JPH10208541A - Conductive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To facilitate manufacturing and enable application to electronic equipment or the like by securing at least one of a metal oxide disengaged in a colloid shape in a solution, a metal oxy-hydroxide, and a metal hydroxide on a substrate. SOLUTION: A metal salt is dissolved in water or the like, a colloid-shaped metal oxide, a metal oxy-hydroxide, and a metal hydroxide are generated by addition of heating energy or pH adjustment or the like, and these colloids are adhered in a substrate soaked in a liquid containing one or more kinds thereof. Preferably, after adhering these colloids, the colloids are soaked in a liquid containing sulfur or a sulfide compound, and binding or adhering of sulfur or the like or adhering of substitution reaction product with the sulfur or the like and oxide or hydroxide is carried out. Then, it is sufficient to carry out heat processing at 150 to 2000 deg.C. Since curing property with the colloids and a substrate is good, covering of the substrate surface is complete, and a specific surface area is large, it is suitable to f with a conductive to a base material, smaller colloid particle size is better. The base material is preferably fibrous or made of particles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material such as fibers or powdered particles having electrical conductivity.

[0002]

2. Description of the Related Art Conventionally, as conductive materials for electronic equipment,
There are metals, but from the viewpoints of equipment design, weight reduction, economy, etc., the transition to polymer materials with measures against electromagnetic interference and electrostatic discharge has been made. In addition, there has been a great movement to shift to polymer materials with measures against electromagnetic interference and electrostatic discharge in the automobile industry. Metal fibers have a large specific gravity and are rigid and difficult to handle. Polymer fibers are used in carpets, textile products, clothing, etc., but the static electricity that is charged causes shock shock to the human body, contamination by adsorbing dust in the air, adhesion due to mutual suction of static electricity, etc. In view of the problem described above, it is desired to impart conductivity.

[0003] As for inorganic compounds such as glass fiber, alumina, titanium oxide and talc, new materials having conductivity have been attracting attention. Examples of a method for imparting conductivity to a non-conductive material, such as a polymer material, include a method of blending a polymer electrolyte (eg, a metal salt of polyvinyl pyridine) or an antistatic agent with the non-conductive material, a metal powder, and carbon black. And a method of kneading a conductive inorganic filler, and a method of mixing a composite material having conductivity in advance. However, when a polymer electrolyte or an antistatic agent is blended, the conductivity of the resulting material is often insufficient, and the blend is released from the molded product and the conductivity decreases with time. The method of kneading the conductive inorganic filler has to be added in a large amount in order to impart conductivity, and thus has a drawback that there is a problem in workability of the material and a decrease in mechanical strength.

As a method of compensating for such a defect, there is a method of forming a conductive film on the surface of a metal compound by vacuum deposition, ion plating, sputtering, electroless plating, electrolytic plating, or the like. However, plating has a problem in adhesion and is expensive. Vacuum deposition, ion plating, and sputtering have a large specific surface area and are not suitable for coating a material with low conductivity, and thus have many problems in productivity and cost.

[0005]

Accordingly, there is a strong practical demand for the development of a new conductive material which eliminates the drawbacks of the conductive material produced by the above-described method.

[0006]

As a result of the research, the present inventors have found that a material having at least one of a colloidal metal oxide, a metal oxyhydroxide, and a metal hydroxide fixed on a substrate has been described. The present invention was completed. That is, the present invention relates to a metal oxide, a metal oxyhydroxide, and a metal hydroxide that are present in a suspended state as a colloid in a substrate and a solution and are fixed to the surface of the substrate from the same solution. Conductive material, a conductive material in which sulfur or a compound containing sulfur is further fixed or bonded to a fixed substance of the conductive material, and the above-mentioned fixed substance on the surface of the substrate is 150 ° C.
Not less than 2000 ° C and preferably not less than 150 ° C and 800 ° C
The present invention relates to a conductive material that has been heat-treated at the following temperature.

[0007]

Next, the present invention will be described in detail. The conductive material of the present invention can be manufactured, for example, by the following means. Dissolving the metal salt, immersing the substrate in a liquid in which at least one of a colloidal metal oxide, a metal oxyhydroxide, and a metal hydroxide is present by adding energy such as heating and adjusting the pH. Thereby, at least one of the colloidal metal oxides, hydroxides, and oxyhydroxides is fixed to the substrate. By dissolving the metal salt, adding energy such as heating, and adjusting the pH, the base material is immersed in a liquid in which at least one of a colloidal metal oxide, a metal oxyhydroxide, and a metal hydroxide is present. After fixing at least one of the various metal oxides, hydroxides, and oxyhydroxides to the substrate,
It is further immersed in a liquid containing sulfur or a sulfur compound to bond or fix the sulfur or fix the oxidation / hydroxide substitution reaction product. The fixed substance is subjected to a heat treatment in a temperature range of 150 ° C. or more and 2000 ° C. or less.

The colloidal metal oxide, metal oxyhydroxide, and metal hydroxide prepared by the above-mentioned method have good adhesion to the substrate, can completely cover the surface of the substrate, and increase the specific surface area. Therefore, it is suitable for imparting conductivity to the substrate. That is, in order to impart conductivity, it is necessary that a conductive substance such as colloidal metal oxide, metal oxyhydroxide, and metal hydroxide be in contact with each other. Hydroxides and metal hydroxides preferably have a small colloidal particle size, and a fibrous or granular substrate having a large specific surface area is desirable for increasing the contact area of the particles. In addition, colloidal metal oxides, metal oxyhydroxides, at least one kind of fixed substance of metal hydroxide and sulfur or a compound containing sulfur is fixed to the fixed substance, or bonded or oxidized with hydroxide and the compound. By fixing the substitution reaction product of the above, or by heating the fixed substance in a temperature range of 150 ° C. or more and 2000 ° C. or less, preferably 150 ° C. or more and 800 ° C. or less, the conductivity of the metal compound is improved. A material having a high level of imparting conductivity is provided.

The metal salt used in the present invention, after being completely dissolved in a solvent, is subjected to energy addition such as heating and pH adjustment to produce a colloidal metal oxide, metal oxyhydroxide and metal hydroxide. Any compound can be used. Specifically, Fe, Cr, Mn, Cu, Zn, Zr,
At least one metal salt selected from the group consisting of Co, Ni, V, Al, Si, Ti, Ga, and Sn is preferable. As metal salts, relatively inexpensive counter ions such as chloride ions, sulfate ions, and nitrate ions are used, but halogen ions such as oxalate ions, sulfite ions, nitrite ions, phosphate ions, phosphite ions, and the like. It may be an inorganic ion such as a phosphite ion, or an organic ion such as an ethoxy group, a methoxy group, a butoxy group, an oxalate ion, a tartrate ion, and a citrate ion.

Water is the most practical solvent for dissolving a metal compound for forming a colloidal metal oxide, a colloidal metal oxyhydroxide, and a colloidal metal hydroxide, but methyl alcohol, ethyl alcohol Other organic solvents are also used. Alternatively, a metal compound may be dissolved by adding an appropriate acid or base and further heating. The acid may be a mineral acid such as hydrochloric acid or sulfuric acid, or an organic acid such as acetic acid or formic acid. As the base, sodium hydroxide,
An industrially available alkali or organic base such as potassium hydroxide or ammonia is used.

For example, the metal compound for forming the colloidal metal oxide, the colloidal metal oxyhydroxide, or the colloidal metal hydroxide is originally a hydroxide or an oxide, or the counter ion is oxalate. , Tartrate ion,
When the substance is an organic substance such as citrate ion or contains a part of the organic substance, in order to completely dissolve the substance, an appropriate acid may be added and heated. When the counter ion is an ethoxy group, a methoxy group, a butoxy group, or the like, it may be dissolved in an appropriate organic solvent such as methyl alcohol or ethyl alcohol. For example, Ti chloride only partially dissolves in water and is partially hydrolyzed. Therefore, when a suitable acid is dissolved and then hydrolyzed, a colloidal metal compound is generated. For example, a chloride of Sn is made alkaline once, dissolved and then hydrolyzed to produce a colloidal metal compound.

The concentration of the solution to be used can be arbitrarily selected. However, the lower the concentration, the smaller the colloid particles that precipitate. Therefore, the concentration is generally 100 g / l or less, more preferably 10 g / l or less. The concentration is appropriate. Depending on the metal species, unless heated, colloid particles are not generated and precipitate. Colloidal particles generated by hydrolysis tend to aggregate at low temperatures.
It is desirable to heat it to at least ℃. Preferably, 50 to
Heat to 80 ° C.

The acids and bases used to precipitate colloidal metal oxides, metal oxyhydroxides and metal hydroxides are not particularly limited. Examples of the acid include mineral acids such as hydrochloric acid and sulfuric acid, acetic acid, and the like. An organic acid such as formic acid can be exemplified. As the base, an industrially available alkali or organic base such as sodium hydroxide, potassium hydroxide, or ammonia is used. The pH may be adjusted by completely dissolving the metal salt in a solvent, applying energy such as heating, and then sufficiently stirring and slowly adding an alkali or an acid. The appropriate pH for depositing colloidal metal oxides, metal oxyhydroxides, and metal hydroxides varies depending on the metal species, counterions, concentration, temperature, and stirring conditions. Under certain conditions, metal compounds such as colloidal metal oxides, metal oxyhydroxides and metal hydroxides may not be deposited. Also, 1
Even if colloidal particles are precipitated as secondary particles, they may aggregate over time and precipitate as secondary particles.

Colloidal metal oxide, metal oxyhydroxide
Preliminary experiments must be performed before
Select by. For example, select iron compounds as metal salts
Then, at a concentration of 10 g / l, FeCl_ThreeIf you use
Stir well so that pH <2.5 at 50 ° C or higher
And bases such as sodium hydroxide and potassium hydroxide
When the pH is adjusted by dropping slowly, colloidal
A precipitate is obtained. Below 50 ° C, precipitation occurs.
U. Even at 50 ° C. or higher, pH> 2.5 or
Insufficient stirring causes precipitation. F
e_Two (SO_Four )_Three When used, concentration, temperature, pH, stirring
Even if the conditions are selected, colloidal precipitates cannot be obtained. Money
When an aluminum compound is selected as the genus salt, 10 g /
1 concentration of AlCl _Three 6H_Two When using O, 30 ° C or less
Above, thoroughly agitate so that pH <5.6,
Slowly remove bases such as sodium hydroxide and potassium hydroxide
When the pH is adjusted by dropping, colloidal precipitates
can get. PH> 6 even at 30 ° C. or higher
If the stirring is insufficient, precipitation will occur.
U.

When a copper compound is selected as a metal salt, 10
CuCl ₂ 2H ₂ O, CuSO ₄ 5H ₂ at a concentration of g / l
When O and Cu (NO ₃ ) ₂ 3H ₂ O are used, the mixture is sufficiently stirred at 30 ° C. or more so as to have a pH <4.5.
When pH is adjusted by slowly dropping a base such as sodium hydroxide or potassium hydroxide, a colloidal precipitate is obtained. Even at a temperature of 30 ° C. or higher, precipitation occurs when the pH is greater than 6 or when stirring is insufficient. As a base, colloidal particles are more easily precipitated when ammonia is used than when sodium hydroxide or potassium hydroxide is used. When a titanium compound is selected as a metal salt, when TiCl ₄ is used at a concentration of 10 g / l, the pH is adjusted to <0.5 with hydrochloric acid, and at 30 ° C. or higher, p
The mixture was sufficiently stirred so that H <1, and a base such as sodium hydroxide or potassium hydroxide was slowly added dropwise.
When the pH is adjusted, a colloidal precipitate is obtained. Even if the pH is not adjusted to <0.5 with hydrochloric acid and the mixture is sufficiently stirred and a base such as sodium hydroxide or potassium hydroxide is slowly dropped, no colloid particles are precipitated.

The composition and particle size of the colloidal particles can be changed by selecting the concentration, temperature and pH conditions in the region where the colloidal particles are deposited. In addition, the amount of fixation is as follows:
It can be controlled by changing the ratio, concentration, temperature, pH conditions and reaction temperature of the substrate. Colloidal metal oxides, metal oxyhydroxides, and metal hydroxides are brought into contact with a substrate by contacting the substrate with the liquid to form colloidal metal oxides, metal oxyhydroxides, metal hydroxides, etc. The metal compound sticks. The term “metal oxide, metal oxyhydroxide, or metal hydroxide” as used herein partially includes metal oxide, metal oxyhydroxide, and metal hydroxide such as CuCl ₂ 3Cu (OH) _2. Is included.

When the colloidal metal oxide, metal oxyhydroxide and metal hydroxide are semiconductors such as titanium oxide, tin oxide and aluminum oxide, platinum, antimony,
Conductivity can be improved by doping a small amount of a zinc compound. Colloidal metal oxides, metal oxyhydroxides,
As a method of contacting the substrate with the liquid in which the metal hydroxide is precipitated, a method in which the substrate is immersed in the liquid in which the colloid compound is precipitated, or a method in which the substrate is immersed and stirred, Uniform methods such as a method of infiltrating a liquid in which metal compounds such as colloidal metal oxides, metal oxyhydroxides, and metal hydroxides are precipitated, and a method of continuously immersing and soaking in the case of fibers. Any method may be used as long as the substrate is brought into contact with a liquid in which a metal compound such as a colloidal metal oxide, metal oxyhydroxide, or metal hydroxide is precipitated.

The fixation of the colloid compound to the base material occurs instantaneously, but it takes at least 10 minutes for the metal oxide, metal oxyhydroxide and metal hydroxide to come into contact with each other. The amount of fixation is not particularly limited, but it is preferable that the amount of the metal compound such as colloidal metal oxide, metal oxyhydroxide, metal hydroxide, etc., which adheres to the surface of the base material, does not fix any more. The amount of fixation varies depending on the surface area of the substrate surface and the particle size of the colloid particles, but is usually in the range of metal compound / substrate = 0.5 / 100 to 50/100. As the energy adding means, heat energy such as heat transfer, convection, and radiation, and wave energy such as ultraviolet rays, infrared rays, electromagnetic waves, and X-rays are appropriately used. Energy is added by depositing metal compounds such as colloidal metal oxides, metal oxyhydroxides, and metal hydroxides, and then attaching them to the substrate. It is desirable to fix metal compounds such as substances, metal oxyhydroxides and metal hydroxides.

Further, sulfur or a compound containing sulfur may be bonded or fixed to the surface of the colloidal metal compound. Further, sulfur or a compound containing sulfur may be mixed with a metal compound such as a metal oxide, a metal oxyhydroxide, or a metal hydroxide, or may further have a substitution reaction product with the metal compound. . When the metal hydroxide is a copper hydroxide,
Compounds containing fixed sulfur are present as Cu _x S _y . Specifically, in the case of monovalent Cu hydroxide, C
In the case of a hydroxide of u ₂ S and divalent Cu, CuS is generated. When both are present, Cu ₉ S is added to CuS and Cu ₂ S in addition to Cu ₉ S.
₅ and so on occur. The sulfur or the compound containing sulfur used in the present invention, sulfur powder, hydrogen sulfide, sodium sulfide,
Metal sulfides such as potassium sulfide, sodium thiosulfate,
Any reducing sulfur compound such as ammonium thiosulfate, and other compounds containing persulfides and sulfur may be used. The solvent used may be water, water containing an acid or alkali, or an organic solvent. Room temperature, cooling, or energy-added heating may be used depending on the type of the compound to be reacted.

For bonding or fixing sulfur or a compound containing sulfur to the metal oxide, metal oxyhydroxide, or metal hydroxide, for example, FeOOH (iron hydroxide oxide) is fixed to the surface of the base material. In this case, an appropriate amount of sulfur powder is suspended in a diethylamine solution, and a substrate to which FeOOH is fixed is immersed and refluxed, and most of sulfur components as sulfur components can be fixed to iron hydroxide oxide. . CuCl
_When 23Cu (OH) ₂ is fixed, it is immersed in an aqueous solution of sodium sulfide at room temperature to obtain CuCl ₂ 3Cu (O
H) ₂ reacts, and most of the sulfur components adhere to the substrate as CuS. After the fixation, washing, drying, etc. may be performed by a known method according to a predetermined use. In order to improve the crystallinity of metal oxides, metal oxyhydroxides, and metal hydroxide colloids and obtain higher conductivity, 15
The heat treatment may be performed at a temperature of 0 to 2000C, preferably 150 to 800C. When a metal oxide, a metal oxyhydroxide, or a metal hydroxide is fixed to an insulating base material such as a synthetic resin, the antistatic property is attained. By improving the crystallinity of the product or metal hydroxide, higher conductivity can be obtained. The higher the heat treatment temperature, the higher the crystallinity of the metal hydroxide and metal oxyhydroxide can be increased in a short time. Therefore, the higher the heat treatment temperature, the longer the heat treatment time required to obtain the desired conductivity. Will get better in a short time. The heat treatment is preferably performed at a temperature at which the physical properties of the base material do not decrease, generally at a temperature lower than the softening point.
For example, 158 ° C for polypropylene, 238 ° C for polyester, 200 ° C for acrylic, and 70 ° C for glass fiber.
0 ° C. In addition, the melting point of alumina is 2050 ° C
Hereinafter, the melting point of titanium oxide is 1640 ° C. or lower.

On the other hand, metal oxides, metal oxyhydroxides,
The temperature must be below the melting point of the metal hydroxide. For example, 1127 ° C for tin, 1640 ° C for titanium oxide,
2050 ° C or less for aluminum oxide, 11 for copper sulfide
The temperature is not higher than 00 ° C. Preferably, the temperature is such that the physical properties of the metal oxide, metal oxyhydroxide, and metal hydroxide do not decrease. For example, tin oxide sinters at 800 ° C. or higher to produce coarse particles. Copper (II) sulfide converts at 220 ° C. to copper (I) sulfide having lower conductivity than copper (II) sulfide. The heat treatment atmosphere may be air, but may be oxidation, reduction, inert atmosphere, or vacuum. Examples of the oxidizing atmosphere include air, oxygen, ozone, chlorine, and the like.
Also, a mixed gas of these and an inert gas may be used. Examples of the reducing atmosphere include hydrogen, hydrogen iodide, hydrogen sulfide, carbon monoxide, and sulfur dioxide. Also, a mixed gas of these and an inert gas may be used. Examples of the inert atmosphere include helium, neon, argon, krypton, xenon, a rare gas such as radon, and nitrogen. Further, to obtain high conductivity, there is a method of causing doping and lattice defects. Also in this method, when the metal oxide or metal oxyhydroxide is a semiconductor, such as titanium oxide, tin oxide, or aluminum oxide, by doping a small amount of platinum, antimony, or a zinc compound, the conductivity can be significantly improved. . On the other hand, even if these compounds are not doped, the conductivity can be improved by generating lattice defects in the molecules. For example, a method of firing tin dioxide particles in a reducing atmosphere or an inert atmosphere (Japanese Patent Laid-Open No. 6-345430).
and so on. In this manner, the present conductive material is similarly calcined in a reducing or inert atmosphere to cause lattice defects in metal oxides, metal oxyhydroxides, and metal hydroxides fixed to the base material, The conductivity can be significantly improved.

Examples of the substrate used in the present invention include synthetic resins, carbon materials, natural resins, inorganic materials and mineral materials. As synthetic resins, polypropylene, polyethylene, polyester, polyamide, acrylic, vinylon,
It is a polyurethane resin or the like, and is not particularly limited to molecular weight, molecular weight distribution, and the like. As the polypropylene resin, a propylene homopolymer and / or a propylene copolymer is used. Here, as the propylene copolymer, there are a propylene-ethylene copolymer, a propylene-butene-1 copolymer and the like, and a block copolymer and a random copolymer thereof are used.

Examples of the polyethylene resin include high-density polyethylene, linear low-density polyethylene, and low-density polyethylene. Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polymethylene terephthalate, and poly-para-ethyleneoxybenzoate. As the polyamide resin, polyamide 6, polyamide 66, polyamide 61
0, homopolymers such as polyamide 12, polyamide 6/66, polyamide 6/12, polyamide 6/66 /
610, such as copolymer polyamides with polyamide 6, and the like. Among them, a homopolymer of polyamide 6 is preferable because of its good moldability and low production cost.

Other examples include synthetic fibers such as acrylic, vinylon, polyurethane, aramid, polystyrene, and vinylidene chloride. Further, these resins may be used alone or in combination of two or more, and may be a blend of two or more resins in the production process. Examples of the carbon material include PAN-based, pitch-based carbon fiber, carbon black, graphite, and various rubbers. Examples of the natural resin include pulp, silk, cotton and the like. As inorganic materials, silicon oxide, alumina, glass,
Examples include titanium oxide, alkali titanate, zirconia, and magnesia. A composite of a blend or the like at the time of manufacturing the above materials may be used.

Examples of the mineral material include talc, kaolin, obsidian, perlite and pine stone. The shape is not particularly limited, but fibrous or granular with a large non-surface area is effective. Further, foams such as polystyrene, polypropylene, polyethylene, and vinylidene chloride are also suitable. Hereinafter, specific examples will be described.

(Example 1) Ti previously diluted with concentrated hydrochloric acid
Cl ₄ 50 a 10g / l-TiCl ₄ aqueous solution with a solution
0 ml, heated to 70 ° C., and NaO was adjusted to pH 0.55.
H to the obtained colloidal TiO ₂ -containing liquid,
Soak a 2 denier polypropylene tow
Hold for 10 minutes. The polypropylene tow was taken out, thoroughly washed with water, and dried at 105 ° C. for 1 hour. Colloidal T
The attachment of iO ₂ was confirmed by X-ray diffraction.
Also, it was observed by an electron microscope that the colloidal particles were fixed as crystals of about 5 nm.

Example 2 Ti previously diluted with concentrated hydrochloric acid
Cl ₄ 50 a 10g / l-TiCl ₄ aqueous solution with a solution
0 ml, heated to 70 ° C., and NaO was adjusted to pH 0.55.
H to the obtained colloidal TiO ₂ -containing liquid,
Soak the polyester tow with 2 denier single yarn, 6
Hold for 0 minutes. The polyester tow was taken out, thoroughly washed with water, and dried at 105 ° C. for 1 hour. Colloidal TiO
_The attachment of ₂ was confirmed by X-ray diffraction. Also, it was observed by an electron microscope that the colloidal particles were fixed as crystals of about 5 nm.

Example 3 Ti previously diluted with concentrated hydrochloric acid
Cl ₄ 50 a 10g / l-TiCl ₄ aqueous solution with a solution
0 ml, heated to 70 ° C., and NaO was adjusted to pH 0.55.
H to the obtained colloidal TiO ₂ -containing liquid,
Soak a polyester tow of 2 denier single yarn,
Hold for 20 minutes. The polyester tow was taken out, thoroughly washed with water, and dried at 105 ° C. for 1 hour. Colloidal Ti
The attachment of O ₂ was confirmed by X-ray diffraction. Also, it was observed by an electron microscope that the colloidal particles were fixed as crystals of about 5 nm.

Example 4 Ti previously diluted with concentrated hydrochloric acid
Cl ₄ 50 a 10g / l-TiCl ₄ aqueous solution with a solution
0 ml, heated to 70 ° C., and NaO was adjusted to pH 0.55.
H to the obtained colloidal TiO ₂ -containing liquid,
Soak the polyester tow with 2 denier single yarn, 6
Hold for 0 minutes. The polyester tow was taken out, thoroughly washed with water, and dried at 105 ° C. for 1 hour. Colloidal TiO
X-ray diffraction confirmed that ₂ was more closely attached to Example 2. Also, it was observed by an electron microscope that the colloidal particles were fixed as crystals of about 5 nm.

(Example 5) Ti previously diluted with concentrated hydrochloric acid
Cl ₄ 50 a 10g / l-TiCl ₄ aqueous solution with a solution
0 ml, heated to 70 ° C., and NaO was adjusted to pH 0.55.
H to the obtained colloidal TiO ₂ -containing liquid,
An acrylic tow of 2 denier single yarn was immersed and held for 10 minutes. Take out the acrylic tow, wash it thoroughly with water,
Dried at 105 ° C. for 1 hour. The attachment of colloidal TiO ₂ was confirmed by X-ray diffraction. Also, it was observed by an electron microscope that the colloidal particles were fixed as crystals of about 5 nm.

Example 6 Ti previously diluted with concentrated hydrochloric acid
Cl ₄ 50 a 10g / l-TiCl ₄ aqueous solution with a solution
0 ml, heated to 70 ° C., and NaO was adjusted to pH 0.55.
H to the obtained colloidal TiO ₂ -containing liquid,
A two-denier single yarn aramid tow was dipped and held for 10 minutes. Take out the aramid tow, wash it thoroughly with water,
Dried at 105 ° C. for 1 hour. The attachment of colloidal TiO ₂ was confirmed by X-ray diffraction. Also, it was observed by an electron microscope that the colloidal particles were fixed as crystals of about 5 nm.

Example 7 Ti previously diluted with concentrated hydrochloric acid
Cl ₄ 50 a 10g / l-TiCl ₄ aqueous solution with a solution
0 ml, heated to 70 ° C., and NaO was adjusted to pH 0.55.
H to the obtained colloidal TiO ₂ -containing liquid,
A glass fiber having an average diameter of 20 μm and a length of 6 mm was immersed and held for 10 minutes. The glass fiber was taken out, sufficiently washed with water, and dried at 105 ° C. for 1 hour. Colloidal Ti
The attachment of O ₂ was confirmed by X-ray diffraction. Also, it was observed by an electron microscope that the colloidal particles were fixed as crystals of about 5 nm.

(Embodiment 8) Ti previously diluted with concentrated hydrochloric acid
Cl ₄ 50 a 10g / l-TiCl ₄ aqueous solution with a solution
And 0ml created, which in the H ₂ PtCl ₆ 6H ₂ O 0.0
5 g, heated to 70 ° C., and immersed in a colloidal TiO ₂ -containing liquid obtained by adjusting the pH to 0.55 with NaOH, immersing glass fiber having an average diameter of 20 μm and a length of 6 mm,
Hold for 0 minutes. The glass fiber was taken out, sufficiently washed with water, and dried at 105 ° C. for 1 hour. The attachment of colloidal TiO ₂ was confirmed by X-ray diffraction. Electron microscopy confirmed that the colloidal particles were fixed as crystals of about 5 nm.

Example 9 10 g / l-Na ₂ SnO
_3. Prepare 500 ml of 3H ₂ O aqueous solution, heat to 70 ° C., and adjust to pH 3.7 colloidal SnO ₂ prepared with sulfuric acid.
A glass fiber having an average diameter of 20 μm and a length of 6 mm was immersed in the liquid solution and held for 10 minutes. The glass fiber was taken out, sufficiently washed with water, and dried at 105 ° C. for 1 hour. The adherence of colloidal SnO ₂ was confirmed by X-ray diffraction. Also, under an electron microscope, it was observed that the colloidal particles had crystals of about 5 nm fixed thereto.

(Example 10) 10 g / l-Na ₂ Sn
500 ml of O ₃ 3H ₂ O aqueous solution was prepared, and SbC
The l ₃ was added 0.05 g, and heated to 70 ° C., and the colloidal SnO ₂ containing solution prepared with sulfuric acid to pH 3.7, the mean diameter of 20 [mu] m, was immersed glass fiber length 6 mm, 10
Minutes. Take out the glass fiber, wash thoroughly with water,
Dried at 105 ° C. for 1 hour. The adherence of colloidal SnO ₂ was confirmed by X-ray diffraction. Also, with an electron microscope, it was observed that crystals of about 5 nm were fixed in the colloidal particles.

(Example 11) 10 g / l-CuCl ₂
Make 500 ml of 2H ₂ O aqueous solution, heat to 70 ° C,
Colloidal CuC prepared with ammonia to pH 3.4
to l ₂ 3Cu (OH) ₂ containing solution, by immersing the single yarn 2 denier polyester tow, and held 10 min. Single yarn 2
The denier polyester tow was removed, washed thoroughly with water and dried at 105 ° C. for 1 hour. It was confirmed by X-ray diffraction that colloidal CuCl ₂ 3Cu (OH) ₂ particles were attached as a copper compound. Electron microscopy confirmed that the colloidal particles were fixed as needle-like crystals of about 15 nm.

(Example 12) 10 g / l-AlCl ₃
Make 500 ml of 6H ₂ O aqueous solution, heat to 70 ° C,
A 2-denier single-filament polyester tow was immersed in a colloidal aluminum hydroxide-containing solution prepared with NaOH at pH 5.3 and held for 10 minutes. The polyester tow was taken out, thoroughly washed with water, and dried at 105 ° C. for 1 hour. X-ray diffraction confirmed that colloidal Al (OH) ₃ had adhered to the tow. Further, it was observed by an electron microscope that the colloidal particles were fixed as needle-like crystals of about 7 nm.

[0038] (Example _{13) 1g / l-Na 2} S aqueous solution was prepared 500 ml, is immersed tow polyester obtained colloidal CuCl ₂ · 3Cu (OH) ₂ particles are deposited in Example 11 For one minute.
Take out the polyester tow, wash it thoroughly with water,
Dried for 1 hour at ° C. X-ray diffraction confirmed that CuS was attached as a copper compound. In addition, under an electron microscope, it was observed that CuS was fixed as needle-like crystals of about 15 nm.

Example 14 The polyester tow to which the colloidal TiO ₂ particles obtained in Example 2 had been adhered was heat-treated at 200 ° C. for 8 hours in air.

Example 15 The aramid tow to which the colloidal TiO ₂ particles obtained in Example 6 were adhered was heated in air at 400 ° C. for 2 hours.

(Example 16) The glass fiber to which the colloidal TiO ₂ particles obtained in Example 7 were adhered was heated in air at 500 ° C for 2 hours.

Example 17 The glass fiber to which the colloidal TiO ₂ particles obtained in Example 8 were adhered was heat-treated in air at 500 ° C. for 2 hours.

(Example 18) The glass fiber to which the colloidal SnO ₂ particles obtained in Example 9 were adhered was heated in air at 500 ° C. for 2 hours.

Example 19 The glass fiber to which the colloidal SnO ₂ particles obtained in Example 9 were adhered was heat-treated in air at 350 ° C. for 6 hours.

Example 20 The glass fiber to which the colloidal SnO ₂ particles obtained in Example 9 had been adhered was heat-treated in air at 600 ° C. for 1 hour.

Example 21 The glass fiber to which the colloidal SnO ₂ particles obtained in Example 9 were adhered was heat-treated at 500 ° C. for 2 hours in a hydrogen / nitrogen = 1: 5 atmosphere.

Example 22 The glass fiber to which the colloidal SnO ₂ particles obtained in Example 9 were adhered was heat-treated at 500 ° C. for 2 hours in a nitrogen atmosphere.

Example 23 The glass fiber to which the colloidal SnO ₂ particles obtained in Example 10 were adhered was subjected to a heat treatment in air at 500 ° C. for 2 hours.

(Example 24) 10 g / l-CuCl ₂
Make 500 ml of 2H ₂ O aqueous solution, heat to 70 ° C,
Colloidal CuC prepared with ammonia to pH 3.4
to l ₂ 3Cu (OH) ₂ containing solution, a polypropylene nonwoven fabric was immersed and held for 10 minutes. Take out the nonwoven,
It was washed thoroughly with water and dried at 105 ° C. for 1 hour. It was confirmed by X-ray diffraction that colloidal CuCl ₂ 3Cu (OH) ₂ was attached as a copper compound. Also, it was observed by an electron microscope that the colloid particles were fixed as needle-like crystals of about 15 nm.

Example 25 500 ml of a 1 g / l-Na ₂ S aqueous solution was prepared, and the polypropylene nonwoven fabric to which the colloidal CuCl ₂ 3Cu (OH) ₂ particles obtained in Example 23 had adhered was immersed. Minutes. The nonwoven fabric was taken out, thoroughly washed with water, and dried at 105 ° C. for 1 hour. It was confirmed by X-ray diffraction that CuS was attached as a copper compound. Also, it was observed by an electron microscope that the CuS was fixed as needle-like crystals of about 15 nm.

(Example 26) T previously diluted with concentrated hydrochloric acid
10 g / l-TiCl ₄ aqueous solution was added to the iCl ₄ solution for 5 hours.
100 ml, heated to 70 ° C. and adjusted to pH 0.55 with Na
An acrylic resin powder having an average particle diameter of 20 μm was immersed in a colloidal TiO ₂ -containing liquid prepared by OH and held for 10 minutes. The acrylic resin powder was taken out, sufficiently washed with water, and dried at 105 ° C. for 1 hour. Colloidal T
The attachment of the iO ₂ particles was confirmed by X-ray diffraction. Also, it was observed by an electron microscope that the colloidal particles were fixed as crystals of about 5 nm.

(Example 27) 10 g / l-CuCl ₂
Make 500 ml of 2H ₂ O aqueous solution, heat to 70 ° C,
The colloidal CuCl ₂ 3Cu (OH) ₂ -containing solution obtained by adjusting the pH to 3.4 with ammonia was added to the solution containing an average particle size of 20
A μm acrylic resin powder was immersed and held for 10 minutes. Take out the acrylic resin powder and wash it thoroughly with water.
Dry at 5 ° C. for 1 hour. Colloidal C as copper compound
The attachment of uCl ₂ 3Cu (OH) ₂ was confirmed by X-ray diffraction. Also, it was observed by an electron microscope that the colloid particles were fixed as needle-like crystals of about 15 nm.

(Example 28) 500 ml of a 1 g / l-Na ₂ S aqueous solution was prepared, and the acrylic resin powder having an average particle diameter of 20 μm to which the colloidal CuCl · 3Cu (OH) ₂ obtained in Example 23 was adhered was used. It was immersed and held for 1 minute. Take out the acrylic resin powder and wash it thoroughly with water.
Dry at 05 ° C for 1 hour. X-ray diffraction confirmed that CuS was attached as a copper compound. Also, it was observed by an electron microscope that the CuS was fixed as crystals of about 5 nm.

(Example 29) T which was previously diluted with concentrated hydrochloric acid
10 g / l-TiCl ₄ aqueous solution was added to the iCl ₄ solution for 5 hours.
100 ml, heated to 70 ° C. and adjusted to pH 0.55 with Na
Alumina powder having an average particle size of 3 μm was immersed in a colloidal TiO ₂ -containing liquid prepared by
Minutes. Take out the alumina powder, wash it thoroughly with water,
Dried at 105 ° C. for 1 hour. TiO ₂ is added to the alumina powder.
The attachment of the particles was confirmed by X-ray diffraction. Further, it was observed by an electron microscope that the TiO ₂ was fixed as crystals of about 5 nm.

Example 30 T previously diluted with concentrated hydrochloric acid
10 g / l-TiCl ₄ aqueous solution was added to the iCl ₄ solution for 5 hours.
100 ml, heated to 70 ° C. and adjusted to pH 0.55 with Na
A 23-fold foam of vinylidene chloride having an average particle size of 500 μm was immersed in a colloidal TiO ₂ -containing liquid prepared by OH and held for 10 minutes. Vinylidene chloride 2
The triple foam was taken out, thoroughly washed with water, and dried at 105 ° C. for 1 hour. Colloidal T is added to the vinylidene chloride foam.
The attachment of iO ₂ was confirmed by X-ray diffraction.
According to an electron microscope, the colloidal TiO ₂ particles were about 5 n
It was observed that they were fixed as crystals of m.

(Comparative Example 1) The 2-denier single-filament polypropylene tow used in Example 1 was dried at 105 ° C for 1 hour. (Comparative Example 2) Examples 2, 3, 4, 11, 12, 13,
Use 1 denier 2 denier polyester tow used in 14
Dry at 05 ° C for 1 hour. (Comparative Example 3) The single-denier 2-denier acrylic tow used in Example 5 was dried at 105 ° C for 1 hour. (Comparative Example 4) The 2-denier single yarn aramid tow used in Examples 6 and 15 was dried at 105 ° C for 1 hour. (Comparative Example 5) Examples 7, 8, 9, 10, 16, 17,
Average diameter 2 used in 18, 19, 20, 21, 22, 23
A glass fiber having a length of 0 μm and a length of 6 mm was dried at 105 ° C. for 1 hour. (Comparative Example 6) The polypropylene nonwoven fabric used in Examples 24 and 25 was dried at 105 ° C for 1 hour. Comparative Example 7 The acrylic resin powder having an average particle diameter of 20 μm used in Examples 26, 27 and 28 was dried at 105 ° C. for 1 hour. (Comparative Example 8) The alumina powder having an average particle diameter of 3 µm used in Example 29 was dried at 105 ° C for 1 hour. (Comparative Example 9) Average particle size 500 μm used in Example 30
Of vinylidene chloride was dried at 105 ° C. for 1 hour.

Next, the results of measuring the conductivity of the materials obtained in the examples and comparative examples are shown below. Measurement results (1) Synthetic fiber-related The synthetic fiber obtained in each of the examples and comparative examples was obtained at 23 ° C. and 60%
After storing under RH conditions for 24 hours, the specific resistance (Ωcm) was measured. Table 1 shows the results.

[0058]

[Table 1]

(2) Related to glass fiber About 170 mg of a sample is placed in a Teflon holder having Ni electrodes of 9 mm in diameter at both ends, and the sample is tightened so that the specific gravity of the sample becomes 1.0 to increase the resistance between the Ni electrodes. The resistance was measured 10 minutes after the load was applied using a resistance measuring instrument. Table 2 shows the results.

[0060]

[Table 2]

(3) Nonwoven Fabric The surface resistance was measured with an applied voltage of 25 V using a surface resistance measuring instrument. Table 3 shows the results.

[0062]

[Table 3]

(4) Relationship between Glass Fiber and Powder After storage at 23 ° C. and 60% RH for 24 hours, the volume resistance was measured by a four-point probe method. Table 4 shows the results.

[0064]

[Table 4]

[0065]

According to the present invention, at least one of a colloidal metal oxide, a metal oxyhydroxide, and a metal hydroxide is fixed on the surface of a nonconductive material such as synthetic fiber, glass fiber, and nonwoven fabric. And its manufacture is easy,
For example, it can be applied to electronic devices and the like, and is extremely useful in practical use.

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[Procedure amendment]

[Submission date] April 16, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0050

[Correction method] Change

[Correction contents]

(Example 25) 500 ml of a 1 g / l-Na ₂ S aqueous solution was prepared, and the polypropylene nonwoven fabric to which the colloidal CuCl ₂ 3Cu (OH) ₂ particles obtained in Example 24 were attached was dipped in Minutes. The nonwoven fabric was taken out, thoroughly washed with water, and dried at 105 ° C. for 1 hour. It was confirmed by X-ray diffraction that CuS was attached as a copper compound. Also, it was observed by an electron microscope that the CuS was fixed as needle-like crystals of about 15 nm.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0053

[Correction method] Change

[Correction contents]

(Example 28) 500 ml of an aqueous 1 g / l-Na ₂ S solution was prepared, and the acrylic resin powder having an average particle diameter of 20 μm to which the colloidal CuCl · 3Cu (OH) ₂ obtained in Example 27 was adhered was used. It was immersed and held for 1 minute. Take out the acrylic resin powder and wash it thoroughly with water.
Dry at 05 ° C for 1 hour. X-ray diffraction confirmed that CuS was attached as a copper compound. Also, it was observed by an electron microscope that the CuS was fixed as crystals of about 5 nm.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0058

[Correction method] Change

[Correction contents]

[0058]

[Table 1]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0064

[Correction method] Change

[Correction contents]

[0064]

[Table 4]

Claims (6)

[Claims] 1. A substrate and at least one of a colloidal metal oxide, a metal oxyhydroxide, and a metal hydroxide which are present as a colloid in a solution and are fixed to the surface of the substrate from the solution. A conductive material consisting of a fixed substance. 2. A base material and at least one of a colloidal metal oxide, a metal oxyhydroxide, and a metal hydroxide which are present as a colloid in a solution and adhered to the surface of the base material from the solution. A conductive material comprising a fixed substance and sulfur bonded or bonded to the fixed substance, or a compound containing sulfur, or a substitution reaction product of the compound and an oxidation / hydroxide compound. 3. The metal of the metal oxide, metal oxyhydroxide and metal hydroxide is Fe, Cr, Mn, Cu, Zn, Z
3. The conductive material according to claim 1, wherein the conductive material is at least one metal selected from the group consisting of r, Co, Ni, V, Al, Si, Ti, Ga, and Sn. 4. The conductive material according to claim 2, wherein the compound containing sulfur is present as Cu _x S _y . 5. The conductive material according to claim 1, wherein the substrate is a fibrous or granular material. 6. The method according to claim 1, wherein the fixed substance on the surface of the base material, sulfur or a sulfur-containing compound fixed to or bonded to the fixed substance, or a substitution reaction product is heat-treated at 150 ° C. or more and 2000 ° C. or less. 6. The conductive material according to any one of 1 to 5.