JP2005255788A - Carbon fiber composite material and its production method, carbon fiber composite molding and its production, carbon fiber composite glass material and its production method, and carbon fiber composite glass molding and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a carbon fiber composite material in which carbon nanofibers are uniformly dispersed and its production method, to provide a carbon fiber composite molding and its production method, to provide a carbon fiber composite glass material and its production method, and a carbon fiber composite glass molding and its production method. <P>SOLUTION: The method for producing the carbon fiber composite material comprises the step of mixing unsaturated bond or group containing elastomer 30 having an affinity for carbon nanofibers 40 with glass particles 50 and the step of dispersing the carbon nanofibers 40 in the elastomer 30 containing the glass particles 50 under shear. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a carbon fiber composite material and a manufacturing method thereof, a carbon fiber composite molded product and a manufacturing method thereof, a carbon fiber composite glass material and a manufacturing method thereof, a carbon fiber composite glass molded product and a manufacturing method thereof.

  In recent years, composite materials using carbon nanofibers have attracted attention. Such a composite material is expected to improve mechanical strength and the like by including carbon nanofibers.

  Further, a fiber-reinforced composite glass material using glass fibers as reinforcing fibers has been proposed (see, for example, Patent Document 1).

  However, since carbon nanofibers have strong cohesiveness with each other, it is very difficult to uniformly disperse the carbon nanofibers in the base material of the composite material. Therefore, at present, it is difficult to obtain a composite material of carbon nanofibers having desired characteristics, and expensive carbon nanofibers cannot be efficiently used.

Further, glass is also required to have a function of absorbing ultraviolet rays and infrared rays. In particular, when infrared rays are absorbed, there is a problem that the temperature of the glass itself increases.
Japanese Patent Laid-Open No. 5-9041

  Therefore, an object of the present invention is to provide a carbon fiber composite material in which carbon nanofibers are uniformly dispersed and a method for producing the same. Another object of the present invention is to provide a carbon fiber composite molded article in which carbon nanofibers are uniformly dispersed and a method for producing the same. Moreover, the objective of this invention is providing the carbon fiber composite glass material in which the carbon nanofiber was disperse | distributed uniformly, and its manufacturing method. Furthermore, the objective of this invention is providing the carbon fiber composite glass molded article in which the carbon nanofiber was disperse | distributed uniformly, and its manufacturing method.

The carbon fiber composite material according to the present invention includes an elastomer, glass particles and carbon nanofibers dispersed in the elastomer,
The elastomer has an unsaturated bond or group having an affinity for the carbon nanofiber.

  In the carbon fiber composite material of the present invention, the carbon nanofibers are more uniformly dispersed in the elastomer as the base material for the reason described later. Even carbon nanofibers having a diameter of about 30 nm or less, which are considered to be particularly difficult to be dispersed, and carbon nanofibers having a curved fiber shape are uniformly dispersed in the elastomer.

  The elastomer in the present invention may be either a rubber-based elastomer or a thermoplastic elastomer. In the case of a rubber-based elastomer, the elastomer may be either a crosslinked body or an uncrosslinked body. As the raw material elastomer, an uncrosslinked product is used in the case of a rubber-based elastomer. Among thermoplastic elastomers, particularly ethylene propylene rubber (EPDM), carbon nanofibers are difficult to disperse, but in the present invention, carbon nanofibers can be uniformly dispersed due to the dispersion effect of the glass particles.

  Further, the carbon fiber composite molded product obtained by crosslinking the carbon fiber composite material according to the present invention and the carbon fiber composite molded product obtained without cross-linking are made of carbon nanofibers by glass particles in the same manner as the carbon fiber composite material. Are uniformly dispersed.

  The carbon fiber composite material or the carbon fiber composite glass material obtained by powder molding the carbon fiber composite molded product according to the present invention has carbon nanofibers uniformly dispersed therein.

  In addition, the carbon fiber composite glass material obtained by mixing the carbon fiber composite material or the carbon fiber composite molded product according to the present invention into molten glass and casting the carbon nanofibers is uniformly dispersed by the glass particles in the same manner as the carbon fiber composite material. Will be.

  Furthermore, in the carbon fiber composite glass molded product in which molten glass is infiltrated into the carbon fiber composite molded product according to the present invention and the elastomer is replaced with glass, the carbon nanofibers are uniformly dispersed by the glass particles in the same manner as the carbon fiber composite material. Will be. In particular, the carbon fiber composite molded product in contact with the molten glass penetrates while the elastomer is thermally decomposed by the molten glass. be able to. In the carbon fiber composite molded article, the amount is 10 to 3000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts by weight of the elastomer. When the glass particles are 10 parts by weight or less, the capillary phenomenon is small and the penetration rate of the molten glass is slow, so that it is difficult to adopt in terms of productivity and cost. Further, when the glass particles are 3000 parts by weight or more, it becomes difficult to impregnate the elastomer when producing the carbon fiber composite material.

  As described above, the carbon fiber composite glass material and the carbon fiber composite glass molded product using the glass in which the carbon nanofibers are dispersed as a matrix are improved in strength, reduced in weight, and improved in heat resistance and wear resistance.

The method for producing a carbon fiber composite material according to the present invention includes a step of mixing an elastomer having an unsaturated bond or group having affinity for carbon nanofibers and glass particles,
Mixing the carbon nanofibers with the elastomer containing the glass particles and dispersing by shearing force;
including.

  According to the production method of the present invention, the unsaturated bond or group of the elastomer is bonded to the active portion of the carbon nanofiber, particularly the radical at the end of the carbon nanofiber, thereby weakening the cohesive force of the carbon nanofiber. Dispersibility can be increased. Furthermore, by using an elastomer containing glass particles, when the carbon nanofibers are dispersed by a shearing force, a turbulent flow of the elastomer occurs around the glass particles. By this flow, the carbon fiber composite material according to the present invention has carbon nanofibers dispersed more uniformly in the elastomer as the base material. Even carbon nanofibers having a diameter of about 30 nm or less, which are considered to be particularly difficult to be dispersed, and carbon nanofibers having a curved fiber shape are uniformly dispersed in the elastomer.

The step of dispersing carbon nanofibers in the elastomer by shearing force,
(A) An open roll method with a roll interval of 0.5 mm or less,
(B) a closed kneading method with a rotor gap of 1 mm or less,
(C) A multi-screw extrusion kneading method with a screw gap of 0.3 mm or less can be used.

  Further, the method for producing a carbon fiber composite molded article further comprising a step of crosslinking the carbon fiber composite material according to the present invention includes cross-linking the carbon fiber composite material in which carbon nanofibers are uniformly dispersed as described above. A carbon fiber composite molded product in which carbon nanofibers can be uniformly dispersed by glass particles can be obtained. In addition, a carbon fiber composite molded product having a desired shape in which carbon nanofibers are uniformly dispersed can be obtained by performing the cross-linking step in a desired molding die. Further, the method for producing a carbon fiber composite molded article further comprising a step of forming the carbon fiber composite material according to the present invention into a desired shape without crosslinking is a carbon fiber in which carbon nanofibers can be uniformly dispersed. A composite molded product can be obtained.

  The method for producing a carbon fiber composite glass material by powder molding the carbon fiber composite material or the carbon fiber composite molded product according to the present invention can provide a carbon fiber composite glass material in which carbon nanofibers are uniformly dispersed.

  The method for producing a carbon fiber composite glass material further comprising a step of mixing the carbon fiber composite material or the carbon fiber composite molded product according to the present invention into a molten glass and casting it in a mold having a desired shape. A carbon fiber composite glass material in which fibers are uniformly dispersed can be obtained.

  Furthermore, the step of arranging a glass lump above the carbon fiber composite molded article according to the present invention, and heating and melting the glass lump to obtain molten glass, and vaporizing the elastomer in the carbon fiber composite molded article The method for producing a carbon fiber composite glass molded article further comprising a step of replacing the molten glass with the molten glass can obtain a carbon fiber composite glass molded article in which carbon nanofibers are uniformly dispersed. Particularly in a carbon fiber composite molded product, the amount is 10 to 3000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts by weight of the elastomer. When the glass particles are 10 parts by weight or less, the capillary phenomenon is small and the penetration rate of the molten glass is slow, so that it is difficult to adopt in terms of productivity and cost. Further, when the glass particles are 3000 parts by weight or more, it becomes difficult to impregnate the elastomer when producing the carbon fiber composite material. Moreover, it is preferable that the carbon fiber composite molded product is molded without being cross-linked, because the elastomer can be easily decomposed and the penetration of the molten glass is quick.

  Moreover, the carbon fiber composite glass material and the carbon fiber composite glass molded product according to the present invention can absorb light such as infrared rays by the carbon nanofibers dispersed in the material. Furthermore, the carbon fiber composite glass material and the carbon fiber composite glass molded article according to the present invention can improve the low thermal conductivity of the glass alone by the carbon nanofibers, and release the heat generated by such light absorption to the outside. it can.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

  The carbon fiber composite material according to the present embodiment includes an elastomer, and glass particles and carbon nanofibers dispersed in the elastomer.

  The carbon fiber composite molded product according to the present invention can be obtained by molding the carbon fiber composite material with or without crosslinking.

  The carbon fiber composite glass material according to the present invention according to the present invention can be obtained by powder molding a carbon fiber composite material or a carbon fiber composite molded product.

  Moreover, the carbon fiber composite glass material concerning this invention is obtained by mixing and casting a carbon fiber composite material or a carbon fiber composite molded product in molten glass.

  Furthermore, the carbon fiber composite glass molded product according to the present invention can be obtained by allowing molten glass to penetrate into the carbon fiber composite material or the carbon fiber composite molded product and replacing the elastomer with glass.

  The method for producing a carbon fiber composite material according to the present embodiment includes a step of mixing an elastomer having an unsaturated bond or group having affinity for carbon nanofibers and glass particles, and the glass particles. Mixing the carbon nanofibers with the elastomer and dispersing them by shearing force.

  Moreover, the manufacturing method of the carbon fiber composite molded article concerning this invention further has the process of shape | molding the said carbon fiber composite material in a desired shape. The method for producing a carbon fiber composite molded product according to the present invention further includes a step of crosslinking and molding the carbon fiber composite material.

  The method for producing a carbon fiber composite glass material according to the present invention further includes a step of powder-molding the carbon fiber composite material or the carbon fiber composite molded product.

  Moreover, the manufacturing method of the carbon fiber composite glass material concerning this invention further has the process of casting a carbon fiber composite material or a carbon fiber composite molded product, and molten glass in a casting_mold | template.

  Furthermore, the method for producing a carbon fiber composite glass molded product according to the present invention includes a step of placing a glass lump above the carbon fiber composite molded product, and a molten glass by heating and melting the glass lump, Vaporizing the elastomer in the carbon fiber composite molded article and replacing the molten glass.

  For example, the elastomer desirably has characteristics such as having a certain molecular length and flexibility in addition to having high affinity with the carbon nanofibers. Moreover, it is desirable that the step of dispersing the carbon nanofibers in the elastomer with a shearing force is kneaded with a shearing force as high as possible.

  (A) First, the elastomer will be described.

  The elastomer preferably has a molecular weight of 5,000 to 5,000,000, more preferably 20,000 to 3,000,000. When the molecular weight of the elastomer is within this range, the elastomer molecules are entangled with each other and connected to each other. Therefore, the elastomer easily invades the aggregated carbon nanofibers, and thus has a great effect of separating the carbon nanofibers. If the molecular weight of the elastomer is less than 5000, the elastomer molecules cannot be sufficiently entangled with each other, and the effect of dispersing the carbon nanofibers is reduced even when a shearing force is applied in a later step. If the molecular weight of the elastomer is greater than 5 million, the elastomer becomes too hard and processing becomes difficult.

  The elastomer preferably has a network component spin-spin relaxation time (T2n / 30 ° C.) of 100 to 3000 μsec, more preferably 200, measured at 30 ° C. by the Hahn echo method using pulsed NMR. Or 1000 μs. By having a spin-spin relaxation time (T2n / 30 ° C.) in the above range, the elastomer can be flexible and have sufficiently high molecular mobility. Accordingly, when the elastomer and the carbon nanofiber are mixed, the elastomer can easily enter the gap between the carbon nanofibers due to high molecular motion. If the spin-spin relaxation time (T2n / 30 ° C.) is shorter than 100 μsec, the elastomer cannot have sufficient molecular mobility. Also, if the spin-spin relaxation time (T2n / 30 ° C.) is longer than 3000 μsec, the elastomer tends to flow like a liquid, and it becomes difficult to disperse the carbon nanofibers.

  The elastomer preferably has a spin-spin relaxation time (T2n) of the network component of 100 to 2000 μsec in the crosslinked product, measured at 30 ° C. by the Hahn echo method using pulsed NMR. The reason is the same as that of the uncrosslinked product described above. That is, when an uncrosslinked product having the above conditions is crosslinked by the production method of the present invention, T2n of the obtained crosslinked product is approximately within the above range.

  The spin-spin relaxation time obtained by the Hahn-echo method using pulsed NMR is a measure representing the molecular mobility of a substance. Specifically, when the spin-spin relaxation time of the elastomer is measured by the Hahn-echo method using pulsed NMR, a first component having a first spin-spin relaxation time (T2n) having a short relaxation time, and relaxation A second component having a longer spin-spin relaxation time (T2nn) is detected. The first component corresponds to a polymer network component (skeleton molecule), and the second component corresponds to a polymer non-network component (branch and leaf component such as a terminal chain). The shorter the first spin-spin relaxation time, the lower the molecular mobility and the harder the elastomer. Further, it can be said that the longer the first spin-spin relaxation time, the higher the molecular mobility and the softer the elastomer.

  As a measurement method in the pulsed NMR method, the solid echo method, the CPMG method (Car Purcell, Mayboom, Gill method) or the 90 ° pulse method can be applied instead of the Hahn echo method. However, since the carbon fiber composite material according to the present invention has a moderate spin-spin relaxation time (T2), the Hahn echo method is most suitable. In general, the solid echo method and the 90 ° pulse method are suitable for short T2 measurement, the Hahn echo method is suitable for medium T2 measurement, and the CPMG method is suitable for long T2 measurement.

  The elastomer has an unsaturated bond or group having an affinity for carbon nanofibers, particularly a radical at its terminal, in at least one of the main chain, side chain and terminal chain, or such a radical or group has Easy to generate. Such unsaturated bonds or groups include double bonds, triple bonds, α hydrogen, carbonyl groups, carboxyl groups, hydroxyl groups, amino groups, nitrile groups, ketone groups, amide groups, epoxy groups, ester groups, vinyl groups, halogen groups. , Urethane groups, burette groups, allophanate groups, and urea groups.

  Carbon nanofibers usually have a six-membered ring of carbon atoms and a closed end with a five-membered ring introduced at the tip. It tends to occur, and it is easy to generate radicals and functional groups in the part. In the present embodiment, at least one of the main chain, side chain, and terminal chain of the elastomer has an unsaturated bond or group having high affinity (reactivity or polarity) with the radical of the carbon nanofiber, so that the elastomer and carbon Nanofibers can be combined. This makes it possible to easily disperse the carbon nanofibers by overcoming the cohesive force.

  Elastomers include natural rubber (NR), epoxidized natural rubber (ENR), styrene-butadiene rubber (SBR), nitrile rubber (NBR), chloroprene rubber (CR), ethylene propylene rubber (EPR, EPDM), and butyl rubber (IIR). ), Chlorobutyl rubber (CIIR), acrylic rubber (ACM), silicone rubber (Q), fluoro rubber (FKM), butadiene rubber (BR), epoxidized butadiene rubber (EBR), epichlorohydrin rubber (CO, CEO), urethane rubber (U), elastomers such as polysulfide rubber (T); olefin (TPO), polyvinyl chloride (TPVC), polyester (TPEE), polyurethane (TPU), polyamide (TPEA), styrene (SBS) ), Etc., thermoplastic elastomer ; And it can be a mixture thereof. According to the research of the present inventors, it has been found that it is difficult to disperse carbon nanofibers particularly in ethylene propylene rubber (EPR, EPDM).

  (B) Next, the glass particles will be described.

The glass particles are mixed and dispersed in the elastomer, and the carbon nanofibers are more favorably dispersed when the carbon nanofibers are mixed. As the glass particles, commercially available glass particles can be appropriately used. For example, SiO ₂ / B ₂ O ₃ system, SiO ₂ / ZnO / B ₂ O ₃ system, SiO ₂ / PbO / B ₂ O ₃ system , SiO ₂ / PbO / Al ₂ O ₃ / B ₂ O ₃ system, SiO ₂ / PbO / ZnO / B ₂ O ₃ system, SiO ₂ / BaO / B ₂ O ₃ system, SiO ₂ / BaO / Al ₂ O ₃ System, SiO ₂ / BaO / Li ₂ O ₃ system, SiO ₂ / MgO / Al ₂ O ₃ system, SiO ₂ / BaO / B ₂ O ₃ system, SiO ₂ / ZnO / Li ₂ O ₃ system, SiO ₂ / ZnO / SnO / P ₂ O ₅ series, SiO ₂ / R ₂ O / B ₂ O ₃ series, SiO ₂ / RO series glass particles, alkali glass such as Na, Kc, Ca, Ti, Fe, Ni, Co The glass containing components, such as these, can be used. It is preferable that a glass particle is an average particle diameter larger than the average diameter of the carbon nanofiber to be used. Moreover, the average particle diameter of glass particles is 500 micrometers or less, Preferably it is 1-300 micrometers. When the infiltration method is used in the casting process, the amount of the glass particles is 10 to 3000 parts by weight, preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the elastomer. When the glass particles are 10 parts by weight or less, the capillary phenomenon is small and the penetration rate of the molten glass is slow, so that it is difficult to adopt in terms of productivity and cost. Further, when the glass particles are 3000 parts by weight or more, it becomes difficult to impregnate the elastomer when producing the carbon fiber composite material. Further, the shape of the glass particles is not limited to a spherical particle shape, and may be a flat plate shape or a flake shape as long as a turbulent flow is generated around the glass particles during mixing.

  (C) Next, the carbon nanofiber will be described.

  The carbon nanofibers preferably have an average diameter of 0.5 to 500 nm, and more preferably 0.5 to 30 nm in order to improve the strength of the carbon fiber composite material. Furthermore, the carbon nanofibers may be straight fibers or curved fibers.

  The compounding quantity of carbon nanofiber is not specifically limited, It can set according to a use. In the carbon fiber composite material of the present embodiment, a crosslinked elastomer, an uncrosslinked elastomer or a thermoplastic polymer can be used as an elastomer material as it is, or can be used as a raw material for a glass composite material. When the carbon fiber composite material of the present embodiment is used as a raw material for a glass composite material, carbon nanofibers can be included at a ratio of 0.01 to 50% by weight. The raw material of such a glass composite material can be used as a so-called master batch as a carbon nanofiber supply source when carbon nanofibers are mixed with glass.

  Examples of carbon nanofibers include so-called carbon nanotubes. Carbon nanotubes have a single-layer structure in which graphene sheets with carbon hexagonal mesh surfaces are closed in a cylindrical shape, or a multilayer structure in which these cylindrical structures are arranged in a nested manner. That is, the carbon nanotube may be composed of only a single-layer structure or a multilayer structure, and the single-layer structure and the multilayer structure may be mixed. A carbon material partially having a carbon nanotube structure can also be used. In addition to the name “carbon nanotube”, it may be called “graphite fibril nanotube”.

  Single-wall carbon nanotubes or multi-wall carbon nanotubes are manufactured to a desired size by an arc discharge method, a laser ablation method, a vapor phase growth method, or the like.

  The arc discharge method is a method of obtaining multi-walled carbon nanotubes deposited on a cathode by performing an arc discharge between electrode materials made of carbon rods in an argon or hydrogen atmosphere at a pressure slightly lower than atmospheric pressure. In addition, the single-walled carbon nanotube is obtained by mixing the carbon rod with a catalyst such as nickel / cobalt to cause arc discharge and adhering to the inner surface of the processing vessel.

  The laser ablation method melts and evaporates the carbon surface by irradiating a strong YAG laser pulsed laser beam onto a carbon surface mixed with a target catalyst such as nickel / cobalt in a rare gas (eg argon). This is a method for obtaining single-walled carbon nanotubes.

  The vapor phase growth method is a method in which hydrocarbons such as benzene and toluene are thermally decomposed in the gas phase to synthesize carbon nanotubes. More specifically, a fluid catalyst method, a zeolite supported catalyst method, and the like can be exemplified.

  The carbon nanofibers can be improved in adhesion and wettability with the elastomer by performing surface treatment such as ion implantation treatment, sputter etching treatment, and plasma treatment in advance before being kneaded with the elastomer.

  (D) Next, the process of mixing glass particles and carbon nanofibers in an elastomer and dispersing them by shearing force will be described.

  In the present embodiment, an example using an open roll method in which a roll interval is 0.5 mm or less will be described as a step of mixing glass particles and carbon nanofibers with an elastomer.

  FIG. 1 is a diagram schematically showing an open roll method using two rolls. In FIG. 1, the code | symbol 10 shows a 1st roll and the code | symbol 20 shows a 2nd roll. The first roll 10 and the second roll 20 are arranged at a predetermined interval d, preferably 1.0 mm or less, more preferably 0.1 to 0.5 mm. The first and second rolls rotate in the normal direction or the reverse direction. In the illustrated example, the first roll 10 and the second roll 20 rotate in the direction indicated by the arrow. When the surface speed of the first roll 10 is V1, and the surface speed of the second roll 20 is V2, the surface speed ratio (V1 / V2) is preferably 1.05 to 1.2. By using such a surface velocity ratio, a desired shear force can be obtained. First, when the elastomer 30 is wound around the second roll 20 while the first and second rolls 10 and 20 are rotated, a so-called bank 32 in which the elastomer is accumulated between the rolls 10 and 20 is formed. The step of mixing the elastomer 30 and the glass particles 50 is performed by adding the glass particles 50 into the bank 32 and further rotating the first and second rolls 10 and 20. Next, the carbon nanofibers 40 are added to the bank 32 in which the elastomer 30 and the glass particles 50 are mixed, and the first and second rolls 10 and 20 are rotated. Further, the distance between the first and second rolls 10 and 20 is reduced to the distance d described above, and in this state, the first and second rolls 10 and 20 are rotated at a predetermined surface speed ratio. Thereby, a high shearing force acts on the elastomer 30, and the carbon nanofibers aggregated by the shearing force are separated from each other so as to be pulled out one by one and dispersed in the elastomer 30. In addition, the shearing force of the roll generates a turbulent flow around the glass particles dispersed in the elastomer. The carbon nanofibers are further dispersed in the elastomer 30 by this complicated flow. If the elastomer 30 and the carbon nanofibers 40 are first mixed before the glass particles 50 are mixed, the movement of the elastomer 30 is constrained by the carbon nanofibers 40, so that it is difficult to mix the glass particles 50. . Therefore, it is preferable to perform the step of mixing the glass particles 50 before adding the carbon nanofibers 40 to the elastomer 30.

  In this process, in order to obtain as high a shearing force as possible, the elastomer and carbon nanofiber are mixed at a relatively low temperature of preferably 0 to 50 ° C., more preferably 5 to 30 ° C. When the open roll method is used, it is desirable to set the temperature of the roll to the above temperature. The distance d between the first and second rolls 10 and 20 is set wider than the average particle diameter of the glass particles 50 even in the narrowest state, so that the carbon nanofibers 40 in the elastomer 30 can be dispersed well. Can do.

  At this time, the elastomer of the present embodiment has the characteristics described above, that is, the molecular morphology (molecular length) of the elastomer, the molecular motion, the chemical interaction with the carbon nanofiber, and the like. Therefore, it is possible to obtain a carbon fiber composite material and a carbon fiber composite molded article excellent in dispersibility and dispersion stability (the carbon nanofibers are difficult to reaggregate). More specifically, when an elastomer and carbon nanofibers are mixed, an elastomer having a reasonably long molecular length and high molecular mobility penetrates into the carbon nanofibers, and a specific portion of the elastomer is chemically interlinked. It binds to the highly active part of the carbon nanofiber by action. In this state, if a strong shearing force acts on the mixture of the elastomer and carbon nanofibers, the carbon nanofibers move as the elastomer moves, and the aggregated carbon nanofibers are separated and dispersed in the elastomer. Will be. The carbon nanofibers once dispersed are prevented from reaggregating due to chemical interaction with the elastomer, and can have good dispersion stability.

  In addition, since a predetermined amount of glass particles are contained in the elastomer, the carbon nanofibers are separated from each other by various complicated flows such as turbulent flow of the elastomer generated around the glass particles. Even shear force will work. Therefore, even in the case of carbon nanofibers having a diameter of about 30 nm or less or curved carbon-like carbon nanofibers, they move in the respective flow directions of the individual elastomer molecules bonded by chemical interaction. Will be distributed.

  The step of dispersing the carbon nanofibers in the elastomer by the shearing force is not limited to the above open roll method, and the above-described closed kneading method or multiaxial extrusion kneading method can also be used. In short, in this step, it is sufficient that a shearing force capable of separating the aggregated carbon nanofibers can be given to the elastomer.

  The carbon fiber composite material obtained by dispersing glass particles and carbon nanofibers in the above-mentioned elastomer and mixing them together (mixing / dispersing process) is formed by crosslinking with a crosslinking agent or not. Can be molded. As the molding method at this time, for example, a carbon fiber composite molded product can be obtained by performing a compression molding process, an extrusion molding process, or the like. In the compression molding process, for example, a carbon fiber composite material in which glass particles and carbon nanofibers are dispersed is added for a predetermined time (for example, 20 minutes) in a molding die having a desired shape set at a predetermined temperature (for example, 175 ° C.). A step of molding in a pressure state.

  In the step of mixing / dispersing the elastomer and the carbon nanofiber, or subsequently, a compounding agent usually used in processing of the elastomer such as rubber can be added. A well-known thing can be used as a compounding agent. Examples of the compounding agent include a crosslinking agent, a vulcanizing agent, a vulcanization accelerator, a vulcanization retarder, a softening agent, a plasticizer, a curing agent, a reinforcing agent, a filler, an antiaging agent, and a coloring agent. it can.

  (E) Next, the carbon fiber composite material and the carbon fiber composite molded product obtained by the above method will be described.

  In the carbon fiber composite material and the carbon fiber composite molded article of the present embodiment, carbon nanofibers are uniformly dispersed in an elastomer as a base material. This can be said to be a state where the elastomer is restrained by the carbon nanofibers. In this state, the mobility of the elastomer molecules constrained by the carbon nanofibers is smaller than that when not constrained by the carbon nanofibers. Therefore, the first spin-spin relaxation time (T2n), the second spin-spin relaxation time (T2nn), and the spin-lattice relaxation time (T1) of the carbon fiber composite material and the carbon fiber composite molded product according to the present embodiment. ) Is shorter than that of a single elastomer that does not contain carbon nanofibers. In particular, when carbon nanofibers are mixed in an elastomer containing glass particles, the second spin-spin relaxation time (T2nn) is shorter than in the case of an elastomer containing carbon nanofibers. In addition, the spin-lattice relaxation time (T1) in the crosslinked body (carbon fiber composite molded product) changes in proportion to the mixing amount of the carbon nanofibers.

  In addition, in the state where the elastomer molecules are constrained by the carbon nanofibers, it is considered that the non-network component (non-network chain component) decreases for the following reason. In other words, when the molecular mobility of the elastomer decreases as a whole due to carbon nanofibers, the non-network component becomes more difficult to move, making it easier to behave like the network component, and the non-network component ( It is considered that the non-network component is reduced due to the fact that the terminal chain is easy to move and is easily adsorbed to the active site of the carbon nanofiber. Therefore, the component fraction (fnn) of the component having the second spin-spin relaxation time is smaller than that in the case of an elastomer alone that does not include carbon nanofibers. In particular, when carbon nanofibers are mixed with an elastomer containing glass particles, the component fraction (fnn) of the component having the second spin-spin relaxation time is smaller than that of the elastomer containing carbon nanofibers. .

  From the above, it is desirable that the carbon fiber composite material and the carbon fiber composite molded product according to the present embodiment have a measurement value obtained by the Hahn echo method using the pulse method NMR in the following range.

  That is, in the uncrosslinked body (carbon fiber composite material), the first spin-spin relaxation time (T2n) measured at 150 ° C. is 100 to 3000 μsec, and the second spin-spin relaxation time (T2nn) is Preferably, the component fraction (fnn) of the component which does not exist or is 1000 to 10000 μsec and has the second spin-spin relaxation time is less than 0.2.

  In the crosslinked product (carbon fiber composite molded article), the first spin-spin relaxation time (T2n) measured at 150 ° C. is 100 to 2000 μs, and the second spin-spin relaxation time (T2nn) is It is preferably not present or 1000 to 4000 μs, and the component fraction (fnn) of the component having the second spin-spin relaxation time is preferably less than 0.08.

  In addition, the carbon fiber composite material and the carbon fiber composite molded product according to the present embodiment desirably have measured values obtained by the Hahn echo method using pulsed NMR in the following range. That is, the amount of change in the spin-lattice relaxation time (T1) (ΔT1) measured at 150 ° C. of the crosslinked body (carbon fiber composite molded product) per 1% by volume of the carbon nanofiber is 1 msec or more lower than that of the elastomer alone. Is more preferable, and it is more preferable to decrease by 2 to 15 msec.

  The spin-lattice relaxation time (T1) measured by the Hahn-echo method using pulsed NMR is a measure representing the molecular mobility of a substance together with the spin-spin relaxation time (T2). Specifically, the shorter the spin-lattice relaxation time of the elastomer, the lower the molecular mobility and the harder the elastomer, and the longer the spin-lattice relaxation time, the higher the molecular mobility and the softer the elastomer.

  In the carbon fiber composite material and the carbon fiber composite molded article according to the present embodiment, the flow temperature in the temperature dependence measurement of dynamic viscoelasticity is preferably 20 ° C. or more higher than the flow temperature of the raw material elastomer alone. In the carbon fiber composite material and the carbon fiber composite molded article of the present embodiment, glass particles and carbon nanofibers are well dispersed in the elastomer. This can be said to be a state where the elastomer is restrained by the carbon nanofibers as described above. In this state, the elastomer has a smaller molecular motion than the case where it does not contain carbon nanofibers, resulting in a decrease in fluidity. By having such flow temperature characteristics, the carbon fiber composite material and the carbon fiber composite molded product of the present embodiment have a low temperature dependency of dynamic viscoelasticity, and as a result, have excellent heat resistance.

  As described above, the carbon fiber composite material and the carbon fiber composite molded article of the present embodiment can be used as an elastomer-based material and can be used as a raw material for a composite glass material. Carbon nanofibers usually have the property of being entangled with each other and difficult to disperse in a medium. However, when the carbon fiber composite material and the carbon fiber composite molded article of the present embodiment are used as the raw material of the composite glass material, the carbon nanofibers are already dispersed in the elastomer. By mixing the carbon nanofibers, the carbon nanofibers can be easily dispersed in the medium.

  (F) Next, the process of obtaining a carbon fiber composite glass material and a carbon fiber composite glass molded product will be described.

  The step of obtaining the carbon fiber composite glass material and the carbon fiber composite glass molded product is performed using the carbon fiber composite material and the carbon fiber composite molded product obtained in the above embodiment, for example, by various molding methods as follows. Can be adopted.

  The carbon fiber composite material and the carbon fiber composite molded article can be implemented by a powder molding process. Specifically, for example, the carbon fiber composite material and the carbon fiber composite molded product obtained in the above embodiment are compressed as they are or by freezing and pulverizing the particles of the carbon fiber composite material and the carbon fiber composite molded product in a mold. And firing at a sintering temperature, for example, 700 ° C., to obtain a carbon fiber composite glass material and a carbon fiber composite glass molded article. Therefore, the powder molding in the present embodiment is the same as the powder molding in the metal molding process, including so-called powder metallurgy, and not only in the case of using a powder raw material but also in the case of a composite elastomer, pre-compression molding in advance. It also includes raw materials that have been made into block shapes by applying.

  In addition, the carbon fiber composite material and the carbon fiber composite molded article, and other glass particles serving as a matrix of the composite glass material are wet-mixed, and then sintered in the same manner to obtain the carbon fiber composite glass material and the carbon fiber composite glass. A molded product can also be obtained. In this case, it is desirable to mix the carbon fiber composite material and the carbon fiber composite molded product with other glass particles in the solvent (wet mixing).

  Furthermore, after freezing and pulverizing, the carbon fiber composite material and carbon fiber composite molded product particles and other glass particles are mixed, for example, dry blended, compression molded in a mold, and then carbonized by a sintering method. A fiber composite glass material and a carbon fiber composite glass molded article can be obtained.

  The carbon fiber composite glass material and the carbon fiber composite glass molded product produced by such powder molding can disperse carbon nanofibers in glass. The other glass particles used in this step are preferably the same material as the glass particles used to obtain the carbon fiber composite material, but the size of the particles is appropriately determined depending on the use of the composite glass obtained by powder molding, etc. You can choose.

  The casting process of the carbon fiber composite glass material is performed by a process of casting the carbon fiber composite material or the carbon fiber composite molded product obtained in the above embodiment, for example, in a mold having a desired shape by mixing in molten glass. can do. In such a casting method, a carbon fiber composite molded product is mixed in molten glass and solidified in a mold to form a carbon fiber composite glass material or a carbon fiber composite glass molded product. In this casting process, the elastomer of the carbon fiber composite material or the carbon fiber composite molded product is decomposed and removed by the heat of the molten glass.

  The molten glass contains the same glass as the glass particles premixed in the carbon fiber composite material or the carbon fiber composite molded product, thereby improving the wettability with the glass particles, and the product carbon fiber composite glass material or carbon. The strength of the fiber composite glass molded product can be improved.

  The carbon fiber composite material or the decomposed elastomer of the carbon fiber composite molded article in powder molding and casting as described above is trapped and removed by a gas trap device or the like.

  In the present embodiment, a step of casting using a so-called non-pressure infiltration method in which a molten metal is infiltrated into a carbon fiber composite molded article will be described in detail with reference to FIGS. 2 and 3.

  FIG.2 and FIG.3 is a schematic block diagram of the apparatus which manufactures a carbon fiber composite glass molded article by the non-pressurization infiltration method. As the carbon fiber composite molded product obtained in the above embodiment, for example, the carbon fiber composite molded product 4 that is heated and compression molded in a molding die having the shape of the final product can be used. The carbon fiber composite molded product 4 is preferably not cross-linked. This is because the penetration rate of the molten glass is increased by not being crosslinked. In FIG. 2, a carbon fiber composite molded product 4 (for example, glass particles 50 and carbon nanofibers 40 are mixed in an uncrosslinked elastomer 30) is placed in a sealed container 1. A glass block 5 is disposed above the carbon fiber composite molded product 4. Next, the carbon fiber composite molded article 4 and the glass lump 5 disposed in the container 1 are heated to the melting point of glass or higher by a heating means (not shown) built in the container 1. The heated glass lump 5 is melted to become a glass melt. In addition, the elastomer 30 in the carbon fiber composite molded product 4 in contact with the molten glass is decomposed and vaporized, and the molten glass penetrates into the void formed by the decomposition of the elastomer 30. The gas generated when the elastomer is decomposed is trapped and removed by the gas trap device 2.

  In the carbon fiber composite molded product 4 of the present embodiment, the void formed by decomposing the elastomer 30 can permeate the entire glass melt faster by capillary action. The glass melt penetrates between the glass particles 50 by capillary action, and the glass melt is completely filled up to the inside of the carbon fiber composite molded product. And the heating by the heating means of the container 1 is stopped, the molten glass which has penetrated into the mixed material 4 is cooled and solidified, and a carbon fiber composite glass molded product in which carbon nanofibers 40 are uniformly dispersed as shown in FIG. 6 can be manufactured. The carbon fiber composite molded product 4 used in the casting process is preferably molded in advance using glass particles of the same type as the molten glass used in the casting process. By doing in this way, it is easy to mix molten glass and glass particles, and a homogeneous glass can be obtained.

  In addition, the flow of the molten glass penetrates the carbon nanofibers into the glass particles. Furthermore, the surface of the carbon nanofiber is activated by the radicals of the decomposed elastomer molecules, and the wettability with the glass melt is improved. The carbon fiber composite glass molded article thus obtained has carbon nanofibers uniformly dispersed in a glass matrix.

  In the above-described embodiment, the non-pressure infiltration method has been described. However, the infiltration method is not limited to this, and for example, a pressure infiltration method in which pressure is applied by an atmospheric pressure such as an inert gas can be used.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

(Examples 1 to 3, Comparative Examples 1 and 2)
(1) Preparation of sample (a) Preparation of uncrosslinked sample (carbon fiber composite material) First step: A predetermined amount (shown in Table 1) on an open roll having a roll diameter of 6 inches (roll temperature: 10 to 20 ° C.) 100 g) of elastomer (100 parts by weight (phr)) was added and wound around a roll. As the elastomer, natural rubber (NR) having a molecular weight of 3 million was used.

  Second step: Glass particles in an amount (parts by weight) shown in Table 1 were added to the elastomer with respect to the elastomer. At this time, the roll gap was set to 1.5 mm.

  Third step: Next, an amount (parts by weight) of carbon nanofibers (described as “CNT” in Table 1) shown in Table 1 was added to the elastomer containing glass particles. At this time, the roll gap was set to 1.5 mm.

  Fourth step: When the carbon nanofibers were charged, the mixture of the elastomer and the carbon nanofibers was taken out from the roll.

  Fifth step: The roll gap was narrowed from 1.5 mm to 0.3 mm, and the mixture was introduced to make it thin. At this time, the surface speed ratio of the two rolls was set to 1.1. Thinning was repeated 10 times.

  Sixth step: The roll was set to a predetermined gap (1.1 mm), and the thinned mixture was charged and dispensed.

  In this way, uncrosslinked samples of Examples 1 to 3 were obtained. Moreover, the 2nd-4th process was abbreviate | omitted and the uncrosslinked sample of the comparative example 1 was obtained.

In addition, as glass particles of Examples 1 to 3, SiO ₂ / PbO / B ₂ O ₃ having an average particle diameter of 30 μm was used as the glass particles. Carbon nanofibers having a diameter (fiber diameter) of about 10 to 20 nm were used.

(B) Production of crosslinked sample (carbon fiber composite molded article) The first to fifth steps were performed in the same manner as the uncrosslinked sample.

  Sixth step: A roll was set at a predetermined gap (1.1 mm), a thinned mixture was charged, and a predetermined amount of a crosslinking agent (2 parts by weight) was further charged. The mixture was then dispensed.

  Seventh step: A sample cut into a mold size was set in a mold and subjected to press crosslinking at 100 ° C. and 100 MPa for 20 minutes.

  Thus, the crosslinked sample of Examples 1-3 was obtained.

(C) Production of carbon fiber composite glass material The uncrosslinked sample (carbon fiber composite material) obtained in the above (a) Examples 1 to 3 was put into a mold, pre-formed at 100 ° C. and 100 MPa, and then in a block shape An uncrosslinked sample (carbon fiber composite molded product) was prepared. Furthermore, an uncrosslinked sample (carbon fiber composite molded article) was placed in a container (furnace), a glass plate was placed on the uncrosslinked sample, and held at the melting point of glass (600 ° C.) for 1 hour in the atmosphere. The glass plate melted to become a glass melt, and the molten glass penetrated to replace the elastomer of the uncrosslinked sample. After impregnating the molten glass, it was naturally allowed to cool and solidify to obtain a carbon black composite material (glass base). The elastomer gas decomposed by heat was trapped and removed by a gas trap device.

  Moreover, as Comparative Example 1, 99 vol% of carbon nanofibers and 1 vol% of glass particles were dry blended, filled into a mold and preformed, and further placed on a glass plate and held in the atmosphere at 600 ° C. for 1 hour to infiltrate the glass. A sample of Comparative Example 2 was obtained.

  Further, as Comparative Example 2, a single glass plate was used.

(2) Measurement of E ′ (dynamic viscoelastic modulus), TB (tensile strength) and EB (cut elongation) E ′, TB and EB were measured according to JIS K 6521-1993 for the crosslinked sample of the composite material. These results are shown in Table 1.

(3) Observation with an electron microscope (SEM) About the bridge | crosslinking sample of Examples 1-3, and the carbon fiber composite glass material of Examples 1-3, Comparative Examples 1 and 2, carbon in a matrix using an electron microscope (SEM) The state of nanofiber dispersion was observed. These results are shown in Table 1 with a circle mark for those having almost no carbon nanofiber aggregates (black dots) and with a mark for those having many carbon nanofiber aggregates (black dots).

(4) Measurement of bending strength About the carbon fiber composite glass material of Examples 1-3 and Comparative Examples 1 and 2, bending strength was measured by JISK7171. More specifically, the bending strength is measured by arranging the sample so that the sample shape is 10 × width 80 × 4 mm thick, and the support is 10 mm from both ends of the sample, and the bending speed is 1 mm / min. A three-point bending test was performed with the maximum stress as the bending strength.

  From Table 1, according to Examples 1 to 3 of the present invention, the following was confirmed. That is, from the results of E ′, TB and EB using the cross-linked sample, increasing the compounding amount of carbon nanofibers improves the dynamic viscoelastic modulus and tensile strength while maintaining the cut elongation. It was confirmed that a reinforcing effect was obtained.

  From the results of Table 1, it was found that Comparative Example 1 had a variation in bending strength for each sample, and Examples 1 to 3 had a small variation in bending strength.

  Moreover, as a result of observing the crosslinked body samples and the carbon fiber composite glass materials of Examples 1 to 3 with an electron microscope (SEM), almost no aggregation of the carbon nanofibers was observed (circles in Table 1). The composite glass material of Comparative Example 1 was confirmed to have many black spots in the observation of the glass molding state (X in Table 1).

  From the above, according to the present invention, it has been clarified that carbon nanofibers, which are generally very difficult to disperse into a substrate, are uniformly dispersed in a matrix material (elastomer and glass). It has also been clarified that by mixing glass particles with an elastomer, carbon nanofibers, particularly thin carbon nanofibers of 30 nm or less, and carbon nanofibers that are easily bent and entangled can be sufficiently dispersed.

It is a figure which shows typically the kneading | mixing method of the elastomer and carbon nanofiber by the open roll method used in this Embodiment. It is a schematic block diagram of the apparatus which manufactures a carbon fiber composite glass material by the non-pressure penetrating method. It is a schematic block diagram of the apparatus which manufactures a carbon fiber composite glass material by the non-pressure penetrating method.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Container 2 Gas trap apparatus 4 Carbon fiber composite molded article 5 Glass lump 6 Carbon fiber composite glass molded article 10 1st roll 20 2nd roll 30 Elastomer 40 Carbon nanofiber 50 Glass particle

Claims (37)

An elastomer, and glass particles and carbon nanofibers dispersed in the elastomer,
The said elastomer is a carbon fiber composite material which has an unsaturated bond or group which has affinity with respect to the said carbon nanofiber. In claim 1,
The said glass particle is a carbon fiber composite material which is 10-3000 weight part with respect to 100 weight part of said elastomers. In claim 1 or 2,
The said glass particle is a carbon fiber composite material which has an average particle diameter larger than the average diameter of the said carbon nanofiber. In any of claims 1 to 3,
The carbon fiber composite material whose average particle diameter of the said glass particle is 500 micrometers or less. In any of claims 1 to 4,
The elastomer is a carbon fiber composite material having a molecular weight of 5,000 to 5,000,000. In any of claims 1 to 5,
The elastomer has at least one of a main chain, a side chain and a terminal chain, a double bond, a triple bond, an α hydrogen, a carbonyl group, a carboxyl group, a hydroxyl group, an amino group, a nitrile group, a ketone group, an amide group, an epoxy group, A carbon fiber composite material having at least one selected from functional groups such as ester groups, vinyl groups, halogen groups, urethane groups, burette groups, allophanate groups, and urea groups. In any one of Claims 1 thru | or 6.
The said elastomer is a carbon fiber composite material whose spin-spin relaxation time (T2n) of a network component is 100 to 3000 microseconds in an uncrosslinked body measured at 30 ° C. by a Hahn echo method using pulsed NMR. In any one of Claims 1 thru | or 6.
The elastomer is a carbon fiber composite material in which a spin-spin relaxation time (T2n) of a network component in a cross-linked body measured at 30 ° C. by a Hahn echo method using pulsed NMR is 100 to 2000 μsec. In any of claims 1 to 8,
The carbon nanofiber is a carbon fiber composite material having an average diameter of 0.5 to 500 nm.   A carbon fiber composite molded article obtained by molding the carbon fiber composite material according to claim 1 into a predetermined shape.   A carbon fiber composite molded article obtained by crosslinking the carbon fiber composite material according to any one of claims 1 to 9.   A carbon fiber composite molded article obtained by crosslinking the carbon fiber composite material according to any one of claims 1 to 9 and molding the carbon fiber composite material into a desired shape. In claim 11 or 12,
The carbon fiber composite molded article has a spin-lattice relaxation time (T1) converted to 1% by volume of mixed carbon nanofibers measured at 150 ° C. by a Hahn echo method using pulse NMR, and the elastomer A carbon fiber composite molded article that is reduced by 1 msec or more from the case of a single substance.   A carbon fiber composite glass material obtained by powder molding the carbon fiber composite material or carbon fiber composite molded product according to any one of claims 1 to 13.   A carbon fiber composite glass material obtained by mixing and casting the carbon fiber composite material or carbon fiber composite molded product according to any one of claims 1 to 13 in molten glass.   A carbon fiber composite glass molded product obtained by impregnating molten glass with a carbon fiber composite molded product according to any one of claims 10 to 13 and replacing the elastomer with the glass. A step of mixing an elastomer having an unsaturated bond or group having affinity for carbon nanofibers and glass particles;
Mixing the carbon nanofibers with the elastomer containing the glass particles and dispersing by shearing force;
A method for producing a carbon fiber composite material, comprising: In claim 17,
The said glass particle is a manufacturing method of a carbon fiber composite material which is 10-3000 weight part with respect to 100 weight part of said elastomers. In claim 17 or 18,
The method for producing a carbon fiber composite material, wherein the glass particles have an average particle diameter larger than an average diameter of the carbon nanofibers. In any one of claims 17 to 19,
The manufacturing method of the carbon fiber composite material whose average diameter of the said glass particle is 500 micrometers or less. In any one of claims 17 to 20,
The method for producing a carbon fiber composite material, wherein the elastomer has a molecular weight of 5,000 to 5,000,000. In any one of claims 17 to 20,
The elastomer has at least one of a main chain, a side chain and a terminal chain, a double bond, a triple bond, an α hydrogen, a carbonyl group, a carboxyl group, a hydroxyl group, an amino group, a nitrile group, a ketone group, an amide group, an epoxy group, A method for producing a carbon fiber composite material having at least one selected from functional groups such as ester groups, vinyl groups, halogen groups, urethane groups, burette groups, allophanate groups, and urea groups. In any of claims 17 to 22,
Production of a carbon fiber composite material in which the elastomer has a spin-spin relaxation time (T2n) of a network component in an uncrosslinked body of 100 to 3000 μsec, measured at 30 ° C. by a Hahn echo method using pulsed NMR. Method. In any of claims 17 to 22,
The method for producing a carbon fiber composite material, wherein the elastomer has a spin-spin relaxation time (T2n) of a network component of 100 to 2000 μsec in a crosslinked body, measured at 30 ° C. by a Hahn echo method using pulsed NMR. . 25. In any one of claims 17 to 24.
The carbon nanofiber is a method for producing a carbon fiber composite material having an average diameter of 0.5 to 500 nm. In any of claims 17 to 25,
The step of dispersing carbon nanofibers in the elastomer by a shearing force is a method for producing a carbon fiber composite material, which is performed using an open roll method with a roll interval of 0.5 mm or less. In claim 26,
The open roll method is a method for producing a carbon fiber composite material in which the surface speed ratio of two rolls is 1.05 to 3.00. In any of claims 17 to 25,
The step of dispersing carbon nanofibers in the elastomer by a shearing force is a method for producing a carbon fiber composite material, which is performed by a closed kneading method with a rotor gap of 1 mm or less. In any of claims 17 to 25,
The step of dispersing carbon nanofibers in the elastomer by shearing force is a method for producing a carbon fiber composite material, which is performed by a multiaxial extrusion kneading method with a screw gap of 0.3 mm or less. 30. In any one of claims 17 to 29.
The method for producing a carbon fiber composite material, wherein the step of dispersing carbon nanofibers in the elastomer by a shearing force is performed at 0 to 50 ° C.   A method for producing a carbon fiber composite molded article, further comprising a step of molding the carbon fiber composite material obtained by the production method according to any one of claims 17 to 29 into a desired shape.   A method for producing a carbon fiber composite molded article, further comprising a step of crosslinking the carbon fiber composite material obtained by the production method according to any one of claims 17 to 29.   30. The production of a carbon fiber composite molded article, further comprising a step of crosslinking and molding the carbon fiber composite material obtained by the production method according to claim 17 in a molding die having a desired shape. Method.   34. A method for producing a carbon fiber composite glass material, wherein the carbon fiber composite material or the carbon fiber composite molded product obtained by the production method according to claim 17 is powder-molded.   34. The method further comprises a step of casting the carbon fiber composite material or the carbon fiber composite molded article obtained by the production method according to any one of claims 17 to 33 in a molten glass mixed in a mold having a desired shape. A method for producing a carbon fiber composite glass material.   34. A carbon fiber composite glass molded article further comprising the step of infiltrating molten glass into the carbon fiber composite molded article obtained by the manufacturing method according to claim 31 to replace the elastomer with the molten glass. Manufacturing method. A step of arranging a glass block above the carbon fiber composite molded article obtained by the production method according to any one of claims 31 to 33;
Heating and melting the glass lump to obtain molten glass, vaporizing the elastomer in the carbon fiber composite molded article, and infiltrating the molten glass to replace the elastomer;
A method for producing a carbon fiber composite glass molded article, further comprising:

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