JPS6314112B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to electrically conductive materials. In recent years, demand for conductive fibers has increased, and various types have been proposed. The present inventors have proposed conductive fibers in which copper sulfide is attached or impregnated to fibers containing cyan groups in acrylic fibers, polyamide fibers, polyester fibers, or natural animal/vegetable fibers (Unexamined Japanese Patent Publication No. No. 128311, No. 56-
169808 and 57-21570). These conductive fibers have higher robustness than other known conductive fibers (for example, those in U.S. Pat. No. 3,940,533), can be dyed, and have the inherent flexibility of fibers. It is actually used in several fields.
However, the moisture resistance, alkali resistance, and wash resistance of these copper sulfide-containing conductive fibers are still not fully satisfactory from a practical standpoint.
If these problems can be overcome, it is expected that the field of application will further expand. As a result of intensive research to overcome the drawbacks of conventional conductive materials as described above, the present inventors surprisingly discovered that a small amount of a specific metal component along with copper sulfide can be adsorbed onto a substance containing a cyano group. The present inventors have discovered that washing resistance such as alkali resistance and washing durability can be dramatically improved by bonding by adhesion or impregnation, and have completed the present invention.
That is, according to the present invention, at least one metal component selected from silver, gold, and platinum group metals is added to a substance containing a cyano group together with copper sulfide as an auxiliary metal component thereof. Provided is a conductive material characterized in that the cyano group is bonded to the surface of a substance having the cyano group. The cyano group-containing substance used in the present invention can be any water-insoluble solid, and includes high-molecular substances and low-molecular compounds.
The cyano group-containing polymeric substance may be either a natural or synthetic polymeric substance. Examples of cyano group-containing synthetic polymers include acrylonitrile-based polymers and copolymers (including random polymers, block polymers, graft polymers, etc.), as well as cyano group-containing materials such as polyamide, polyester, rayon, and kyupra. Examples include polymers that have cyano groups introduced into them. Any conventional method can be used to introduce such a cyano group, such as a method of reacting with dicyandiamide, a method of grafting acrylonitrile, a cyanoethylation method, a mixed spinning method, and the like. These cyano group-containing synthetic polymer substances are available in powder form,
Various molded objects, such as films, fibers,
board, cloth, paper, sheet, block, pellet, thread,
Used in the form of rods, pipes, etc. Cyano group-containing natural polymer substances are obtained by introducing cyano groups into animal or vegetable natural polymers, such as polypeptides such as silk and wool, and polysaccharides such as cellulose, by the method exemplified above. , fiber, etc. Examples of the cyano group-containing low-molecular compound include phthalonitrile, isophthalonitrile, N-cyanomethylaniline, and N-β-cyanoethylaniline, which are usually applied in powder form. The conductive material of the present invention is made by bonding the above-mentioned cyano group-containing substance with copper sulfide and at least one metal component selected from silver, gold, and platinum group metals as an auxiliary metal component. be.
In this case, platinum group metals include ruthenium, rhodium, palladium, osmium, iridium and platinum. The amount of copper sulfide to be bonded to the cyano group-containing substance is not particularly limited, but is usually about 0.5 to 30% by weight, preferably 1 to 15% by weight, as metallic copper, relative to the cyano group-containing substance. The amount of the auxiliary metal component used in the present invention may be extremely small compared to the amount of copper sulfide bonded, and is usually 0.0005 to 10% by weight, preferably 0.0005 to 10% by weight in terms of metal, based on the cyano group-containing substance.
It is 0.005 to 5% by weight. In addition, the ratio of the auxiliary metal component to the copper sulfide bonded to the cyano group-containing substance is the atomic molar ratio M/Cu
(M: Ag, Au, Ru, Rh, Pd, Os, Ir and/or Pt) is usually 0.0001 to 0.5, preferably 0.001 to 0.3, more preferably 0.01 to 0.2. A small amount of this auxiliary metal component is enough to produce a sufficient effect, and as mentioned above, a substantial addition effect can be obtained when the amount is 0.0001 mol or more per 1 mol of bound copper, that is,
Stabilizes the bond of copper sulfide to cyano group-containing substances, improving the wash resistance and moisture resistance of products. On the other hand, there is no particular restriction on the upper limit of the amount of the auxiliary metal component bound, but it is best not to exceed 0.5 mol per 1 mol of bound copper; if it exceeds 0.5 mol, conductivity may be impaired. This is not desirable because it is also disadvantageous from an economic point of view. In the present invention, the auxiliary metal component that binds to the cyano group-containing substance usually exists in the form of sulfide, but in some cases it may also exist in the metal state, and copper sulfide is present in the cyano group-containing substance. There is no particular restriction as long as it can be combined together.
In the present invention, the bond to the cyano group-containing substance with respect to copper sulfide and the auxiliary metal component includes both physical and chemical bonds. The conductive material of the present invention described above can be manufactured by various methods, and the manufacturing method will be described in detail next. In one embodiment of the manufacturing method, a cyano group-containing conductive material to which copper sulfide is bonded in advance is used. This cyano group-containing conductive material bonded with copper sulfide is known in the art, for example,
No. 56-128311, No. 56-169808 and No. 57-21570
It can be obtained by the method described in the publication, etc., and the detailed explanation will be omitted, but the outline will be shown as follows.
This is a method in which the above-described cyano group-containing substance is treated with a monovalent copper ion source and a sulfur-containing compound. In this case, treatment with sulfur-containing compounds is 1
This may occur simultaneously with or subsequent to treatment with a source of valent copper ions. In the present invention, regarding the cyano group-containing conductive substance bonded with copper sulfide,
Commercially available products can be used as they are. In the present invention, the above-described conductive material bonded with copper sulfide is treated by bringing it into contact with a solution containing auxiliary metal ions. In this case, the auxiliary metals to be dissolved are used in soluble form, for example sulfates,
Examples include inorganic acids such as nitrates, organic acid salts such as acetates and benzoates, and various complex salts such as rhodan complexes and thiosulfate complexes. The concentration of the auxiliary metal compound in the solution is not particularly restricted, but it is usually
The amount is 0.005 to 10 g/, preferably 0.01 to 6 g/. When treating a conductive substance bonded with copper sulfide by immersing it in a solution, the bath ratio for the conductive substance is 1 part by weight of the conductive substance to 5 to 50 parts by weight of the solution.
parts by weight, preferably 10 to 30 parts by weight. The treatment temperature is usually room temperature to 100°C, preferably 30 to 80°C, and the treatment time is 0.5 to 20 hours, preferably 1 to 10 hours. As described above, simply by bringing a solution containing auxiliary metal ions into contact with a conductive material bound to copper sulfide, the stability of the bonding of copper sulfide to the conductive material is increased, resulting in improved wash resistance, moisture resistance, etc. A product with improved properties can be obtained, and in this treatment, a reducing sulfur compound can be used in combination if necessary, thereby further increasing the bonding stability of copper sulfide. The sulfur compound in this case is
Any substance that has a reducing effect may be used, such as sodium sulfide (Na ₂ S), hydrogen sulfide (H ₂ S), sulfur dioxide (SO ₂ ), sodium hydrogen sulfite (NaHSO ₃ ), and sodium thiosulfate (Na ₂ S). _{2O3 )} ,
Sulfite (H ₂ SO ₃ ), Sodium Disulfite (Na ₂ S ₂ O ₅ ), Sodium Nithionite (Na ₂ S ₂ O ₄ ), Nithionite (H ₂ S ₂ O ₄ ), Rongarit (Nithionite) and formalin adducts),
Alternatively, a mixture of the above may be mentioned. When using gaseous sulfur compounds such as hydrogen sulfide or sulfur dioxide, after immersing them in a solution containing auxiliary metal components,
It is preferable to bring the removed conductive substance into contact with the gas under pressure in an autoclave or the like, or to continuously blow a gaseous sulfur compound into the solution. The amount of the sulfur compound added is generally in the range of 0.2 to 5 mol, preferably 0.4 to 3 mol, per 1 mol of the auxiliary metal compound in the solution. The use of this sulfur compound promotes and stabilizes the binding of the auxiliary metal component onto the copper sulfide-bound conductive material, and also exhibits the effect of improving conductivity. When the reducing sulfur compound is used in combination, treatment with a solution containing auxiliary metal ions can be performed in the presence of the sulfur compound, and treatment with the sulfur compound can be performed after the treatment with the solution. In the above embodiment, when using a commercially available cyano group-containing conductive material bonded with copper sulfide, it is immersed in the solution of the auxiliary metal component-containing compound as described above, and if necessary, added to the solution. The above-mentioned sulfur compound is present or post-treatment is performed with a sulfur compound after immersion, but when starting from the step of binding copper sulfide, the step of binding copper sulfide is completed or most of the step is completed, and then post-treatment is performed with a sulfur compound. The conductive material of the present invention can also be obtained by adding the above-mentioned auxiliary metal component-containing compound to the composition.
In this case as well, a sulfur compound may be added simultaneously if necessary. In the above embodiment, the auxiliary metal component is bonded to the conductive substance to which copper sulfide has been bonded in advance, but separately, the auxiliary metal component is bonded to the cyano group-containing substance. Occasionally,
It is also possible to combine them simultaneously, and this aspect will be explained next. In this embodiment, the above-mentioned cyano group-containing substance is treated in a bath containing (a) a source of monovalent copper ions, (b) auxiliary metal-containing ions, and (c) a reducing sulfur compound. As monovalent copper ion sources, monovalent copper salts and complex salts can be used, but usually, divalent copper salts and complex salts and other cupric compounds and divalent copper are used as monovalent copper ion sources.
A combination of reducing agents capable of reducing copper to valent copper is used. Examples of cupric compounds include copper sulfate, cupric chloride, cupric nitrate, cupric acetate, and the like.
On the other hand, examples of the reducing agent include metallic copper, hydroxylamine and its salts, ferrous sulfate, ammonium vanadate, furfural, sodium hypophosphite, and glycose. As the reducing sulfur compound, thiosulfate or a mixture of thiosulfate and other sulfur compounds is used, and the auxiliary metal ions are the same as those used in the embodiments described above. Note that the reducing sulfur compound can be used in place of or as a part of the reducing agent for reducing cupric to cuprous. When performing the one-bath method, the cyano group-containing substance is
Immersed in a bath containing ingredients (a), (b), and (c), usually 20
The treatment is carried out at ~150°C, preferably at 30-100°C for 1-24 hours. When performing heat treatment, the temperature of the bath is 1 to 3.
It is preferable to gradually heat from room temperature at a heating rate of °C/min. The pH of the bath is usually 1.5 to 6, and if necessary, inorganic acids such as sulfuric acid, hydrochloric acid, and phosphoric acid, organic acids such as citric acid and acetic acid, salts such as disodium hydrogen phosphate, sodium citrate, and sodium acetate, A PH adjuster such as and a mixture thereof is added. In the above method, the proportion of the monovalent copper ion supply source, which is component (a), to the cyano group-containing substance is usually in the range of 2 to 15 g in terms of metallic copper per 100 g of the cyano group-containing substance. , 1~ in the bath
Used at a concentration of 10g/. The amount of the auxiliary metal ion used as component (b) is about 0.001 to 0.5 mol per mol of cuprous used in the treatment. The amount of the sulfur compound used as component (c) is 1 to 3 times the mole of the total amount of components (a) and (b). After washing with water, the treated product obtained in the present invention has a
The product is dried at a temperature of 60 to 80 °C, preferably 60 to 80 °C. This product is suitable for use on the surface of cyano group-containing substances and/or
Alternatively, it has good electrical conductivity due to the continuous copper sulfide layer formed therein, as well as significantly improved cleaning resistance and moisture resistance due to the combination of auxiliary metal components. As mentioned above, the auxiliary metal components in the product are
Usually, it exists as a sulfide, but in this case, the auxiliary metal component may combine with the sulfur atoms of copper sulfide to form a type of mixed crystal. Next, the present invention will be explained in detail with reference to examples. Note that the wash resistance and moisture resistance tests in Examples were conducted under the following conditions. Washing resistance test Samples were washed with commercially available detergent (all temperature Cheer) for 3 days.
g/added to the aqueous solution at a bath ratio of 1:50 (wt/wt), and stirred and washed at 50°C for 30 minutes in a laundry fastness tester together with 10 steel balls. Dry after washing with water. Such a cleaning process is repeated a predetermined number of times, and the electrical specific resistance value (Ω-cm) at that time is measured. Alkaline Spotting Test According to JIS L 0864, 1 part by weight of the sample is immersed in 30 parts by weight of a 10 g/aqueous sodium carbonate solution, and after refluxing for 1 hour, the fastness is determined. Example 1 5 g of Cashmilon, acrylic fiber (product name: 2 denier, cut length 51 mm, type FWBR, manufactured by Asahi Kasei Industries, Ltd.) was mixed with 20 g of copper sulfate, 6 g of silver sulfate, and 20 g of sodium thiosulfate. , 20g/
of sodium bisulfite, 30g/2 of phosphoric acid
100ml of solution containing sodium, 12g/citric acid
After processing at 50°C for 5 hours, the sample is washed with water and dried. The specific resistance value of the treated fiber is 1.2×10 ^-1 Ω・
cm, and withstood 100 repeated washings. For comparison, this example was repeated without using silver sulfate, and the resulting conductive fibers could only withstand repeated washing 40 times. Example 2 Polyacrylonitrile type (product name: Silparon
100 denier, 40 filament, Mitsubishi Rayon Co., Ltd.
Conductive fibers were obtained by processing in exactly the same manner as in Example 1 except that the same amount of palladium chloride was used instead of silver sulfate. The specific resistance value of this thing is 3×
10 ^-1 Ω・cm and withstood repeated washing 100 times. Example 3 Nylon film with a thickness of 15 μm (product name: B0
#15 (manufactured by Toray Industries, Inc.) 2.5 g was immersed in 200 ml of a solution containing 10 g/ammonium persulfate and 10 g/sodium bisulfite at room temperature for 30 minutes, then placed in a stainless steel container and soaked with acrylonitrile vapor. The mixture is introduced into a container and a graft polymerization reaction is carried out at 38 to 40°C for 3 hours. This reaction results in a weight of 32.8
% increase. The obtained cyano group-containing nylon film was treated in the same manner as in Example 1 to obtain a conductive film. The surface resistivity of this film (ρ _s )
was 180Ω. The alkali spotting fastness was improved by two grades compared to the product that did not use silver sulfate. Example 4 Polyacrylonitrile powder pulverized to 10 μm or less is treated in the same manner as in Example 1. The obtained powder is
It showed a 12% weight increase and good electrical conductivity. When 5wt% of this was added to a polyvinyl chloride melt and injected into work gloves, a good antistatic product was obtained. Example 5 10 g of powder obtained by pulverizing phthalonitrile crystals to a size of 10 μm or less was treated in the same manner as in Example 1. The obtained powder was blackish gray in color and showed a weight increase of 11% and good conductivity. Apply this to commercially available paint (Acrylite 500)
When it was applied to an iron plate at a weight ratio of 1:1 and dried, it exhibited a surface resistance of 2×10 ² Ω and a reflection attenuation coefficient of −25 bB. Example 6 Copper sulfide-containing conductive acrylic fibers having an electrical resistivity value of 3.6×10 ^-2 Ω·cm obtained by the method described in Example 1 of JP-A No. 57-21570 were mixed with 5% by weight of silver nitrate, It was immersed in an aqueous solution containing 15% by weight of sodium thiosulfate and 5% by weight of sodium sulfite at a bath ratio of 1:20 and treated at 55°C for 2 hours. Although the conductive fibers before treatment lost their conductivity after being washed 40 times, the conductive fibers obtained in this example showed satisfactory conductivity even after being washed 100 times. In this example, when this example was repeated in exactly the same manner except that palladium chloride, chloroauric acid, and platinum chloride were used in place of silver nitrate, the cleaning resistance was almost the same as when silver nitrate was used. A conductive fiber was obtained. Example 7 In Example 1 of JP-A-57-21570,
Copper sulfide-containing conductive acrylic fiber (electrical resistivity value 1.16×10 ^{− 1Ω}・cm)
were immersed in silver nitrate aqueous solutions of various concentrations and heated at 50°C.
Conductive fibers having various silver contents shown in Table 1 were obtained. Table 1 shows the results of washing resistance tests on these fibers. 【table】

Claims (1)

[Scope of Claims] 1. At least one metal component selected from silver, gold, and platinum group metals is added as an auxiliary metal component to a substance having a cyano group together with copper sulfide. An electrically conductive material, characterized in that the material is bonded to the surface of the material via the cyano group. 2. The conductive material according to claim 1, wherein the auxiliary metal component is bonded in the form of sulfide. 3. A cyano group-containing conductive substance to which copper sulfide has been bonded in advance is mixed with at least one auxiliary metal ion selected from silver, gold, and platinum group metals,
A method for producing a conductive material, comprising processing in the presence of a reducing sulfur compound. 4 A cyano group-containing conductive material to which copper sulfide has been bonded in advance is treated with a solution containing at least one auxiliary metal ion selected from silver, gold, and platinum group metals, and then treated with a reducing sulfur compound. A method for producing a conductive material, characterized by: