JPH0813328A - Production of fiber or woven fabric whose surface is coated with ultrafine particles - Google Patents

Abstract

PURPOSE:To provide a method for producing a fiber or woven fabric which has an improved strength for a fiber-reinforced composite material and whose surface is coated with ultrafine particles. CONSTITUTION:This method for producing a fiber or woven fabric whose surface is coated with ultrafine particles comprises introducing an organic material, inorganic material, metal material or single body element fiber or woven fabric to be coated into a flow containing inorganic material, metal material or single body element ultrafine particles produced by a gaseous phase method to bring the ultrafine particles into contact with the fiber or woven fabric to be coated in a state in which the ultrafine particles are active, and subsequently allowing the fiber or woven fabric to pass through an ultrasonic vibration liquid tank.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an organic material, an inorganic material, a metal material or a single element fiber or woven cloth, the surface of which is coated with ultrafine particles of an inorganic material, a metal material or a single element, In particular, it concerns post-treatment of coated fibers or woven fabrics.

This organic material, inorganic material, metallic material, or fiber or woven fabric whose surface is coated with ultrafine particles has fibers and synthetic resin or adhesive when synthetic resin or adhesive is applied. Since the bond between the two is extremely large, as a fiber or woven fabric for the fiber-reinforced composite,
It is also useful as a reinforcing material for a reinforced resin, as a fiber or a woven material having good adhesiveness.

[0003]

2. Description of the Related Art Organic fiber materials such as polyester fiber, polyamide fiber and polyimide fiber, glass fiber, silicon carbide fiber, inorganic fiber material such as asbestos and rock wool, elemental fiber such as carbon fiber, and iron. Fibers of metals such as aluminum, titanium, copper, gold, silver, nickel, cobalt, tungsten, especially iron, aluminum,
A fiber material such as a metal fiber such as titanium or tungsten is a material for producing a fiber-reinforced composite, and a liquid thermosetting resin or a thermoplastic resin is blended with or applied to this, or a liquid material Kneading with a thermosetting resin or a thermoplastic resin to produce a fiber reinforced composite by an appropriate molding means such as compression molding, transfer molding, injection molding, extrusion molding or lamination molding with other plate materials. Used as a reinforcing material when doing. By the way, in this case, the surface of the reinforcing material is often smooth,
Since the adhesiveness with the thermosetting resin etc. is not sufficient, the strength of the molded product is not always satisfactory. Attempts have also been made to surface-treat the fiber material in order to improve this adhesion, but the strength of the fiber material is reduced,
The processing itself has drawbacks such as a large cost, and in many cases, the satisfactory results have not been obtained.

It is a well-known method for producing a catalyst that a fiber material such as carbon fiber, asbestos, glass fiber or rock wool is used as a carrier and a catalyst substance is supported on the surface of the carrier to produce a catalyst. Also in this case, the catalyst substance easily falls off the carrier surface due to the smoothness of the carrier surface and the roughness of the place (anchor site) where the catalyst substance is connected.

As described above, the fiber or woven fabric used in the fiber-reinforced composite has not only the strength as the fiber material itself but also
High connectivity with the matrix is also required. From such a point, an inorganic material, a metal material or an organic material whose surface is coated with ultrafine particles of a single element, an inorganic material, a metal material or a single element fiber or woven fabric is an inorganic material produced by a vapor phase method, An organic material, an inorganic material, a metal material or a single element fiber or woven fabric to be coated is introduced into a flow containing a metal material or a single element ultrafine particle, and the above ultrafine particle and the above-mentioned coating are to be coated. It has already been found that it is obtained by contacting a fiber or a woven fabric with the ultrafine particles in an active state, and has already disclosed in Japanese Patent Application No. 3-273.
Filed as 633.

[0006]

However, various studies on the strength of the fiber or woven fabric produced in this manner have revealed that the strength expected is not sufficient in some cases. It is required to improve this point and find a measure for improving the strength as originally expected or higher.

[0007]

As a result of research for solving this problem, the present inventors have found that an organic material to be coated in a flow of an inorganic material, a metal material, or ultrafine particles of a single element produced by a gas phase method. Introducing a material, an inorganic material, a metal material or a fiber or woven fabric of a simple element, and contacting the above-mentioned ultrafine particles with the above-mentioned fiber or woven fabric to be coated in an active state of the ultrafine particles, The present invention has been completed by finding that a fiber or woven fabric whose surface is coated with the above ultrafine particles can be obtained by passing the fiber or woven fabric through an ultrasonic vibration liquid tank.

That is, the inorganic material of the present invention, a metal material or an organic material whose surface is coated with ultrafine particles of a single element,
Inorganic materials, metallic materials, or fibers or woven fabrics of simple elements may be CVD or PVD methods such as RF plasma methods (Ra
dio frequency plasma), an organic material, an inorganic material, a metal material or a single element fiber to be coated in a flow containing an inorganic material, a metal material or ultrafine particles of a single element, which are generated in a gas phase by a laser method or the like. Alternatively, a woven fabric is continuously or semi-continuously supplied, and the above-mentioned ultrafine particles are brought into contact with the above-mentioned fiber or woven fabric to be coated in a state where the ultrafine particles are active to adhere them to each other. Ultrafine particles are firmly bonded and adhered to the surface of the organic material, inorganic material, metal material, or fiber or woven fabric of a single element to be coated through the sonic vibration liquid tank, and there is no free ultrafine particle. It can be obtained as a completely new fiber or woven material.

When the fibers or the woven fabric are passed through the flow of the ultrafine particles immediately after being produced by the vapor phase method to adhere the ultrafine particles, all the ultrafine particles are not adhered to the surface of the fiber or the woven fabric but are released. A lot of remaining ultrafine particles remain, and after a while, the ones that are simply attached to the fibers by cohesive force or simply deposited on the fibers also behave as the ultrafine particles that are apparently attached to the fibers or the woven fabric. Is shown. When a molded body is made with resin or an adhesive in this state, as shown in FIG. 3A, in addition to the originally strongly adhered ultrafine particles A, they are present on the surface of the fiber only by the adhesive force (cohesive force). Or, if there are ultrafine particles (shown in B) attached to the originally adhered ultrafine particles themselves,
As shown in, when a molded body is made of a resin or an adhesive, the resin and the adhered ultrafine particles indicated by B are sufficiently strongly adhered, but a sufficient adhesive force is exerted between the ultrafine particles indicated by A and the ultrafine particles indicated by B. 3B, the adhesion between the fiber and the resin in the state as shown in FIG. 3B is not achieved, and therefore the desired effect may not be obtained, and the opposite effect may be exhibited. all right. Since the free ultrafine particles have a small particle size, they are easily aggregated and cannot be separated by a usual method such as applying an air flow or vibration. However, when the fibers or woven fabric treated by the present inventors are dipped in a liquid and the high frequency vibration is applied, the apparently adhered ultrafine particles are sufficiently separated, and the time for which they are left in the liquid is several seconds to + several seconds. It turns out that is effective enough. Such a treatment method is also advantageous in that it can continuously treat fibers or woven fabrics.
The vibrating medium to be placed in the liquid tank is not particularly limited, such as water and alcohol, and may be selected depending on the material of the fibers and the properties of the ultrafine particles. A high frequency of 10 KHz to 100 KHz is effective, and 30 KHz to 50 KHz is particularly effective.

The fibers or woven fabrics whose surface is coated with the ultrafine particles of the present invention include those derived from organic materials, for example, fibers from polyester, polyamide, polyimide, polyphenyl sulfide, etc. or woven fabrics and inorganic materials from these. Origins such as fiberglass, asbestos, rock wool,
Fibers such as silicon carbide or woven fabrics thereof, derived from metallic materials such as Fe, Ni, Co,
Examples thereof include fibers that are filaments of Al, Ti, Au, Ag, W or the like, or woven fabrics derived from these, and those derived from simple elements, such as carbon fibers or woven fabrics derived therefrom. Organic material whose surface is coated with these ultrafine particles,
It may be in the state of a single fiber of an inorganic material, a metal material, or a fiber of a simple element, or may be in a woven state.

The constituents of the ultrafine particles for coating the surface of the fibers or woven fabrics of the organic material, inorganic material, metal material or simple element described above are obtained with respect to the obtained fiber or woven fabric coated with ultrafine particles. Depending on the desired properties and functions, various inorganic materials, metallic materials or elemental elements whose surface is the same as or different from the fiber or woven material to be coated, specific examples of which are: Various inorganic substances such as oxides Al ₂ O ₃ , SiO ₂ , Zr
O ₂ , Y ₂ O ₃ , CaO, and other nitrides such as Si ₃ N ₄ and A
1N, BN, etc., carbides such as WC, SiC, etc., boronides, such as BP, BN, etc., elemental metals such as Si,
Examples include Al, Ni, Co, Cu, Fe, Ti, W, and various intermetallic compounds and alloys, and simple elements such as C and B that are a composite of these materials.

The ultrafine particles for coating the organic material, inorganic material, metallic material, or fiber or woven fabric of a simple element has an average particle diameter of 1 μm or less, usually 0.1 μm or less. This inorganic material, metallic material, or ultrafine particles of a simple element can be generated by known technical means, for example, by generation of plasma jet by arc discharge, by arc melting, by generation of high-frequency plasma, vaporization in gas. It can be produced by physical means, such as by method, or by chemical means involving the reduction or oxidation of inorganic or metallic material vapors.

According to the present invention, an organic material, an inorganic material, a metal material or a simple substance to be coated is contained in a gas flow containing the inorganic material, the metallic material or the ultrafine particles of the simple substance element produced as described above. The elemental fiber or woven fabric is introduced by any means to bring the ultrafine particles into contact with the fiber or woven fabric to be coated in the active state of the ultrafine particles. In this case, since the ultrafine particles have just been produced by physical or chemical means and are themselves in a nascent state, that is, they have free radicals and are activated, Alternatively, by contacting with the woven cloth, it is covalently bonded to the fiber or the woven cloth, and both are strongly chemically bonded, but some of them are not contacted or insufficiently contacted to remove ultrafine particles that are not firmly bonded. Things are needed. By carrying out such a treatment, the fiber or woven fabric of the present invention can be obtained as a fiber or woven fabric in which the surface of an organic material, an inorganic material, a metal material or a simple element is firmly coated with ultrafine particles.

The treatment of the fiber or the woven fabric is usually carried out by rewinding the wound form on a bobbin or a drum, and in the meantime, in the present invention, such treatment means, that is, the fiber or the woven fabric is fed from the supply bobbin. This can be done by performing ultra-fine particle treatment while unwinding (releasing) the woven fabric and then winding it up on the winding bobbin placed on the opposite side, and then performing ultrasonic treatment, and in some cases In some cases, the fine particles may be contacted multiple times, but even in this case, the fine particles are taken up through the vibrating liquid tank in the final stage.
Next, the present invention will be described by way of examples.

Example 1 Production of particles in which carbon fibers were coated with ultrafine glass particles A glass powder having a particle size distribution of 0.6 to 125 μm and an average diameter of 18 μm was dispersed and supplied into a high temperature plasma obtained by high frequency heating of argon gas, A gas stream containing ultrafine glass particles was generated. Carbon fibers were introduced into the lower part of this gas flow to produce fibers in which the carbon fibers were coated with ultrafine glass particles. The device used has the overall configuration shown in FIG.
That is, this device is a fiber supply device shown in FIG.
From the ultrafine particle coating device indicated by B, the ultrasonic vibration liquid tank indicated by C, the sizing tank indicated by D, the dryer indicated by E, the feed roll indicated by F and the fiber winding device indicated by G Become.

Details of the ultrafine particle coating apparatus indicated by B are as shown in FIG. This ultrafine particle coating apparatus is a plasma torch shown by H in FIG. 2, an ultrafine particle raw material supply apparatus shown by I, an ultrafine particle coating section by J,
It comprises a chamber indicated by K and an ultrafine particle recovery portion indicated by L. Plasma torch H has an inner diameter of 55 mm and a length of 1
A 70 mm quartz tube 1 is mainly used, a coil (2) for high frequency oscillation is attached to the outside, and a jacket tube (3) for cooling is provided on the outside thereof. Gas outlets (4), (5) and (6) whose ejection directions are tangential, axial and radial are provided in the upper part of the plasma torch, and gas supply sources (7) and (8) are provided at these ejection ports. ) And (9), 20 l / min of argon is supplied. This jetted gas is turned into plasma by the applied high frequency power source, and forms a plasma flame in the plasma torch.

An ultrafine particle raw material supply port (10) is provided above the plasma torch, and the raw material glass powder supplied from the ultrafine particle raw material supply device I is introduced into the plasma flame by a carrier gas of 5 to 15 liters / minute. It The chamber K is composed of a tube (13) having an inner diameter of 440 mm and a length of 1800 mm, and a jacket tube (14) for cooling outside the tube (13). In the raw material fiber supply device indicated by A, the carbon fibers CF to be coated are 1 to 1 from the winding roll through the tension roll.
It is sent out at a rate of 0 m / min and wound by a fiber winding device indicated by G.

The ultrafine-particle coating portion J is provided with an opening as a through hole for the raw material fiber and is connected to the atmosphere. In this part, the ultrafine particles come into contact with and coat the fibers in the freshly formed active state. At this time, it did not adhere sufficiently to the fiber due to insufficient contact, or after the completion of generation of ultrafine particles, it became ultrafine particles in a free state and no longer adhered to the fiber. By the cohesive force, it can be placed on the fiber. The fibers with the ultrafine particles in various states of this degree of adhesion are passed through an ultrasonic bath C filled with water. The ultrasonic tank has a vibration frequency of 45 KHz and an output of 300 W. The fiber that has passed through the ultrasonic water tank is passed through a sizing tank D, passed through a dryer E, and after being dried through a feed roll F, wound by a winding device indicated by G.

Example 2 A fiber reinforced composite material was prepared by using the fiber which was passed through the ultrasonic bath prepared in Example 1 as Sample A. On the other hand, the same composite material was prepared as the sample B using the fibers prepared by the method of Example 1 except that the ultrasonic bath was not passed, and the carbon fiber was not subjected to any treatment. The reinforced composite material thus prepared was used as sample C. Test pieces were made in exactly the same manner except for the carbon fibers used from Samples A, B and C. The way to make it is to draw a fiber from a bobbin around a large diameter drum and wind it, inject resin into it and mold it into a cylindrical shape by applying pressure and heat, remove it from the drum and make a sheet and stack it It is made into 3 mm and further cut into 10 × 150 mm. This test piece was subjected to JIS K7074 (bending test method for carbon fiber reinforced plastic) and JIS K7078.
A physical property test was conducted by (testing method for interlayer shearing force of carbon fiber reinforced plastic). In the bending test, the test speed was 5.0 mm / min, the distance between fulcrums was 96 mm, and in the shear test, the test speed was 1.3 mm / min, the distance between fulcrums was 12 mm. The results are shown in the table below.

[0020]

[Table 1] It can be seen that the one using the ultrasonically treated fiber has enhanced bending strength and shear strength as compared with the non-treated one or the one treated with the ultrafine particles.

[Brief description of drawings]

FIG. 1 shows the configuration of an apparatus for carrying out the present invention.

FIG. 2 shows an ultrafine particle coating device that is part of a device for practicing the present invention.

FIG. 3 is a schematic diagram for explaining a decrease in adhesive force due to free ultrafine particles.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technical display location // D06M 101: 40 (72) Inventor Naoto Sonoike 5-3 Tsurugaoka, Oi-cho, Iruma-gun, Saitama Prefecture No. 1 Inside Production Engineering Laboratory, Nisshin Seifun Co., Ltd. (72) Inventor Hideo Iida 5-3 Tsurugaoka, Oi-cho, Iruma District, Saitama Prefecture Inside Production Research Institute, Nisshin Seifun Co., Ltd. (72) Akihiko Fukushima 5-3-1 Tsurugaoka, Oi-cho, Iruma-gun, Saitama Nisshin Seifun Co., Ltd.

Claims (4)

[Claims] 1. An organic material, an inorganic material, a metallic material or a single element fiber or woven fabric to be coated in a flow containing an inorganic material, a metallic material or ultrafine particles of a single element produced by a vapor phase method. And introducing the above ultrafine particles and the above-mentioned fibers or woven fabrics to be coated in a state where the ultrafine particles are in an active state and then passing through an ultrasonic vibration liquid tank, an inorganic material, a metal material or a simple substance. A method for producing an organic material, an inorganic material, a metal material, or a fiber or woven fabric of a simple element whose surface is coated with ultrafine particles of an element. 2. The manufacturing method according to claim 1, wherein the flow containing the inorganic material, the metal material, or the ultrafine particles of a simple element is produced by the CVD method or the PVD method. 3. The manufacturing method according to claim 2, wherein the PVD method is an RF plasma method. 4. The method according to claim 1, wherein the ultrasonic wave has a frequency of 10 Hz to 100 Hz.