WO2020166717A1

WO2020166717A1 - Resin filled fiber base material, fiber reinforced composite material and method for producing same

Info

Publication number: WO2020166717A1
Application number: PCT/JP2020/005887
Authority: WO
Inventors: 成相廣瀬; 明子平林
Original assignee: 第一工業製薬株式会社
Priority date: 2019-02-15
Filing date: 2020-02-14
Publication date: 2020-08-20
Also published as: JPWO2020166717A1; CN113412189A; KR20210126574A

Abstract

The purpose of the present invention is to prevent the occurrence of voids and to improve fixation force between reinforcing fibers and a matrix resin that is composed of a thermoplastic resin, thereby enhancing mechanical characteristics such as strength and elastic modulus with respect to a fiber reinforced composite material which is molded with use of a fiber base material, while using a thermoplastic resin as the matrix resin. A resin filled fiber base material, which is obtained by filling the spaces among fibers of a fiber base material with a thermoplastic polyurethane, and which is configured such that the amount of the thermoplastic polyurethane applied to the fiber base material is from 25 parts by mass to 100 parts by mass (inclusive) relative to 100 parts by mass of the fiber base material in terms of solid content.

Description

Resin-filled fiber base material, fiber-reinforced composite material, and method for producing the same

Cross-reference of related applications

This application is based on Japanese application No. 2019-025614 filed on February 15, 2019, the content of which is incorporated herein by reference.

The present disclosure relates to a resin-filled fiber base material, a fiber-reinforced composite material, and a manufacturing method thereof.

Conventionally, fiber-reinforced composite materials have been used that add physical properties such as tensile strength of synthetic resin products by adding carbon fibers and glass fibers to synthetic resins. A thermosetting resin such as an epoxy resin has been mainly used as the matrix resin of the fiber-reinforced composite material (see Patent Document 1).

However, when a thermosetting resin is used as the matrix resin, since a chemical reaction (curing reaction) of the thermosetting resin is involved during the molding of the fiber-reinforced composite material, it takes a long time to cure and the time required for molding becomes long, There was a problem that productivity was low. Further, there is a problem that it is not easy to reprocess the intermediate product of the fiber-reinforced composite material using the thermosetting resin as the matrix resin by changing the shape by pressing or the like.

On the other hand, unlike a thermosetting resin, a thermoplastic resin does not involve a chemical reaction (curing reaction) at the time of molding a fiber-reinforced composite material, so that the time required for molding can be shortened. Since it can be processed into an arbitrary shape by laminating and heating under pressure, and it can be easily processed into a molded article of another shape by melting, thermoplastic resin has begun to be used as the matrix resin of the fiber-reinforced composite material. There is.

Further, when a thermoplastic resin is used as a matrix resin, the affinity for fibers is low, and the strength of the fiber-reinforced composite material is low. Therefore, a sizing agent for improving the affinity between the thermoplastic resin and the fibers on the fiber surface. A technique for treating a sizing agent has been proposed (Patent Documents 2 to 4).

Conventionally, in molding a fiber-reinforced composite material using a thermoplastic resin, the reinforcing fiber is cut into about 10 mm or less, mixed with thermoplastic resin pellets as short fibers, extruded using an extruder, and molded in a mold. The method is generally used. However, according to such a material and method, the reinforcing fibers are oriented shorter and randomly in the extruder, so that the strength and elastic modulus of the fibers cannot be efficiently utilized in the fiber-reinforced composite material. In order to effectively utilize the performance of the reinforcing fiber, it is desirable to produce a fiber-reinforced composite material by using a continuous long fiber as a reinforcing material and adding a resin to a base material made of continuous fiber.

Japanese Patent Laid-Open No. 5-132863 JP, 2006-124847, A JP, 2011-21281, A JP, 2011-214175, A

The amount of voids inside the fiber-reinforced composite material is one of the factors that affect the performance of the fiber-reinforced composite material other than the affinity between the matrix resin and the fiber. Since the physical properties such as tensile strength can be enhanced as the amount of voids decreases, it is desirable to reduce the amount of voids. However, the form of the reinforcing fiber used in the fiber-reinforced composite material is a yarn bundle formed by bundling thousands to tens of thousands of single yarns having a diameter of about 5 to 10 μm. When the viscosity is high, it is difficult to infiltrate and embed the resin in the spaces between the single yarns in the yarn bundle or between the yarn bundles, and many voids are formed to form a fiber-reinforced composite material with excellent mechanical properties. Becomes difficult.

And, in the case of a thermoplastic resin, since the melt viscosity is higher than the viscosity of the thermosetting resin before curing, it is difficult to impregnate the resin into the gaps between single yarns or yarn bundles, especially as a reinforced fiber. It was difficult to produce a void-free fiber-reinforced composite material when using a woven fabric or a non-woven fabric-like base material of continuous fiber bundles.

The invention described in Patent Document 1 is a urethane having a hydroxyl group obtained from an epoxy resin having a viscosity at 50° C. of more than 1,000 poise and not more than 20,000 poise, a polyol having an oxyalkylene unit and a polyisocyanate. It is an invention relating to forming a sizing agent from a compound and treating the carbon fiber with the sizing agent, and discloses a carbon fiber in which the amount of the sizing agent attached is 0.1 to 10% by weight in terms of solid content. .. However, with such an amount of the sizing agent attached, it is not an amount that can completely fill the voids between the single yarns of the yarn bundle composed of continuous fibers and between the yarn bundles, and it is possible to form a fiber-reinforced composite material without voids. It was difficult.

Further, the inventions described in Patent Documents 2, 3 and 4 are techniques for improving the affinity between the thermoplastic resin as the matrix resin and the fiber by adding the modified polyolefin as the sizing agent to the continuous fiber bundle.

In addition, in the techniques described in Patent Documents 2 to 4, the amount of the sizing agent applied is 1 to 10% by mass with respect to the fiber, and the amount is not such that the gap between the single yarns can be completely filled and filled. However, it is only to connect single yarns by point contact, and it is difficult to form a fiber-reinforced composite material without voids. Further, since the modified polyolefin is thermally cured by the drying treatment, it cannot be applied to a fiber base material for a continuous fiber reinforced composite material using a thermoplastic resin as a matrix.

However, due to the superiority of thermoplastic resins such as ease of molding over thermosetting resins, there is a strong demand for application of fiber-reinforced composite materials using thermoplastic resins as matrix resins as a means for reducing the weight of automobiles and the like. ing.

Therefore, the present disclosure aims to prevent the occurrence of voids and enhance mechanical properties such as strength and elastic modulus in a fiber-reinforced composite material in which a thermoplastic resin is used as a matrix resin and molded using reinforcing fibers.

Also, the purpose is to improve the fixing force between the reinforcing fiber and the matrix resin of the thermoplastic resin and increase the strength of the fiber-reinforced composite material without using a sizing agent or a sizing agent.

The present disclosure as a means for solving the above problems is constituted by filling a space between fibers of a fiber base material with a thermoplastic polyurethane, and an application amount of the thermoplastic polyurethane to the fiber base material is a solid. The resin-filled fiber base material may be 25 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the fiber base material in terms of minutes.

In the resin-filled fiber base material, the amount of the thermoplastic polyurethane applied to the fiber base material is 25 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the fiber base material in terms of solid content. It may be a characteristic resin-filled fiber base material.

Further, in the resin-filled fiber base material, a cross-linking agent may be added to the thermoplastic polyurethane, which may be a resin-filled fiber base material.

In the resin-filled fiber base material, the amount of the crosslinking agent added is 0.5 parts by mass or more and 10 parts by mass or less in terms of solid content based on 100 parts by mass of the fiber base material. It may be a fiber base material.

In the resin-filled fiber base material, the cross-linking agent may be at least one of an oxazoline group-containing compound and a carbodiimide group-containing compound, and may be a resin-filled fiber base material.

Further, in the above resin-filled fiber base material, the fiber base material has a sheet shape or a yarn bundle shape, and the resin-filled fiber base material has a sheet shape or a string shape. Good.

In the resin-filled fiber base material, the diameter of the thermoplastic polyurethane particles may be 0.01 μm or more and 0.2 μm or less, and the resin-filled fiber base material may be used.

Alternatively, a fiber-reinforced composite material may be formed by laminating the above resin-filled fiber base material.

Also, a fiber-reinforced composite material molded article characterized by being molded from the above fiber-reinforced composite material may be used.

Further, to the fiber substrate, an aqueous resin dispersion in which thermoplastic polyurethane particles are dispersed in an aqueous medium is applied, and the aqueous medium is removed by a drying treatment to form a space between the fibers of the fiber substrate. A method for producing a resin-filled fiber base material, the method comprising: filling a thermoplastic polyurethane, and imparting the thermoplastic polyurethane to 25 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the fiber base material and molding. May be.

Further, in the above method for producing a resin-filled fiber base material, a method for producing a resin-filled fiber base material may be characterized in that a crosslinking agent is added to the thermoplastic polyurethane.

Further, in the method for producing a resin-filled fiber base material, the addition amount of the crosslinking agent is 0.5 parts by mass or more and 10 parts by mass or less in terms of solid content based on 100 parts by mass of the fiber base material. A method for producing a resin-filled fiber base material may be used.

Further, in the method for producing a resin-filled fiber base material, the fiber base material is a sheet shape or a yarn bundle shape, and the resin-filled fiber base material is a sheet shape or a string shape. A method of manufacturing the base material may be used.

Further, as a method for producing a fiber-reinforced composite material, the resin-filled fiber base material formed by the method for producing a resin-filled fiber base material described above is laminated, pressed and heated, and integrally formed. Good.

Further, the fiber-reinforced composite material formed by the above-described method for producing a fiber-reinforced composite material is singly laminated or aligned, heated under pressure and simultaneously formed into a predetermined shape, It may be a method of manufacturing a molded product.

According to the present disclosure as described above, since the space between the fibers of the fiber base material is configured to be filled with the thermoplastic polyurethane, it becomes possible to fill the synthetic resin between the fibers without a gap, and Prevents the occurrence of voids in the fiber-reinforced composite material that uses the thermoplastic resin as a matrix resin for molding, and strengthens the fixation between the matrix resin and the fiber base material, and improves the mechanical properties such as strength and rigidity of the fiber-reinforced composite material. It has become possible to raise it.

Furthermore, since a cross-linking agent is added to the thermoplastic polyurethane, it is possible to firmly hold the synthetic resin filled between the fibers, so that the thermoplastic resin molded using the reinforcing fibers is used as the matrix resin and is reinforced with fibers. Voids can be further prevented in the composite material, the matrix resin and the fiber base material are more firmly fixed, and the mechanical properties such as strength and rigidity of the fiber reinforced composite material can be further enhanced.

Further, since the thermoplastic polyurethane filled in the spaces between the fibers of the fiber base material and the thermoplastic polyurethane of the matrix resin laminated on the outer surface of the fiber base material firmly adhere to each other, a sizing agent or a sizing agent is used. Even without it, the fixing force between the reinforcing fiber and the matrix resin of the thermoplastic resin can be improved, and the strength of the fiber-reinforced composite material can be increased.

Also, it was possible to realize a fiber-reinforced composite material that is easy to mold and has a high degree of freedom in shape. Further, since this fiber-reinforced composite material uses a thermoplastic resin as a matrix resin, it becomes easy to reheat and re-mold it into a fiber-reinforced composite material having a desired shape. By applying the characteristics of these fiber-reinforced composite materials to the body of an automobile and the like, the weight of the automobile can be reduced and the fuel consumption can be improved.

Further, since the thermoplastic resin does not involve a chemical reaction, the resin can be impregnated between the fibers in a short time, so that the molding cycle of the fiber-reinforced composite material can be shortened and the productivity can be reduced to reduce the cost. ..

An embodiment of the present disclosure will be described below. The resin-filled fiber substrate of the present disclosure is configured by filling the spaces between the fibers of the fiber substrate with thermoplastic polyurethane, and the amount of the thermoplastic polyurethane applied to the fiber substrate is 100 parts by mass of the fiber substrate. It is a resin-filled fiber base material of 25 parts by mass or more and 100 parts by mass or less. Here, between the fibers means between the single yarns and between the yarn bundles in which the single yarns are bundled. Further, the fiber-reinforced composite material of the present disclosure is a fiber-reinforced composite material formed by laminating the resin-filled fiber base material of the present disclosure. Further, the fiber-reinforced composite material molded product of the present disclosure is a molded product molded from one or more fiber-reinforced composite materials of the present disclosure into a predetermined shape.

The fiber base material is a skeleton portion of a fiber reinforced composite material formed by using fibers for reinforcing synthetic resin, and the fibers and the fiber base material are for reinforcing a matrix resin composed of a thermoplastic resin. .. The shape of the fiber base material is not particularly limited, but may be a sheet shape or a yarn bundle shape.

The form of the sheet-shaped fibrous base material is not limited to this, but may be a knitted product obtained by knitting a single yarn or a bundle of plural single yarns in a bundle, a single yarn or a woven fabric of the yarn bundle, and a single yarn. Examples thereof include non-woven bonded or entangled non-woven fabrics, single yarns or yarn bundles aligned in one direction, interdigital products, paper-like products, and the like. The form of the fiber base material in the form of a yarn bundle is not limited to this, but a plurality of single yarns are knitted, or a yarn bundle formed into a bundle without knitting, a plurality of yarn bundles are knitted, or knitted. For example, a bundled product may be used.

In the case of a knitted fabric, a woven fabric, a fiber bundle in a state of being aligned in one direction, or a fiber base material in one direction, it is preferable to use continuous fibers from one end to the other end of the fiber base material. It is preferable to use a fiber having a continuous length or more from one end to the other end. That is, it is preferable to use continuous long fibers in the portion for reinforcing the fiber-reinforced composite material. With such a structure, the strength of the fiber-reinforced composite material can be increased. Further, the thickness of the fiber base material is not particularly limited as long as it is equal to or less than the fiber reinforced composite material.

The fiber as the reinforcing material of the thermoplastic resin is not particularly limited, but carbon fiber, aramid fiber, glass fiber, vinylon fiber, PBO fiber, etc. can be used. These fibers may be used alone or in combination of two or more. Although the diameter of the fiber is not particularly limited, a fiber having a diameter of 5 to 10 μm can be used. The yarn bundle in which the single yarns are bundled is not particularly limited, but a bundle of about 1,000 to 50,000 single yarns can be used.

・The space between the fibers of the fiber base material is filled with thermoplastic polyurethane, and the outer surface of the fiber base material is laminated with thermoplastic polyurethane to form a resin-filled fiber base material.

The thermoplastic polyurethane is for filling the spaces between the fibers of the fiber base material to prevent generation of voids in the fiber reinforced composite material, and for increasing the stress against displacement of the fiber reinforced composite material. Is. The reason why the thermoplastic polyurethane is used as the thermoplastic resin that fills the spaces between the fibers of the fiber base material is that it has good film-forming properties that can connect the single yarns in a dry state. The thermoplastic resin with which the space between the fibers is filled is preferably as high in heat resistance as possible. Furthermore, since the fiber-reinforced composite material is laminated in one layer or a plurality of layers to be reformed into another shape, it is preferable that it has thermoplasticity even after the thermoplastic resin is dried or cured. As the thermoplastic resin, thermoplastic polyurethane is used. Is preferable since it is easy to remold a flat fiber-shaped fiber-reinforced composite material into a product having a curved surface or the like, which has sufficient thermoplasticity even after being dried or cured.

Further, the form of filling the space between the fibers of the fiber base material with the thermoplastic polyurethane is not particularly limited, but in order to surely and uniformly fill the space between the fibers, the particles of the thermoplastic polyurethane are mixed with an aqueous medium. It is preferably in the form of an aqueous resin dispersion dispersed therein.

The average particle size of the thermoplastic polyurethane particles is not particularly limited, but may be set to about 0.01 to 1 μm in order to uniformly fill the spaces between the fibers, but the space between the fibers of the fiber base material may be shortened in a short time. In order to fill and evenly fill, 1/10 or less of the fiber diameter is preferable. Specifically, since the diameter of the fiber is usually 5 to 10 μm, it is preferably 0.5 μm or less, more preferably 0.1 μm or less, still more preferably 0.03 μm or less. The average particle diameter of the thermoplastic polyurethane particles is preferably 0.01 μm or more and 0.2 μm or less. The average particle diameter of the thermoplastic polyurethane particles means the 50% particle diameter (D50) measured by the laser diffraction light scattering method.

The concentration of non-volatile components in the water-based resin dispersion in which thermoplastic polyurethane particles are dispersed in water is not particularly limited, but the thermoplastic resin easily spreads into the space between single yarns and completely fills the space between single yarns. Therefore, the viscosity is preferably low, while the concentration is preferably high. Therefore, the mass ratio of the particles of the thermoplastic resin in the aqueous resin dispersion is preferably 20 to 40% by mass, more preferably 25 to 36% by mass. % Is preferred.

For the thermoplastic polyurethane, the polyol is not particularly limited, and a polyether type, a polyester type, a polycarbonate type, or the like is used. In particular, since a high hardness coating excellent in heat resistance can be formed, the polyether type is used. preferable.

The amount of the thermoplastic polyurethane applied to the fiber base material is preferably an amount capable of filling the spaces between the fibers of the fiber base material more, and more preferably, the amount more than completely filling the spaces between the fibers of the fiber base material. preferable. Here, assuming that the cross section of the single yarn constituting the fiber bundle is a circle and the single yarn in the fiber bundle is in a close packing state, the volume of the space between the single yarns is calculated by the following formula 1.
(Equation 1) 100×(3 ^1/2 −π/2)/(π/2)=10.2

Therefore, the thermoplastic polyurethane can completely fill the space between the fibers of the fiber base material by giving a volume of 10.2% to the volume of the fiber base material, that is, the fiber base material. Therefore, the amount of the thermoplastic polyurethane filled in the space between the fibers applied to the fiber base material is 10% or more in volume conversion with respect to the volume of the fiber base material, depending on the material of the fiber base material. You can

However, in practice, it is preferable to cover the surface of the single yarn between the single yarns with thermoplastic polyurethane, and to improve the adhesion with the matrix resin by appropriately laminating the outer surface of the fiber bundle, that is, the outer surface of the fiber base material. In order to obtain a void-free thermoplastic resin composite material, the amount of thermoplastic polyurethane applied to the fiber base material is a synthetic resin having a volume not less than that required to fill the space between the single yarns. Is preferably applied to the fiber base material. The applied amount of the thermoplastic polyurethane to the fiber base material is more preferably 11% to 30%, and even more preferably 11% to 20%, based on the volume of the fiber base material.

The method of filling the space between the fibers of the thermoplastic polyurethane is not particularly limited, using a water-based resin dispersion prepared by dispersing particles of the thermoplastic polyurethane in an aqueous medium, a known spray method, It is possible to use a method such as a dipping method or a roller impregnation method that can uniformly apply a required amount. Moreover, after applying the thermoplastic polyurethane between the fibers of the fiber base material, a drying treatment is performed to remove components other than the aqueous medium and the thermoplastic polyurethane in the aqueous resin dispersion. As a drying method, a method of contacting with hot air or a drying roller, a commonly used drying method such as infrared heating, sunlight, or other heating can be adopted.

Thus, by impregnating the fiber base material with the water-based resin dispersion in which the particles of the thermoplastic polyurethane are dispersed in the water-based medium, the thermoplastic polyurethane easily spreads between the single yarns and between the yarn bundles, and between the fibers. The space can be completely filled with the thermoplastic polyurethane, the generation of voids can be prevented, and a fiber-reinforced composite material with higher mechanical properties can be realized.

Further, the thermoplastic polyurethane is a base material of the fiber reinforced composite material, and the thermoplastic resin used as the matrix resin is the same thermoplastic polyurethane as the thermoplastic resin filled in the spaces between the fibers. The thermoplastic polyurethane as the matrix resin is laminated on the entire outer surface of the fiber base material, but may be laminated on only a part of the outer surface of the fiber base material.

The thermoplastic polyurethane laminated on the outer surface of the fiber base material is, for example, when the fiber base material is in the form of a sheet, both the upper and lower surfaces of the sheet-like fiber base material and the entire surface or a part of one of the upper and lower surfaces. It is also possible to have a structure in which only one layer is laminated. Then, the matrix resin has a three-layer structure in which it is arranged on both upper and lower surfaces of one resin-filled fiber base material, and a two-layer structure in which one of the upper surface and the lower surface of one resin-filled fiber base material is arranged. And so on. When the fiber base material is in the form of a yarn bundle, the fiber base material in the form of a yarn bundle may be laminated on the entire side surface or only a part thereof.

The reason why thermoplastic polyurethane is used as the matrix resin is that it has good film-forming properties that can connect yarn bundles or fiber substrates in a dry state. Further, the higher the heat resistance of the matrix resin is, the more preferable, and the thermoplastic polyurethane having excellent heat resistance is preferable. Furthermore, since the fiber reinforced composite material is laminated in one layer or a plurality of layers to be reformed into another shape, it is preferable that it has thermoplasticity, and has sufficient thermoplasticity even after being dried or cured to have a flat plate shape or the like. This is because it is easy to remold the fiber-reinforced composite material of (1) into a product having a curved surface, which is preferable.

In addition, as a form of laminating the thermoplastic polyurethane of the matrix resin on the fiber base material, in order to surely and evenly laminate on the fiber base material, an aqueous resin in which particles of the thermoplastic polyurethane are dispersed in an aqueous medium is used. It is preferably in the form of a dispersion. Incidentally, the diameter of the particles of thermoplastic polyurethane as the matrix resin, the concentration of non-volatile components of the water-based resin dispersion prepared by dispersing the particles of thermoplastic polyurethane in water, and the polyol are not particularly limited, but the spaces between the fibers are filled. It can be the same as the thermoplastic polyurethane.

At the time of producing a resin-filled fiber base material or a fiber-reinforced composite material, the method for laminating thermoplastic polyurethane on the fiber base material as a matrix resin is not particularly limited, and filling of spaces between fibers of thermoplastic polyurethane and It is preferable to carry out at the same time. By carrying out at the same time, the production of the fiber-reinforced composite material can be facilitated. When it is carried out simultaneously, it can be carried out by a method of filling the space between the fibers of the fiber base material with the above-mentioned thermoplastic polyurethane. It should be noted that the step of laminating the thermoplastic polyurethane as a matrix resin on the fiber base material is performed separately from the step of filling the space between the fibers of the fiber base material of the thermoplastic polyurethane, and the thermoplastic polyurethane is laminated on the fiber base material independently. May be In this case, for example, but not limited thereto, a film-shaped thermoplastic polyurethane serving as a matrix resin is laminated on a fiber substrate filled with thermoplastic polyurethane, and the matrix resin is heated under pressure to melt the matrix resin, It can be manufactured by bonding a fiber base material and a matrix resin.

The fiber-reinforced composite material is formed by laminating a plurality of fiber base materials in which spaces between the fibers are filled with thermoplastic polyurethane and a matrix resin, in other words, by laminating a resin-filled fiber base material to form a fiber base material. Is sandwiched between or covered with a matrix resin. The form of lamination is not particularly limited, and when the resin-filled fiber base material is in the form of a sheet, a resin-filled fiber base material having a three-layer structure in which a matrix resin is arranged on both upper and lower surfaces of one fiber base material is laminated. It is possible to adopt a structured structure, a structure in which a plurality of fiber base materials and a matrix resin are alternately laminated, or the like. When the resin-filled fiber base material is in the form of a string, a matrix resin is arranged on the outer surface of one fiber base material, and a two-layer structure in which the fiber base material and the matrix resin are laminated, and one fiber base material One or more resin-filled fiber base materials may be arranged on the outer side surface of the material on the outer side of the matrix resin, and the matrix resin may be arranged on the outer side surface of the resin-filled fiber base material to form a laminated structure.

Here, laminating the fiber base material and the matrix resin also includes covering the fiber base material with the matrix resin, and laminating the string-shaped resin-filled fiber base material includes two or more string-shaped resins. Bundling the filled fiber substrates is also included.

The amount of thermoplastic polyurethane applied to the fiber base material is preferably 25 parts by mass or more and 100 parts by mass or less based on 100 parts by mass of the fiber base material in terms of solid content. The amount of the thermoplastic polyurethane applied to the fiber base material is preferably 25 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the fiber base material in terms of solid content. Further, the amount of the thermoplastic polyurethane applied to the fiber base material is more preferably 40 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the fiber base material in terms of solid content.

The content of the fiber in the fiber-reinforced composite material and the content of the thermoplastic polyurethane are not particularly limited, and may be selected depending on the type of fiber, the form of the fiber base material, etc. in order to produce a predetermined fiber-reinforced composite material. I can.

A crosslinking agent may be added to the thermoplastic polyurethane. The cross-linking agent cross-links the thermoplastic polyurethane molecules filled in the spaces between the fibers, the thermoplastic polyurethane molecules as the matrix, and the thermoplastic polyurethane molecules filled in the spaces between the fibers and the thermoplastic polyurethane molecules as the matrix. The purpose of this is to prevent the thermoplastic polyurethane from flowing out from the space between the fibers and to securely fix the matrix resin to the fiber base material. Therefore, the cross-linking agent is for increasing the stress against the displacement of the fiber-reinforced composite material.

As the cross-linking agent in the present disclosure, a cross-linking agent having a self-crosslinking property and a compound having a plurality of functional groups that react with a carboxy group in the molecule can be used. Specific examples include an oxazoline group-containing compound, a carbodiimide group-containing compound, an isocyanate group-containing compound, an epoxy group-containing compound, a melamine compound, a urea compound, a zirconium salt compound, a silane coupling agent, and the like. You may mix and use thing. Among them, from the viewpoint of easy handling, oxazoline group-containing compounds, carbodiimide group-containing compounds, isocyanate group-containing compounds and epoxy group-containing compounds are preferable, and oxazoline group-containing compounds and carbodiimide group-containing compounds are more preferable. That is, it is preferable that the crosslinking agent contains at least one of an oxazoline group-containing compound and a carbodiimide group-containing compound.

The oxazoline group-containing compound is not particularly limited as long as it has at least two or more oxazoline groups in the molecule. For example, 2,2'-bis(2-oxazoline), 2,2'-ethylene-bis(4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline) Examples thereof include compounds having an oxazoline group such as bis(2-oxazolinylcyclohexane)sulfide, and polymers containing an oxazoline group. These compounds may be used alone or in combination of two or more. Among these, a compound having an oxazoline group is preferable from the viewpoint of easy handling.

The carbodiimide group-containing compound is not particularly limited as long as it has at least two carbodiimide groups in the molecule. Compounds having a carbodiimide group such as p-phenylene-bis(2,6-xylylcarbodiimide), tetramethylene-bis(t-butylcarbodiimide), cyclohexane-1,4-bis(methylene-t-butylcarbodiimide) And polycarbodiimide, which is a polymer having a carbodiimide group. These may be used alone or in combination of two or more. Among these, polycarbodiimide is preferable because it is easy to handle. Examples of commercially available products of polycarbodiimide include carbodilite series manufactured by Nisshinbo. Specific products include, for example, water-soluble type "SV-02", "V-02", "V-02-L2", "V-04", emulsion type "E-01", "E". -02”, organic solution type “V-01”, “V-03”, “V-07”, “V09”, solventless type “V-05” and the like.

The isocyanate group-containing compound is not particularly limited as long as it has at least two isocyanate groups in the molecule. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane 2,4'- or 4,4'-diisocyanate, polymethylene polyphenyl diisocyanate, tolidine diisocyanate, 1,4-diisocyanatobutane, Hexamethylene diisocyanate, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- or 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 4,4′-diisocyanatodicyclohexylmethane, hexahydrotoluene 2, 4- or 2,6-diisocyanate, perhydro-2,4'- or 4,4'-diphenylmethane diisocyanate, naphthalene 1,5-diisocyanate, xylylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, tetra Examples thereof include polyfunctional isocyanate compounds such as methylxylylene diisocyanate, and modified products thereof. Here, the modified product is obtained by modifying the diisocyanate of the polyfunctional isocyanate compound by a known method, for example, allophanate group, buret group, carbodiimide group, uretonimine group, uretdione group, Examples thereof include polyfunctional isocyanate compounds having an isocyanurate group and the like, and further adduct type polyfunctional isocyanate compounds modified with a polyfunctional alcohol such as trimethylolpropane. The isocyanate group-containing compound may contain monoisocyanate in the range of 20% by mass or less. In addition, these compounds may be used alone or in combination of two or more.

The isocyanate group-containing compound can be usually obtained by reacting a polyfunctional isocyanate compound with a monovalent or polyvalent nonionic polyalkylene ether alcohol. Examples of commercially available products of such an aqueous polyfunctional isocyanate compound include Bayhydur 3100, Bayhydur VPLS2150/1, SBU isocyanate L801, Desmodur N3400, Desmodur VPLS2102, and Desmodur VPLS2025 manufactured by Sumitomo Bayer Urethane Co., Ltd. /1, SBU isocyanate 0772, Desmodur DN, Mitsui Chemicals Takenate WD720, Takenate WD725, Takenate WD730, Asahi Kasei Duranate WB40-100, Duranate WB40-80D, Duranate WX-1741, BASF Bathonate ( Basonat) HW-100, Bathonate LR-9056 and the like.

The epoxy group-containing compound is not particularly limited as long as it has at least two epoxy groups in the molecule. For example, bisphenol A diglycidyl ether, bisphenol A β-dimethylglycidyl ether, bisphenol F diglycidyl ether, tetrahydroxyphenylmethane tetraglycidyl ether, resorcinol diglycidyl ether, brominated bisphenol A diglycidyl ether, chlorinated bisphenol A diglycidyl ether, Hydrogenated bisphenol A diglycidyl ether, bisphenol A alkylene oxide adduct diglycidyl ether, novolac glycidyl ether, polyalkylene glycol diglycidyl ether, glycerin triglycidyl ether, pentaerythritol diglycidyl ether, glycidyl ether type such as epoxy urethane resin, Glycidyl ether/ester types such as p-oxybenzoic acid glycidyl ether/ester, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, acrylic acid diglycidyl ester, dimer acid diglycidyl ester Glycidyl ester type such as glycidyl aniline, tetraglycidyl diaminodiphenylmethane, triglycidyl isocyanurate, glycidyl amine type such as triglycidyl aminophenol, epoxidized polybutadiene, linear aliphatic epoxy resin such as epoxidized soybean oil, 3,4- Epoxy-6 methylcyclohexylmethyl-3,4-epoxy-6 methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl (3,4-epoxycyclohexane)carboxylate, bis(3,4-epoxy-6 methylcyclohexylmethyl) Examples thereof include alicyclic epoxy resins such as adipate, vinylcyclohexene diepoxide, dicyclopentadiene oxide, bis(2,3-epoxycyclopentyl) ether, and limonenedioxide. These compounds may be used alone or in combination of two or more.

Examples of commercially available epoxy compounds include water-based ones suitable for the present disclosure, for example, Denacol series (EM-150, EM-101, etc.) manufactured by Nagase Chemtex, and Adeka Resin series manufactured by Adeka. ..

When the cross-linking agent is added to the thermoplastic polyurethane filled in the spaces between the fibers of the fiber base material and/or the thermoplastic polyurethane as the matrix resin, the form of the spaces between the fibers and the thermoplastic polyurethane molecules are In order to reliably and uniformly fill the space, it is preferable that the resin is dispersed in an aqueous solution or an organic solution. The composition containing the thermoplastic polyurethane and the cross-linking agent may be filled in the space between the fibers of the fiber base material and laminated on the outer surface of the fiber base material. For example, but not limited to, when the thermoplastic polyurethane is in the form of an aqueous resin dispersion, a fiber base material as a composition in which a crosslinking agent is dispersed in the aqueous medium by the method as described above. It is also possible to fill the space between the fibers with the thermoplastic polyurethane and the crosslinking agent, and laminate the thermoplastic polyurethane and the crosslinking agent on the outer surface of the fiber base material.

The addition amount of the cross-linking agent is not limited to this, because the processability and recyclability of the resin laminated base material and mechanical properties such as strength and elastic modulus are compatible with each other, but the solid content relative to 100 parts by mass of the fiber base material. It is preferably 0.5 to 10 parts by mass in terms of conversion. The addition amount of the crosslinking agent is more preferably 1 part by mass or more and 8 parts by mass or less, and further preferably 1.5 parts by mass or more and 5 parts by mass or less, in terms of solid content, based on 100 parts by mass of the fiber base material. The addition amount of the crosslinking agent is not limited to this, but is preferably 1 part by mass to 15 parts by mass in terms of solid content with respect to 100 parts by mass of the thermoplastic polyurethane. The addition amount of the cross-linking agent is more preferably 2 parts by mass or more and 12 parts by mass or less, and further preferably 3 parts by mass or more and 8 parts by mass or less in terms of solid content with respect to 100 parts by mass of the thermoplastic polyurethane.

The fiber-reinforced composite material molded product is a molded product molded into a predetermined shape by using one or more fiber-reinforced composite materials of the present disclosure, and a product manufactured using the fiber-reinforced composite material or a part thereof. It will be.

Next, a method of manufacturing the resin-filled fiber base material and the fiber-reinforced composite material will be described. In the following description, the case where a crosslinking agent is added will be described, but when the crosslinking agent is not added, the step of adding the crosslinking agent in the following method may be omitted. Using a water-based resin dispersion as a composition in which particles of a thermoplastic polyurethane and a cross-linking agent are dispersed in an aqueous medium, the fiber base material and the water-based resin dispersion are contacted by a known spray method or roller impregnation method. Let Then, the spaces between the fibers of the fiber base material are filled with particles of the thermoplastic polyurethane, and the particles of the thermoplastic polyurethane are adhered to the outer surface of the fiber base material to be laminated, and at the same time, a cross-linking agent is applied between the fibers of the fiber base material. And is added between the thermoplastic polyurethane molecules attached to the outer space of the fiber and the outer surface of the fiber. Next, in order to remove the aqueous medium in the aqueous resin dispersion, a drying treatment such as heat drying is performed to form a resin-filled fiber base material.

It should be noted that, using an aqueous resin dispersion prepared by dispersing thermoplastic polyurethane particles in an aqueous medium, the spaces between the fibers of the fiber base material are filled with the thermoplastic polyurethane particles, and heat is applied to the outer surface of the fiber base material. After the particles of the plastic polyurethane are adhered and laminated, a cross-linking agent dispersed in an aqueous solution or an organic solution is used to contact the particles of the thermoplastic polyurethane adhered to the fiber substrate by a known spray method or roller impregnation method. Alternatively, the cross-linking agent may be attached in the spaces between the fibers of the fiber base material and between the thermoplastic polyurethane molecules attached to the outer surfaces of the fibers. Further, after applying a cross-linking agent to the spaces between the fibers of the fiber base material and the outer surface, particles of thermoplastic polyurethane are applied to the spaces between the fibers of the fiber base material and the outer surface, and the cross-linking agent is added to the fiber base material. It may be added in the spaces between the fibers and between the thermoplastic polyurethane molecules attached to the outer surfaces of the fibers.

In the case of a sheet-shaped fiber base material, a space between the fibers is filled with thermoplastic polyurethane and a crosslinking agent, and a matrix resin is laminated on both upper and lower surfaces, that is, one resin-filled fiber. A plurality of sheet-shaped resin-filled fiber base materials having a structure in which the matrix resin is arranged on the upper and lower surfaces of the base material are laminated, and the matrix resin is heated under pressure to melt the matrix resin. Then, the matrix resins of the resin-filled fiber base material are adhered to each other to produce a sheet-shaped fiber-reinforced composite material.

In the case of a fiber base material in which the matrix resin is laminated only on one side of the upper and lower sides of the fiber base material, the resin-filled fiber base material is made into a plurality of layers with the surface on which the matrix resin is laminated and the surface not laminated facing each other. Layering, heating the matrix resin under pressure, melting the matrix resin, and adhering the fiber base material of one resin-filled fiber base material and the matrix resin of the other resin-filled fiber base material facing each other To manufacture.

Also, in the case of a yarn bundle-shaped fiber base material, a resin-filled fiber base material is formed by using a yarn bundle-shaped fiber bundle as the fiber base material. A fiber bundle-like fiber base material in which a space between fibers is filled with thermoplastic polyurethane and a cross-linking agent and a matrix resin is laminated on the surface of the fiber base material, that is, a matrix is provided on the outer surface of one resin-filled fiber base material. A two-layer structure string-shaped resin-filled fiber base material in which a resin is arranged is manufactured, and a plurality of the two-layer structure resin-filled fiber base materials are bundled and laminated, and the matrix resin is heated under pressure. , Melt the matrix resin. Then, the matrix resins of the resin-filled fiber base material are adhered to each other to manufacture a string-shaped fiber-reinforced composite material. In addition, laminating the fiber base material and the matrix resin also includes covering the fiber base material with the matrix resin.

Alternatively, a plurality of thread-bundle-shaped resin-filled fiber base materials may be bundled, heated under pressure to melt the matrix resin, and the matrix resins are adhered to each other to produce the fiber-reinforced composite material.

Also, as described above, the matrix resin may be attached to the fiber base material in a separate step, instead of being attached to the fiber base material at the same time as the thermoplastic polyurethane filling the space between the fibers. For example, a film-like thermoplastic polyurethane is used, a fiber base material in which spaces between fibers are filled with the thermoplastic polyurethane and a film-like matrix resin are laminated, and heated under pressure to melt the matrix resin, The resin-filled fiber base material or the fiber-reinforced composite material may be manufactured by adhering the fiber base material filled with the thermoplastic polyurethane with each other. In the case of such a production method, the cross-linking agent can be added to both the thermoplastic polyurethane filled in the spaces between the fibers and the thermoplastic polyurethane as the matrix resin, but can be added to only one of them. ..

When a film-shaped matrix resin is used, the matrix resin may be installed on the entire surface of the fiber substrate filled with thermoplastic polyurethane, but it may be installed on only one of the upper and lower surfaces of the sheet-shaped fiber substrate, or The yarn bundle may be manufactured without being installed on both end surfaces in the length direction and the matrix resin may be installed only on a part of the surface of the resin-filled fiber base material.

In addition, the resin-filled fiber base material is obtained by injecting molten matrix resin into a mold or the like, and applying the matrix resin to the fiber base material filled with thermoplastic polyurethane in the space between the fibers, which is placed in the mold. Alternatively, the fiber base material and the matrix resin may be adhered and solidified and laminated to manufacture.

When manufacturing a fiber-reinforced composite material, a plurality of fiber-reinforced composite materials molded as described above may be laminated and heated under pressure to melt and bond the matrix resins to each other. ..

Next, a method for manufacturing a fiber-reinforced composite material molded product will be described. The fiber-reinforced composite material alone is put into a mold, heated under pressure, and simultaneously molded into a predetermined shape to manufacture a fiber-reinforced composite material molded product. Further, a plurality of fiber-reinforced composite materials are laminated, bundled or aligned, put in a mold, heated under pressure, and simultaneously molded into a predetermined shape to manufacture a fiber-reinforced composite material molded product.

Hereinafter, the present invention will be described in more detail with reference to examples. As the fiber substrate, a unidirectional non-crimp fabric (made by Sakai Sangyo Co., Ltd.) having a width of 250 mm and using 84 carbon roving T300-12K manufactured by Toray Industries, Inc. was used. Each of these 250 mm×125 mm fibrous base materials has a water-based polyurethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as a thermoplastic polyurethane (Superflex 130 (SF-130), non-yellowing, ether-based, average particle size 0.03 μm , Solid content 35 wt%) in an amount of 25 parts by mass or more and 70 parts by mass or less in terms of solid content based on 100 parts by mass of the fiber base material, and after drying in the sun, dried in a vacuum dryer at 100° C. for 1 hour. To form a resin-filled fiber base material. The dry film of Superflex 130 has a glass transition temperature of 101°C, a softening temperature of 174°C, and a heat melting temperature of 216°C.

Then, after applying a silicon mold release agent to a flat plate mold at room temperature, four resin-filled fiber base materials formed as described above are placed on the flat plate mold and melted at 240° C. for 5 minutes, While maintaining the temperature at 240° C., the fiber-reinforced composite material having a thickness of about 1 mm was obtained by pressurizing with a pressure of 3 MPa to integrate the materials (Examples 1 and 2).

Further, as the fiber base material, a unidirectional non-crimp fabric (made by Sakai Sangyo Co., Ltd.) having a width of 250 mm and using 84 carbon roving T300-12K manufactured by Toray Industries, Inc. was used. Each of these 250 mm×125 mm fibrous base materials has a water-based polyurethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd. as a thermoplastic polyurethane (Superflex 130 (SF-130), non-yellowing, ether-based, average particle size 0.03 μm). , Solid content 35 wt%) in an amount of 70 parts by mass or more in terms of solid content based on 100 parts by mass of the fiber base material, dried in the sun, and then dried in a vacuum dryer at 100° C. for 1 hour to obtain a resin-filled fiber base. The material was formed.

Then, after applying a silicone release agent to a vacuum mold at room temperature, eight resin-filled fiber base materials formed as described above are placed on the vacuum mold in a stacked manner and melted at 240° C. for 10 minutes, While maintaining the temperature at 240° C., the fiber-reinforced composite material having a thickness of about 2 mm was obtained by pressurizing at a pressure of 6.8 MPa to integrate the materials (Example 3).

Further, as the fiber base material, a unidirectional non-crimp fabric of width 250 mm using 84 carbon roving T300-12K manufactured by Toray Industries, Inc. (manufactured by Sakai Sangyo Co., Ltd.) was used, and each of these fiber base materials of 250 mm×125 mm was used. In addition, as a thermoplastic polyurethane, a water-based polyurethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (Superflex 210 (SF-210), non-yellowing, ester-based, average particle size 0.04 μm, solid content 35 wt%) was used as a fiber base material. It was applied in an amount of 25 parts by mass or more and 100 parts by mass or less in terms of solid content with respect to 100 parts by mass, dried in the sun and then dried in a vacuum dryer at 100° C. for 1 hour to form a resin-filled fiber base material.

Then, after applying a silicon mold release agent to a flat plate mold at room temperature, four resin-filled fiber base materials formed as described above are placed on the flat plate mold and melted at 240° C. for 5 minutes, While maintaining the temperature of 240° C., the fiber-reinforced composite material having a thickness of about 1 mm was obtained by pressurizing with a pressure of 3 MPa and integrating (Example 4).

As a comparative example, the fiber base material used in Examples 1 and 2 was used, a frame mold was placed in a flat plate mold at room temperature, and a silicone mold release agent was applied to the inside of the frame mold. A polypropylene (PP) film having a basis weight of 136 g/m ² is placed on the upper and lower surfaces, melted at 200° C. for 5 minutes, and pressed at a pressure of about 7 MPa while maintaining 200° C. to integrate to obtain a fiber-reinforced composite material. (Comparative example 1).

Further, as the fiber base material, a unidirectional non-crimp fabric of width 250 mm using 84 carbon roving T300-12K manufactured by Toray Industries, Inc. (manufactured by Sakai Sangyo Co., Ltd.) was used, and each of these fiber base materials of 250 mm×125 mm was used. As a thermoplastic polyurethane, a water-based polyurethane resin manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (Superflex 130 (SF-130), non-yellowing, ether-based, average particle diameter 0.03 μm, solid content 35 wt%) was used as a fiber base material. It is added in an amount of 25 parts by mass or more and 100 parts by mass or less in terms of solid content with respect to 100 parts by mass, and "Carbodilite V-02-L2" (solid content 40 wt%) manufactured by Nisshinbo Chemical Co., Ltd. is used as a carbodiimide crosslinking agent, or oxazolidine. "Epocros WS-700" (solid content 25 wt%) manufactured by Nippon Shokubai Co., Ltd. as a system cross-linking agent was applied to 100 parts by mass of the fiber base material in the range of 0.5 parts by mass or more and 10 parts by mass or less in terms of solid content. After drying in the sun, it was dried in a vacuum dryer at 100° C. for 1 hour to form a resin-filled fiber base material.

Then, after applying a silicon mold release agent to a flat plate mold at room temperature, four resin-filled fiber base materials formed as described above are placed on the flat plate mold and melted at 240° C. for 5 minutes, While maintaining 240° C., pressure was applied at a pressure of 3 MPa for integration to obtain a fiber-reinforced composite material having a thickness of about 1 mm (Examples 5 to 8, Example 10).

Further, as the fiber base material, a unidirectional non-crimp fabric of width 250 mm using 84 carbon roving T300-12K manufactured by Toray Industries, Inc. (manufactured by Sakai Sangyo Co., Ltd.) was used, and each of these fiber base materials of 250 mm×125 mm was used. In addition, as a thermoplastic polyurethane, a water-based polyurethane resin (Superflex 130 (SF-130), non-yellowing, ether-based, average particle size 0.03 μm, solid content 35 wt%) manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was used as a fiber base material. 70 parts by mass or more in terms of solid content is added to 100 parts by mass, and "Carbodilite V-02-L2" (solid content 40 wt%) manufactured by Nisshinbo Chemical Co., Ltd. (solid content 40 wt%) is added to 100 parts by mass of the fiber substrate as a carbodiimide crosslinking agent. Then, it was applied in the range of 0.5 parts by mass or more and 10 parts by mass or less in terms of solid content, dried in the sun, and then dried in a vacuum dryer at 100° C. for 1 hour to form a resin-filled fiber base material.

Then, after applying a silicone release agent to a vacuum mold at room temperature, eight resin-filled fiber base materials formed as described above are placed on the vacuum mold in a stacked manner and melted at 240° C. for 10 minutes, While maintaining the temperature at 240° C., the fiber-reinforced composite material having a thickness of about 2 mm was obtained by pressurizing with a pressure of 6.8 MPa to integrate (Example 9).

Using a diamond cutter, these fiber reinforced composite materials were cut into a piece having a width of 15 mm and a length of 100 mm to prepare a test piece, and a bending test was carried out under the following measurement conditions according to JIS K7074 to measure the bending strength. ..
Crosshead speed: 5mm/min
Distance between spans: 80 mm

The results of Examples 1 to 4 and Comparative Example 1 are shown in Table 1. The numerical values of water-based polyurethane resin SF-130 (Superflex 130), water-based polyurethane resin SF-210 (Superflex 210), and PP (polypropylene) in Table 1 are parts by mass with respect to 100 parts by mass of the fiber base material. .. For the water-based polyurethane resins SF-130 and SF-210, the physical adhesion amount and the solid content conversion adhesion amount are described.

Table 2 shows the results of Examples 5 to 10. The numerical values of the water-based polyurethane resin SF-130 (Superflex 130), the carbodiimide-based cross-linking agent and the oxazolidine-based cross-linking agent in Table 2 are parts by mass based on 100 parts by mass of the fiber base material. The water-based polyurethane resin SF-130, the carbodiimide-based cross-linking agent, and the oxazolidine-based cross-linking agent are described in terms of the physical adhesion amount and the solid content conversion adhesion amount, respectively.

As is clear from Table 1 and Table 2, the thermoplastic polyurethane is applied to 25 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the fiber base material, and the space between the fibers of the fiber base material is filled with the thermoplastic polyurethane. In addition, it is understood that the bending strength is increased by laminating the thermoplastic polyurethane as the matrix resin on the outer surface of the fiber base material. Further, it is found that the bending strength is further increased by adding the crosslinking agent to the thermoplastic polyurethane in the range of 0.5 parts by mass or more and 10 parts by mass or less in terms of solid content with respect to 100 parts by mass of the fiber base material. ..

A fiber-based material is impregnated with an aqueous resin dispersion in which thermoplastic polyurethane particles are dispersed in an aqueous medium to fill the spaces between the fibers of the fiber-based material with the thermoplastic polyurethane, and at the same time, the thermoplastic polyurethane matrix resin is used. By producing a fiber reinforced composite material by sandwiching a fiber base material, a void-free fiber reinforced thermoplastic resin composite material can be easily produced and the production time can be shortened. Therefore, it is possible to reliably supply a fiber-reinforced composite material having excellent mechanical properties, which can contribute to weight reduction and strength improvement of various products such as automobiles, and can be used as a material for various products. Can be done.

Claims

The space between the fibers of the fiber base material is filled with thermoplastic polyurethane, and the amount of the thermoplastic polyurethane applied to the fiber base material is 25 parts by mass based on 100 parts by mass of the fiber base material in terms of solid content. A resin-filled fiber base material, characterized in that the content is not less than 100 parts by mass.
The amount of the thermoplastic polyurethane applied to the fiber base material is 25 parts by mass or more and 70 parts by mass or less based on 100 parts by mass of the fiber base material in terms of solid content. Filled fiber base material.
The resin-filled fiber base material according to claim 1 or 2, wherein a cross-linking agent is added to the thermoplastic polyurethane.
The resin-filled fiber base material according to claim 3, wherein the amount of the crosslinking agent added is 0.5 parts by mass or more and 10 parts by mass or less in terms of solid content with respect to 100 parts by mass of the fiber base material.
The resin-filled fiber base material according to claim 3 or 4, wherein the crosslinking agent contains at least one of an oxazoline group-containing compound and a carbodiimide group-containing compound.
The resin filling according to any one of claims 1 to 5, wherein the fiber base material has a sheet shape or a yarn bundle shape, and the resin-filled fiber base material has a sheet shape or a string shape. Fiber substrate.
The resin-filled fiber base material according to any one of claims 1 to 6, wherein the thermoplastic polyurethane particles have an average particle size of 0.01 µm or more and 0.2 µm or less.
A fiber-reinforced composite material, characterized in that the resin-filled fiber base material according to any one of claims 1 to 7 is laminated.
A fiber-reinforced composite material molded product, which is molded with the fiber-reinforced composite material according to claim 8.
To the fiber base material, an aqueous resin dispersion in which thermoplastic polyurethane particles are dispersed in an aqueous medium is applied, and the aqueous medium is removed by a drying treatment, and the space between the fibers of the fiber base material is heated. A method for producing a resin-filled fiber base material, which comprises filling a thermoplastic polyurethane and applying the thermoplastic polyurethane in an amount of 25 parts by mass or more and 100 parts by mass or less to 100 parts by mass of the fiber base material in terms of solid content and molding. ..
The method for producing a resin-filled fiber base material according to claim 10, wherein a crosslinking agent is added to the thermoplastic polyurethane.
The amount of the cross-linking agent added is 0.5 parts by mass or more and 10 parts by mass or less in terms of solid content based on 100 parts by mass of the fiber substrate, and the resin-filled fiber substrate according to claim 11. Production method.
The resin filling according to any one of claims 10 to 12, wherein the fiber base material has a sheet shape or a yarn bundle shape, and the resin-filled fiber base material has a sheet shape or a string shape. A method for manufacturing a fiber base material.
A resin-filled fiber base material formed by the method for producing a resin-filled fiber base material according to any one of claims 10 to 13, is laminated, pressed and heated, and integrally formed. A method for producing a fiber-reinforced composite material.
The fiber-reinforced composite material formed by the method for producing a fiber-reinforced composite material according to claim 14, wherein the fiber-reinforced composite material is singly laminated or aligned, heated under pressure, and simultaneously formed into a predetermined shape. Manufacturing method of composite molded article.