JP6576865B2 - Non-combustible carbon fiber composite material - Google Patents

Description

  The present invention relates to a carbon fiber composite material having incombustibility or quasi-incombustibility.

  Carbon fibers are excellent in mechanical performance such as tensile strength and elastic modulus, corrosion resistance to acids and alkalis, and are lightweight. Therefore, it is used in various industrial fields such as automobiles, aircraft, electrical / electronic devices, toys, and home appliances, and is also being applied to buildings. For example, in order to improve the earthquake resistance of a building, a carbon fiber composite material is used as a tensile material such as braces (bars) in the frame, as a wire, and as a reinforcing bar for concrete.

Since the carbon fiber composite material is manufactured by being baked at 1000 ° C. or higher, it is said that it has practical strength up to about 1600 ° C. under non-oxygen, but in air it is said to have oxygen at about 450 ° C. or higher. And disappears as carbon dioxide.
In buildings, the Building Standard Act defines incombustible materials and quasi-incombustible materials. However, as mentioned above, carbon fiber composites disappear at about 450 ° C or higher, so incombustible materials and quasi-incombustible materials It does not have performance as.

  Therefore, various studies have been made to use carbon fiber composites as non-combustible materials. For example, Patent Document 1 mentions the use of a carbon fiber composite material formed by impregnating a carbon fiber with a matrix resin, and an epoxy added with a filler such as a phenol resin, a polyimide resin, or aluminum hydroxide as a matrix resin. The use of an epoxy resin containing a resin or an additive such as a halogen compound or a phosphorus compound is mentioned. These are materials in which the heat resistance of the carbon fiber composite material is improved by using a resin excellent in heat resistance or a resin kneaded with a flame retardant.

JP-A-2005-14449

However, when the present inventors examined, in the rod-shaped carbon fiber composite material, when the heat-resistant resin such as the polyimide resin is used or aluminum hydroxide is added to the epoxy resin as a filler, the carbon fiber composite The material could not be given sufficient durability against combustion.
Therefore, an object of the present invention is to provide a carbon fiber composite material that has excellent non-combustibility and is quasi-incombustible or non-combustible equivalent to non-combustibility based on the Building Standard Law, while being a carbon fiber composite material. is there.

  As a result of intensive studies to solve the above problems, the present inventor has found that the following inventions meet the above-mentioned object, and have reached the present invention.

That is, the present invention relates to the following inventions.
<1> A nonflammable carbon fiber composite material having the core material of any one of (1) to (3) below and a metal coating layer on the outer periphery of the core material.
(1) Core material comprising a core wire including a carbon fiber bundle integrated with a solidifying agent (2) Two or more core wires including a carbon fiber bundle integrated with a solidifying agent are arranged or twisted together Core material composed of strand core wires (3) Two or more core wires including carbon fiber bundles integrated with a solidifying agent are aligned or twisted, and two or more strand core wires are aligned or twisted The core material <2> made of a multi-strand core wire configured together. The metal coating layer is a nonflammable carbon fiber composite material according to the item <1>, which is a metal foil.
<3> The nonflammable carbon fiber composite material according to <2>, wherein the metal coating layer is a metal foil having a multilayer structure.
<4> The metal coating layer according to any one of <1> to <3>, wherein the metal coating layer is a metal coating layer including at least one selected from the group consisting of aluminum, stainless steel, soft copper, titanium, and alloys thereof. Non-combustible carbon fiber composite material.
<5> The metal coating layer according to any one of <2> to <4>, wherein the metal coating layer is a metal coating layer arranged in a spiral shape so as to overlap a tape-shaped metal foil with respect to an axis of the core material. The incombustible carbon fiber composite material described.
<6> The carbon fiber bundle integrated by the solidifying agent has a binding material wound around the carbon fiber bundle and bound, and the carbon fiber bundle and the binding material are both integrated by the solidifying agent. The nonflammable carbon fiber composite material according to any one of <1> to <5>.
<7> The nonflammable carbon according to any one of <1> to <6>, wherein the core wire is a core wire provided with a heat-resistant layer so as to cover an entire outer surface of a carbon fiber bundle integrated with the solidifying agent. Fiber composite material.
<8> The nonflammable carbon fiber according to any one of <1> to <7>, wherein the strand core wire or the multi-strand core wire is further provided with a heat-resistant layer so as to cover the entire outer surface thereof. Composite material.
<9> A building material comprising the noncombustible carbon fiber composite material according to any one of <1> to <8>.

  ADVANTAGE OF THE INVENTION According to this invention, the nonflammable carbon fiber composite material which has the original tensile strength of carbon fiber and was excellent in nonflammability is provided. The incombustible carbon fiber composite material of the present invention can be used for building materials and the like that are required to have strength and incombustibility.

It is a perspective view of the nonflammable carbon fiber composite material concerning Embodiment 1 of the present invention. It is a cross-sectional schematic diagram of the nonflammable carbon fiber composite material of FIG. It is a cross-sectional schematic diagram of the nonflammable carbon fiber composite material which concerns on Embodiment 2 of this invention. It is a perspective view of the core material of the nonflammable carbon fiber composite material of FIG. It is a cross-sectional schematic diagram of the nonflammable carbon fiber composite material which concerns on Embodiment 3 of this invention.

  Hereinafter, embodiments of the non-combustible carbon fiber composite material according to the present invention will be described. However, the present invention is not limited to the following embodiments, and may be arbitrarily changed without departing from the gist of the present invention. Can be implemented. Further, when the expression “to” is used in the present specification, it is used as an expression including numerical values before and after the expression.

[Non-combustible carbon fiber composite]
The present invention provides a non-combustible carbon fiber composite material (hereinafter referred to as “non-combustible carbon fiber composite of the present invention”) having any one of the following core materials (1) to (3) and a metal coating layer on the outer periphery of the core material. Material "or simply" noncombustible carbon fiber composite material ").
(1) Core material comprising a core wire including a carbon fiber bundle integrated with a solidifying agent (2) Two or more core wires including a carbon fiber bundle integrated with a solidifying agent are arranged or twisted together Core material composed of strand core wires (3) Two or more core wires including carbon fiber bundles integrated with a solidifying agent are aligned or twisted, and two or more strand core wires are aligned or twisted Core material consisting of multi-strand core wire configured together

In such a configuration, since any one of the core materials (1) to (3) is coated with a metal having high heat resistance and high heat ray reflectivity, heating of the core material is suppressed. Moreover, since it can suppress discharge | release of the combustible gas which generate | occur | produces from a core material, it is suppressed that the combustible gas which generate | occur | produces from a core material exists in high concentration in the surface vicinity of a nonflammable carbon fiber composite material. Moreover, the permeation | transmission of combustible gas and auxiliary combustion gas to the core material from the outside is suppressed. For this reason, it is estimated that nonflammability is provided to the nonflammable carbon fiber composite material of the present invention.
In addition, since the “core wire including a carbon fiber bundle integrated with a solidifying agent” in the above (1) to (3), carbon fibers are integrated with a solidifying agent, so even if a strong force is applied from the outside, carbon It is possible to suppress the carbon fibers constituting the fiber bundle from being scattered, and to stably exhibit the original tensile strength of the carbon fibers.

  In this specification, “non-combustible” means the performance related to the certification of non-combustible materials based on Article 2-9 of the Building Standard Law or quasi-incombustible materials based on Article 1-5 of the Building Standard Law Enforcement Ordinance. As an evaluation, 4.12. Nonflammability performance test / evaluation method 4.10.2 Exothermic test / evaluation method 4.11 Semi-incombustibility performance test / evaluation method Tests / evaluation according to the exothermic test / evaluation method of 4.11. The evaluation method will be described later in Examples.

  The incombustible carbon fiber composite material of the present invention is long and has a longer length in the axial direction of the incombustible carbon fiber composite material than the diameter (diameter) of the cross section perpendicular to the axial direction of the incombustible carbon fiber composite material. It has a long rod-like structure. When the cross section perpendicular to the axial direction of the incombustible carbon fiber composite material is not a circle, the major axis is taken as the cross section.

The length of the incombustible carbon fiber composite material of the present invention is not particularly limited, but is preferably 3 cm or more. In the present specification, “the length of the non-combustible carbon fiber composite material” refers to the length in the axial direction of the non-combustible carbon fiber composite material. Although there is no upper limit in particular, it is about 100 m in consideration of storage of the non-combustible carbon fiber composite material. Moreover, if it winds around a drum and stores, an upper limit may be 100 m or more, and it is about 10000 m although it depends on the size of the drum and the diameter of the non-combustible carbon fiber composite material.
Moreover, although the diameter of a nonflammable carbon fiber composite material is suitably changed according to the kind and use purpose of a core material, it is about 0.5 mm-100 mm, 1-50 mm is preferable and it is 2-10 mm. More preferred.

  Hereinafter, the core material and the metal coating layer, which are constituent elements of the incombustible carbon fiber composite material of the present invention, will be described in detail.

(Core material)
In the present invention, the core material is a long carbon fiber material including a carbon fiber bundle that occupies most of the incombustible carbon fiber composite material of the present invention, and is any one of the above (1) to (3). .

In the present specification, “(1) a core material including a carbon fiber bundle integrated with a solidifying agent” as a constituent element of “(1) a core material including a core fiber including a carbon fiber bundle integrated with a solidifying agent” is referred to as “core wire. (A) "may be described.
In addition, “(2) by the solidifying agent” which is a constituent element of “(2) a core material composed of a strand core wire formed by aligning or twisting two or more core wires including a carbon fiber bundle integrated by a solidifying agent” The core wire including the integrated carbon fiber bundle may be described as “core wire (B)”.
Also, "(3) Two or more core wires including carbon fiber bundles integrated with a solidifying agent are aligned or twisted, and two or more strand core wires are aligned or twisted. The core wire including the carbon fiber bundle integrated with the solidifying agent, which is a constituent element of the “core material composed of the multi-strand core wire”, may be referred to as “core wire (C)”.

  Hereinafter, “core wire (A)”, “core wire (B)”, and “core wire (C)” are simply referred to as “core wire”.

The “strand core wire” is a core wire having a strand structure, which is configured by using “a core wire including a carbon fiber bundle integrated by a solidifying agent” as a strand. “Strand structure” means a structure in which two to several tens of strands having the same diameter or different diameters are arranged in a single layer or multiple layers, or two to several tens of strands having the same diameter or different diameters. It means a structure in which wires are twisted into a single layer or multiple layers.
Further, the “multi-strand core wire” is a core wire having a multi-strand structure that is configured by using a strand core wire as a strand. “Multi-strand structure” means a structure in which strands having two to several tens of strand structures of the same diameter or different diameters are arranged in a single layer or multiple layers, or two of the same diameter or different diameters to It means a structure in which strands having several tens of strand structures are twisted into a single layer or multiple layers.

(Core wire)
In the present invention, the core wires (core wire (A), core wire (B), core wire (C)) include “carbon fiber bundles integrated with a solidifying agent”. The core wire may be composed of only a carbon fiber bundle integrated with a solidifying agent. As described later, the configuration using a restraining material or the outer periphery of the carbon fiber bundle integrated with the solidifying agent is covered with a heat-resistant layer. It may be a configuration.

The core wire preferably has a diameter of 0.5 to 25 mm, more preferably 1 to 10 mm in diameter, and still more preferably 1 to 5 mm in diameter. When the core wire has a diameter of 0.5 to 25 mm, the core material and the non-combustible carbon fiber composite material can be easily wound around the drum, and the flexibility such as following an arbitrary shape can be improved. Nonflammability can be maintained while imparting properties.
The diameter of the core wire is the diameter of the cross section cut perpendicular to the axial direction of the carbon fiber bundle integrated with the solidifying agent, and when the cross section cut perpendicular to the axial direction of the carbon fiber bundle is not a circle, The diameter of the carbon fiber bundle and the application amount of the solidifying agent are selected so as to be the major axis of the cross section and to be the target diameter. In addition, when the core wire has a configuration using a constraining material as will be described later, or when the outer periphery of a carbon fiber bundle integrated with a solidifying agent is covered with a heat-resistant layer, Including thickness.

  Moreover, the cross section when cut perpendicularly to the axial direction of the core wire may be arbitrary, such as a circular shape or a flat shape, but a circular shape is preferable. The strength of the obtained non-combustible carbon fiber composite material is stabilized, and a stable structure can be obtained even when the strands of carbon fiber bundles described below are covered with a restraining material are used as strands of the strand core wire. Can do.

The “carbon fiber bundle integrated with a solidifying agent” constituting the core wire is formed by integrating a carbon fiber bundle formed by bundling carbon fibers with a solidifying agent.
A carbon fiber bundle is a bundle of carbon fibers (usually thousands to hundreds of thousands, or millions), and the cross section when cut perpendicular to the axial direction is circular. Any shape such as a flat shape may be used, but a circular shape is preferred. The bundle of carbon fibers used in the non-combustible carbon fiber composite material is preferably integrated by a solidifying agent in a state where a predetermined number of twists are applied. The number of twists in the bundle of carbon fibers takes into account the bending stress resistance of the resulting non-combustible carbon fiber composite material, the anti-breaking property of the carbon fiber bundles, and the strength against twisting of the carbon fiber bundles (the carbon fiber yarn cannot be cut by twisting). To be determined.
The twist number of the carbon fiber bundle is 0 to 100 times / m, preferably 2 to 50 times / m, more preferably 5 to 40 times / m, and further preferably 10 to 30 times / m.

As the carbon fiber of this embodiment, any of polyacrylonitrile (PAN) -based and pitch-based carbon fibers can be used. Among these, PAN-based carbon fiber yarn is preferable from the viewpoint of the balance between the strength and the elastic modulus of the obtained noncombustible carbon fiber composite material.
Moreover, the carbon fiber bundle which bundled this carbon fiber has 3000 carbon fibers (3K), 6000 (6K), 12000 (12K), 24000 (24K), 40000 (40K), 60000 (60K). ) Or the like, and carbon fiber bundles supplied from a carbon fiber maker bundled in one or more (two or more) can be used depending on the required strength. The number of carbon fiber bundles in the case of bundling a plurality of carbon fiber bundles obtained by bundling carbon fibers is not particularly limited and is appropriately determined depending on the intended use, but is usually 100 or less.

As the solidifying agent, either a thermoplastic resin or a thermosetting resin can be used. Further, a solidifying agent having high affinity with carbon fiber is preferable. Since it is not necessary to perform refrigerated storage, it is easy to store and recyclable, and in particular, it can be made variable by heating. Therefore, a thermoplastic resin is preferably used as a solidifying agent.
Specific examples of suitable solidifying agents include polyetheretherketone (PEEK), polypropylene, polyethylene, polystyrene, polyamide (nylon 6, nylon 66, nylon 12, nylon 42, etc.), ABS resin, acrylic resin, vinyl chloride resin, Vinylidene chloride resin, polyphenylene oxide, polybutylene terephthalate, polyethylene terephthalate, polysulfone, polyethersulfone, polyetherimide, polyarylate, epoxy resin, urethane resin, polyimide resin, phenol resin, silicone resin, polycarbonate resin, resorcinol resin, etc. Although it is mentioned, it is not restricted to this.

  Among these, from the viewpoint of durability against acids and alkalis, polyether ether ketone (PEEK), acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyethylene resin, epoxy resin, urethane resin, polycarbonate resin, resorcinol resin are preferable. In particular, an epoxy resin excellent in impact resistance is suitable. Moreover, if it is a thermoplastic epoxy resin, it can melt | dissolve in a ketone solvent and can separate a material and can recycle. Moreover, a polyimide resin and a silicone resin are preferable from a heat resistant viewpoint.

In particular, among thermoplastic epoxy resins, a polymerizable thermoplastic epoxy resin that polymerizes is preferable, and a polymerizable thermoplastic epoxy resin that polymerizes in a straight chain is particularly preferable.
If the carbon fiber bundle is twisted or the carbon fiber bundle is covered with a restraining material as will be described later, it is difficult to impregnate the resin into the carbon fiber bundle. .
On the other hand, the polymerization-type thermoplastic epoxy resin can be easily adjusted in viscosity because the thermoplastic epoxy resin before polymerization can be diluted with an organic solvent.
For this reason, by using a low-viscosity resin solution diluted with an organic solvent, the inside of the carbon fiber bundle that is twisted (even if it is covered with a restraint material, the inner periphery of the restraint material is Can be impregnated with a thermoplastic epoxy resin prior to polymerization. After impregnating the thermoplastic epoxy resin before polymerization into the inside of the carbon fiber bundle, the carbon fiber bundle and the restraining material were integrated with the thermoplastic epoxy resin by polymerizing the thermoplastic epoxy resin of the polymerization type, A core wire with excellent strength can be obtained.

  In addition, a general thermoplastic resin used to impart fluidity by heating and melting is difficult to adjust the viscosity, and the crystal arrangement is changed by heating or melting because it is generally a crystalline resin, Although the properties such as strength of the original resin may be altered, the polymerizable thermoplastic epoxy resin is amorphous before and after polymerization, so it can be melted and deformed by heating. The risk of alteration is small.

  The method of applying the above resin (solidifying agent) to the carbon fiber bundle may be a spray coating method or a method of coating the carbon fiber with a brush, but from the viewpoint of productivity, a dip-nip method or a resin ( After dipping into the (solidifying agent) solution, a method of removing excess resin through a die and adjusting the cross-sectional shape of the carbon fiber bundle in the axial direction to cure the resin (solidifying agent) is preferable.

  Further, in the present invention, the carbon fiber bundle integrated with the solidifying agent, which is a constituent element of the core wire, has a binding material that is wound around the carbon fiber bundle and bound, and the carbon fiber bundle and the binding material are It is preferable that both are integrated by a solidifying agent. That is, the carbon fiber bundle in which the carbon fiber bundle and the restraining material are integrated together by the solidifying agent is not only the carbon fiber bundle constituting the core wire (A) but also the carbon fiber bundle constituting the core wire (B) or the core wire. As the carbon fiber bundle constituting (C), it is preferable to use a carbon fiber bundle and a restraint material integrated together by a solidifying agent. By adopting such a configuration, the carbon fibers of the carbon fiber bundle are further suppressed from being twisted, entangled, or loosened by a strong force from the outside, and during the manufacturing process of the incombustible carbon fiber composite material Since the core material composed of such a carbon fiber bundle is protected from breakage of the metal coating layer, nonflammability is improved, and the original tension of the carbon fiber bundle is improved. The strength can be maintained.

  The restraining material can bind the carbon fiber bundle so that the carbon fibers are not separated from the peripheral surface, and can stabilize the shape of the core wire.

  For example, a braided constraining material can be formed by winding a fiber serving as a constraining material around the outer circumference of a carbon fiber bundle and assembling a tubular braid (round punching). By binding the binding material into a braided shape, the carbon fiber bundle can be bundled, and the resulting core wire, the core material formed thereby, and the shape of the non-combustible carbon fiber composite material can be further stabilized. Functions as a protective layer for protecting the carbon fibers constituting the inner carbon fiber bundle.

Therefore, when using a non-combustible carbon fiber composite material having a core wire with such a configuration as a tensile material, brace material, reinforcing reinforcing material for concrete, etc., it exhibits stable strength, good appearance quality, gravel, etc. Even if it comes into contact with sharps, it can be prevented from being disconnected. Moreover, the disconnection by the external force in the manufacturing process of a nonflammable carbon fiber composite material can be prevented.
In addition, after dipping the carbon fiber bundle restrained by the restraint material into the resin (solidifying agent) solution, when the excess resin is squeezed by handling with a die, tension is applied in the length direction of the fiber. Then, the eyes do not open like a knitted fabric, but the diameter of the braid is reduced with the eyes closed. Therefore, it is possible to improve the adhesion between the restraining material and the carbon fiber bundle while suppressing the exposure of the inner carbon fiber bundle, which is preferable from the viewpoint of the strength of the obtained core wire and the nonflammable carbon fiber composite material.

In addition, the restraint material should just be able to bind so that the carbon fiber which comprises a carbon fiber bundle may not become disjoint, and arrangement | positioning of a restraint material is not limited to braid shape. Further, it is not necessary to completely cover the surface of the carbon fiber bundle with the restraining material, and a part of the surface of the carbon fiber bundle may not be covered.
As an example of arrangement by other restraint materials, a single restraint material is spirally wound to bind a carbon fiber bundle, or a fiber that serves as a restraint material is wound around the carbon fiber bundle to form a coarse tube Constraints in which carbon fiber bundles are bundled with a knitted string-like restraint material knitted in a circular shape, or fibers listed as restraint materials are arranged at predetermined intervals as a restraint material for binding carbon fiber bundles The form which binds a carbon fiber bundle with a material may be sufficient.
On the other hand, from the viewpoint of protecting the carbon fiber bundle, stabilizing the strength by stabilizing the shape of the core wire, and appearance, it is preferable to form a restraint material in the form of braid to cover the entire surface of the carbon fiber bundle.

  The binding material is preferably a flexible material, such as polyamide (nylon, etc.), vinylon, polyacryl, polypropylene, vinyl chloride, aramid, cellulose, polyamide, polyester, polyacetal, etc., regenerated fiber such as rayon, acetate, etc. Semi-synthetic fibers, natural fibers such as silk, wool, hemp and cotton can be used. Moreover, the fiber excellent in heat stability is preferable, a glass fiber and a basalt fiber are preferable, and especially a glass fiber is preferable. By using fibers with excellent thermal stability, such as glass fibers, when heated, they have excellent nonflammability and suppress the occurrence of misalignment between the carbon fiber bundle and the restraint material, providing stable tensile strength and nonflammability. Sex can be expressed.

  In order to bind the carbon fiber bundles more firmly, it is preferable to impregnate the carbon fiber bundles bundled with the restraining material with a solidifying agent and harden the carbon fiber bundles together with the restraining material. By doing so, a carbon fiber bundle and a restraint material can be firmly integrated.

  Moreover, in this invention, a coating layer can be provided so that the whole outer periphery of the carbon fiber bundle integrated with the solidifying agent may be covered, and it is preferable that the heat resistant layer which has heat resistance is provided as a coating layer. That is, the heat resistant layer is provided so as to cover the entire outer surface of the carbon fiber bundle constituting the core wire (A), the carbon fiber bundle constituting the core wire (B), or the carbon fiber bundle constituting the core wire (C). Preferably it is.

As a heat-resistant layer that can be provided so as to cover the entire outer surface of the carbon fiber bundle integrated by the solidifying agent, from the viewpoint of improving nonflammability, a heat-resistant resin layer using polyimide resin or silicone resin, silica Examples thereof include particles, resin layers containing aluminum-based compound particles such as aluminum, aluminum oxide, and aluminum hydroxide, and phosphorus-based flame retardants. The resin layer can be used with either a thermoplastic resin or a thermosetting resin, but when a thermoplastic resin is used as a solidifying agent, the resin used for the heat-resistant layer is also preferably a thermoplastic resin. . By combining with such a resin layer, generation of combustible gas and contact between carbon fiber and oxygen are less likely to occur in a high temperature region.
Moreover, the heat-resistant layer does not need to be one layer, and two or more layers may be laminated, and can be appropriately designed as long as the object of the present invention can be achieved.
Moreover, you may form a heat resistant layer using the cylindrical body which consists of fiber materials.

  The strand core wire and the multi-strand core wire will be described later in Embodiment 2 and Embodiment 3.

(Metal coating layer)
A metal coating layer is a layer formed in the outer periphery of a core material with a metal, and plays the role which makes combustion of a core material difficult to occur.
The metal coating layer only needs to cover the outer periphery of the core material to such an extent that the obtained non-combustible carbon fiber composite material can have non-combustibility, and the metal coating layer is 90% or more of the entire surface around the core material. Is preferably coated, more preferably 95% or more is coated, and even more preferably the whole is coated.

  The metal coating layer may be a single layer structure or a multilayer structure, but is preferably a multilayer structure of two or more layers. In particular, the entire outer peripheral surface of the core material is formed in a multilayer structure, Reflectivity is likely to increase, and the presence of high concentrations of flammable gas generated from the core material near the surface of the non-combustible carbon fiber composite material is further suppressed. Gas permeation may be further suppressed, and the incombustibility of the obtained incombustible carbon fiber composite material may be further improved. When the metal coating layer has a multilayer structure, each layer may be formed of different metals and alloys thereof.

  The total thickness of the metal coating layer is appropriately designed depending on the configuration of the core material to be coated, the size of the diameter, etc., but is preferably 1 μm to 2000 μm, more preferably 5 μm or more from the viewpoint of nonflammability. Is preferably 10 μm or more. From the viewpoint of stably forming the coating layer, the thickness is preferably 5 μm to 1000 μm, more preferably 10 μm to 500 μm.

  Examples of the metal coating layer include a coating layer formed of a metal foil, a coating layer formed using a molten metal, a coating layer formed of a metal film formed by a plating method, and the like. However, it is preferable that the coating layer is formed of a metal foil.

  By using the metal foil, even if the nonflammable carbon fiber composite material is bent or deformed due to the flexibility of the metal foil, the core wire is suppressed from being exposed, and the nonflammability can be maintained. Moreover, nonflammability can be easily given to a carbon fiber composite material by using metal foil. Further, by using a flexible metal foil, it is easy to form a metal coating layer on the core material without a gap in accordance with the shape even when a core wire using a constraining material is used as the core material.

  When the metal coating layer is formed of a metal foil, the metal foil is wound in a direction perpendicular to the axis of the core, or the tape-shaped metal foil is spirally formed (also referred to as a spiral) around the core of the core. ) And the like wrapped around.

  The metal foil may be coated so that the metal foils overlap each other so that the core material to be coated is not exposed. In such a case, when gas is generated from the core material or the like, the gas is released to the outside through a slight gap between the overlapped metal foils within a range that does not adversely affect the nonflammability, and the gas generated by the metal coating layer It is possible to prevent rupture. For this reason, it becomes possible to further maintain the nonflammability of the nonflammable carbon fiber composite material. This effect can be expected when the metal foil is in the form of a tape.

  When a tape-shaped metal foil is used, the formed metal coating layer is a spirally-arranged tape-shaped metal foil with respect to the axis of the core material, in particular, with respect to the axis of the core material, It is preferable that they are arranged in a spiral so as to overlap each other.

  The “tape-shaped metal foil” is a metal foil that can be wound.

  If the tape-shaped metal foil is spirally wound around the axis of the core material, that is, if it is arranged spirally with respect to the axis of the core material, Even if it exists, a metal coating layer can be easily formed in the outer periphery. In addition, a tape-shaped metal foil is spirally wound around the core material so as to overlap the axis of the core material, that is, spirally arranged with respect to the axis of the core material. If so, the larger the overlapping width of the overlapping parts in the width direction of the metal foil, the more the non-flammable carbon fiber composite material is bent and deformed, which suppresses the core material from being exposed, and the non-flammability is reduced. It is preferable because it can be maintained, and it is easy to form a multilayer structure with a metal foil on the outer periphery of the core material.

In the present invention, the metal coating layer may be a metal foil having a multilayer structure. The “multilayer structure using metal foil” refers to a structure in which the outer periphery of the core material is covered with at least two metal foil layers.
The metal foil having a multilayer structure may be partial, but the entire outer peripheral surface of the core material is preferably a metal foil having a multilayer structure. Moreover, the number of layers of the metal foil to be coated may be partially different as long as it is at least two layers or more, and there are a portion coated with two metal foil layers and a portion coated with three metal foil layers. May be.

  When the metal coating layer is made of a metal foil having a multilayer structure of two or more layers, the amount of heat ray reflection increases, and when gas is generated from the core material, the gas can be released from the inside by a minute amount. Combustible gas can be released while suppressing the impact on nonflammability, and the amount of combustible gas on the surface is further suppressed. Further, inflow of oxygen from the outside can be suppressed. Moreover, heat insulation improves with the air which exists between metal foil and metal foil (at the level which does not have a bad influence on carbon fiber), and can suppress the heating of a core material. Furthermore, it is possible to further prevent the metal foil from being broken and the core material from being exposed by the force from the outside and inside. For this reason, the nonflammability of a carbon fiber composite material may improve more.

  The method of forming a multilayer structure with metal foil is not particularly limited. For example, when a tape-shaped metal foil is used and the core material is wound around the axis of the core material in a spiral shape, the core material is covered. The first layer and the second layer may be wound in different directions such that the first layer is wound clockwise and the second layer is wound counterclockwise. Further, it may be wound two or more times in the same direction. Moreover, the width of the overlap of the tape-shaped metal foil when winding may be set to be 1/2 or more of the width of the tape-shaped metal foil.

  Since the metal coating layer can easily form a metal coating layer having a multilayer structure over the entire core material, the width of the tape-shaped metal foil is determined with respect to the axis of the core material. It is good that it is spirally wound so that 1/2 or more of the two overlap.

  Alternatively, a sheet-like metal foil may be used, the metal foil may be wound twice or more in the direction perpendicular to the axis of the core material, and the core material may be covered in multiple layers with the metal foil.

  In addition, the metal foil is wound around the axis of the core material in a spiral manner, and then the metal foil is wound in a direction perpendicular to the axis of the core material. It may be what.

In addition, the thickness of the metal coating layer formed of the metal foil is appropriately designed within a range that does not impair the original performance of the carbon fiber depending on the configuration of the core material to be coated, the size of the diameter, and the like, but 1 μm to 2000 μm. The metal coating layer may be formed of one metal foil layer or a multilayer structure of two or more layers so that the thickness of the target metal coating layer is obtained. Preferably it is. Moreover, when forming the multilayer structure of two or more layers with metal foil, the thickness of the single layer formed with metal foil (thickness of the metal foil) is preferably 1 μm to 500 μm, and 5 μm or more from the viewpoint of nonflammability. More preferred. From the viewpoint of stably forming the metal coating layer, the thickness is preferably 8 μm to 150 μm, more preferably 10 to 75 μm, and still more preferably 10 to 30 μm.
The metal foil may have a pressure-sensitive adhesive on the surface, but the pressure-sensitive adhesive preferably has heat resistance, for example, a silicone-based pressure-sensitive adhesive.

In addition, the metal forming the metal coating layer of the present invention can be appropriately selected within the range in which the object of the present invention can be achieved. Aluminum, copper, iron, tin, zinc, stainless steel, titanium, and alloys thereof Etc. The metal coating layer may be composed of two or more metals, but preferably includes at least one selected from the group consisting of aluminum, stainless steel, copper, titanium, and alloys thereof. It is more preferable that any one of aluminum, stainless steel, and soft copper is included from the viewpoint of easiness, and it is more preferable that the metal coating layer is composed of any one of aluminum, stainless steel, and soft copper, and it is aluminum. Is most preferred.
If it is aluminum, the heat of the core material is suppressed due to its high heat reflectivity and thermal conductivity, and the nonflammability improvement effect is excellent, and it is easy to coat the core material with aluminum foil (aluminum foil) This is also preferable from the viewpoint of workability.

  Moreover, you may provide another coating layer on the metal coating layer of the outer periphery of a core material further for protection of a metal coating layer, provision of designability, and improvement of nonflammability performance. The coating layer is preferably made of non-flammable materials, such as glass fiber, gypsum, silica, or other inorganic compounds, polyimide resins, silicone resins, or a combination of inorganic compounds and organic compounds, such as silica. Examples thereof include resins containing particles, aluminum-based compound particles, and phosphorus-based flame retardants. When a thermoplastic resin is used as the solidifying agent, the other coating layer is preferably a coating layer that can be deformed when heated, and when the thermoplastic resin is used as a resin for the coating layer. preferable. Moreover, you may have a structure which has flexibility like a braid. By combining with such a resin layer, generation of combustible gas and auxiliary combustible gas, and contact between carbon fiber and oxygen are less likely to occur in a high temperature region.

  Hereinafter, the nonflammable carbon fiber composite material of the present invention will be described in more detail with reference to (Embodiment 1) to (Embodiment 3).

(Embodiment 1)
With reference to FIG.1 and FIG.2, the nonflammable carbon fiber composite material 100 which has the core material 10a and the metal coating layer 20a is demonstrated. In addition, Embodiment 1 is “(1) a non-combustible carbon fiber composite material having a core material including a core wire including a carbon fiber bundle integrated with a solidifying agent, and a metal coating layer on the outer periphery of the core material”. Corresponds to the aspect.

  The metal coating layer 20a was formed by winding a tape-shaped aluminum foil having a thickness of 10 μm to 100 μm and a width of 10 mm to 100 mm in a spiral shape so as to cover the entire outer periphery of the core material 10a so that the aluminum foils overlap each other. Is. The metal coating layer 20a has a multilayer structure of two or more layers, and the total thickness of the metal coating layer 20a is 10 μm to 500 μm. The metal coating layer 20a may have a single layer structure. Further, a structure in which the number of layers is partially different can be taken.

  By using the metal foil, the metal coating layer 20a can be easily and inexpensively formed, and the nonflammability of the nonflammable carbon fiber composite material can be improved. In addition, due to the stretchability caused by winding the metal foil in a spiral shape, the core material 10a is prevented from being exposed even if the nonflammable carbon fiber composite material is bent or deformed, and nonflammability is maintained. Can do.

  The core material 10a is obtained by applying a predetermined number of twists to the carbon fiber bundle 5 formed by bundling the carbon fibers 4, constraining the carbon fiber bundle 5 with a restraining material (not shown), and applying a solidifying agent thereto. 5 and the restraint material are comprised from the core wire 1 integrated with the solidifying agent.

  Further, the restraining material is formed in a braided shape by winding a fiber serving as the restraining material around the outer circumference of the carbon fiber bundle 5 to form a tubular braid (round punching). By making the restraining material into a braided shape, the shapes of the core material 10a and the non-combustible carbon fiber composite material 100 can be further stabilized.

  As described above, the core wire 1 is provided with a heat-resistant layer (a cylindrical body or a resin layer made of a fiber material) so as to cover the entire outer surface of the carbon fiber bundle integrated with the solidifying agent. Also good.

  Further, the non-combustible carbon fiber composite material 100 may be used as a strand structure having a strand structure or a multi-strand structure having a multi-strand structure, and the outer periphery of the strand structure or the multi-strand structure is coated with metal. A layer may be provided. By having such a configuration, the constructed strand structure is composed of the non-combustible carbon fiber composite material having the above-mentioned properties, so while maintaining the performance of the above-described non-combustible carbon fiber composite material of the present invention, Furthermore, it is excellent in nonflammability.

(Embodiment 2)
FIG. 3 shows a non-combustible carbon fiber composite material 110 having a core material 10b and a metal coating layer 20b. In addition, Embodiment 2 is "(2) Core material which consists of a strand core wire comprised by aligning or twisting two or more core wires including the carbon fiber bundle integrated by the solidifying agent, and the said core material. This corresponds to the embodiment of the “non-combustible carbon fiber composite material having a metal coating layer on the outer periphery”.

  The metal coating layer 20b is the same as the configuration of the metal coating layer 20a of Embodiment 1 described above, and the configuration of the metal coating layer 20b can be appropriately designed as long as the object of the present invention is not impaired.

  FIG. 4 is a perspective view of the core material 10b before forming the metal coating layer. The core material 10b includes seven core wires 1 of the first embodiment, and includes a strand core wire 2 having a strand structure in which one core wire 1 disposed at the center is surrounded by the other six core wires 1.

  The strand core wire 2 according to Embodiment 2 has a strand structure in which the core wire 1 serving as the core and the other six core wires 1 surrounding the core wire serving as the core are twisted together, thereby using a resin. Even if they are not integrated, they can be prevented and integrated. For this reason, the metal coating layer 20b is less likely to be scattered during the formation, and the metal coating layer 20b is easily formed. Moreover, the nonflammable carbon obtained by using the core material 10b comprised by the said strand core wire 2 by using the strand core wire 2 which has the original tensile strength of carbon fiber, and is excellent in durability with respect to a bending stress. The fiber composite material 110 can impart incombustibility while maintaining excellent tensile strength even when it is used after being subjected to bending stress applied to the drum and then stretched or used in a place where bending stress is applied. it can.

  The strand core wire may have a structure in which a plurality of the above-described core wires are aligned, but a strand core having a structure in which a plurality of the core wires are twisted together is preferable.

  Moreover, although the core wire 1 was illustrated as a core wire which comprises the strand core wire 2, it is not limited to this, What is according to the structure of the core wire of this invention may be used, and a heat-resistant layer is formed around the core wire 1 As a core wire, a core wire without a constraining material, or a core wire without a constraining material formed with a heat-resistant layer around it can be used. Moreover, in the strand core wire 2 in this embodiment, although the core wire which comprises the strand core wire 2 is the same core wire, as long as the core wire which satisfy | fills the requirements of the core wire of this invention, you may use a different core wire combining. .

Also, as the direction to form the twist,
Carbon fiber bundle × strand core wire = S direction × Z direction, S direction × S direction, Z direction × Z direction, Z direction × S direction are all possible.

  The number of twists of the strand core wire 2 is selected from 1.1 to 50 times / m depending on the purpose. When the number of twists is too small, it becomes easy to break apart in 110 units of the non-combustible carbon fiber composite material. On the other hand, if the number of twists is too large, the tensile strength may decrease. When the number of core wires is 7 to 37, 1.5 to 20 times / m is preferable. More preferably, it is 2 to 10 times / m.

  In addition, although the core wire 1 and the other core wire 1 are twisted together so that the strand core wire 2 of this embodiment may surround the one core wire 1, as a structure of a strand structure, required number (for example, , 2 to 50) core wires 1 may be bundled, and the bundled core wires 1 may be twisted.

The number of the core wires 1 constituting the strand core wire 2 is seven, but is not limited to this, and is appropriately determined in consideration of the intended performance (particularly tensile strength) and application, and is not particularly limited. Usually, there are 2-50. The number is preferably 7 to 37.
For example, when a bundle of 24,000 carbon fibers (24k) is used as a carbon fiber bundle, the number of core wires constituting the strand structure is about 2 to 50, which is suitable for uses such as braces. It is.

  When the diameter of the strand core wire 2 is 2 to 100 mm (more preferably 4 to 50 mm), the non-combustible carbon fiber composite material 110 and the strand core wire 2 are easily wound around a drum, and follow an arbitrary shape. The nonflammable carbon fiber composite material 110 having flexibility and nonflammability can be obtained.

  Moreover, the strand core wire 2 may be further provided with a coating layer so as to cover the entire outer periphery. For example, the strand core wire 2 may be configured such that a heat-resistant layer is further provided so as to cover the entire outer periphery. By adopting such a configuration, nonflammability tends to be further improved. The heat resistant layer can be formed in the same manner as the heat resistant layer on the outer periphery of the core wire described above.

  In addition, when the strand core wire 2 has a strand structure in which a plurality of core wires 1 are aligned, the non-combustible carbon fiber composite material 120 is formed by, for example, using a restraining material or a solidifying agent after aligning a plurality of core wires 1. After bundling, it can be obtained by winding a tape-shaped metal foil.

(Embodiment 3)
FIG. 5 shows a non-combustible carbon fiber composite material 120 having a core material 10c and a metal coating layer 20c. In addition, Embodiment 3 is "(3) Two or more core wires including a carbon fiber bundle integrated with a solidifying agent, or two or more strand core wires formed by twisting or aligning, or This corresponds to the aspect of “a non-combustible carbon fiber composite material having a core material composed of a multi-strand core wire formed by twisting and a metal coating layer on the outer periphery of the core material”.

  The metal coating layer 20c is the same as the configuration of the metal coating layer 20a of Embodiment 1 described above, and the configuration of the metal coating layer 20c can be appropriately designed as long as the object of the present invention is not impaired.

The core material 10 c is composed of a multi-strand core wire 3.
The multi-strand core wire 3 includes seven strand core wires 2 of the second embodiment, and has a multi-strand structure in which one strand core wire 2 disposed at the center is surrounded by the other six strand core wires 2. .

  In addition, in the multi-strand core wire 3, although the strand core wire 2 is used as the component, it is not limited to this, As long as it applies to the strand core wire of this invention, all can be used.

  The number of strand core wires 2 constituting the multi-strand core wire 3 is seven, but is not limited thereto, and is appropriately determined in consideration of the intended performance (particularly tensile strength) and application, and usually 2 to 40 strands. It is. If the number exceeds 40, it may be difficult to twist at a predetermined pitch, so the number is preferably 7 to 37.

The number of twists of the multi-strand core wire 3 is appropriately determined in consideration of intended performance (particularly tensile strength) and application.
The number of twists of the multi-strand core wire 3 is preferably 0.3 to 30 times / m, and when the number of strand core wires 2 is 7 to 37, 0.5 to 15 times / m is preferable.

  When the diameter of the multi-strand core wire 3 is 4 to 200 mm, the non-combustible carbon fiber composite material 120 and the multi-strand core wire 3 can be easily wound around a drum, and can improve flexibility such as following an arbitrary shape. It is possible to obtain a nonflammable carbon fiber composite 120 having flexibility and nonflammability.

  Further, the multi-strand core wire 3 may be further provided with a coating layer so as to cover the entire outer periphery. For example, the multi-strand core wire 3 may be configured such that a heat-resistant layer is further provided so as to cover the entire outer periphery. By adopting such a configuration, nonflammability tends to be further improved. The heat resistant layer can be formed in the same manner as the heat resistant layer on the outer periphery of the core wire described above.

[Building materials]
The present invention also relates to a building material containing the above-described non-combustible carbon fiber composite (hereinafter sometimes referred to as “building material of the present invention”).

Since the non-combustible carbon fiber composite material of the present invention has excellent non-combustible performance, the non-combustible carbon fiber composite material exhibits excellent non-flammability even when used in buildings, and has excellent strength by using carbon fiber as a core wire. have. For this reason, the nonflammable carbon fiber composite material of the present invention can be suitably used as a building material.
Furthermore, in the case of using a thermoplastic resin as a solidifying agent, the incombustible carbon fiber composite material can be used not only in a linear shape or an arch shape, but also in an arbitrary shape, so that it has excellent incombustibility and strength. It can be used as a building material.

  For example, since the building material of the present invention includes the non-combustible carbon fiber composite material of the present invention that has excellent strength and non-combustibility derived from carbon fiber and is lightweight, it is a building, bridge such as a steel structure, reinforced concrete, or wooden structure. It can preferably be used as a brace material or a reinforcing material (including a replacement for a reinforcing metal fitting) used for a bridge or the like. In addition, even if it is thin, it has sufficient strength, so lighting, furniture such as tables, wires that hang stairs, furniture such as partitions, interiors such as tables, chairs and handrails, fences, fences, Supports for ivy and the like used for green curtains, exteriors such as nets can be used for various things, and it is also possible to manufacture buildings with excellent design. It is also suitable as an alternative to chains used for mooring offshore wind power generation facilities and ships that are prone to salt damage. Further, since it is difficult to bend even when bending stress is applied, it can be preferably used by being wound around a drum and used as a long one, or at a place where bending stress is applied.

  The building material of the present invention may be combined with the noncombustible carbon fiber composite material of the present invention and an arbitrary member to form a composite structure member. As an example of a suitable composite structural member, at least one end of the non-combustible carbon fiber composite material is inserted into the body of the fixing jig, and the end of the non-combustible carbon fiber composite material and the body of the fixing jig By adhering and fixing, a composite structure member formed by integrating the fixing jig with the fixing jig can be used.

  Moreover, even if it uses as other materials, such as civil engineering materials other than a building, machine tool material, robot material, and transport equipment material, it has the outstanding intensity | strength which is hard to burn.

  As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above can also be employ | adopted within the scope of the technical idea of this invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is changed.

  First, a core wire or a strand core wire was manufactured.

(Production Example 1): Production of core wire (1A)
Three bundles of 24K carbon fiber bundles (PAN-based carbon fiber, manufactured by Toray Industries, Inc., T700SC), one twisted 30 times / m in the S direction, are used as carbon fiber bundles, and glass fiber is used as a restraining material. , And the entire surface around the carbon fiber bundle was constrained with braided glass fibers by using a string making machine (24 hammering machine) with 8 stone punches.

Next, the carbon fiber bundle restrained with glass fiber,
Polymerization type thermoplastic epoxy resin (DENATITE XNR6850V, solid content 85% by mass, manufactured by Nagase ChemteX Corporation), 100 parts by mass,
Curing agent (DENATEITE XNH6850V, solid content 30% by mass,
Manufactured by Nagase ChemteX Corporation) 6.5 parts by mass,
Dipping into a solution (viscosity of 80 mPa · s) consisting of 10 parts of methyl ethyl ketone (MEK), passing through a die to remove excess solution, and rounding the cross-sectional shape when cut perpendicular to the axis of the carbon fiber bundle A solidifying agent was applied to the aligned and restrained carbon fiber bundle. Thereafter, the core wire in which the thermoplastic thermoplastic resin of the polymerization type is polymerized by performing heat treatment (150 ° C., 20 minutes), and the carbon fiber bundle and the binding material are integrated with the thermoplastic epoxy resin (solidifying agent). (1A) was obtained.

The obtained core wire (1A) had a circular cross section and a diameter of 3 mm (measured with calipers).
When the core wire (1A) was wound on a drum having a diameter of 100 cm at a room temperature of 3000 m, it could be smoothly wound without breaking.

(Manufacture example 2): Manufacture of a core wire (1B) It carried out similarly to manufacture example 1, and obtained the core wire (1A).
Next, the core wire (1A) is dipped into a silicone resin emulsion (viscosity 6000 mPa · s), passed through a die to remove excess solution, and a cross section when cut in a direction perpendicular to the axis of the core wire (1A). The shape was adjusted to a circle, and a silicone resin was applied to the surface of the core wire (1A). Then, the heat treatment (150 degreeC, 20 minutes) was performed, and the core wire (1B) which coat | covered the core wire (1A) with the silicone resin was obtained.

The obtained core wire (1B) had a circular cross section and a diameter of 3 mm (measured with calipers).
When the core wire (1B) was wound 3000 m on a drum having a diameter of 100 cm at room temperature, it could be wound smoothly without breaking.

(Production Example 3): Production of core wire (1C)
A core wire (1C) was obtained in the same manner as in Production Example 2 except that a compound of polyimide resin and aluminum hydroxide was used instead of the thermoplastic epoxy resin as a solidifying agent.

(Production Example 4): Production of Core Wire (1D) A core wire (1D) was obtained in the same manner as in Production Example 2 except that the carbon fiber bundle was not restrained by a restraining material.

(Production Example 5): Production of Strand Core Wire (2A) Using seven core wires (1A) (not coated with silicone resin) obtained in Production Example 1, one core wire (1A) at the center and the periphery Was twisted while being heated to 120 ° C. so as to be covered with six core wires (1A), and a strand core wire (2A ′) was manufactured to 100 m. It was wound on a drum having a diameter of 70 cm at room temperature.

Next, the strand core wire (2A ′) was covered with a resin layer using a resin containing acrylic resin, silica particles, aluminum particles, and a phosphorus-based flame retardant to obtain a strand core wire (2A).
The surface of the strand core wire (2A) and the space between the core wire (1A) and the core wire (1A) constituting the strand core wire (2A) were also filled with the resin.
The obtained strand core wire (2A) had a diameter of 10 mm (measured with calipers).

(Production Example 6): Production of Strand Core Wire (2B) Seven core wires (1B) obtained in Production Example 2 were used, one core wire (1B) at the center and six core wires (1B) around it. As it covered, it twisted together, heating at 120 degreeC, and manufactured 100m of strand core wires (2B) which have a strand structure. The strand core wire (2B) was stored in a state of being wound around a drum having a diameter of 70 cm at room temperature.
The obtained strand core wire (2B) was 10 mm in diameter (measured with calipers).

(Production Example 7): Production of strand core wire (2B ′)
The strand core wire (2B) of Production Example 6 was further coated with a resin containing the acrylic resin, silica particles, aluminum particles, and phosphorus-based flame retardant used in Production Example 5 to obtain a strand core wire (2B ′).
The obtained strand core wire (2B) was 10 mm in diameter (measured with calipers).

(Production Example 8): Production of strand core wire (2C)
7 core wires (1C) obtained in Production Example 3 were used, twisted while heating to 120 ° C. so as to cover one core wire (1C) at the center and 6 core wires (1C) around it. A strand core wire (2C) was produced 100 m. It was stored in a state wound around a drum having a diameter of 70 cm at room temperature.
The obtained strand core wire (2C) of Comparative Example 3 had a diameter of 10 mm (measured with calipers).

  Next, using the core wires of Production Examples 1 to 4 or the strand core wires of Production Examples 5 to 8 as a core material, a non-flammable carbon fiber composite material is produced, and the non-flammable performance of the obtained non-flammable carbon fiber composite material Was measured.

In addition, the measurement of non-combustible performance is based on the performance evaluation related to the certification of non-combustible materials based on the provisions of Article 2-9 of the Building Standards Act or semi-incombustible materials based on Article 1-5 of the Building Standards Act Enforcement Order. 4.10 Non-combustible performance test / evaluation method 4.10.2 “Exothermic test / evaluation method” 4.11 Quasi-incombustibility performance test / evaluation method 4.11.1 Tests / evaluations were conducted according to the exothermic test / evaluation method, and those satisfying the respective standard values were accepted and those not met were rejected.
In addition, although these tests are performed with respect to a plate-shaped object, since the nonflammable carbon fiber composite material and carbon fiber composite material of a present Example are rod-shaped objects, a 10-cm-long rod-shaped object is used as a sample. The rod-shaped objects were arranged in parallel on the test specimen holder, and the test was performed with a length of 10 cm in length and width. (10 non-combustible carbon fiber composite materials and 10 carbon fiber composite materials arranged in a line perpendicular to the axial direction of the carbon fiber composite material if the diameter is 1 cm). The cross section of the both ends of the nonflammable carbon fiber composite material used as the sample was covered with the aluminum foil when the outer periphery of the core material used as the sample was covered with the aluminum foil. In addition, the carbon fiber composite material of Comparative Examples 1 to 3 in which the outer periphery of the core material used as the sample is covered with soft copper is covered with the soft copper foil and does not have the metal coating layer. The test was carried out with the cut surface remaining uncovered.

Example 1
The core wire (1B) of Production Example 2 was cut into 10 cm and used as the core material (1). An aluminum foil having a width of 12 cm and a thickness of 20 μm is wrapped in a triple (three layers) direction perpendicular to the axis of the core material (1) so as to cover all the core material (1), and non-combustible carbon fiber A composite material (1) was obtained. In addition, the cross section of the core material (1) was covered with the aluminum foil which protruded from the both ends of the axial center direction of the nonflammable carbon fiber composite material.
The obtained incombustible carbon fiber composite material (1) had a diameter of 3 mm.
The incombustible performance of the obtained incombustible carbon fiber composite material (1) was measured, and the results are shown in Table 1.

(Example 2)
The long strand core wire (2B) obtained in Production Example 6 was cut into 2 m to form a rod, and the core material (2) was used.

  Next, a tape-shaped aluminum foil having a thickness of 20 μm and a width of 20 mm is rotated clockwise at an angle of about 45 degrees with respect to the axial direction of the core material (2) so that the sides of the aluminum foil overlap each other by 10 mm. Once wound, the entire core material (2) was covered with aluminum foil. Subsequently, the same tape-shaped aluminum foil was counterclockwise rotated at an angle of about 45 degrees with respect to the axial direction of the core material (2), and once again, the entire wound core material (2) was covered again with the aluminum foil. . Further, the core material (2) is wound once in the clockwise direction at an angle of about 45 degrees with respect to the axial direction of the core material (2), and the whole core material (2) is covered again with aluminum foil, and the nonflammable carbon fiber composite material (2) was obtained.

The obtained non-combustible carbon fiber composite material (2) had a diameter of 10 mm. Moreover, the core material (2) covered with the aluminum foil was covered with 6 layers of the aluminum foil, and the metal coating layer had a multilayer structure.
The incombustible performance of the obtained incombustible carbon fiber composite material (2) was measured, and the results are shown in Table 1.

(Example 3)
In the same manner as in Example 2, the long strand core wire (2B) obtained in Production Example 6 was cut into 2 m to form a rod, and the core material (2) was used.
A tape-shaped aluminum foil having a thickness of 10 μm and a width of 20 mm is placed on the core material (2) at an angle of about 45 degrees with respect to the axial direction of the core material (2) so that the sides of the aluminum foil overlap each other by 10 mm. Once wound clockwise, the entire core material (2) was coated to obtain a nonflammable carbon fiber composite material (3).

The obtained incombustible carbon fiber composite material (3) had a diameter of 10 mm. Moreover, the core material (2) covered with the aluminum foil was covered with two layers of the aluminum foil by the overlapping portion when the aluminum foil was wound, and the metal coating layer had a multilayer structure.
The incombustible performance of the obtained incombustible carbon fiber composite material (3) was measured, and the results are shown in Table 1.

Example 4
In the same manner as in Example 2, the long strand core wire (2B) obtained in Production Example 6 was cut into 2 m to form a rod, and the core material (2) was used.
A tape-shaped heat-resistant aluminum foil with a silicone adhesive with a thickness of 100 μm and a width of 50 mm is placed on the core material (2) so that the sides of the aluminum foil overlap each other by 25 mm with respect to the axial direction of the core material (2). The core material (2) was entirely covered by wrapping once clockwise at an angle of about 45 degrees. Subsequently, the same tape-shaped heat-resistant aluminum foil is wound counterclockwise at an angle of about 45 degrees with respect to the axial center direction of the core material (2), and then the core material (2) as a whole is wound once in the same manner. Was coated again to obtain a nonflammable carbon fiber composite material (4).

The obtained incombustible carbon fiber composite material (4) had a diameter of 10 mm. Moreover, the core material (2) covered with the aluminum foil was covered with four layers of the aluminum foil by the overlapping portion when the aluminum foil was wound, and the metal coating layer had a multilayer structure.
The incombustible performance of the obtained incombustible carbon fiber composite material (4) was measured, and the results are shown in Table 1.

(Example 5)
In the same manner as in Example 2, the long strand core wire (2B) obtained in Production Example 6 was cut into 2 m to form a rod, and the core material (2) was used.
A tape-shaped heat-resistant aluminum foil with a silicone adhesive with a thickness of 100 μm and a width of 50 mm is placed on the core material (2) so that the sides of the aluminum foil overlap each other by 25 mm with respect to the axial direction of the core material (2). The core material (2) was covered only once in a clockwise direction at an angle of about 45 degrees, and the entire core material (2) was coated to obtain a nonflammable carbon fiber composite material (5).

The obtained incombustible carbon fiber composite material (5) had a diameter of 10 mm. Moreover, the core material (2) covered with the aluminum foil was covered with two aluminum foil layers, and the metal coating layer had a multilayer structure.
The incombustible performance of the obtained incombustible carbon fiber composite material (5) was measured, and the results are shown in Table 1.

(Example 6)
Instead of the core material (1), the core wire (1A) of Production Example 1 was cut to 10 cm and used as the core material (3) in the same manner as in Example 1 except that the nonflammable carbon fiber composite material (6 )
The incombustible performance of the obtained incombustible carbon fiber composite material (6) was measured, and the results are shown in Table 1.

(Example 7)
Instead of the core material (1), the core wire (1D) of Production Example 4 was cut to 10 cm and used as the core material (4) in the same manner as in Example 1 except that the nonflammable carbon fiber composite material (7) Got. The obtained noncombustible carbon fiber composite material (7) was crushed and deformed in some places.
The incombustible performance of the obtained incombustible carbon fiber composite material (7) was measured, and the results are shown in Table 1.

(Example 8)
The non-flammable carbon was coated in the same manner as in Example 3 except that the core material (2) was covered with an aluminum foil and the entire core material (2) was covered with a tape-shaped soft copper foil having a thickness of 10 μm and a width of 20 mm. A fiber composite material (8) was obtained.

The obtained incombustible carbon fiber composite material (8) had a diameter of 10 mm. Moreover, the core material (2) covered with the soft copper foil was covered with two layers of the soft copper foil by an overlapping portion when the soft copper foil was wound, and the metal coating layer had a multilayer structure.
The incombustible performance of the obtained incombustible carbon fiber composite material (8) was measured, and the results are shown in Table 1.

Example 9
The long strand core wire (2A) obtained in Production Example 5 was cut into 2 m to form a rod, and the core material (5) was used.
A tape-shaped aluminum foil having a thickness of 20 μm and a width of 20 mm is placed on the core material (5) at an angle of about 45 degrees with respect to the axial direction of the core material (5) so that the sides of the aluminum foil overlap each other by 10 mm. In the clockwise direction, the entire core material (5) was covered only once to obtain a nonflammable carbon fiber composite material (9).

The obtained incombustible carbon fiber composite material (9) had a diameter of 10 mm. Moreover, the core material (5) covered with the aluminum foil was covered with two layers of the aluminum foil by the overlapping portion when the aluminum foil was wound, and the metal coating layer had a multilayer structure.
The incombustible performance of the obtained incombustible carbon fiber composite material (9) was measured, and the results are shown in Table 1.

(Comparative Example 1)
The long strand core wire (2B) obtained in Production Example 6 was used as the carbon fiber composite material (1).
The incombustible performance of the obtained carbon fiber composite material (1) was measured, and the results are shown in Table 1.

(Comparative Example 2)
The long strand core wire (2B ′) obtained in Production Example 7 was used as the carbon fiber composite material (2).
In addition, this carbon fiber composite material (2) is a resin containing an acrylic resin, silica particles, aluminum particles, and a phosphorus flame retardant for the metal coating layer of the aluminum foil of the non-combustible carbon fiber composite material (2) of Example 2. The structure is replaced with the coating layer.
The incombustible performance of the obtained carbon fiber composite material (2) was measured, and the results are shown in Table 1.

(Comparative Example 3)
The long strand core wire (2C) obtained in Production Example 8 was used as the carbon fiber composite material (3).
The incombustible performance of the obtained carbon fiber composite material (3) was measured, and the results are shown in Table 1.

  Carbon fiber composite materials of Comparative Examples 1 to 3 using a heat-resistant resin containing a polyimide resin, aluminum hydroxide, and a phosphorus-based flame retardant, which have been used for improving heat resistance in the past, are non-combustible and / or semi-incombustible. The non-flammable carbon fiber composite materials of Examples 1 to 9 satisfied the non-flammability and / or quasi-non-flammability test / evaluation standards. From the above results, it can be seen that the non-combustible carbon fiber composite materials of Examples 1 to 9 have the performance of the non-combustible material or the semi-incombustible material defined by the Building Standard Law.

  Since the non-combustible carbon fiber composite material of the present invention has the original tensile strength and excellent non-combustibility of carbon fiber, it can be applied as a non-combustible material to all industrial fields such as civil engineering, construction, ships, mining and fishing. This is industrially promising.

DESCRIPTION OF SYMBOLS 1 Core wire 2 Strand core wire 3 Multi strand core wire 4 Carbon fiber yarn 5 Carbon fiber bundle 10a, 10b, 10c, Core material 20a, 20b, 20c, Metal coating layer 100, 110, 120 Nonflammable carbon fiber composite material

Claims (13)

And any of the core material of the following (1) to (3), have a, and a metal coating layer on the outer periphery of the core material, the metal coating layer, incombustible carbon fiber composite material is a metal foil.
(1) Core material comprising a core wire including a carbon fiber bundle integrated with a solidifying agent (2) Two or more core wires including a carbon fiber bundle integrated with a solidifying agent are arranged or twisted together Core material consisting of strand core wire (3) Two or more core wires including carbon fiber bundles integrated with a solidifying agent, two or more strand core wires formed by aligning or twisting,
Core material consisting of multi-strand core wire that is formed by drawing or twisting The nonflammable carbon fiber composite material according to claim 1 , wherein the metal coating layer is a metal foil having a multilayer structure. The nonflammable carbon fiber composite material according to claim 1 or 2 , wherein the metal coating layer is a metal coating layer containing at least one selected from the group consisting of aluminum, stainless steel, soft copper, titanium, and alloys thereof. The non-flammable property according to any one of claims 1 to 3 , wherein the metal coating layer is a metal coating layer arranged in a spiral shape so that a tape-shaped metal foil overlaps with an axis of the core material. Carbon fiber composite material. The core material according to any one of (1) to (3) below, and a metal coating layer on the outer periphery of the core material, and the metal coating layer is made of aluminum, stainless steel, soft copper, titanium, and an alloy thereof. A non-combustible carbon fiber composite material which is a metal coating layer containing at least one selected from the group.
(1) Core material comprising a core wire including a carbon fiber bundle integrated with a solidifying agent
(2) A core material composed of a strand core wire constituted by aligning or twisting two or more core wires including a carbon fiber bundle integrated with a solidifying agent.
(3) Two or more core wires including carbon fiber bundles integrated with a solidifying agent, two or more strand core wires configured by aligning or twisting,
Core material consisting of multi-strand core wire that is formed by drawing or twisting   2. The carbon fiber bundle integrated with the solidifying agent has a restraining material wound around the carbon fiber bundle and bound, and the carbon fiber bundle and the restraining material are both integrated with the solidifying agent. The nonflammable carbon fiber composite material according to any one of 1 to 5. A nonflammable carbon fiber composite material comprising the core material according to any one of (1) to (3) below and a metal coating layer on the outer periphery of the core material.
(1) Core material comprising a core wire including a carbon fiber bundle integrated with a solidifying agent
(2) A core material composed of a strand core wire constituted by aligning or twisting two or more core wires including a carbon fiber bundle integrated with a solidifying agent.
(3) Two or more core wires including carbon fiber bundles integrated with a solidifying agent, two or more strand core wires configured by aligning or twisting,
Core material consisting of multi-strand core wire that is formed by drawing or twisting
  Here, the carbon fiber bundle integrated with the solidifying agent contained in the core wire in the above (1) to (3) has a restraining material that is wound around and bundled around the carbon fiber bundle, and the carbon fiber bundle And the constraining material are integrated by a solidifying agent. The nonflammable carbon fiber composite material according to any one of claims 1 to 7 , wherein the core wire is a core wire provided with a heat-resistant layer so as to cover an entire outer surface of a carbon fiber bundle integrated with the solidifying agent. . A nonflammable carbon fiber composite material comprising the core material according to any one of (1) to (3) below and a metal coating layer on the outer periphery of the core material.
(1) Core material comprising a core wire including a carbon fiber bundle integrated with a solidifying agent
(2) A core material composed of a strand core wire constituted by aligning or twisting two or more core wires including a carbon fiber bundle integrated with a solidifying agent.
(3) Two or more core wires including carbon fiber bundles integrated with a solidifying agent, two or more strand core wires configured by aligning or twisting,
Core material consisting of multi-strand core wire that is formed by drawing or twisting
  Here, the said core wire in said (1)-(3) is a core wire in which the heat resistant layer is provided so that the whole outer periphery of the carbon fiber bundle integrated with the said solidifying agent may be covered. The nonflammable carbon fiber composite material according to any one of claims 1 to 9 , wherein the strand core wire or the multi-strand core wire is further provided with a heat-resistant layer so as to cover the entire outer periphery thereof. A nonflammable carbon fiber composite material having the following (2) or (3) core material and a metal coating layer on the outer periphery of the core material.
(2) A core material composed of a strand core wire constituted by aligning or twisting two or more core wires including a carbon fiber bundle integrated with a solidifying agent.
(3) Two or more core wires including carbon fiber bundles integrated with a solidifying agent, two or more strand core wires configured by aligning or twisting,
Core material consisting of multi-strand core wire that is formed by drawing or twisting
  Here, the strand core wire or the multi-strand core wire in the above (2) and (3) is further provided with a heat-resistant layer so as to cover the entire outer periphery. The building material containing the nonflammable carbon fiber composite material of any one of Claim 1 to 11 . A building material containing a non-combustible carbon fiber composite material,
  The building material which is a non-combustible carbon fiber composite material in which the non-combustible carbon fiber composite material has any one of the following core materials (1) to (3) and a metal coating layer on the outer periphery of the core material.
(1) Core material comprising a core wire including a carbon fiber bundle integrated with a solidifying agent
(2) A core material composed of a strand core wire constituted by aligning or twisting two or more core wires including a carbon fiber bundle integrated with a solidifying agent.
(3) Two or more core wires including carbon fiber bundles integrated with a solidifying agent, two or more strand core wires configured by aligning or twisting,
Core material consisting of multi-strand core wire that is formed by drawing or twisting

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