JPH02277849A - Fiber material for composite material and production thereof - Google Patents

Abstract

PURPOSE:To improve wetting properties to metallic matrix by attaching fine particles of heat-resistant substance to the surface of carbonaceous inorganic fibers from a specific metal-containing polycyclic aromatic polymer containing an element such as titanium and silicon. CONSTITUTION:Fine particles are attached to the surface of inorganic fibers obtained from (A) a carbonaceous substance showing a crystalline arrangement state, such as radical structure of a polycyclic aromatic compound in a mesophase, (B) crystalline carbon or amorphous carbon in non-orientated state of optically isotropic polycyclic aromatic compound containing an organic solvent-insoluble component and (C) a Si-M-C-O substance of an amorphous substance comprising M(M is Ti, Zr of Hf), Si, C and O as components and/or aggregate consisting of crystal ultrafine particles comprising MC, beta-SiC, a solid solution of MC and beta-SiC and and MC1-x as components and amorphous SiOy and MO2 (0<x<1; 0<y<Z, 0<z<=2; weight ratio of Si, M, C and O is (5-70):(0.5-45):(20-40):(0.01-30).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a fiber body for composite materials and a method for producing the same, and more particularly, to a fiber body for use in composite materials such as fiber-reinforced metals, fiber-reinforced plastics, and fiber-reinforced ceramics. It relates to its manufacturing method.

(Prior art) In recent years, glazed composite materials, such as fiber-reinforced metals (FR
M) etc. are used.

The reinforcing fibers used in the production of FRM etc. are difficult to wet with matrix metals, especially aluminum alloys and magnesium alloys, but once they get wet, they react and deteriorate the fibers. For this reason, reinforcing fibers are generally subjected to surface treatment.

Examples of the treatment method include a CVD method and a plating method. In these methods, the surface of reinforcing fibers is uniformly coated with metal or ceramic in the form of a film, but peeling occurs due to the difference in thermal expansion coefficient between the reinforcing fibers, reducing the effectiveness of the surface treatment, and the coating When the reinforcing fibers are made thicker, they lose their flexibility and become hard and brittle, causing many problems such as the fibers being easily damaged. Furthermore, in order to perform surface treatment on the fibers, a complicated device is required, which is disadvantageous in terms of cost.

Furthermore, when FRM is manufactured by high-pressure coagulation casting using these reinforcing fibers, the fibers are likely to be skewed and the distribution of fibers tends to be coarse in some areas and dense in some areas. For this reason, it is difficult to control the fiber volume fraction (vr) in FRM, and especially when vr is small, the original feature of FRM, in which reinforcing fibers are uniformly dispersed, is lost. .

As a method and fibrous body to solve this problem, JP-A No. 6
1-266666 discloses a fiber body in which short fibers, whiskers or powder are attached to the surface of each fiber by immersing a continuous fiber bundle in a solution in which short fibers, whiskers or powder are suspended. and methods of manufacturing them are disclosed. However, in the above publication, for example, when carbon fibers are used as continuous fibers, the carbon fibers do not have sufficient wettability with the matrix metal, and FRMs using fibrous bodies obtained using carbon fibers as reinforcement materials are not expected. Moreover, when silicon carbide fibers are used as continuous fibers, there is a limit to the elastic modulus because silicon carbide fibers are amorphous fibers. FRM cannot be said to have sufficient mechanical strength depending on the application.

(Problems to be Solved by the Invention) The present invention is intended to solve the above-mentioned problems in the prior art. It improves wettability with the matrix and at the same time prevents the strength of continuous fibers from decreasing due to reactions with added elements in the matrix.
Another object of the present invention is to provide a fiber body for a composite material that can improve the mechanical properties of the composite material by uniformly dispersing continuous fibers in the composite material and controlling the fiber volume fraction, and a method for producing the same.

(Means for Solving the Problems) The carbonaceous inorganic fiber body for composite materials of the present invention has a carbonaceous inorganic fiber body selected from the group consisting of titanium, zirconium, and hafnium.
An inorganic fiber obtained from a metal-containing polycyclic aromatic polymer containing one type of element and silicon, the constituent components of which are: a) a polycyclic aromatic compound in a mesophase state constituting the polymer; a carbonaceous material exhibiting at least one type of crystal orientation selected from the group consisting of a radial structure, an onion structure, a random structure, a core radial structure, a skin onion structure, and a mosaic structure; b) an organic solvent insoluble component constituting the polymer; C) non-oriented crystalline carbon and/or amorphous carbon derived from an optically isotropic polycyclic aromatic compound containing C) ■Amorphous carbon consisting essentially of St, M, C and O and/or ■ crystalline ultrafine particles with a particle size of 500 Å or less consisting essentially of β-3iC, MC, a solid solution of β-3iC and MC, and MC+-x, and amorphous 5iOy and MO. The proportion of constituent elements is St; 5 to 70% by weight, Mio, 5 to 70% by weight.
45% by weight, C; 20-40% by weight and 0; 0.0
1 to 30% by weight of SiM-C-0 (in the above formula, M is at least one element selected from Ti, Zr, and Hf, 0 < x < 1.0, y ≦ 2, O
<z≦2. ) Continuous fiber bundles or continuous fiber bundles having at least one type selected from the group consisting of fine particles of heat-resistant substances, short fibers, and whiskers (hereinafter sometimes referred to as "adhesive substances") attached to the surface of carbonaceous continuous inorganic fibers consisting of It is characterized by being made of a woven fabric made of the continuous fiber bundles.

The continuous fiber bundle, which is a component of the carbonaceous inorganic fiber for composite materials of the present invention, is itself new and can be prepared by the manufacturing method consisting of the following first to fourth steps.

First step: 1) Bonding unit (Si CHz) or bonding unit (Si
-CH,) and a bonding unit (Si-3t), which has a hydrogen atom, a lower alkyl group, a phenyl group, or a silyl group in the silicon side chain, and the silicon atom of the main skeleton consisting of the bonding unit, A transition metal-containing organosilicon in which M (M is at least one element selected from the group consisting of titanium, zirconium, and hafnium) is bonded to at least a portion of silicon atoms directly or via an oxygen atom. 2) A random copolymer in which at least a part of the silicon atoms of the polymer are bonded to the carbon atoms of the aromatic ring of a polycyclic aromatic compound obtained from petroleum-based or coal-based pitch or its heat-treated product, and 2) petroleum-based pitch. or a mesophase state obtained by heat-treating coal-based pitch, or a polycyclic aromatic compound consisting of both mesophase and optically isochastic phases (hereinafter both may be collectively referred to as "mesophase polycyclic aromatic compound") .)
A metal-containing polycyclic aromatic polymer is obtained by heating reaction and/or heating melting at a temperature in the range of 200 to 500°C.

Second step: A spinning dope of the metal-containing polycyclic aromatic polymer is prepared and spun.

Third step: The spun yarn is infusible under tension or without tension.

Fourth step: The infusible spun fiber bundle is fired at a temperature in the range of 800 to 3000'C in vacuum or in an inert gas atmosphere.

Preferred embodiments of the fibrous body manufacturing method of the present invention include, for example, the following method.

Each of the above steps will be specifically explained. In the following description, all "parts" are parts by weight, and "%" are percentages by weight.

First step: A precursor polymer (1) is prepared by heating and reacting an organosilicon polymer and pitch in an inert gas, preferably at a temperature in the range of 250 to 500"C.

The organosilicon polymer, which is one of the starting materials for the precursor polymer (1), can be obtained, for example, by heating polymethylsilane obtained by the reaction of dimethyldichlorosilane and metallic sodium to 400°C or higher in an inert gas. can get. The organosilicon polymer has a bonding unit (S i CHz )
, or bonding unit (Si-CH,) and bonding unit (Si-3
i), and the bonding unit (S i CHz
) to the total number of bonding units (Si-3t) is 1
: Within the range of 0 to 20.

The weight average molecular weight (M) of this organosilicon polymer is -innermost 300 to 1000, and those with Mw of 400 to 800 are random copolymer, which is an intermediate raw material for obtaining excellent carbon-based inorganic fibers. Particularly preferred for preparing polymer (2).

Pitch, which is another starting material for the precursor polymer (1), is a pitch obtained from petroleum or coal, and particularly preferred pitch is heavy oil obtained by fluid catalytic cracking of petroleum, or heavy oil thereof. These are distillate components or residual oils obtained by distilling , as well as heat-treated products thereof.

The above pitch contains 5 to 9 components insoluble in organic solvents such as benzene, toluene, xylene, and tetrahydrofuran.
It is preferable that the content is 8% by weight, especially 40 to 90%, and if pitch containing less than 5% by weight of insoluble components is used as a raw material, the strength and elastic modulus of the inorganic fibers tend to be poor.
Furthermore, if pitch containing more than 98% by weight of insoluble components is used as a raw material, the resulting spinning polymer will have a high melting point, making spinning difficult.

The weight average molecule it (M) of this optically isotropic pitch.

) is 100-3000. The weight average molecular weight is a value determined as follows. That is, if the pitch does not contain organic solvent-insoluble components for gel verminion chromatography (GPC) measurement, such as benzene, toluene, xylene, tetrahydrofuran, chloroform, and dichlorobenzene, the pitch is directly measured by GPC, and the pitch is free from organic solvent-insoluble components. If it does, it is hydrogenated under mild conditions to convert the organic solvent-insoluble components into organic solvent-soluble components, followed by OPC measurement. The weight average molecular weight of the polymer containing organic solvent insoluble matter is a value determined by performing the same treatment as above.

The ratio of pitch used is 8 parts per 100 parts of organosilicon polymer.
It is preferably 3 to 4900 parts.

If the ratio of pitch used is too small, the silicon carbide component in the resulting inorganic fiber will increase, making it impossible to obtain an inorganic fiber with a high modulus of elasticity. is reduced, making it impossible to obtain inorganic fibers with excellent oxidation resistance.

If the reaction temperature of the above reaction is too low, it will be difficult to form bonds between silicon atoms and aromatic carbon, and if the reaction temperature is too high, the resulting precursor polymer (1) will be violently decomposed and its molecular weight will increase. Undesirable.

The precursor polymer (1) mentioned here includes a copolymer in which an organosilicon polymer and pitch are bonded via a silicon-carbon linking group, as well as polycondensates of the organosilicon polymer and pitch. .

As the inert gas, nitrogen, argon, etc. are preferably used.

Next, the precursor polymer (1) and the transition metal compound represented by the formula MX are reacted at a temperature in the range of 100 to 500°C.

In the above MX, M is at least one element selected from Ti5Zr and Hf, and X is by condensation,
M may be anything as long as it can be bonded directly or via an oxygen atom to the silicon of the precursor polymer (1), and is preferably a halogen atom, an alkoxy group, or a complex-forming group such as β-diketone, although there is no particular limitation. .

If the reaction temperature is too low, the precursor polymer (1) and 2MX4
If the condensation reaction with M does not proceed and the reaction temperature is excessively high, M
The cross-linking reaction of the precursor polymer (1) may proceed excessively, resulting in gelation, or the precursor polymer (I) itself may condense and increase its molecular weight, or in some cases, MX may volatilize, which is undesirable. .

- For example, when M is Ti and X is 0CsHq, a suitable reaction temperature is 200-400°C.

Through this reaction, a random copolymer (2) in which at least some of the silicon atoms of the precursor polymer (1) are bonded to M directly or via oxygen atoms is prepared.

M is -MX to the silicon atom of the precursor polymer (1)! Or-
It may be bonded in a side chain form in a bonding manner such as O-MXj, or may be crosslinked directly or via oxygen to the silicon atom of the precursor polymer (1).

In addition to the above-mentioned method, the random copolymer (2) can also be prepared by reacting an organosilicon polymer with MX4 and further reacting the resulting product with pitch.

In the first step, the random copolymer (2) and the mesophase polycyclic aromatic compound are finally reacted and/or heated and melted to prepare a metal-containing polycyclic aromatic polymer.

Mesophase polycyclic aromatic compounds can be prepared, for example, by heating petroleum-based or coal-based pitch to 300 to 500°C in an inert gas and subjecting it to condensation polymerization while removing the generated soft fraction. .

If the temperature of the condensation polymerization reaction is too low, the growth of the condensed ring will not be sufficient, and if the temperature is too high, insoluble and infusible products will be produced due to coking.

The above mesophase polycyclic aromatic compound has a melting point of 20
The temperature is in the range of 0 to 400°C, and the weight average molecular weight is in the range of 200 to 10,000.

Among mesophase polycyclic aromatic compounds, 20 to 10
It has an optical anisotropy of 0%, especially 40-100%, and has a degree of optical anisotropy of 3
Those containing 0 to 100% of insoluble matter in benzene, toluene, xylene or tetrahydrofuran are preferred in order to obtain inorganic fibers with excellent mechanical performance.

The proportion of the mesophase polycyclic aromatic compound to be used is preferably 5 to 50,000 parts per 100 parts of the random copolymer (2). If it is less than 5 parts, the mesophase content in the product will be insufficient, so high elasticity If yarn cannot be obtained and the amount exceeds 50,000 parts, inorganic fibers with excellent oxidation resistance cannot be obtained due to the lack of silicon component.

The random copolymer (2) and the mesophase polycyclic aromatic compound are heated and melted and/or reacted in a temperature range of 290 to 500°C.
A metal-containing polycyclic aromatic polymer in which at least a portion of 2) is bonded to a mesophase polycyclic aromatic compound is obtained.

However, the bond mentioned here refers to a chemical bond between silicon and carbon of a polycyclic aromatic compound and/or a random copolymer (2
) means a physical bond such as a van der Waals bond between the polycyclic aromatic ring moiety chemically bonded to silicon in the mesophase polycyclic aromatic compound.

If the above-mentioned melt mixing temperature is lower than 200°C, unmelted portions will occur, the yarn will become non-uniform, and the strength and elastic modulus of the inorganic fiber will be adversely affected, and if the melt mixing temperature is higher than 500°C, the condensation reaction will be intense. As the process progresses, the resulting polymer has a high melting point,
Spinning the polymer becomes extremely difficult.

As a method for preparing a metal-containing polycyclic aromatic polymer,
In addition to the above-mentioned method, it is also possible to prepare a product by reacting an organosilicon polymer and pitch, adding mesophase pitch and MX simultaneously or sequentially to the resulting product, and further reacting.

The weight average molecular weight of the metal-containing polycyclic aromatic polymer is 200
~11000, melting point 2oo~4o.

It is °C.

2nd step: The spinning polymer, which is a metal-containing polycyclic aromatic polymer obtained in the 1st step, is heated and melted, and in some cases, it is filtered to remove substances that are harmful during spinning, such as microgels and impurities. This is then spun using a commonly used synthetic fiber spinning device.

The temperature of the spinning dope during spinning varies depending on the softening temperature of the raw material polymer, but a temperature in the range of 220 to 420'C is advantageous.

In the spinning device, a spinning tube is attached as necessary,
After setting the atmosphere in the spinning tube to one or more atmospheres selected from the group consisting of air, inert gas, hot air, hot inert gas, steam, and ammonia gas, the winding speed is increased to create a thin diameter. fibers can be obtained. The spinning speed in the melt spinning is determined by the average molecular weight of the raw materials,
Although it varies depending on the molecular weight distribution and molecular structure, 50 to 500
A range of 0 m/min is preferable.

Third step: The spun fibers obtained in the second step are made infusible under the action of tension or no tension.

A typical infusibility method is to heat spun fibers in an oxidizing atmosphere. The infusibility temperature is preferably 50 to 4
The temperature is in the range of 00°C. If the infusibility temperature is too low, the polymers that make up the spinning filament will not form.
Also, if this temperature is too high, the polymer will burn.

The purpose of infusibility is to make the polymer that makes up the spun fibers into a three-dimensional structure that is infusible and insoluble, so that it does not melt during the next firing process and does not fuse with adjacent fibers. It is. Gases constituting the oxidizing atmosphere during infusibility include air, ozone, oxygen, chlorine gas, bromine gas, ammonia gas, and mixed gases thereof.

As an infusibilization method different from the above, the spun fibers are infusibilized by irradiation with gamma rays or electron beams in an oxidizing or non-oxidizing atmosphere, under tension or without tension, while heating at a low temperature as necessary. method can also be adopted.

The purpose of irradiating with gamma rays or electron beams is to further polymerize the polymer that forms the spun fibers.
The purpose is to prevent the spun yarn from melting and losing its fiber shape.

The appropriate irradiation dose of gamma rays or electron beams is 106 to 10'' land.

Irradiation can be carried out in a vacuum, an inert gas atmosphere, or an oxidizing gas atmosphere such as air, ozone, oxygen, chlorine gas, bromine gas, ammonia gas, and mixtures thereof.

Infusibility by irradiation can be carried out at room temperature, and if necessary, infusibility can be achieved in a shorter time by heating in the temperature range of 50 to 200°C.

If infusibility is carried out without tension, the spun fibers will shrink and take on a wavy shape, but this can sometimes be corrected in the next firing process, and tension is not necessarily required. In this case, good results can be obtained if the tension is large enough to minimize or at least prevent the spun fibers from shrinking and becoming wavy during infusibility.

The tension applied during infusibility is 1 to 500 g.
A range of /ff1l112 is preferable, and even if a tension of Ig/mn+" or less is applied, it is not possible to apply tension that will not cause the fibers to slack, and if a tension of more than 500 g/nun" is applied, the fibers will break. Sometimes.

Fourth step: By firing the infusible yarn obtained in the third step at a temperature in the range of 800 to 3000°C in a vacuum or inert gas atmosphere, inorganic fibers mainly composed of carbon, M, silicon, and oxygen are produced. is obtained.

In the firing process, it is not necessarily necessary to apply tension, but if the fiber is fired at a high temperature while applying tension in the range of 0.001 to 100 Kg/am'' 0), a high-strength inorganic fiber with less bending can be obtained.

In the heating process, it is estimated that mineralization becomes intense from about 700°C and is almost completed at about 800"C. Therefore, it is preferable to perform the calcination at a temperature of s o o' c or higher. Furthermore, since obtaining a temperature higher than 3000"C requires expensive equipment, firing at a higher temperature than 3000"C is not practical from a cost standpoint.

The inorganic fibers in the present invention are the above-mentioned constituent components a) and b).
and C), S 1 ; O-01 to 30
%, M; 0.01-10%, c; 65-99.9% and O; 0.001-io%, preferably S1; O-
1-25%, M:O, OL-8%, C; 74-99.8
% and O: substantially composed of 0.01 to 8%.

Crystalline carbon, which is a component of this inorganic fiber, has a crystallite size of 500 Å or less, and is oriented in the fiber axis direction in a high-resolution electron microscope with a resolution of 1.5 people.
It is an ultrafine graphite crystal in which a fine lattice image corresponding to two (002) planes can be observed.

The crystalline carbon in the inorganic fibers can have a radial structure, an onion structure, a random structure, a core radial structure, a skin onion structure, a mosaic structure, a random structure including a partial radial structure, and the like. This is due to the presence of mesophase polycyclic aromatic compounds in the raw materials.

The total of constituent components a) and b) in this inorganic fiber is 10
The ratio of component C) to 0 parts is 0.015 to 200
and the ratio of constituent components a) and b) is 1:0.0
It is 2-4.

If the ratio of component C) to 100 parts of the total of components a) and b) is less than 0.015, the fibers are almost the same as pitch fibers, and no improvement in oxidation resistance or wettability can be expected. If the proportion exceeds 200 parts, fine graphite crystals will not be effectively generated and fibers with high elastic modulus will not be obtained.

Component C) will be explained in more detail.

The form of the Si-M-C-0 substance which is component C) is:
It is determined by the manufacturing conditions employed in the first to fourth steps. - In terms of boat fishing, if the firing temperature in the fourth step is lower than, for example, 1000°C, it is substantially composed of an amorphous material consisting of St, M, and C10.

On the other hand, if the firing temperature in the fourth step is, for example, 1700°C or higher, particles with a diameter of 500 Å or less and consisting essentially of β-3iCSMC, a solid solution of β-3iC and MC, and MCI4 (however, 0<x<1) Fine particles and Sin, (however,
o<y≦2) and MO□ (where O<z≦2).

At an intermediate temperature, the system is composed of a mixed system of each aggregate. Further, the amount of oxygen in the inorganic fibers can be controlled, for example, by the addition ratio of M(OR)4 in the first step or the infusibility conditions in the third step.

Further, the distribution state of component C) can also be controlled by the atmosphere at the time of firing and the size and concentration of mesophase in the raw material. For example, when the mesophase is grown to a large size, component C) is easily extruded into the fiber surface phase.

The advantage of using the inorganic fiber of the present invention as a core wire of fiber for composite materials is that the inorganic fiber itself has high strength and high modulus of elasticity, and the silicon component in the fiber shows good wettability and low reactivity with the matrix. Furthermore, since heat-resistant deposits are easily attached, the mechanical properties of the composite material are significantly improved.

Next, fine particles of heat-resistant material are applied to the surface of the carbonaceous continuous inorganic fiber.
A method for attaching an attachment substance that is at least one selected from the group consisting of short fibers and whiskers will be explained.

Examples of heat-resistant materials include metals, ceramics, and carbon.

Among heat-resistant materials, specific examples of metals include steel, stainless steel, molybdenum, and tungsten, and specific examples of ceramics include 5iC1T i C, WC, B
4C, nitrides such as 5itN4, BN, AAN, borides such as TiBz, ZrB2, and A1. tOz, B201, MgO, ZrO,, S to
Examples include oxides such as . Other examples of ceramics include fired products of polycarbosilane and polymetallocarbosilane, and metal-containing polycyclic aromatic polymers (products of the first step) that are the spinning raw materials for the continuous inorganic fibers in the present invention. MC (M is Ti
, Zr, and Hf) are uniformly dispersed therein.

The shape of the attached substance varies depending on the combination with continuous inorganic fibers and the required properties, but short fibers and whiskers have an average diameter of 1/3000 to 115 of the average diameter of continuous fibers and an aspect ratio of 50 to 1000. Further, it is desirable that the fine particles have an average diameter of 1.15000 to 1/2 of the average diameter of the continuous fibers.

The amount of the attached substance attached to the continuous fibers varies depending on the properties of the two and the purpose of the manufactured fiber body, but when used for FRM, the volume ratio of the attached substance to the continuous fiber is 0.1.
It is preferable to set it to about 500%.

The adhering substance may be used alone or in combination of two or more types, but for example, the carbonaceous inorganic fiber body of the present invention may be used to strengthen A2 with Cu, Si, Mg, and Zn added. When used, it is particularly preferable to attach fine particles near the surface of the continuous fibers and attach short fibers and/or whiskers to the outside thereof in order to prevent micro-segregation of the additive elements on the surface of the continuous fibers. In this case, the ratio of fine particles to short fibers and/or whiskers is 0.1:5 to
A range of 40:1 is suitable.

It is preferable for the fibrous body of the present invention to be prepared by immersing the continuous fibers in a suspension of the adhering substance in terms of simplicity and wide applicability.

FIG. 1 schematically shows an example of an apparatus used in manufacturing the fibrous body of the present invention.

The continuous fiber bundle wound around the bobbin 5 (a woven fabric made of continuous fiber bundles can also be used instead of the continuous fiber bundle) is rewound, guided to movable rollers 6 and 7, and the agitator 13 suspends the adhered substances. After passing through the cloudy liquid 3, it is pressed by pressure rollers 8 and 9 and wound onto the bobbin 10 again.

The fiber bundle or woven fabric thus obtained is a continuous fiber
A substance adheres to the surface of each book. In this case, the number of processing tanks containing the processing liquid may be one, but for various modification methods, two or more processing tanks containing processing liquids of different compositions may be used.

In order to promote the adhesion of substances to the continuous fibers, air can be blown from the blower 11 or ultrasonic vibrations can be applied to the treatment liquid 3 by the ultrasonic adder 2. It is also possible to dry the fiber body in a drying oven 12 after pressing with rolls 8.9. In addition, when attaching two or more types of adhesion substances to continuous fibers, the treatment liquid may be one in which fine particles and short fibers and/or whiskers are suspended at the same time, or one in which fine particles are suspended. The treated liquid and the treated liquid in which the short fibers and/or whiskers are suspended may be placed in two types of treatment tanks. In the latter case, the order in which the continuous fiber bundle or woven fabric is immersed may be in the treatment liquid in which the fine particles are suspended or in the treatment liquid in which the short fibers and/or whiskers are suspended.

(Effect of the invention) As described above, the carbonaceous inorganic fiber body for composite materials of the present invention has the following properties:
Since it is made up of continuous fiber bundles with a substance attached to each surface of high-strength, high-modulus inorganic fibers, each continuous fiber can be uniformly dispersed in the composite material, and the volume ratio of the fibers can be increased. can be controlled over a very wide range. In addition, contact between continuous fibers is reduced, and when a composite material is formed, its composition becomes uniform, which improves mechanical properties such as strength.

Furthermore, the manufacturing method of the present invention is a method in which continuous fibers or bundles thereof or woven fabrics thereof are immersed in a treatment liquid in which the material to be attached is suspended, for example, by unwinding and winding means, so it is simple and production efficient. is high. Further, by adding ultrasonic waves to the treatment liquid, it becomes easier to disperse the adhered substances into the continuous fiber bundle or woven fabric. Furthermore, various modifications such as using an organic solvent as the treatment liquid are possible, and since the amount of adhesion can be controlled by this, various composite material fiber bodies can be manufactured with the same equipment.

(Example) The present invention will be explained below with reference to Examples.

Reference Example 1 (Production of Organosilicon Polymer) 2.52 g of anhydrous xylene and 400 g of sodium were placed in a 52-meter three-hole flask, heated to the boiling point of xylene under a nitrogen gas stream, and 12 dimethyldichlorosilane was added dropwise over 1 hour. After the dropwise addition was completed, the mixture was heated under reflux for 10 hours to form a precipitate. The precipitate was filtered and washed with methanol and then water to obtain 420 g of white powder polydimethylsilane.

400 g of this polydimethylsilane was charged into a 31-hole flask equipped with a gas inlet tube, a stirrer, a condenser, and a distillation tube, and heated at 420 degrees under a nitrogen stream of 50 components/min while stirring.
C. to obtain 350 g of a colorless and transparent slightly viscous liquid in a distillation receiver.

The number average molecular weight of this liquid was 470 as measured by vapor pressure osmosis.

When the infrared absorption spectrum of this substance was measured, it was found that 6
8l-CH at 50-900cm-' and 1250cm-'
Absorption of 3, absorption of 5i-H at 2100c+++-', 1
5t-CH near 020cm-' and 1355cm-'.

-3t absorption, C at 2900cl' and 2950cm-'
-H absorption was observed, and when the far infrared absorption spectrum of this material was measured, 5i-3 at 380 cm-'
Since absorption of t is observed, the obtained liquid substance is
Mainly (St CHz) bonding units and (St-3t
) was found to be an organosilicon polymer consisting of bonding units and having hydrogen atoms and methyl groups in silicon side chains.

From the measurement results of nuclear magnetic resonance analysis and infrared absorption analysis, this organosilicon polymer is a polymer in which the ratio of the total number of (St CHz) bond units to the total number of (Si-3i) bond units is approximately 1:3. This was confirmed.

300 g of the above organosilicon polymer was treated with ethanol to remove low molecular weight substances to obtain 40 g of a polymer having a number average molecular weight of 1200.

When the infrared absorption spectrum of this substance was measured, absorption peaks similar to those above were observed, and this substance mainly consists of (St CH2) bond units and (Si-3t) bond units, and contains hydrogen atoms and silicon side chains. It turned out to be an organosilicon polymer with methyl groups.

From the measurement results of nuclear magnetic resonance analysis and infrared absorption analysis, this organosilicon polymer is a polymer in which the ratio of the total number of (Si CHz) bond units to the total number of (Si-3i) bond units is approximately 7:1. This was confirmed.

Reference Example 2 (Production of inorganic fiber ■) Among petroleum fractions, substances with a higher boiling point than light oil are subjected to fluid catalytic cracking and rectification at a temperature of 500°C in the presence of a silica/alumina cracking catalyst. A residue was obtained from the bottom. Hereinafter, this residue will be referred to as FCC slurry oil.

As a result of elemental analysis, this FCC slurry oil had an atomic ratio of carbon atoms to hydrogen atoms (C/H) of 0.75, and an aromatic carbon ratio of 0.55 as determined by nuclear magnetic resonance analysis.

500 g of the above FCC slurry oil was heated at 450°C for 1 hour under a nitrogen gas flow of 12/min, and after distilling off the distillate at the same temperature, the residue was filtered while hot at 200°C.
Remove the infusible part at the same temperature, light bone removal pitch 22
5g was obtained.

This light bone removal pitch was an optically isotropic pitch containing 75% xylene insolubles.

21 g of the organosilicon polymer obtained in Reference Example 1 and 20 d of xylene were added to 49 g of this light bone-removed pitch, heated while stirring, distilled off the xylene, and reacted at 400°C for 6 hours to produce 39 g of precursor polymer. (1) was obtained.

As a result of infrared absorption spectrum measurement, this precursor polymer (1) was found to have 5t-H bonds (IR:
2100cr') and the formation of a new 5i-C<carbon of the benzene ring) bond (IR: 1135C1l-'), some of the silicon atoms in the organosilicon polymer are considered to be polycyclic aromatic rings. It turned out to be a copolymer with directly bonded moieties.

A xylene solution (25% xylene solution 11 g) of 2.75 g of tetraoctoxytitanium (T i (OCm H+t)4) was added to 39 g of precursor polymer (1), and after the xylene was distilled off, the mixture was heated at 340°C for 2 hours. The reaction was carried out to obtain 38 g of random copolymer (2).

This copolymer contained no xylene-insoluble portion, had a weight average molecular weight of 1650, and a melting point of 272'C.

In parallel, 400 g of FCC slurry oil was heated to 450°C under a nitrogen gas flow, and after distilling off the distillate at the same temperature, the residue was filtered hot at 200°C. Remove infusible part and remove light bone pitch 180
I got g. 180 g of the obtained light bone removal pitch was heated under a nitrogen stream for 400 g while removing the light bone produced by the reaction.
Polycondensation was carried out at °C for 7 hours to obtain 85 g of heat-treated pitch.

This heat-treated pitch has a melting point of 268°C and a xylene insoluble content of 9
It was a mesophase polycyclic aromatic compound containing 12% quinolinol and 12% quinoline solubles, and had an optical anisotropy of 89% when observed with a polarizing microscope on the polished surface.

35 g of the random copolymer (2) and 70 g of the mesophase polycyclic aromatic compound were mixed and melted and heated at 350°C for one hour in a nitrogen atmosphere to obtain a metal-containing polycyclic aromatic polymer in a uniform state. I got it.

This polymer had a melting point of 272°C and contained 59% xylene insolubles.

The above high molecular weight material is used as the raw material for spinning, and the nozzle diameter is 0.15 m.
Melt spinning was performed at 360 °C using a metal nozzle of 300 °C, and the obtained spun yarn was made infusible at 300 °C in air, and further fired at 1300 °C in an argon atmosphere.
Inorganic fibers with a diameter of 10 μm were obtained.

This fiber has a tensile strength of 320 Kg/rrm" and a tensile modulus of 32 t/mm", and observation of the fractured surface using a scanning electron microscope reveals that it has a coral-like random and radial mixed structure with many overlapping crystal layers. Met.

Reference Example 3 (Production of Inorganic Fiber H) An ethanol-xylene solution (1.5%) of 5.4 g of tetrakisacetylacetonatosilconium was added to 39 g of the precursor polymer (1) obtained in Reference Example 2, and xylene was added. After distilling off the ethanol, polymerization was carried out at 250"C for 1 hour.
．． 5 g of random copolymer (2) was obtained.

20 g of this polymer and 50 g of a mesophase polycyclic aromatic compound prepared in the same manner as in Reference Example 1 were pulverized and mixed.
It was melted at 50°C and spun at 340°C using a nozzle with a nozzle diameter of 0.2 mm.
It becomes infusible at 50°C and further heated to 1400° in an argon atmosphere.
By firing at C, an inorganic fiber (■) with a diameter of 11 μm was obtained.

The fiber had a tensile strength of 325 kg/mm" and a tensile modulus of 35 kg/rm".

Reference Example 4 (Manufacture of inorganic fiber m) 57 g of precursor polymer (1) was obtained in the same manner as Reference Example 1 except that the amounts of light bone-removed pitch and organic silicon polymer were changed to 60 g and 40 g, respectively. Ta.

To 40 g of this precursor copolymer (1) was added 7.2 g of hafnium chloride in an ethanol-xylene solution (1.5%), and after distilling off the xylene and ethanol, the mixture was heated at 250°C for 1 hour.
Polymerization was carried out for a period of time to obtain 43.5 g of random copolymer (2).

20 g of this polymer and 8 mesophase polycyclic aromatic compounds
12. After finely pulverizing and mixing 0 g, melt degassing is performed at 350°C, melt-spun at 350°C, infusible at 270°C, and calcined at 1200°C in argon.
Inorganic fibers (■) of 5 μm were obtained.

This fiber had a tensile strength of 315 kg/mm" and a tensile modulus of 35 t/an2.

Reference Example 5 (Production of Inorganic Fiber ①) 700 g of the obtained FCC slurry oil was heated in the same manner as in Reference Example 2 at 450°C under a nitrogen gas flow of 22/min.
After heating for 5 hours and distilling off the distillate at the same temperature, the residue was filtered while hot at 200°C to remove the infusible portion at the same temperature to obtain 200 g of light bone-removed pitch.

This light bone removal pitch was an optically isotropic pitch containing 25% xylene insolubles.

To 57 g of this light bone-removed pitch, 25 g of the organosilicon polymer obtained in Reference Example 1 and 20 relatives of xylene were added, the temperature was raised while stirring, the xylene was distilled off, and the mixture was reacted at 400°C for 4 hours to give 57.4 g. A precursor polymer (1) was obtained.

As a result of infrared absorption spectrum measurement, this precursor polymer (1) was found to contain 5i-H bonds (I R
: 2100 cm-') and a new 5i-C (
The formation of a carbon bond (IR: 1135 cm-') in the benzene ring indicates that the organosilicon polymer is a copolymer in which some of the silicon atoms are directly bonded to a polycyclic aromatic ring. Understood.

Precursor polymer (1) 57.4 g and tetraoctoxytitanium (T i (QCs H+t)n) 3.87
g of xylene solution (25% xylene solution 15.5 g) was added, and after xylene was distilled off, the reaction was carried out at 340°C for 1 hour.
56 g of random copolymer (2) was obtained.

This copolymer does not contain xylene-insoluble parts, has a weight average molecular weight of 1580, a melting point of 258°C, and a softening point of 292°C.
Met.

On the other hand, 180 g of the light bone removal pitch was heated at 400°C under a nitrogen stream while removing light bones generated by the reaction.
Time bath polymerization was performed to obtain 97.2 g of heat-treated pitch.

This heat-treated pitch has a melting point of 263°C and a softening point of 308°C.
It was a mesophase polycyclic aromatic compound containing 77% of 1-xylene insoluble matter and 31% of quinoline-soluble matter, and had an optical anisotropy of 75% when observed with a polarizing microscope on the polished surface.

6.4 g of the random copolymer (1) and 90 g of the mesophase polycyclic aromatic compound were mixed, and under a nitrogen atmosphere,
The mixture was melted and heated at 380°C for one hour to obtain a metal-containing polycyclic aromatic polymer in a uniform state.

This polymer has a melting point of 264°C and a softening point of 307°C.
C and contained 68% xylene insoluble matter.

The above high molecular weight material is used as the raw material for spinning, and the nozzle diameter is 0°15m.
Melt spinning was performed at 360 °C using a metal nozzle of 300 °C, and the obtained spun yarn was made infusible at 300 °C in air, and further fired at 1300 °C in an argon atmosphere.
Inorganic fibers with a diameter of 7.5 μm were obtained.

This fiber has a tensile strength of 358 kg/ml112 and a tensile modulus of 32 t 7 mm, and observation of the fractured surface using a scanning electron microscope reveals that it has a coral-like random and radial mixed structure with many layers of crystals. there were.

After pulverizing the inorganic fibers, they were melted with alkali and treated with hydrochloric acid to form an aqueous solution, which was then subjected to high-frequency plasma emission spectroscopy (ICP).
), the silicon content was 0.95% and the titanium content was 0.06%.

Reference Example 6 (Production of Inorganic Fiber V) Random copolymer (2) obtained in the same manner as Reference Example 51.
8g and 90g of mesophase polycyclic aromatic compound were melt-mixed at 400°C for 1.5 hours under a nitrogen stream to obtain a melting point of 265°.
C. A spinning polymer having a xylene insoluble content of 55% was obtained.

Using a nozzle with a nozzle diameter of 0.15 mm, this polymer was
After melt spinning at 350'C and infusibility at 300°C, 2
It was fired at 500°C to obtain inorganic fibers (2) with a diameter of 7 μm.

As a result of ICP analysis of this inorganic fiber in the same manner as in Reference Example 5, the silicon content was 0.3% and the titanium content was 0.015%. In addition, the tensile strength of this fiber is 345 kg/mm.
, tensile modulus of elasticity was 60 t/mm''.

Reference Example 7 (Production of inorganic fiber ①) To 39 g of the precursor copolymer (1) obtained in Reference Example 5, an ethanol-xylene solution (1.5%) of 5.4 g of tetrakisacetylacetonatosilconium was added, After distilling off xylene and ethanol, polymerization was carried out at 250°C for 1 hour.
．． 5 g of random copolymer (2) was obtained.

20 g of this polymer and 50 g of a mesophase polycyclic aromatic compound prepared in the same manner as in Reference Example 5 were pulverized and mixed.
The mixture was melt-mixed at 60"C for 1 hour, spun at 340°C using a nozzle with a nozzle diameter of 0.2 mm, and the resulting spun yarn was infusible at 250°C in air, and further heated at 1400°C in an argon atmosphere. By firing at ℃, an inorganic fiber (■) with a diameter of 11 μm was obtained.

The tensile strength of this fiber was 345 kg/IIIlz, and the tensile modulus was 35 t/111 m''.

Reference Example 8 (Production of inorganic fiber ■) 68 g of precursor polymer (1) was obtained in the same manner as Reference Example 5, except that the amounts of light bone-removed pitch and organic silicon polymer were changed to 60 g and 40 g, respectively. Ta.

A solution of 7.2 g of hafnium chloride in ethanol-xylene (1.5%
) and distill off xylene and ethanol at 250°C.
43.5 g of random copolymer (2)
I got it. After finely pulverizing and mixing 20 g of this polymer and 80 g of a mesophase polycyclic aromatic compound prepared in the same manner as in Reference Example 5, melt-mixing was performed at 360°C, followed by heating at 350°C.
Melt-spun at 270°C, infusible at 270°C,
By firing at 200°C, 12.5μ inorganic fibers (■) were obtained.

The tensile strength of this fiber is 335 kg/dish 2, and the tensile modulus is 3.
It was 5t/2 dishes.

Example 1 A fibrous body was manufactured using the apparatus shown in FIG. After putting 250 g of silicon carbide fine particles (average particle size 0.28 μm) into a treatment tank 1 containing 5000 cc of ethyl alcohol, ultrasonic vibration was applied to the mixture using an ultrasonic adder 2 to suspend it, thereby preparing a treatment liquid 3.

The continuous fiber bundle 4 of the inorganic fibers I obtained in Reference Example 2 was unwound from the bobbin 5, and the immersion time was adjusted by the movable rollers 6 and 7 so that the immersion time was about 15 seconds, and the continuous fiber bundle 4 was immersed in the treatment liquid 3. Ultrasonic waves were applied to the treatment liquid 3, and air was further blown into the treatment liquid 3 to stir it, and then it was pressed by pressure rollers 8 and 9, wound up again on a bobbin 10, and dried at room temperature in the atmosphere.

As a result of weighing after treatment, it was found that 6% by volume of fine particles were attached.

Example 2 As a treatment liquid in treatment tank 1, 100 g of silicon carbide whiskers (average diameter approximately 0.2 μm, average length approximately 100 μm) and 250 g silicon carbide fine particles (average particle diameter 0.28 μm) were suspended in 5000 cc of ethyl alcohol. The treatment was carried out in the same manner as in Example 1 except that a cloudy slurry was used.

The obtained fibrous body exhibited a gray-green color and was observed under an electron microscope (SEM).
As a result of observation, it was observed that fine particles were mainly attached to the surface of the continuous fibers, and whiskers were mainly attached to the outside of the particles. Further, as a result of weighing after treatment, 10% by volume of fine particles and whiskers were found to be attached.

Example 3 Example 1 was carried out using a suspension of 100 g of silicon nitride whiskers (average diameter of about 0.3 μm, average length of about 200 μm) and 100 g of the aforementioned silicon carbide fine particles in 5000 cc of water instead of silicon carbide whiskers. Reference example 3 using the same method as
When the continuous fiber bundle 4 of the inorganic fibers H obtained in the above was treated, about 5% by volume of fine particles and whiskers were attached.

Example 4 While applying ultrasonic waves to a liquid in which 100 g of silicon carbide fine particles were stirred and suspended in 500 cc of ethanol, the continuous fiber bundle 4 of the inorganic fibers obtained in Reference Example 4 was continuously immersed. Then, when 150 g of silicon nitride whiskers were stirred and suspended in 500 cc of ethanol and then immersed and dried in the same manner, the volume ratio was about 1.
4% of fine particles and whiskers were attached.

Example 5 The metal-containing polycyclic aromatic polymer containing silicon and titanium obtained in Reference Example 2 was finely pulverized and then calcined at 1300°C in an argon stream to produce crystalline carbon with an average particle size of 0.5 μm. A fine powder mainly composed of amorphous carbon and 5t-Ti-C-0 was obtained. 100 g of this fine powder was stirred and suspended in 500 cc of ethanol, and while applying ultrasonic waves, the continuous fiber bundle 4 of the inorganic fiber I obtained in Reference Example 2 was continuously immersed, and then nitrided. When 150 g of silicon whiskers were stirred and suspended in 500 cc of ethanol and immersed and dried in the same manner, about 12% by volume of fine particles and whiskers were attached.

Comparative Example 1 Commercially available acrylonitrile carbon fiber (HM
-3, 5), a fibrous body to which silicon carbide powder was attached and a fibrous body to which silicon carbide whiskers were attached were obtained according to the method of Example 1.

Example 6 A unidirectionally reinforced FRM was produced using the fibrous body obtained in Example 1 and using aluminum as a matrix. This F.R.M.
The fiber volume fraction (■,) is 50″%, and the bending strength is 170
kg/mm” (ROM value is 175 kg/M
”).

Comparative Example 2 Using the fibrous body to which the silicon carbide powder obtained in Comparative Example 1 was attached, unidirectional reinforcement F was made using aluminum as a matrix.
RM was produced. The fiber volume fraction (Vr) of this FRM was 60%, and the bending strength was 130 kg/mm''.
A considerable decrease in strength was observed compared to the OM value (160 kg/nun'').

Example 7 Using the fibrous body obtained from the inorganic fiber I in Example 2, a unidirectionally reinforced FRM was produced using aluminum containing a total of 5% of copper and magnesium as a matrix. The fiber volume fraction of the obtained FRM was 50% by volume. This FR
The bending strength of M is 173 kg/mm”, and the ROM value (17
5kg/ram”), there was almost no difference.

Comparative Example 3 An FRM was produced in the same manner as in Example 7 except that the fibrous body obtained in Comparative Example 1 was used. The fiber volume percentage of the obtained FRM was 60% by volume in the case of the silicon carbide powder-attached fiber body, and 50 volume% in the case of the silicon carbide whisker-attached fiber body.

In addition, the bending strength of the obtained FRM is 125 kg/mm'' in the case of the fiber body with silicon carbide powder attached, and 100 kg/a+m'' in the case of the fibrous body with silicon carbide whiskers attached, and compared to each ROM value. (The ROM value in the case of the silicon carbide powder-adhered fiber body was 160 k
g/mm”, R in case of silicon carbide whisker attached fiber body
The OM value was 130 kg/threshold 2. ).

Example 8 A fibrous body was manufactured using the apparatus shown in FIG. After 250 g of silicon carbide fine particles (average particle size 0.28 μm) were put into a treatment tank 1 containing 5000 cc of ethyl alcohol, ultrasonic vibration was applied to the particles using an ultrasonic adder 2 to suspend them, thereby preparing a treatment liquid 3.

The continuous fiber bundle 4 of the inorganic fibers obtained in Reference Example 5 is unwound from the bobbin 5, and the movable rollers 6 and 7 are used to adjust the I! It is passed through the processing liquid 3 while being immersed in it using ffL, and at the same time, ultrasonic waves are applied to the processing liquid 3, and air is further blown in and stirred.Then, after being pressed by pressure rollers 8 and 9, it is wound onto the bobbin 10 again. ,room temperature,
Dry in air.

As a result of weighing after treatment, it was found that 7% by volume of fine particles were attached.

Example 9 As a treatment liquid in treatment tank 1, 100 g of silicon carbide whiskers (average diameter approximately 0.2 μm, average length approximately 100 μm) and 250 g silicon carbide fine particles (average particle diameter 0.28 μm) were suspended in 5000 cc of ethyl alcohol. Continuous fiber bundle 4 of inorganic fibers (1) was treated in the same manner as in Example 8, except that the slurry was made cloudy.

The obtained fibrous body exhibited a gray-green color and was observed under an electron microscope (SEM).
As a result of observation, it was observed that fine particles were mainly attached to the surface of the continuous fibers, and whiskers were mainly attached to the outside of the particles. Further, as a result of weighing after treatment, 10% by volume of fine particles and whiskers were found to be attached.

On the other hand, a continuous fiber bundle 4 of inorganic fibers V was subjected to the same treatment to obtain a fibrous body to which 8% by volume of fine particles and whiskers were attached.

Example 10 An example was carried out using a suspension of 100 g of silicon nitride whiskers (average diameter of about 0.3 μm, average length of about 200 am) and 100 g of the aforementioned silicon carbide fine particles in 5000 cc of water instead of silicon carbide whiskers. When the continuous fiber bundle 4 of the inorganic fibers (1) obtained in Reference Example 7 was treated in the same manner as in Example 8, about 5% by volume of fine particles and whiskers were attached.

Example 11 Continuous fiber bundle 4 of inorganic fibers obtained in Reference Example 8 was continuously immersed while applying ultrasonic waves to a liquid in which 100 g of silicon carbide fine particles were stirred and suspended in 500 cc of ethanol. Later, when 150 g of silicon nitride whiskers were stirred and suspended in 500 cc of ethanol and immersed and dried in the same manner, the volume ratio was approximately 1.
4% of fine particles and whiskers were attached.

Example 12 The polycyclic aromatic polymer containing silicon and titanium obtained in Reference Example 5 was finely pulverized and then pulverized at 1300 °C in an argon stream.
It was fired at °C to obtain a fine powder mainly composed of crystalline carbon, amorphous carbon, and 5i-Ti-C-0 with an average particle size of 0.5 μm. This fine powder 100
The inorganic fibers obtained in Reference Example 5
After continuous immersion of the continuous fiber bundle 4, 150 g of silicon nitride whiskers were stirred and suspended in 500 cc of ethanol and then immersed and dried in the same manner. Volume % of fine particles and whiskers were attached.

Example 13 A unidirectionally reinforced FRM was produced using the fibrous body obtained in Example 8 and using aluminum as a matrix. This F.R.M.
The fiber volume percentage (■,) is 50%, and the bending strength is 179
kg/rrta" (ROM value is 190 kg/2 cats).

Example 14 Using the fibrous body obtained from the inorganic fiber (1) in Example 9, a unidirectionally reinforced FRM was produced using aluminum containing a total of 5% of copper and magnesium as a matrix. The fiber volume fraction of the obtained FRM was 50% by volume. This FR
The bending strength of M is 185 kg/mm”, and the ROM value (19
0kg/mm”), there was almost no difference.

Similarly, in the FRM using the fiber body obtained from the inorganic fiber V in Example 9, the bending strength was 175 kg/ll.
1lI12 Tea Tsuta, ROM value (178kg/mm”)
There was almost no difference.

[Brief explanation of drawings]

FIG. 1 is a schematic configuration diagram showing an example of a manufacturing apparatus used for manufacturing a fibrous body for a composite material of the present invention. 1.-Processing tank 2-Ultrasonic adder 3-Processing liquid
4-Continuous fiber bundle 5.10-Pobbin 6.7-Movable roller 8.9-Pressure roller 11--Blower 12--Drying oven 1
3-・- Stirrer == Door

Claims (2)

[Claims] (1) An inorganic fiber obtained from a metal-containing polycyclic aromatic polymer containing silicon and at least one element selected from the group consisting of titanium, zirconium, and hafnium, the constituent components of which are: a) the polymer; Carbonaceous material exhibiting at least one type of crystalline arrangement state selected from the group consisting of radial structure, onion structure, random structure, core radial structure, skin onion structure, and mosaic structure derived from polycyclic aromatic compounds in the mesophase constituting the coalescence. , b) crystalline carbon and/or amorphous carbon in a non-oriented state derived from an optically isotropic polycyclic aromatic compound containing an organic solvent-insoluble component constituting the polymer, and c) [1 ] An amorphous material consisting essentially of Si, M, C and O, and/or [2] A particle size of 500 Å consisting essentially of β-SiC, MC, a solid solution of β-SiC and MC, and MC_1_-_x The following crystalline ultrafine particles and amorphous SiO_y and MO_z
The proportion of the constituent elements is Si: 5-70% by weight, M: 0.5-70% by weight.
45% by weight, C: 20-40% by weight and O: 0.01-
30% by weight of Si-M-C-O material (in the above formula:
M is at least one element selected from Ti, Zr, and Hf, and satisfies 0<x<1, 0<y≦2, and 0<z≦2. ) A continuous fiber bundle having at least one selected from the group consisting of fine particles of a heat-resistant substance, short fibers, and whiskers attached to the surface of carbonaceous continuous inorganic fibers, or a woven fabric made of the continuous fiber bundle. Fibrous bodies for composite materials. (2) 1) Mainly composed of a bonding unit (Si-CH_2), or a bonding unit (Si-CH_2) and a bonding unit (Si-Si), with a hydrogen atom, a lower alkyl group, a silicon side chain,
M (M is at least one element selected from the group consisting of titanium, zirconium, and hafnium) is directly or oxygen-containing to the silicon atom of the main skeleton that has a phenyl group or a silyl group and consists of the above-mentioned bonding units. through atoms,
At least a portion of the silicon atoms of the transition metal-containing organosilicon polymer bonded to at least a portion of the silicon atoms are aromatic compounds of a polycyclic aromatic compound obtained from petroleum-based or coal-based pitch or a heat-treated product thereof. a random copolymer bonded to ring carbon; and 2) a polycyclic aromatic compound consisting of mesophase or both phases of mesophase and optically isotropic phase obtained from petroleum-based or coal-based pitch. A first step of obtaining a metal-containing polycyclic aromatic polymer containing M and silicon by heating reaction and/or heating melting at a temperature in the range of 500 ° C., a spinning stock solution of the metal-containing polycyclic aromatic polymer described above. A second step of preparing and spinning the yarn, and a third step of infusibleizing the spun yarn under tension or without tension.
and a fourth step of firing the infusible spun fibers at a temperature in the range of 800 to 3000°C in a vacuum or in an inert gas atmosphere. A fiber bundle made of continuous inorganic fibers or a woven fabric made of the continuous fiber bundle is immersed in a treatment liquid in which at least one selected from the group consisting of fine particles of a heat-resistant substance, short fibers, and whiskers is suspended. A method for producing a fiber body for a composite material, which comprises attaching at least one type selected from the group consisting of fine particles of a heat-resistant substance, short fibers, and whiskers to the surface of a single book.