contain nitrile groups.

Japanese Patent Application No. 1987-7587 filed by the present applicant has an amide group,
By treating a polymeric material containing a water rR group, a calgexyl group, an amino group, a urethane group, or a urea group with a copper salt, a conductive layer consisting of copper sulfide is formed, and a highly conductive polymeric material is obtained. Proposed. This technology costs
Although it has excellent conductivity, it cannot be applied to polymeric materials that do not contain the above-mentioned functional groups. Also,
Even when the above-mentioned functional group is contained, the uniformity of the conductive layer and the adhesion between the conductive layer and the polymeric material are sometimes insufficient, and there are problems with durability.

[Problem that the invention seeks to solve]

The present inventors have conducted extensive research in order to make polymeric materials that do not contain the above functional groups conductive, and to obtain highly conductive materials that have even better uniformity, adhesion, and durability even when they contain the above functional groups. As a result of repeated efforts, we have arrived at the present invention.

[Means and effects for solving the problem] The present invention provides a conductive polymer material in which a conductive layer made of copper sulfide is formed on or inside a polymer material having continuous recesses on its surface. Furthermore, by forming a conductive layer of copper sulfide in the recesses of the polymer material, a highly conductive and highly durable polymer material is provided.

The present invention will be explained in detail below.

Examples of polymeric materials having continuous recesses in the present invention include polyolefins (polyethylene, polypropylene, poly-4-methylpentene-1, etc.), yl'' IJ esters (aliphatic polyesters, aromatic polyesters, unsaturated polyesters), and polystyrene. and its derivatives (polystyrene, poly-α-methylstyrene, poly-p-methylstyrene), polycarbanates (aliphatic polycarbanates, aromatic recarbinates), poly(meth)acrylic esters, polyethers (fatty group polyethers, aromatic polyethers), halogen-containing polymers (polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride,
polytetrafluoroethylene, etc.), acrylonitrile-containing polymers (polyacrylonitrile, methacrylonitrile, vinylidene cyanide, cyanethyl cellulose, etc.)
, polyvinyl alcohol u conductor <z ribinyl petral, polyvinyl formal, drlJ vinyl acetate, etc.), cellulose 84 bodies (m ammonium rayon, viscose rayon, cellulose acetate, etc.), polyamide (aliphatic polyamide, aromatic polyamide, silk, protein fibers such as wool), carboxyl group-containing -limers (polymers containing (meth)acrylic acid as the (co)monomer, etc.), polymers containing amine groups (I?lipenzimidazole, polytriazine, polyethyleneimine, etc.), urethanes group-containing polymers (polytetramethylenehexamethyleneurethane, polyhexamethylenetetramethyleneurethane, etc.), polymers containing urea bonds (polyhexamethyleneurea, polyhebutamethyleneurea, etc.), diene rubbers (natural rubber, S
BR, etc.), silicone polymers, etc.

The shape of the conductive polymer material obtained in the present invention is not particularly limited, but a fibrous shape is preferably used.

The polymeric material having continuous recesses on its surface according to the present invention refers to a material having an irregular cross-sectional shape, and refers to a material having a cross-sectional shape having at least one recess on its surface. That is, referring to FIG. 1, when the shape of the recess is d1, which is the shortest distance connecting both ends of the entrance, and t is the distance to the deepest part of the recess, alt≦
Items that satisfy condition 2 and are simply slightly dented are excluded. The initial purpose can be sufficiently achieved with a number of recesses of about 1 to 5. The purpose of the presence of the recesses is that a conductive layer of copper sulfide is formed in the recesses, thereby increasing the adhesion rate of copper sulfide and obtaining a polymeric material with high conductivity. Furthermore, the copper sulfide formed in the recesses exhibits excellent durability against cleaning, abrasion, soft cloth, etc.

Preferably, the concave shape is such that d/l is a small number, from 0.2 to 1.5.

If even higher durability is required, semi-permanent conductivity can be obtained by forming a conductive layer in the recesses and then covering them with resin.

The polymer having continuous recesses on the surface of the present invention can be obtained by changing the shape of the nozzle during spinning, by dissolving and removing an easily soluble polymer from a composite fiber made of two types of polymers with different solubility, There are methods such as adding specific inorganic fine particles), alkali treatment of a blend of easily soluble polymer, etc., but they are not particularly limited to these methods. It is sufficient if it has one or more.

Various methods can be used to form sulfurized steel on or inside the polymeric material as used in the present invention. Specific examples include a method of treatment in an aqueous solution containing a copper salt and a reducing sulfur compound; A method of treating with a compound capable of releasing either sulfur atoms or sulfur ions, ■, after adsorbing -valent copper ions, it is possible to release both sulfur atoms or sulfur ions. Examples include a method of treatment with a compound, (2) a method of treatment with hydrogen sulfide, and then treatment with an aqueous solution containing at least a copper salt.

Copper salts used in the above method include divalent copper salts such as cupric chloride, copper sulfate, copper nitrate, cupric acetate, copper oxalate, etc.
Copper, cuprous iodide, cuprous cyanide, cuprous thiocyanide
A monovalent copper salt such as copper is used.

When using a monovalent copper salt, in order to increase solubility,
It is recommended to add hydrochloric acid, potassium iodide, ammonia, etc.

As the reducing sulfur compound, sulfoxylates, dithiomite/acid salts, thiosulfates, sulfites, bisulfites, pyronisulfates, thiourea, etc. can be used.

Examples of reducing agents capable of reducing divalent copper ions to monovalent ones include metallic copper, hydroxylamine sulfate, ferrous sulfate, ammonium vanadate, furfural, hyposulfite/sodium acid, and glucose. Compounds that can release sulfur atoms and/or sulfur ions include:
Sodium sulfide, sulfite, dithionite, sodium dithionite, sodium thiosulfate, sodium acid sulfite, sodium pyrosulfite, sulfur dioxide, thiourea dioxide, hydrogen sulfide, Rongarit C or Rongarit) Z
etc.

The conductive polymer material of the present invention can be used in various ways.

Conductive fibers can be made into textile products such as yarn, woven or knitted fabrics, nonwoven fabrics, mats, and felt, and can be used in antistatic clothing, antistatic carpets, car mats, car seats, lingerie, and the like. Furthermore, it can be applied to surface heating elements, electromagnetic shields, etc.

〔Example〕

Hereinafter, the present invention will be further specifically explained with reference to Examples.

It was revealed by X-ray diffraction that the conductive layer of the polymeric material having conductivity obtained in Examples 1 to 3 was substantially copper sulfide.

Example-1 A plain woven fabric made of polyester 75 d/36 f fibers having the irregular cross section shown in Figure 2 was treated with 0.05 mol of copper sulfate.
/l and sodium thiosulfate 0.45 mol/A, and gradually raised the temperature from room temperature to 80°C.
It was treated at 0°C for 30 minutes. After further washing with water, 1
Dry for an hour. The obtained plain woven fabric had black edges and a stain specific resistance value of 2.5×10 Ω·F. For comparison, a plain woven fabric made of polyester 75 d/36 f fibers with a round cross section was similarly treated with copper sulfide, but the copper sulfide, which could not be easily washed with water, fell off and the electrical resistivity after drying was 6.2 x 10.
Only a material with poor conductivity was obtained at Ω・(7).

Example-2゜5-'j tosoum sulfoiso7 as easily soluble polymer
talley) (5 mol%)/ethylene terephthalate (95
75d/48f consisting of copolymerized polyester (molti) and polyethylene terephthalate as a poorly soluble polymer.
The circular knitted fabric was treated in 4097 tons of caustic soda aqueous solution at boiling temperature for 10 minutes to obtain nine knitted fabrics having a cross-sectional shape as shown in FIG.

This silk fabric was immersed in an aqueous solution containing copper chloride (0.08 mol/l) and sodium thiosulfate (0.6 mol/l),
Room temperature! The temperature was gradually raised to 185°C and treated at 85°C for 20 minutes. 75d/48f with triangular cross section for comparison
Nine knitted fabrics of polyethylene terephthalate were subjected to the same treatment. These knitted fabrics were washed for 30 minutes with overflow water using a household washing machine, and then dried at 80°C in a hot air dryer.
It was dried for 1 hour. When the surface resistance was measured after drying, the product of the present invention showed excellent conductivity at 12Ω/hole. On the other hand, the comparative product showed no conductivity at all.

Example 3 A tricot knitted fabric made of nylon 670d/24f fibers having the irregular cross-sectional shape shown in Figure 4 was coated with 0.0 copper acetate.
5 mol/l and sodium thiosulfate 0.45 mol/l
The sample was immersed in an aqueous solution containing 100 ml of chlorine, gradually heated from room temperature to 0° C., and treated at 70° C. for 60 minutes. After further washing with water, 120℃
and dried for 5 minutes. The obtained tricot was green in color and exhibited excellent conductivity with an electric resistance of 1.5 Ω·tan. For comparison, the same treatment was carried out on the tricot of nylon-6 fiber in the original cross section, but the sulfurized steel fell off during washing with water, and the electrical resistivity after drying was 8.5X10.
Ashi 4τ, I could only get bad things.

〔Effect of the invention〕

The highly conductive polymer material of the present invention makes a polymer material that does not contain a functional group that has an affinity for copper sulfide conductive, and even when it contains a functional group, it becomes a highly conductive material with even better adhesion and durability. A remarkable effect is obtained in that a flexible polymeric material can be obtained.

[Brief explanation of drawings]

Figures 1 to 4 are diagrams for explaining the recessed portions of the polymer material according to the present invention, and Figures 2 to 4 are cross-sectional views showing the cross-sectional shapes of the polymer materials used in the examples of the present invention. is.

Claims (1)

[Claims] A highly conductive polymer material comprising a conductive layer made of copper sulfide formed on or inside a polymer material having continuous recesses on its surface.