JP2012251378A - String-like reinforcement fiber composite - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a string-like reinforcement fiber composite which has not only excellent tensile strength derived from a basalt fiber but also excellent shear strength, which has shape changeability, and which utilizes the basalt fiber.SOLUTION: Characteristically, a string-like reinforcement fiber composite includes an inner layer which is made of a core wire of one or more string-like basalt fiber bundles, an intermediate layer which contains a resin and which is provided around the core wire, and an outer layer which is made of a braided tubular string and which is provided around the intermediate layer. The string-like reinforcement fiber composite, which has shape changeability while maintaining mechanical performance such as excellent tensile strength and an elastic coefficient derived from a basalt fiber as the core wire, can be suitably used particularly as a concrete reinforcement material.

Description

  The present invention relates to a string-like reinforcing fiber composite. More specifically, the present invention relates to a string-like reinforcing fiber composite having a basalt fiber as a core wire.

  Conventionally, so-called reinforcing bars made of metal are used as reinforcements embedded in concrete for reinforcement of concrete. However, because the reinforcing bars are heavy (specific gravity), the weight load per unit area such as high-rise buildings is high. When used for a large structure, it is necessary to design so that the weight of the reinforcing bar itself can be maintained, which contributes to design restrictions and high costs. Also, conventional rebars are often transported to the construction site as they are manufactured at the factory, and there are restrictions on the shape and size, making it difficult to manufacture and transport long objects, and poor workability. There is a problem. With regard to workability and workability, a major limitation in use is that bending and other processing cannot be performed freely on site. In addition, when reinforcing bars are used as reinforcing materials for concrete, the cement that is the main component of concrete is alkaline, but corrosion occurs in the reinforcing bars due to neutralization of the cement due to the intrusion of carbon dioxide gas from the outside. There is also the problem of doing. In addition, when corrosion occurs in the reinforcing bar, the corroded part of the reinforcing bar expands, causing cracks in the concrete. Further, water, air, acid, etc. enter from the crack, and the corrosion of the reinforcing bar progresses further. The result is a vicious circle. Against this background, there is a need for an alternative to reinforcing bars.

Carbon fibers and basalt fibers are excellent in mechanical properties such as tensile strength and elastic modulus, corrosion resistance to acids and alkalis, and are lightweight, so many attempts have been made to use them directly as a substitute for reinforcing bars in concrete. . For example, Patent Document 1 describes a metal bar that uses a basalt fiber instead of a reinforcing bar by forming a core material with a basalt fiber. However, basalt fibers are not widely used for concrete structures.
This is because the adhesive strength between basalt fiber and concrete is not so high, and the strength of basalt fiber is not fully exhibited. In addition, basalt fiber is not so high in shear strength, so the surface included as aggregate in concrete May be damaged by sharp gravel.
In addition, if the basalt fiber is hardened with a thermosetting resin, the flexibility of the basalt fiber cannot be used, so that it is not possible to bend and bend freely on site in the same way as reinforcing bars. .

JP 2008-274667 A

The maximum tensile strength of string-like reinforcing fiber composites using basalt fiber yarns is theoretically considered to depend on the amount of basalt fibers used, but in fact, the basalt fibers that make up the string-like reinforcing composites Is weak to the shearing force (lateral force), the stage of manufacturing the reinforced fiber composite, the storage of the reinforced fiber composite, during transportation, during construction work, Some may break and shear.
Further, when the string-like reinforcing fiber composite is used as a concrete reinforcing steel bar or a brace material, a horizontal force is applied to the basalt fiber yarn at the joint location with other building materials. A part of the basalt fiber yarn breaks and shears. For the above reasons, the actual strength is not obtained as the theoretical value derived from the basalt fiber. In addition, if the basalt fiber is simply covered with another fiber or resin, a sufficient effect for improving the shear force of the basalt fiber cannot be obtained.
Thus, no string-like material using basalt fibers has been found that sufficiently satisfies mechanical strength (especially with respect to the force in the horizontal direction) and variability.
Under such circumstances, the object of the present invention is to have excellent tensile strength derived from basalt fiber, and also excellent shear strength, and in a more preferred form, a string shape using basalt fiber having shape variability. It is to provide a reinforced fiber composite.

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

<1> an inner layer composed of a core wire of one or a plurality of string-like basalt fiber bundles;
An intermediate layer including a resin provided around the core wire;
An outer layer formed of a knitted tubular cord provided around the intermediate layer;
A string-like reinforcing fiber composite comprising
<2> The string-like reinforcing fiber composite according to <1>, wherein the intermediate layer includes a plurality of reinforcing yarns arranged in a direction coaxial with the resin and the core wire.
<3> The string-like reinforcing fiber composite according to <1> or <2>, wherein the core wire constituting the inner layer is a string-like basalt fiber bundle coated with a resin.
<4> The string-like reinforcing fiber composite according to <3>, wherein the resin that coats the core wire and the resin that forms the intermediate layer are the same resin.
<5> The string-like reinforcement according to any one of <1> to <4>, wherein the inner layer, the intermediate layer, and the outer layer are bonded and integrated with the same resin as that forming the intermediate layer. Fiber composite.
<6> The resin constituting the intermediate layer is at least one selected from the group consisting of polyetheretherketone, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyethylene resin, epoxy resin, urethane resin, polycarbonate resin, and polypropylene resin. The string-like reinforcing fiber composite according to any one of <1> to <5>, which is a seed.
<7> The string-like reinforcing fiber composite according to any one of <1> to <6>, wherein the resin constituting the intermediate layer is a thermoplastic resin.
<8> A concrete reinforcing bar comprising the string-like reinforcing fiber composite according to any one of <1> to <7>.
<9> A brace material comprising the string-like reinforcing fiber composite according to any one of <1> to <7>.

  ADVANTAGE OF THE INVENTION According to this invention, the string-like reinforced fiber composite excellent also in the shear strength can be provided, maintaining the outstanding tensile strength derived from the basalt fiber which is a core wire.

It is a schematic diagram of the string-like reinforcing fiber composite of the present invention, (a) is an external view, (b) is a cross-sectional view (string-like basalt fiber bundles constituting the core wire: seven). It is a figure showing arrangement | positioning of the string-like basalt fiber bundle in the core wire of the string-like reinforcement fiber composite of this invention, and this string-like basalt fiber bundle is (a) 1 piece, (b) 3 pieces, (c) 7 It is an example of a book. It is a schematic diagram of a resin coating apparatus.

Hereinafter, the present invention will be described in detail.
As shown schematically in FIG. 1, the string-like reinforcing fiber composite of the present invention includes an inner layer composed of a core wire (preferably circular in cross section) of a string-like basalt fiber bundle, and an intermediate layer including a resin provided around the core wire. And an outer layer composed of a knitted tubular cord provided around the intermediate layer, and is a multilayer structure having other layers between the intermediate layer and the outer layer or outside the outer layer as necessary. In addition, it has shear strength due to the presence of the intermediate layer and the outer layer, while maintaining excellent mechanical properties such as tensile strength and elastic modulus derived from the basalt fiber that is the core wire.

In addition, although mentioned later in detail, one of the preferable aspects of this invention is a string-like reinforcement fiber composite_body | complex which an intermediate | middle layer consists of a some reinforcement thread | yarn arrange | positioned coaxially with resin and a core wire.
By including the reinforcing yarn arranged in this way in the intermediate layer, the basalt fiber yarn used for the core wire when a lateral force is applied to the basalt fiber during storage, transportation, handling or use It is possible to suppress breakage or shearing.

From the viewpoint of strength, a preferred embodiment of the present invention is a string-like reinforcing fiber composite in which the inner layer, the intermediate layer, and the outer layer are bonded and integrated with the same resin as that forming the intermediate layer. The intermediate layer may include the reinforcing yarn.
If the adhesion between the inner layer and the intermediate layer and the outer layer with high tensile strength is insufficient, the tensile strength derived from the basalt fiber yarn that is the inner layer cannot be obtained, and the outer layer portion or the outer layer and the intermediate layer are torn off when pulled. There is a risk of being. Moreover, when the adhesiveness between the intermediate layer and the outer layer or the inner layer and the intermediate layer is not sufficient, only the intermediate layer and the outer layer or the outer layer may come off during construction.
On the other hand, since the inner layer, the intermediate layer, and the outer layer are integrated with resin in the string-like reinforcing fiber composite of the present invention, the adhesion of each layer is improved and the above problem does not occur.
In particular, since the resin used to integrate the inner layer, the intermediate layer and the outer layer is the same resin as that constituting the intermediate layer, the adhesiveness of each layer that may occur when using different types of resins is reduced. Can be avoided.

In addition, as a resin which comprises the said intermediate | middle layer, although both a thermoplastic resin and a thermosetting resin can be used, it is preferable that it is a thermoplastic resin.
By using this resin as a thermoplastic resin, it can be stored and transported on a drum or the like by having heat by applying heat.

The diameter of the string-like basalt fiber composite of the present invention is arbitrary depending on the application and is not particularly limited, but is usually about 1 mm to 150 mm.
Further, the length of the cord-like basalt fiber composite of the present invention is also arbitrary and may be determined according to the use etc., but is usually about several tens of centimeters to several hundreds of meters, but is longer than this. Also good.

The string-like reinforcing fiber composite of the present invention can take various shapes such as a rod shape and a curved shape. In particular, when a thermoplastic resin is used as the resin constituting the intermediate layer (including the case where the inner layer, the intermediate layer and the outer layer are bonded and integrated with the same resin as the resin constituting the intermediate layer), the core wire The cord-like basalt fiber bundle to be formed has a very high tensile strength, the outer layer has an appropriate flexibility, and the intermediate layer provided between them includes the thermoplastic resin, so that the thermoplastic resin is softened. Since it can be deformed by heating to a temperature, it can be formed not only in a rod shape but also in a curvilinear shape, or a shape wound around a spool.
Therefore, when storing and moving, the long string-like reinforcing fiber composite is wound up, heated when used, drawn to the required length, cut, and used as a rod-like straight line You can also.

  Hereinafter, the core wire (inner layer), the intermediate layer, and the outer layer constituting the string-like reinforcing fiber composite of the present invention will be described.

[Core wire (inner layer)]
The core wire constituting the inner layer of the string-like reinforcing fiber composite of the present invention is composed of one or a plurality of string-like basalt fiber bundles.
This string-like basalt fiber bundle is a mixture of basalt fiber yarn alone or basalt fiber yarn mixed with yarn made of carbon fiber, glass fiber, aramid fiber, and other organic fibers as long as its strength and bendability are not impaired. In general, it is a filamentous body in which basalt fiber yarns (filaments) are bundled. In addition, the basalt fiber yarn constituting this string-like basalt fiber bundle can be either twisted or untwisted, but if it is twisted, the shearing force and tensile strength are reduced, so twisting is applied. It is better not to. That is, it is preferable that the basalt fiber yarns constituting the inner layer are arranged to be aligned.

  Moreover, as a string-like basalt fiber bundle, any form of string-like basalt fiber such as a twisted string shape, a braided string shape, a braided string shape, a woven string shape, a tie string shape, a bundle string shape, a cut string shape, or a synthetic string shape It is possible to use a bundle. On the other hand, if there are entanglement points consisting of the above-mentioned basalt fiber yarn or other yarns in the string-like basalt fiber bundle, the shearing force in the lateral direction is likely to be applied to the basalt fiber yarn at the entanglement point, and the basalt fiber yarn is cut. As a result, the tensile strength of the string-like basalt fiber bundle may be reduced. Further, like the basalt fiber yarn, the string-like basalt fiber bundle is preferably not twisted. For this reason, among the above-mentioned forms, the cord-like basalt fiber bundle is preferably one in which basalt fiber yarns are aligned so that there is no twist and no entanglement point is generated.

  The string-like basalt fiber bundle is preferably temporarily bonded with an adhesive resin (referred to as a sizing agent or a sizing agent) or the like in order to prevent the basalt fiber yarns from being loosened. As the sizing agent and the sizing agent, those having high affinity with the resin constituting the intermediate layer may be used.

  Although the average diameter of the basalt fiber yarn constituting the string-like basalt fiber bundle is not particularly limited, it is usually in the range of 1 to 20 μm from the viewpoint of mechanical properties and workability of the obtained molded product. In the string-like basalt fiber bundle used for the core wire, the outer diameter is determined by the thickness and number of basalt fiber yarns used, and is usually about 1 mm to 100 mm.

In the string-like reinforcing fiber composite of the present invention, when a thicker core wire is required, it may be arranged so as to bundle a plurality of string-like basalt fiber bundles, and in particular, the section may be arranged in a circular shape. preferable.
FIG. 2 illustrates the case where the cord-like basalt fiber bundles constituting the core wire are (a) one, (b) three, and (c) seven.
Here, the diameter d of the core wire is the diameter of a virtual circle that is in contact with the outer periphery of the cord-like basalt fiber bundle constituting the core wire when the cross section is circular. When the cross section of the core wire is not elliptical, such as an ellipse, the major axis direction of the virtual circle is the diameter d of the core wire.
In addition, the number of the string-like basalt fiber bundles constituting the core wire is not limited to this, and is appropriately determined according to the purpose of use. For example, the string-like reinforcing fiber composite of the present invention is used as a concrete reinforcing bar or brace. When used as a material, the diameter d of the core wire is about 1 mm to 100 mm. The diameter d of the core wire can be measured with a caliper, or the cross section can be measured with a microscope (including an electron microscope).
When a plurality of string-like basalt fiber bundles are used, the basalt fiber yarns constituting each string-like basalt fiber bundle may be converged and integrated to form one string-like basalt fiber bundle as a whole. .

  The length of the string-like basalt fiber bundle is appropriately determined depending on the purpose of use, and is usually about several tens of centimeters to several hundreds of meters.

Here, it is preferable that the string-like basalt fiber bundle constituting the core wire is coated with a resin. The cord-like basalt fiber bundle constituting the core wire is coated with a resin. When the core wire is constituted of one cord-like basalt fiber bundle, the cord-like basalt fiber bundle is coated with a resin. Say something. In this case, the internal basalt fiber yarns constituting the string-like basalt fiber bundle may be bonded and integrated with the resin.
In addition, when the core wire is composed of a plurality of string-like basalt fiber bundles,
(1) Although each string-like basalt fiber bundle is individually coated with resin, the entire core wire is not bonded with resin and is not integrated,
(2) Each string-like basalt fiber bundle is not individually coated with resin, but as the whole core wire, the string-like basalt fiber bundle is coated with resin and bonded and integrated,
(3) Each cord-like basalt fiber bundle is individually coated with a resin, and the entire core wire is also bonded and integrated with the resin.

The cord-like basalt fiber bundle is coated with a resin, but depending on the production method, the presence of the resin in advance on the surface of the core wire improves the adhesiveness with the intermediate layer. Strength as a body improves.
When a plurality of cord-like basalt fiber bundles are used as the core wire, the core wires in which the respective string-like basalt fiber bundles are bonded and integrated by resin as in (2) and (3) above. As a result, the strength is further improved.
In particular, from the viewpoint of strength, it is preferable that the thermoplastic resin is impregnated into the inside of the cord-like basalt fiber bundle, and the basalt fiber yarn inside the cord-like basalt fiber bundle is also bonded and integrated with the resin.

The resin used may be either a thermoplastic resin or a thermosetting resin, but a thermoplastic resin is preferably used in order to provide variability.
Preferred examples 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, polycarbonate resin, and the like, but are not limited thereto.
Among these, polyether ether ketone (PEEK), acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyethylene resin, epoxy resin, urethane resin, and polycarbonate resin are preferable from the viewpoint of durability against acids and alkalis.
In addition, the resin used for the coating of the string-like basalt fiber bundle and the resin constituting the intermediate layer need not be the same as long as each has an adhesive property, but in order to improve the adhesive force more. It is preferable to use the same resin.

The method of coating the above-mentioned resin on the string-like basalt fiber bundle is not particularly limited, such as coating the basalt fiber with a spray or a brush, but from the viewpoint of productivity, a dip-nip method or a die was used. An apparatus as shown in FIG. 3 can be used.
In the case where a thermoplastic resin is coated as a resin, when a device as shown in FIG. 3 is used, a string-like basalt fiber bundle supplied from a creel is melted or a thermoplastic resin dissolved in a solvent, or thermoplastic. Immerse in an emulsion containing resin and pass it through, then squeeze with mangle as necessary, remove excess thermoplastic resin, adjust the wire diameter with a die, and then dry and cure as necessary. Can do.

[Middle layer]
The intermediate layer of the string-like reinforcing fiber composite of the present invention contains a resin and is provided between the core wire (inner layer) and the outer layer.
In the string-like reinforcing fiber composite of the present invention, the intermediate layer prevents the core wire and the outer layer from coming into direct contact, and bonds the core wire and the outer layer with the resin contained. Furthermore, when the resin constituting the intermediate layer is a thermoplastic resin, it is hard at room temperature, but has an appropriate flexibility in the softening temperature range, so it is heated above the softening temperature of the thermoplastic resin. By doing so, the string-like reinforcing fiber composite of the present invention can be bent into various shapes. Therefore, the string-like reinforcing fiber composite of the present invention can be not only in the form of a rod, but also in a curved shape, and further in a state wound around a bobbin.
In addition, you may provide another layer (for example, contact bonding layer etc.) between this intermediate | middle layer and an outer layer in the range which does not impair the effect of this invention.

The resin used for the intermediate layer may be either a thermoplastic resin or a thermosetting resin, and has a high bondability with the string-like basalt fiber bundle constituting the core wire and the knitted tubular string constituting the outer layer. It is done. In particular, when a thermoplastic resin is used, an appropriate one is selected in consideration of a balance between curability at normal temperature and flexibility during heating.
Preferred examples include polypropylene, polyethylene, polyetheretherketone (PEEK), 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, polyester resin, epoxy resin, urethane resin, polycarbonate resin and the like.
Among these, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyethylene resin, polypropylene resin, epoxy resin, urethane resin, and polycarbonate resin are preferable from the viewpoint of durability against acids and alkalis.
In addition, when a thermoplastic resin is used for the intermediate layer, any thermoplastic resin may be used in consideration of the application and heat resistance of the material for forming the basalt fiber yarn, the following reinforcing yarn, and the outer layer, but the softening temperature is 50. A thermoplastic resin having a temperature of from about 200 ° C. to about 200 ° C. is preferable because it is excellent in workability. Of course, a thermoplastic resin having a softening temperature exceeding 200 ° C. may be used depending on the application.
In addition, when using the cord-like basalt fiber bundle coated with resin as the core wire as described above, the resin used for coating the core wire and the resin used for the intermediate layer are the same from the viewpoint of improving the adhesion between the core wire and the intermediate layer. It is preferable that

The intermediate layer needs to have a thickness that gives sufficient bendability when softened and can be covered by the cord-like basalt fiber bundle constituting the core wire. Although it depends on the purpose of use and the thickness of the core wire, the thickness of the intermediate layer is preferably 0.05 mm or more, more preferably 0.1 mm or more, and further preferably 0.5 mm or more. There is no particular upper limit on the thickness of the intermediate layer. The thickness of the intermediate layer is usually about 30 mm or less, but may be more depending on the intended use.
The thickness of the intermediate layer can be determined by measuring the distance between the inner layer and the outer layer of the cross section of the string-like basalt fiber bundle with a caliper or with a microscope (including an electron microscope).

The intermediate layer preferably includes a reinforcing yarn. By including the reinforcing yarn together with the resin in the intermediate layer, the basalt fiber yarn used for the core wire may break when a lateral force is applied to the basalt fiber during storage, transportation, handling or use. , Shearing can be suppressed.
The direction in which the reinforcing yarn is arranged in the intermediate layer is preferably arranged in the direction coaxial with the core wire from the viewpoint of the manufacturing process, and protects the string-like basalt fiber bundle from shearing.
Moreover, the string-like reinforcing fiber composite of the present invention in which the string-like basalt fiber bundle is an inner layer (core wire) is particularly excellent in strength in the tensile direction, but from the viewpoint of increasing the other strength, It is good also as a structure containing the reinforcement thread | yarn arrange | positioned in the orthogonal direction.
Further, a reinforcing thread may be wound around the core wire in a spiral shape, or may include a reinforcing thread disposed in an oblique direction with respect to the core line.
Further, the reinforcing yarn is preferably arranged so as to cover the outer periphery of the core wire from the viewpoint of protection of the core wire. In particular, it is preferable that the core wire is disposed so as to cover the outer periphery without any gap.
In this way, by including the reinforcing yarn in the intermediate layer, the basalt fiber yarn used for the core wire is protected, the disconnection of the basalt fiber yarn is prevented, and the strength of the intermediate layer itself is also improved. The strength of the entire reinforcing fiber composite is improved.
In addition, a thick intermediate layer can be formed around the reinforcing yarn. Therefore, even when the diameter of the core wire is relatively large or relatively small relative to the diameter required for the finally obtained string-like basalt fiber composite, an intermediate layer having an arbitrary thickness is formed correspondingly. The string-like basalt fiber composite having the required thickness can be supplied. Therefore, a string-like reinforcing fiber composite having a necessary thickness can be obtained at an appropriate cost by using a necessary amount of basalt fiber according to a necessary tensile strength.

As the reinforcing yarn, any of natural fiber, synthetic fiber, glass fiber, and carbon fiber can be used. Usually, synthetic fiber is preferably used. As synthetic fibers, fibers such as polyamide (nylon, etc.), vinylon, polyacryl, polypropylene, vinyl chloride, aramid, polyester and the like can be used, and these may be used alone or in combination of two or more. Among these, polyamide and polyaramid are particularly preferable from the viewpoint of toughness. Polyester fibers are preferred from the viewpoint of cost and form stability.
Further, the yarn may be any of filament yarn, span yarn, and covering yarn.
Since such a reinforcing yarn has a higher shear resistance than the basalt fiber constituting the core wire, by arranging the reinforcing yarn in the middle layer in the direction coaxial with the core wire, the cord-like basalt fiber bundle of the core wire is formed. Protects against shearing.

In addition, there is no restriction | limiting in particular as a method of forming an intermediate | middle layer around a core wire, For example, a core wire is used using a spray, a brush, etc. similarly to the method of coating the said string-like basalt fiber bundle which comprises a core wire with resin. And a method of forming a resin layer around the core and a method of winding a resin film around a core wire.
In the case where this resin is a thermoplastic resin, from the viewpoint of improving productivity, the core wire is melted or dissolved in the same manner as the method of coating the thermoplastic resin on the cord-like basalt fiber bundle constituting the core wire. And a method of immersing and passing in a thermoplastic resin dissolved in or an emulsion containing a thermoplastic resin.
In particular, in order to form an intermediate layer containing a reinforcing thread with high productivity, a string-shaped basalt fiber bundle or a string in which a reinforcing thread is arranged around a string-shaped basalt fiber bundle is used by a dip-nip method or a die. It is preferable to use an apparatus as shown in FIG. 3 and apply a thermoplastic resin around the core wire to form an intermediate layer. In this method, a string-like basalt fiber bundle supplied from a creel or a string in which reinforcing yarns are arranged around a string-like basalt fiber bundle is melted or dissolved in a thermoplastic resin or an emulsion containing a thermoplastic resin. It is possible to obtain an intermediate layer including a reinforcing yarn by dipping and passing, and then squeezing with mangle if necessary, removing excess thermoplastic resin, adjusting the wire diameter with a die, and drying and curing as necessary. .

[Outer layer]
The outer layer of the string-like reinforcing fiber composite of the present invention is composed of a knitted tubular string, and has a role of protecting the string-like basalt fiber bundle that is a core wire from the outside. The “knitted tubular string” is a tubular body having a knitted structure in which fibers are knitted or a braided structure in which fibers are assembled as shown in FIG.

As described above, the basalt fiber has high tensile strength but not so high shear strength. Therefore, when a sharp object comes into contact with the string-like basalt fiber bundle constituting the core wire from the outside, it breaks through the intermediate layer provided around it. The basalt fiber yarn may be cut and the strength of the core wire may be reduced.
In particular, in concrete, there are many aggregates such as gravel and crushed stone that become sharp objects, so only the core wire composed of a string-like basalt fiber bundle, or the core wire is covered with the above-mentioned intermediate layer containing the resin Only by doing this, the internal string-like basalt fiber bundle cannot be sufficiently protected, and the strength of the string-like basalt fiber bundle may be lowered, and the strength of the concrete may not be sufficiently improved.
Here, by providing an outer layer made of a knitted tubular cord having high strength, the inner cord-like basalt fiber bundle can be protected from sharp objects and external forces.
As long as the role of the outer layer is not impaired, further coating or the like may be performed on the outer layer. For example, in order to improve the designability, the outside of the outer layer may be colored with a paint, or may be coated with various inorganic or organic substances.
Further, when the string-like reinforcing fiber composite of the present invention is used as a concrete reinforcing material, the outer layer of the knitted tubular string having an uneven surface contributes to the improvement of the strength of the concrete. Further, when the braided reinforcing fiber composite of the present invention is used as a brace material, the outer layer of the braided tubular cord is a braided tubular cord having a knitted structure or a braided structure according to the space design used. Use it.

One of the characteristics of the string-like reinforcing fiber composite of the present invention is that the outer layer is a knitted tubular string. Since the outer layer of the string-like reinforcing fiber composite of the present invention is a knitted tubular string, it has flexibility and can be deformed with respect to some external force, so that the external force can be released. In this way, the braided tubular cord can maintain the shape of the cord, and the flexibility can be maintained even when the thickness of the outer layer is sufficiently protected from sharps and external force from the outside. There are advantages.
On the other hand, when the outer layer is formed only by the resin coating, it is impossible to achieve both the role as the protective layer and the flexibility.
Note that the balance between flexibility and strength can be achieved by changing the density of the fibers used in the outer layer.
Further, the knitted tubular string includes a tubular knitted structure in which fibers are knitted as described above (hereinafter also referred to as “round knitting”), and a braided structure in which fibers are assembled in a cylindrical shape (hereinafter referred to as “round punching”). The braid structure is preferably used because it has an appropriate hardness and flexibility, and more excellent strength and shape stability.
Further, in the braid structure, since the diameter is reduced when the braided structure is stretched, it is more preferable that the adhesiveness between the outer layer and the intermediate layer and the inner layer included in the outer layer is increased when the tension is applied.

As fibers constituting the outer layer of the knitted tubular string, resin fibers made of natural resin or synthetic resin, glass fibers, basalt fibers, carbon fibers and the like can be used, and these can be used in combination. Of these, synthetic resin fibers are preferably used.
Preferable specific examples of the fibers constituting the outer layer include fibers such as polyamide (nylon, etc.), vinylon, polyacryl, polypropylene, vinyl chloride, aramid, cellulose, polyamide, polyester, polyacetal and the like. Among these, vinylon, cellulose, polyamide, and polyacetal, which have a good balance of chemical resistance (particularly alkali resistance) and variability, are preferable, and vinylon is particularly preferable. These fibers not only have sufficient strength as the outer layer, but also have strong resistance to alkali.
In addition, when heat treatment is performed depending on the manufacturing process and usage of the string-like reinforcing fiber composite, if the outer knitted tubular string is made of polyester fiber, it is difficult to cause shrinkage or expansion due to heat or moisture, and dimensional stability From the viewpoint of

  The diameter, length, and thickness of the outer layer of the knitted tubular string can be appropriately determined according to the purpose of use, and can be set to an arbitrary thickness and length according to the inner core wire and the intermediate layer.

  Also, the fibers constituting the outer layer knitted tubular string can be colored in various colors to enhance the design. Moreover, you may enable it to distinguish the kind, etc. of an outer layer, an intermediate | middle layer, and an inner layer by coloring an outer layer.

  The outer layer knitted tubular string manufacturing method is not particularly limited. For example, a conventionally known string knitting machine, circular knitting machine, or a known sock manufacturing apparatus is partially modified to form a knitted cylindrical string manufacturing apparatus. It can be made by diverting.

Hereinafter, a method of providing a knitted tubular string as an outer layer around the core wire and the intermediate layer will be described.
The method of providing the outer layer is not particularly limited. For example, first, an intermediate layer is formed around the inner layer (core wire), and then the outer layer is assembled or knitted around the outer layer to form the outer layer;
First, a method of forming an outer layer as a knitted tubular string, and inserting a core wire provided with an intermediate layer around the outer layer;
Etc.
In addition, when the adhesiveness between the knitted tubular string as the outer layer and the resin is poor, an adhesive layer having higher adhesiveness may be provided on the intermediate layer.
In addition, when the resin constituting the intermediate layer is a thermoplastic resin, the thermoplastic layer constituting the intermediate layer is heated by heating with the core wire provided around the intermediate layer inside the braided tubular cord. The resin may be softened and integrated with a knitted tubular string as an outer layer.
Further, the knitted tubular string that is the outer layer to be used may be coated by the same method as described above using the same resin as the resin constituting the above-described intermediate layer, and such a knitted tubular string is used. Thereby, adhesiveness with an intermediate | middle layer improves.

[Method for Producing String-like Reinforcing Fiber Composite of Preferred Embodiment]
Hereinafter, the manufacturing method of the string-like reinforcing fiber composite of the preferred embodiment of the present invention will be described.
One of the preferred embodiments of the present invention is a cord-like reinforcing fiber composite having an intermediate layer made of a plurality of reinforcing yarns arranged in the same direction as the resin and the core wire, and an outer layer made of a knitted tubular cord. Hereinafter, an example of the manufacturing method will be described.
(1) The periphery of the core wire composed of one or a plurality of cord-like basalt fiber bundles is arranged so as to cover the entire outer periphery of the core wire with a reinforcing thread that is a part of the intermediate layer without gaps, and is disposed on the outer periphery of the core wire A braiding machine is used to form appropriate knitted tubular cords as outer layers by using a stringing machine, and then a string-like object composed of the core wire, reinforcing yarns and knitted tubular cords is formed. Resin is applied by a dip-nip method, and if necessary, a die is passed, and if necessary, drying, heat treatment, cooling, etc. are performed, and the resin is outer layer (knitted tubular string), intermediate layer (reinforcing yarn), inner layer ( A string-like basalt fiber bundle), and an inner layer, an intermediate layer, and an outer layer are bonded and integrated to produce a string-like reinforcing fiber composite. In addition, after dipping a string-like object into resin, you may pass through a die | dye, without niping, and you may remove excess resin.
(2) The entire outer periphery of the core wire is formed around the core wire having a circular cross section composed of one or a plurality of cord-like basalt fiber bundles with a reinforcing thread so as to form a double circle centering on the core wire without any gaps. Cover, then, apply thermoplastic resin by dip-nip method, pass through a die as needed, dry, heat treatment, cool, etc., coat thermoplastic resin on inner layer, intermediate layer, inner layer, intermediate layer Are bonded and integrated. Next, the outer layer fibers are assembled around the intermediate layer using a string making machine to manufacture a string-like reinforcing fiber composite. Moreover, by heat-treating this, the inner layer, the intermediate layer, and the outer layer can be bonded and integrated by softening and cooling the thermoplastic resin. In addition, after dipping the string-like thing which covered the outer periphery of the core wire with the reinforcing thread to the thermoplastic resin, the excess resin may be removed by passing through a die without nip.
Also, according to the methods (1) and (2), the core wire is coated with a resin, and the resin that coats the core wire and the resin that constitutes the intermediate layer are the same, and the inner layer, the intermediate layer, and the outer layer are Bonding and integrating with the same resin as the resin constituting the intermediate layer can be performed in a single resin application step.

Further, a particularly preferable aspect of the present invention is a string-like reinforcing fiber composite in which an inner layer, an intermediate layer, and an outer layer are bonded and integrated with the same resin as that forming the intermediate layer. Hereinafter, an example of the manufacturing method will be described.
In particular, applying a resin to a string-like material in which an inner layer, a reinforcing thread, and an outer layer are arranged, forming an inner layer, an intermediate layer, and an outer layer, in particular, simultaneously bonding these layers with a resin and integrating them, It is preferable from the viewpoint of strength and productivity.
At this time, from the viewpoint of facilitating the penetration of the resin into the inner layer, the outer layer of the knitted tubular cord preferably has a gap between the yarns forming the outer layer. A struck braid is good.
In addition, the state of the resin at the time of applying the resin may be any of a molten state, a state dissolved in a solvent, and an emulsion state containing the resin, but the inside of each fiber constituting the outer layer, the intermediate layer, and the inner layer. Those having a low viscosity that are easy to penetrate are preferred.
The viscosity is preferably 50000 mPa · s or less, more preferably 10000 mPa · s or less, and particularly preferably 1000 mPa · s or less (measurement method: B-type viscometer, rotor No. 4 12 rpm). The lower limit is about 1 mPa · s, preferably 10 mPa · s or more.
When the viscosity exceeds 50000 mPa · s, the resin may not sufficiently penetrate into the outer layer, the intermediate layer, and the inner layer, and the strength may decrease. On the other hand, if it is less than 1 mPa · s, a resin sag occurs during processing, and a sufficient amount of resin cannot be applied to the string-like reinforcing fiber composite, which may reduce the strength.
In addition, from the viewpoint of allowing the resin to penetrate into the inside of the cord-like basalt fiber bundle that is the core wire, it is preferable to use the cord-like basalt fiber bundle constituting the inner layer that is not previously coated with the resin. In addition, in the production of the string-like basalt fiber bundle, what is called a sizing agent or a sizing agent that is slightly imparted in order to prevent the basalt fiber yarn from being scattered often has no effect on the effect of the present invention. As long as it is a thing, it may be previously given to the string-like basalt fiber bundle also in the said manufacturing method. Preferably, a sizing agent or sizing agent having a high affinity with the resin to be coated is used.

[Use of multi-layered string-like reinforcing fiber composite]
The string-like reinforcing fiber composite of the present invention can be applied to all industrial fields such as civil engineering, construction, marine, mining and fishing, and its use is not limited.
Among the usage applications, the string-like reinforcing fiber composite of the present invention has strength derived from basalt fibers that is not covered with reinforcing bars, is lightweight and has good compatibility with concrete, and also has high resistance to alkali in concrete. Therefore, when used as a concrete reinforcing material, the strength of the concrete can be improved, and the strength deterioration of the concrete structure due to corrosion of the reinforcing material can be avoided. Therefore, it is not desirable to use reinforcing bars in the string-like reinforcing fiber composite of the present invention, such as buildings that use precision machinery that is problematic when magnetized, environments that are prone to salt damage, and high maintenance costs such as high-rise buildings. It can be particularly suitably used for applications.

In addition, in concrete structures, corrosion of the reinforcing bars occurs due to the alkaline neutralization of the cement contained in the concrete, causing abnormal expansion and accompanying cracks. However, the outer layer of the string-like reinforcing fiber composite of the present invention is knitted. Since it is a braided tubular string having a shape structure or a braid structure and is not made of metal with corrosion, it has flexibility and is not affected by such a phenomenon.
In addition, the string-like reinforcing fiber composite of the present invention has excellent strength derived from basalt fiber, which is not surpassed by reinforcing bars, and is lightweight, so it has a steel structure, reinforced concrete and wooden buildings, bridges, etc. It can be preferably used as a brace material and a reinforcing material (including a substitute for a reinforcing metal fitting) used in the above. Moreover, since it has sufficient intensity | strength even if it is a thin thing, it is also possible to manufacture the building excellent in design property.
In particular, in the string-like reinforcing fiber composite of the present invention, when a thermoplastic resin is used for the intermediate layer, it can be stored and transported on a drum or the like because it has variability by applying heat. Can supply brace material with a scale.

  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.

  The diameter (outer diameter) of the string-like reinforcing fiber composite and the thickness of each layer in this example were measured with calipers.

Example 1
The cord-like basalt that is not twisted between the basalt fiber yarns at the time of manufacture, and is not substantially twisted even in the entire cord-like basalt fiber bundle in which the basalt fiber yarns are bundled. A fiber bundle was used as a core wire (inner layer). Then, 20 polyester filaments (1100 dtex) combined with 5 polyester filaments around the core wire as reinforcing yarns were arranged in the direction coaxial with the core wire, and the core wire was covered without a gap.
Next, use 12 pieces of vinylon spun (10th yarn) combined on the outer periphery of the reinforcing yarn, assemble with 12 stitches using a string making machine (24 punching machine), and knit around the reinforcing yarn An outer layer made of a tubular string was formed to obtain a string-like product.
Next, a solution made of a thermoplastic epoxy resin (XNR6850A, manufactured by Nagase ChemteX Corporation), a curing agent (XNH6850AY, manufactured by Nagase ChemteX Corporation), and an organic solvent (methyl ethyl ketone) (viscosity 66 mPa · s, B-type viscometer, rotor No. 4, 12 rpm) was applied at room temperature (20 ° C.) by a dip-nip method, passed through a die, the cross section was made circular, and heat treatment was performed at 150 ° C. for 10 minutes. After cooling. In this way, the cord-like basalt fiber bundle is coated with the thermoplastic resin, and an intermediate layer made of the thermoplastic resin including the reinforcing yarn is formed, and the inner layer, the intermediate layer, and the outer layer are bonded and integrated with the thermoplastic resin. The string-like reinforcing fiber composite of Example 1 was obtained. The string-like reinforcing fiber composite had an outer diameter of 6.6 mm, an outer layer thickness of 0.4 mm, an intermediate layer thickness of 0.9 mm, and an inner layer diameter of 4 mm. Further, it was confirmed that the basalt fiber yarn at the center of the string-like basalt fiber bundle was also bonded.
Further, the obtained string-like reinforcing fiber composite could be wound around a drum while still softening at 100 ° C.
Furthermore, the string-like reinforcing fiber composite wound around the drum could be pulled out while being heated to about 100 ° C. using a hot air fan.

(Example 2)
A string-like basalt fiber bundle not twisted was used in the same manner as in Example 1, and this was used as a core wire (inner layer). Then, 20 polyester filaments (1100 dtex) combined with 5 polyester filaments around the core wire as reinforcing yarns were arranged in the direction coaxial with the core wire, and the core wire was covered without a gap.
Next, the outer periphery of the reinforcing yarn is assembled using 12 polyester yarns (10th yarn) combined with 12 yarns, using a string making machine (24 punching machine) with 12 stones, and knitted around the reinforcing yarn. An outer layer made of a tubular string was formed to obtain a string-like product.
Next, a solution made of a thermoplastic epoxy resin (XNR6850A, manufactured by Nagase ChemteX Corporation), a curing agent (XNH6850AY, manufactured by Nagase ChemteX Corporation), and an organic solvent (methyl ethyl ketone) (viscosity 66 mPa · s, B-type viscometer, rotor No. 4, 12 rpm) was applied by a dipping method at room temperature (20 ° C.), and excess thermoplastic resin was removed while the cross section was made circular through a die. Next, heat treatment was performed at 150 ° C. for 10 minutes, followed by cooling. In this way, the cord-like basalt fiber bundle is coated with the thermoplastic resin, and an intermediate layer made of the thermoplastic resin including the reinforcing yarn is formed, and the inner layer, the intermediate layer, and the outer layer are bonded and integrated with the thermoplastic resin. The string-like reinforcing fiber composite of Example 2 was obtained. The string-like reinforcing fiber composite had an outer diameter of 6.6 mm, an outer layer thickness of 0.4 mm, an intermediate layer thickness of 0.9 mm, and an inner layer diameter of 4 mm. Further, it was confirmed that the basalt fiber yarn at the center of the string-like basalt fiber bundle was also bonded.
Further, the obtained string-like reinforcing fiber composite could be wound around a drum while still softening at 100 ° C.
Furthermore, the string-like reinforcing fiber composite wound around the drum could be pulled out while being heated to about 100 ° C. using a hot air fan.

(Example 3)
A string-like basalt fiber bundle not twisted was used in the same manner as in Example 1, and this was used as a core wire (inner layer). Then, 20 polyester filaments (1100 dtex) combined with 5 polyester filaments around the core wire as reinforcing yarns were arranged in the direction coaxial with the core wire, and the core wire was covered without a gap.
In contrast, a solution (viscosity 66 mPa · s, B-type viscometer) composed of a thermoplastic epoxy resin (XNR6850A, manufactured by Nagase ChemteX Corporation), a curing agent (XNH6850AY, manufactured by Nagase ChemteX Corporation), and an organic solvent (methyl ethyl ketone). , Rotor No. 4, 12 rpm) was applied with a brush at room temperature (20 ° C.), the excess solution was removed while squeezing with a gloved hand, heat treatment was performed at 150 ° C. for 10 minutes, and the cross section was cooled. Was arranged in a circle. In this way, an intermediate layer comprising a thermoplastic resin containing an inner layer composed of a string-like basalt fiber bundle coated with a thermoplastic resin and a reinforcing yarn was produced (1.5 m).
Next, 12 reinforcing yarns made of 5 vinylon filaments (1100 dtex) were combined around the outer periphery of the reinforcing yarn, and then knitted around the reinforcing yarn using a string making machine (24 punching machine). An outer layer made of a tubular cord was formed, heat treatment (150 ° C.) was performed, and the inner layer, the intermediate layer, and the outer layer were bonded and integrated.
The obtained string-like reinforcing fiber composite of Example 3 had an outer diameter of 6.6 mm, an outer layer thickness of 0.4 mm, an intermediate layer thickness of 0.9 mm, and an inner layer diameter of 4 mm. Further, it was confirmed that the basalt fiber yarn at the center of the string-like basalt fiber bundle was also bonded.
Moreover, the obtained string-like reinforcing fiber composite was softened at 100 ° C. and could be wound around a drum.
Furthermore, the string-like reinforcing fiber composite wound around the drum could be pulled out while being heated to about 100 ° C. (100 ° C.) using a hot air fan.

Example 4
A string-like basalt fiber bundle not twisted was used in the same manner as in Example 1, and this was used as a core wire (inner layer). Then, 20 polyester filaments (1100 dtex) combined with 5 polyester filaments around the core wire as reinforcing yarns were arranged in the direction coaxial with the core wire, and the core wire was covered without a gap.
Next, use 12 pieces of vinylon spun (10th yarn) combined on the outer periphery of the reinforcing yarn, assemble with 12 stitches using a string making machine (24 punching machine), and knit around the reinforcing yarn An outer layer made of a tubular string was formed to obtain a string-like product.
Next, a rod-shaped body obtained by cutting this string-like material by 1.5 m was used as a thermosetting epoxy resin (XNR3324, manufactured by Nagase ChemteX Corporation), a curing agent (XNH3324, manufactured by Nagase ChemteX Corporation), an organic solvent ( A solution composed of methyl ethyl ketone (viscosity 850 mPa · s, B-type viscometer, rotor No. 4, 12 rpm) was applied by a dip-nip method at room temperature (20 ° C.), and the cross-section was adjusted to a circular shape through a die. The resin was cured by standing at 20 ° C. for 7 days to obtain a string-like reinforcing fiber composite of Example 4. In the string-like reinforcing fiber composite of Example 4, a string-like carbon fiber bundle is coated with a resin, an intermediate layer made of a resin including a reinforcing thread is formed, and the inner layer, the intermediate layer, and the outer layer are bonded and integrated with the resin. The outer diameter was 6.6 mm, the outer layer thickness was 0.4 mm, the intermediate layer thickness was 0.9 mm, and the inner layer diameter was 4 mm. Further, it was confirmed that the basalt fiber yarn at the center of the string-like basalt fiber bundle was also bonded.

(Example 5)
A string-like basalt fiber bundle not twisted was used in the same manner as in Example 1, and this was used as a core wire (inner layer). Then, 20 polyester filaments (1100 dtex) combined with 5 polyester filaments around the core wire as reinforcing yarns were arranged in the direction coaxial with the core wire, and the core wire was covered without a gap.
Next, the outer periphery of the reinforcing yarn is assembled using 12 polyester yarns (10th yarn) combined with 12 yarns, using a string making machine (24 punching machine) with 12 stones, and knitted around the reinforcing yarn. An outer layer made of a tubular string was formed to obtain a string-like product.
Next, the rod-shaped body obtained by cutting this string-like material 2 m is a thermosetting epoxy resin (XNR3311, manufactured by Nagase ChemteX Corporation), a curing agent (XNH3311, manufactured by Nagase ChemteX Corporation), an organic solvent (methyl ethyl ketone). A solution (viscosity 850 mPa · s, B-type viscometer, rotor No. 4, 12 rpm) is applied by a dip method at room temperature (20 ° C.), and excess resin is removed while a circular cross section is passed through a die. The resin was cured by standing at room temperature (20 ° C.) for 7 days to obtain a string-like reinforcing fiber composite of Example 5. In the string-like reinforcing fiber composite of Example 5, a string-like basalt fiber bundle is coated with a resin, and an intermediate layer made of a resin including a reinforcing yarn is formed, and the inner layer, the intermediate layer, and the outer layer are bonded and integrated with the resin. The outer diameter was 6.6 mm, the outer layer thickness was 0.4 mm, the intermediate layer thickness was 0.9 mm, and the inner layer diameter was 4 mm. Further, it was confirmed that the basalt fiber yarn at the center of the string-like basalt fiber bundle was also bonded.

  The string-like reinforcing fiber composite of the present invention has a shape variability while maintaining mechanical performance such as tensile strength and elastic modulus derived from the basalt fiber that is a core wire, so that civil engineering, construction, marine, mining, Since it can be applied to all industrial fields such as fishery, and can be suitably used particularly as a concrete reinforcing bar, it is industrially promising.

Claims (9)

An inner layer comprising a core wire of one or more string-like basalt fiber bundles;
An intermediate layer including a resin provided around the core wire;
An outer layer formed of a knitted tubular cord provided around the intermediate layer;
A string-like reinforcing fiber composite comprising:   The string-like reinforcing fiber composite according to claim 1, wherein the intermediate layer is composed of a plurality of reinforcing yarns arranged in the same direction as the resin and the core wire.   The string-like reinforcing fiber composite according to claim 1 or 2, wherein the core wire constituting the inner layer comprises a string-like basalt fiber bundle coated with a resin.   The string-like reinforcing fiber composite according to claim 3, wherein the resin that coats the core wire and the resin that constitutes the intermediate layer are the same resin.   The string-like reinforcing fiber composite according to any one of claims 1 to 4, wherein the inner layer, the intermediate layer, and the outer layer are bonded and integrated with the same resin as that forming the intermediate layer.   The resin constituting the intermediate layer is at least one selected from the group consisting of polyether ether ketone, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyethylene resin, epoxy resin, urethane resin, polycarbonate resin, and polypropylene resin. The string-like reinforcing fiber composite according to any one of claims 1 to 5.   The string-like reinforcing fiber composite according to any one of claims 1 to 6, wherein the resin constituting the intermediate layer is a thermoplastic resin.   A concrete reinforcing bar comprising the string-like reinforcing fiber composite according to any one of claims 1 to 7.   A brace material comprising the string-like reinforcing fiber composite according to any one of claims 1 to 7.

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