WO2019163578A1 - Method for producing carbon-fiber-reinforced thermoplastic-resin composite material - Google Patents

Method for producing carbon-fiber-reinforced thermoplastic-resin composite material Download PDF

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Publication number
WO2019163578A1
WO2019163578A1 PCT/JP2019/004807 JP2019004807W WO2019163578A1 WO 2019163578 A1 WO2019163578 A1 WO 2019163578A1 JP 2019004807 W JP2019004807 W JP 2019004807W WO 2019163578 A1 WO2019163578 A1 WO 2019163578A1
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Prior art keywords
carbon fiber
composite material
resin
fiber
thermoplastic
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PCT/JP2019/004807
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French (fr)
Japanese (ja)
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角田　敦
杉山　和夫
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有限会社文殊工学医学研究所
ビードローン株式会社
株式会社星山工業
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Publication of WO2019163578A1 publication Critical patent/WO2019163578A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4242—Carbon fibres

Definitions

  • the present invention relates to a method for producing a fiber-reinforced thermoplastic resin composite material from carbon fibers.
  • Fiber reinforced composite material such as carbon fiber is attracting attention as a lightweight material and is widely used in aircraft, automobiles, windmill blades, robot arms, drones, sports equipment and the like.
  • the reduction in weight leads to an improvement in fuel consumption and a reduction in environmental burden, and therefore the market for fiber-reinforced composite materials is expected to continue to expand.
  • scrap materials in the process of manufacturing fiber reinforced composite materials and waste composite materials with a long service life are already on the scale of tens of thousands of tons per year. Therefore, CFRP waste material recycling technology is extremely important, and several methods have been proposed (Patent Documents 1 and 2).
  • Citation 1 relates to a technique (thermal decomposition method) for recovering carbon fiber from a composite material (hereinafter CFRP) in which a thermosetting resin (mainly epoxy resin) is reinforced with carbon fiber.
  • CFRP composite material
  • the discarded CFRP is cut into an appropriate size and oxidized in air at about 550 ° C. to recover the remaining carbon fiber.
  • the high temperature treatment is performed in an oxidizing atmosphere, there is a problem that the carbon fiber is oxidized and the strength is lowered.
  • the recovered carbon fibers are entangled in the thermal decomposition process, it is difficult to process the composite material.
  • Patent Document 2 cuts discarded CFRP into a size of about 20 mm, and heat-treats it at about 450 ° C. or less at which no carbon fiber oxidation reaction occurs in air.
  • the heat-treated CFRP is immersed in an electrolyte solution, and when CFRP is used as an anode for the electrolytic treatment, the resin residue carbonized by the heat treatment is released and the carbon fiber is recovered.
  • the electrolytic treatment since the electrolytic treatment is performed in a stationary state, the orientation of the collected carbon fiber is linear and wet in the state of CFRP, so that it is easy to form a nonwoven fabric and easy to process into a composite material. is there. Further, there is almost no decrease in the strength of the carbon fiber in the recovery process.
  • the productivity is good.
  • the resin is thermosetting, it may be cured and molded by impregnating the resin between single yarns constituting the fiber base while the resin viscosity before curing is low.
  • melt viscosity is high when the resin is thermoplastic, it is difficult to impregnate the resin between the single yarns constituting the fiber base material.
  • Increasing the basis weight of the nonwoven fabric in order to increase molding productivity will further reduce the resin impregnation property, making it difficult to produce high performance composite materials.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 6-298993
  • Patent Document 2 Japanese Patent No. 6044946 The entire description of Patent Documents 1 and 2 is specifically incorporated herein by reference.
  • thermoplastic resin When mass-producing a composite material in which a thick carbon fiber nonwoven fabric is used as a reinforcing material and a thermoplastic resin is used as a matrix resin, there are the following problems. (1) Since the melt viscosity of a thermoplastic resin is generally extremely high, it is difficult to impregnate the resin between the reinforcing fiber single yarns constituting the nonwoven fabric. (2) In order to increase the productivity of the composite material, it is conceivable to use a thick non-woven fabric as a reinforcing material, but the difficulty of impregnation with the thermoplastic resin is further increased.
  • An object of the present invention is to solve the above-mentioned two problems by providing a method for producing a composite material that is simple and excellent in mechanical properties for making a carbon fiber non-woven fabric and making it a fiber-reinforced thermoplastic resin composite material. It is to provide.
  • the present invention is as follows. [1] (A) Carbon fiber is made into a nonwoven fabric together with a water-based self-emulsifying emulsion of a thermoplastic urethane resin, or (B) A water-based self-emulsifying emulsion of a thermoplastic urethane resin is added to a wetted carbon fiber nonwoven fabric to produce a thermoplastic urethane.
  • a method for producing a fiber-reinforced thermoplastic resin composite material [2]
  • the said thermoplastic urethane resin is a manufacturing method as described in [1] whose glass transition temperature is 40 degreeC or more.
  • thermoplastic urethane resin is a non-yellowing ester-based, non-yellowing ester-ether-based, non-yellowing carbonate-based, or aromatic isocyanate-based water-based urethane resin
  • the emulsion has a particle size of 0.01 to
  • the carbon fibers used in the step (1) are obtained by heat-treating the carbon fiber composite material in an oxidizing atmosphere, then anodizing, and separating and collecting the carbon fibers from the resin component contained in the carbon fiber composite material.
  • the wet carbon fiber in (A), the wet carbon fiber is used as it is for making a non-woven fabric, and in (B), a wet carbon fiber non-woven fabric is used to obtain a wet carbon fiber non-woven fabric.
  • [6] The production method according to any one of [1] to [5], wherein the nonwoven fabric obtained in the step (1) has a basis weight in a range of 100 g to 2000 g / m 2 .
  • a composite material having excellent mechanical properties using a thermoplastic resin as a matrix can be produced. According to this production method, high productivity can be achieved. Mass production of composite materials is also possible.
  • the manufacturing method of the fiber reinforced thermoplastic resin composite material of the present invention includes the following steps (1) and (2).
  • Step (1) Carbon fiber is made into a nonwoven fabric together with an aqueous self-emulsifying emulsion of thermoplastic urethane resin, or
  • An aqueous self-emulsifying emulsion of thermoplastic urethane resin is added to the wetted carbon fiber nonwoven fabric. And dried to obtain a nonwoven fabric sheet adhered and coated with a thermoplastic urethane resin.
  • Step (2) At least one nonwoven fabric sheet obtained in Step (1) and at least one thermoplastic resin sheet as a matrix member are alternately laminated, and then heated to obtain a fiber-reinforced thermoplastic resin composite material. .
  • Carbon fiber is made into a nonwoven fabric together with a water-based self-emulsifying emulsion of thermoplastic urethane resin.
  • carbon fibers are mixed with a water-based self-emulsifying emulsion of a thermoplastic urethane resin, and then made into a nonwoven fabric by a conventional method.
  • a water-based self-emulsifying emulsion of a thermoplastic urethane resin is applied to the wetted non-woven carbon fiber, followed by drying to obtain a non-woven fabric sheet bonded and coated with the thermoplastic urethane resin.
  • the wet carbon fiber nonwoven fabric preferably has a moisture content of, for example, 10% or more, and more preferably 30% or more.
  • the water-based emulsion is a self-emulsifying type, it does not contain extra components such as surfactants, and does not impair the physical properties of the composite material when made into a composite material, and has excellent strength even when using recovered carbon fibers. It is suitable because a composite material can be obtained.
  • a new cut carbon fiber may be a new cut carbon fiber alone or a mixture of recovered carbon fibers described in Patent Document 2.
  • a new cut carbon fiber it is used in the method (A) of the step (1), or after the new cut carbon fiber is wetted by a conventional method, the method of the step (1) (B) It can also be used.
  • thermoplastic urethane resin used here forms a thermoplastic film having a heat resistance of 250 ° C. or higher after drying.
  • the particle size of the water-based emulsion is preferably in the range of 0.01 to 0.1 ⁇ m, for example, from the viewpoint that it can be impregnated between carbon fibers having a single yarn diameter of about 5 to 10 ⁇ m.
  • the glass transition temperature is, for example, The temperature is preferably in the range of 40 ° C. or higher, more preferably in the range of 80 ° C. or higher.
  • the material of the thermoplastic urethane resin is not particularly limited, and examples thereof include a non-yellowing ester-based, a non-yellowing ester / ether-based, a non-yellowing carbonate-based, or an aromatic isocyanate-based water-based urethane resin.
  • a water-based self-emulsifying emulsion of a thermoplastic urethane resin having the glass transition temperature and the particle size of the emulsion can be obtained as a commercial product, for example, from Daiichi Kogyo Seiyaku Superflex series.
  • the amount of the emulsion used is such that the emulsion is used in a solid content of, for example, 5 to 15 parts by mass with respect to 100 parts by mass of the carbon fiber, even when recycled carbon fiber is used. This is suitable from the viewpoint of improving the adhesiveness to the thermoplastic resin by coating and obtaining a composite material having excellent mechanical strength. If it is less than 5 parts by mass, it is difficult to completely fill the voids between the single yarns with resin, and it tends to be difficult to obtain a composite material having excellent mechanical properties. Even if it exceeds 15 parts by mass, there is a tendency that a composite material having more excellent mechanical properties cannot be obtained.
  • the nonwoven fabric obtained in the step (1) preferably has a basis weight in the range of 100 g to 2000 g / m 2 . If the basis weight is 100 g / m 2 or less, the productivity of the composite material is low, so the economic effect of the present invention tends to be poor. On the other hand, if it is 2000 g / m 2 or more, it tends to be technically difficult to make a nonwoven fabric, and it takes time for drying after making the nonwoven fabric, so that the economy tends to decrease.
  • the nonwoven fabric bonded and coated with the thermoplastic urethane resin is preferably heat-dried before being subjected to the step (2).
  • the heat drying can be appropriately determined in consideration of the thermal characteristics of the thermoplastic urethane resin and the good adhesion and coating of the carbon fibers. For example, it can be dried in the range of 100 to 160 ° C. Examples of the drying method include hot air drying, hot plate drying, and infrared drying. It is preferable to flatten by pressurization after drying.
  • the dried nonwoven fabric has a moisture content of 5% or less, preferably 1% (almost absolutely dry).
  • step (2) at least one nonwoven fabric obtained in step (1) and at least one thermoplastic resin sheet as a matrix member are alternately laminated, and then heated to obtain a fiber-reinforced thermoplastic resin composite material.
  • the thermoplastic resin sheet used in the step (2) constitutes a matrix member of a composite material.
  • the thermoplastic resin with high adhesive force with the thermoplastic urethane resin for filling is preferable.
  • a synthetic resin that melts below the thermal decomposition temperature of the thermoplastic urethane resin is preferred.
  • nylon, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or the like can be used.
  • At least one non-woven fabric and at least two thermoplastic resin sheets as a matrix member are alternately laminated.
  • the nonwoven fabric is sandwiched so that both sides of the nonwoven fabric are covered with the thermoplastic resin sheet. That is, n + 1 thermoplastic resin sheets are alternately laminated on n nonwoven fabrics.
  • the thickness of the thermoplastic resin sheet can be appropriately determined according to the basis weight of the nonwoven fabric and further according to a desired mass ratio between the nonwoven fabric in the composite material and the thermoplastic resin as the matrix member.
  • the mass ratio between the nonwoven fabric and the thermoplastic resin as the matrix member is not particularly limited, but can be in the range of 10 to 1000 parts by mass of the thermoplastic resin as the matrix member with respect to 100 parts by mass of the nonwoven fabric.
  • the ratio of the fiber and the resin is not particularly limited, but the fiber volume content is preferably 20 to 80%. If it is 20% or less, the mechanical properties as a composite material are low, and there is little meaning to apply. If it exceeds 80%, the mechanical properties may deteriorate.
  • the obtained laminate is heated to obtain a fiber reinforced thermoplastic resin composite material. It is preferable to apply pressure from both sides of the laminate during heating.
  • the heating temperature can be appropriately determined in consideration of the thermoplasticity (melting temperature) of the thermoplastic resin constituting the thermoplastic resin sheet. Furthermore, the pressure of pressurization can be appropriately determined in consideration of the heating temperature and the viscosity of the thermoplastic resin at that temperature.
  • the uppermost surface of the flattened nonwoven fabric, the nonwoven fabric, and the thermoplastic resin film are alternately arranged and integrated by heating and pressurization to produce a fiber-reinforced thermoplastic resin composite material.
  • Example 1-1 (in the case of recycled carbon fiber) (1) The CFRP collected with reference to the cited document 2 was cut to 20 mm and then heated at 375 ° C. for 1 hour to remove most of the matrix resin. Subsequently, it was immersed in a 0.2 N aqueous sulfuric acid solution and anodized at 12 V for 3 minutes. (2) The collected massive carbon fibers were washed with water and dehydrated to obtain recovered carbon fibers having a moisture content of 50%. A nonwoven fabric having a fiber weight per unit area of 360 g / m 2 (water content 50%) was prepared according to a conventional method.
  • Example 1-2 Collected carbon fibers recovered in the same manner as in Example 1-1 (1) were washed with water and dehydrated to obtain recovered carbon fibers having a moisture content of 50%. To this, an amount corresponding to a solid content of 36 g / m 2 of a non-yellowing ether-based self-emulsifying type polyurethane emulsion “Superflex 130” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was added. Produced a non-woven fabric of 360 g / m 2 (water content 50%). Next, it was dried with hot air at 120 ° C. for 2 hours on a wire mesh. After drying, the sheet was removed from the wire mesh to obtain a plate-like sheet having a thickness of 0.2 mm. A plate-like composite material was obtained from this sheet in the same procedure as in Example 1-1 (4). A composite tensile strength almost equivalent to that of the plate-like composite material of Example 1-1 was obtained.
  • Example 2-1 Normal Nonwoven Fabrication Method (1) 360 g of continuous carbon fibers composed of 12,000 single yarns having a diameter of 7 microns were cut into a length of 20 mm and dispersed in water in which an anionic surfactant was dissolved. (2) The dispersion was filtered through a 100 cm square wire mesh to obtain a wet nonwoven fabric (fiber basis weight in a dry state: 360 g / m 2 ). The whole wire mesh was pressed to make the moisture content 50%.
  • Example 2-2 A non-yellowing ether manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was used in a dispersion obtained by dispersing carbon fibers in water in which an anionic surfactant was dissolved, obtained in the same manner as in Example 1-1 (1).
  • a solid content of 36 g of the system self-emulsifying type polyurethane emulsion liquid “Superflex 130” was added and filtered through a 100 cm square metal mesh to obtain a wet nonwoven fabric (fiber basis weight in a dry state: 360 g / m 2 ). The whole wire mesh was pressed to make the moisture content 50%. This was dried with hot air at 120 ° C. for 2 hours.
  • Example 1-1 After drying, it was removed from the wire mesh and hot pressed to obtain a plate-like nonwoven fabric (thickness: 0.2 mm). A plate-like composite material was obtained from this nonwoven fabric sheet by the same procedure as in Example 1-1 (4). A composite tensile strength almost equivalent to that of the plate-like composite material of Example 2-1 was obtained.
  • the present invention is useful for effective utilization of carbon fibers recovered from a carbon fiber composite material.

Abstract

The present invention relates to a method for producing a fiber-reinforced thermoplastic-resin composite material, the method comprising: step (1), in which (A) carbon fibers are formed into nonwoven fabric together with an aqueous emulsion of a self-emulsifiable thermoplastic urethane resin or (B) an aqueous emulsion of a self-emulsifiable thermoplastic urethane resin is added to wet-state nonwoven carbon fiber fabric, thereby obtaining nonwoven carbon fiber fabric bonded and coated with the thermoplastic urethane resin; and step (2), in which at least one sheet of the nonwoven fabric obtained in step (1) and at least one thermoplastic-resin sheet as a matrix member are stacked alternately and then heated to obtain the fiber-reinforced thermoplastic-resin composite material. The present invention provides the method whereby a fiber-reinforced thermoplastic-resin composite material having excellent composite properties is produced from either carbon fibers recovered from collected CFRPs or new cut carbon fibers.

Description

炭素繊維強化熱可塑性樹脂複合材料の製造方法Method for producing carbon fiber reinforced thermoplastic resin composite material
　本発明は、炭素繊維から繊維強化熱可塑性樹脂複合材料を製造する方法に関する。
関連出願の相互参照
　本出願は、２０１８年２月２０日出願の日本特願２０１８－２７５０１号の優先権を主張し、その全記載は、ここに特に開示として援用される。 The present invention relates to a method for producing a fiber-reinforced thermoplastic resin composite material from carbon fibers.
This application claims the priority of Japanese Patent Application No. 2018-27501 filed on Feb. 20, 2018, the entire description of which is specifically incorporated herein by reference.
　炭素繊維等の繊維強化複合材料（ＣＦＲＰ）は軽量化材料として注目され、航空機、自動車、風車の羽根、ロボットアーム、ドローン、スポーツ具などに広く利用されている。軽量化することにより、燃費の向上、環境負荷の低下に繋がるので、繊維強化複合材料の市場は今後も拡大していくと予想されている。その一方で、繊維強化複合材料製造工程途中の端材や使用寿命の来た廃棄複合材料（まとめて廃材と呼称）がすでに年間何万トンという規模となりつつある。そのため、ＣＦＲＰ廃材のリサイクル技術が極めて重要であり、いくつかの方法が提案されている（特許文献１、２）。 Fiber reinforced composite material (CFRP) such as carbon fiber is attracting attention as a lightweight material and is widely used in aircraft, automobiles, windmill blades, robot arms, drones, sports equipment and the like. The reduction in weight leads to an improvement in fuel consumption and a reduction in environmental burden, and therefore the market for fiber-reinforced composite materials is expected to continue to expand. On the other hand, scrap materials in the process of manufacturing fiber reinforced composite materials and waste composite materials with a long service life (collectively referred to as waste materials) are already on the scale of tens of thousands of tons per year. Therefore, CFRP waste material recycling technology is extremely important, and several methods have been proposed (Patent Documents 1 and 2).
　引用文献１は熱硬化性樹脂（主としてエポキシ樹脂）を炭素繊維で補強した複合材料（以下ＣＦＲＰ）から炭素繊維を回収する技術（熱分解法）に関するものである。廃棄されたＣＦＲＰを適当なサイズに切断し、空気中約５５０℃で酸化処理して、残った炭素繊維を回収する方法である。この場合、酸化雰囲気中で高温処理するため炭素繊維が酸化され、強度が低下するという問題点がある。また、回収した炭素繊維が熱分解工程で絡むため、複合材料への加工が難しい。 Citation 1 relates to a technique (thermal decomposition method) for recovering carbon fiber from a composite material (hereinafter CFRP) in which a thermosetting resin (mainly epoxy resin) is reinforced with carbon fiber. In this method, the discarded CFRP is cut into an appropriate size and oxidized in air at about 550 ° C. to recover the remaining carbon fiber. In this case, since the high temperature treatment is performed in an oxidizing atmosphere, there is a problem that the carbon fiber is oxidized and the strength is lowered. Moreover, since the recovered carbon fibers are entangled in the thermal decomposition process, it is difficult to process the composite material.
　特許文献２は廃棄されたＣＦＲＰを２０ｍｍサイズ程度に切断し、空気中で炭素繊維の酸化反応が起こらない約４５０℃以下で加熱処理する。熱処理したＣＦＲＰを電解質溶液に浸漬し、ＣＦＲＰを陽極にして電解処理すると熱処理で炭化した樹脂残渣が離脱し、炭素繊維を回収する方法である。この方法では、静置状態で電解処理されるので、回収した炭素繊維の配向はＣＦＲＰの状態が保持されて直線状で、湿潤状態であるので、不織布化しやすく、複合材料への加工が容易である。また、回収工程で炭素繊維の強度低下もほとんどない。 Patent Document 2 cuts discarded CFRP into a size of about 20 mm, and heat-treats it at about 450 ° C. or less at which no carbon fiber oxidation reaction occurs in air. In this method, the heat-treated CFRP is immersed in an electrolyte solution, and when CFRP is used as an anode for the electrolytic treatment, the resin residue carbonized by the heat treatment is released and the carbon fiber is recovered. In this method, since the electrolytic treatment is performed in a stationary state, the orientation of the collected carbon fiber is linear and wet in the state of CFRP, so that it is easy to form a nonwoven fabric and easy to process into a composite material. is there. Further, there is almost no decrease in the strength of the carbon fiber in the recovery process.
　一般に繊維基材を樹脂で補強して構造体を製造する場合、繊維基材が厚いと生産性が良い。樹脂が熱硬化性であると、硬化前の樹脂粘度が低い間に繊維基材を構成する単糸間に樹脂を含浸して硬化・成形すればよい。 Generally, when a structure is manufactured by reinforcing a fiber base with a resin, if the fiber base is thick, the productivity is good. If the resin is thermosetting, it may be cured and molded by impregnating the resin between single yarns constituting the fiber base while the resin viscosity before curing is low.
　しかし、樹脂が熱可塑性の場合、溶融粘度が高いので、繊維基材を構成する単糸間に樹脂を含浸することは困難である。成形生産性を上げるため、不織布の目付を上げるとますます樹脂含浸性が低下し、高性能の複合材料を製造することが困難となる。

However, since the melt viscosity is high when the resin is thermoplastic, it is difficult to impregnate the resin between the single yarns constituting the fiber base material. Increasing the basis weight of the nonwoven fabric in order to increase molding productivity will further reduce the resin impregnation property, making it difficult to produce high performance composite materials.

特許文献１：日本特開平６－２９８９９３号公報
特許文献２：日本特許第６０４４９４６号公報
特許文献１および２の全記載は、ここに特に開示として援用される。 Patent Document 1: Japanese Patent Application Laid-Open No. 6-298993 Patent Document 2: Japanese Patent No. 6044946 The entire description of Patent Documents 1 and 2 is specifically incorporated herein by reference.
　厚い炭素繊維の不織布を補強材とし、マトリックス樹脂として熱可塑性樹脂を構成とした複合材料を量産する場合、次のような課題がある。
（１）熱可塑性樹脂の溶融粘度は一般に極めて高いので、不織布を構成する補強繊維単糸間に樹脂を含浸することが難しい。
（２）複合材料の生産性を上げるには、厚手の不織布を補強材として使用することが考えられるが、熱可塑性樹脂の含浸の困難さがさらに拡大する。 When mass-producing a composite material in which a thick carbon fiber nonwoven fabric is used as a reinforcing material and a thermoplastic resin is used as a matrix resin, there are the following problems.
(1) Since the melt viscosity of a thermoplastic resin is generally extremely high, it is difficult to impregnate the resin between the reinforcing fiber single yarns constituting the nonwoven fabric.
(2) In order to increase the productivity of the composite material, it is conceivable to use a thick non-woven fabric as a reinforcing material, but the difficulty of impregnation with the thermoplastic resin is further increased.
　本発明の目的は、上記２つの課題を解決するため、炭素繊維を不織布化し、さらにそれを繊維強化熱可塑性樹脂複合材料とするための、簡便で力学特性に優れた複合材料を製造する方法を提供することにある。 An object of the present invention is to solve the above-mentioned two problems by providing a method for producing a composite material that is simple and excellent in mechanical properties for making a carbon fiber non-woven fabric and making it a fiber-reinforced thermoplastic resin composite material. It is to provide.
　本発明は以下の通りである。
［１］
（Ａ）炭素繊維を熱可塑性ウレタン樹脂の水系自己乳化型エマルジョンとともに不織布化する、又は（Ｂ）湿潤化した炭素繊維不織布に熱可塑性ウレタン樹脂の水系自己乳化型エマルジョンを添加して、熱可塑性ウレタン樹脂で接着及び被覆された炭素繊維不織布を得る工程（１）、
工程（１）で得た不織布の少なくとも１枚とマトリックス部材としての熱可塑性樹脂シートの少なくとも１枚を交互に積層し、次いで加熱して繊維強化熱可塑性樹脂複合材料を得る工程（２）
を含む、繊維強化熱可塑性樹脂複合材料の製造方法。
［２］
前記熱可塑性ウレタン樹脂はガラス転移温度が、４０℃以上である、［１］に記載の製造方法。
［３］
前記熱可塑性ウレタン樹脂は、無黄変エステル系、無黄変エステル・エーテル系、無黄変カーボネート系、又は芳香族イソシアネート系の水系ウレタン樹脂であり、かつ前記エマルジョンの粒子径が０．０１～０．１μｍの範囲である、［１］又は［２］に記載の製造方法。
［４］
工程（１）において、炭素繊維１００質量部に対して、前記エマルジョンを固形分で５～１５質量部の範囲で用いる、［１］～［３］のいずれかに記載の製造方法。
［５］
工程（１）において用いる炭素繊維の一部又は全部は、炭素繊維複合材料を酸化雰囲気で加熱処理し、その後陽極酸化して、炭素繊維複合材料に含まれる樹脂分から炭素繊維を分離回収することで得られる、湿潤状態の炭素繊維であり、（Ａ）では湿潤状態の炭素繊維をそのまま不織布化に用い、（Ｂ）では湿潤状態の炭素繊維を不織布として湿潤化した炭素繊維不織布を得る、［１］～［４］のいずれかに記載の製造方法。
［６］
工程（１）で得られる不織布は、目付が１００ｇ～２０００ｇ/ｍ２の範囲である、［１］～［５］のいずれかに記載の製造方法。 The present invention is as follows.
[1]
(A) Carbon fiber is made into a nonwoven fabric together with a water-based self-emulsifying emulsion of a thermoplastic urethane resin, or (B) A water-based self-emulsifying emulsion of a thermoplastic urethane resin is added to a wetted carbon fiber nonwoven fabric to produce a thermoplastic urethane. A step (1) of obtaining a carbon fiber nonwoven fabric bonded and coated with a resin;
Step (2) in which at least one nonwoven fabric obtained in step (1) and at least one thermoplastic resin sheet as a matrix member are alternately laminated and then heated to obtain a fiber-reinforced thermoplastic resin composite material
A method for producing a fiber-reinforced thermoplastic resin composite material.
[2]
The said thermoplastic urethane resin is a manufacturing method as described in [1] whose glass transition temperature is 40 degreeC or more.
[3]
The thermoplastic urethane resin is a non-yellowing ester-based, non-yellowing ester-ether-based, non-yellowing carbonate-based, or aromatic isocyanate-based water-based urethane resin, and the emulsion has a particle size of 0.01 to The production method according to [1] or [2], which is in a range of 0.1 μm.
[4]
The production method according to any one of [1] to [3], wherein in the step (1), the emulsion is used in a range of 5 to 15 parts by mass in solid content with respect to 100 parts by mass of the carbon fiber.
[5]
Part or all of the carbon fibers used in the step (1) are obtained by heat-treating the carbon fiber composite material in an oxidizing atmosphere, then anodizing, and separating and collecting the carbon fibers from the resin component contained in the carbon fiber composite material. In the obtained wet carbon fiber, in (A), the wet carbon fiber is used as it is for making a non-woven fabric, and in (B), a wet carbon fiber non-woven fabric is used to obtain a wet carbon fiber non-woven fabric. ] To [4].
[6]
The production method according to any one of [1] to [5], wherein the nonwoven fabric obtained in the step (1) has a basis weight in a range of 100 g to 2000 g / m 2 .
　本発明によれば、炭素繊維不織布を基材として用いても、熱可塑性樹脂をマトリックスとした力学特性の優れた複合材料を製造することができ、この製造方法によれば、高生産性での複合材料の量産も可能である。 According to the present invention, even if a carbon fiber nonwoven fabric is used as a base material, a composite material having excellent mechanical properties using a thermoplastic resin as a matrix can be produced. According to this production method, high productivity can be achieved. Mass production of composite materials is also possible.
　例えば、特許文献２に記載の方法でＣＦＲＰ廃材から回収した湿潤状態にある炭素繊維（リサイクル炭素繊維）をそのまま用いる場合、湿式法による不織布（紙）を製造することが容易である。湿潤状態にある炭素繊維の単糸は屈折や湾曲状態のないまっすぐな状態で配置され、繊維の方向が平面内でランダムな擬似等方材料を得ることが可能である。 For example, when carbon fiber in a wet state (recycled carbon fiber) recovered from CFRP waste material by the method described in Patent Document 2 is used as it is, it is easy to produce a nonwoven fabric (paper) by a wet method. It is possible to obtain a pseudo-isotropic material in which the carbon fiber monofilament in a wet state is arranged in a straight state without refraction or bending, and the direction of the fiber is random within a plane.
　本発明の繊維強化熱可塑性樹脂複合材料の製造方法は以下の工程（１）及び（２）を含む。
工程（１）：（Ａ）炭素繊維を熱可塑性ウレタン樹脂の水系自己乳化型エマルジョンとともに不織布化する、又は（Ｂ）湿潤化した炭素繊維不織布に熱可塑性ウレタン樹脂の水系自己乳化型エマルジョンを添加して乾燥し、熱可塑性ウレタン樹脂で接着及び被覆された不織布シートを得る。
工程（２）：工程（１）で得た不織布シートの少なくとも１枚とマトリックス部材としての熱可塑性樹脂シートの少なくとも１枚を交互に積層し、次いで加熱して繊維強化熱可塑性樹脂複合材料を得る。 The manufacturing method of the fiber reinforced thermoplastic resin composite material of the present invention includes the following steps (1) and (2).
Step (1): (A) Carbon fiber is made into a nonwoven fabric together with an aqueous self-emulsifying emulsion of thermoplastic urethane resin, or (B) An aqueous self-emulsifying emulsion of thermoplastic urethane resin is added to the wetted carbon fiber nonwoven fabric. And dried to obtain a nonwoven fabric sheet adhered and coated with a thermoplastic urethane resin.
Step (2): At least one nonwoven fabric sheet obtained in Step (1) and at least one thermoplastic resin sheet as a matrix member are alternately laminated, and then heated to obtain a fiber-reinforced thermoplastic resin composite material. .
　炭素繊維は、熱可塑性ウレタン樹脂の水系自己乳化型エマルジョンとともに不織布化する。具体的には、炭素繊維を熱可塑性ウレタン樹脂の水系自己乳化型エマルジョンと混合し、次いで常法により不織布化する。もしくは、湿潤化した不織布化した炭素繊維に熱可塑性ウレタン樹脂の水系自己乳化型エマルジョンを付与した後、乾燥して、熱可塑性ウレタン樹脂で接着及び被覆された不織布シートを得る。湿潤化した炭素繊維不織布は、水分率が例えば、１０％以上であることが好ましく、より好ましくは３０％以上である。水系エマルジョンは、自己乳化型であるので、界面活性剤等の余分な成分を含まず、複合材料としたときに複合材料の物性を損なわないこと、回収炭素繊維を用いた場合でも優れた強度の複合材料を得られるということから適当である。 Carbon fiber is made into a nonwoven fabric together with a water-based self-emulsifying emulsion of thermoplastic urethane resin. Specifically, carbon fibers are mixed with a water-based self-emulsifying emulsion of a thermoplastic urethane resin, and then made into a nonwoven fabric by a conventional method. Alternatively, a water-based self-emulsifying emulsion of a thermoplastic urethane resin is applied to the wetted non-woven carbon fiber, followed by drying to obtain a non-woven fabric sheet bonded and coated with the thermoplastic urethane resin. The wet carbon fiber nonwoven fabric preferably has a moisture content of, for example, 10% or more, and more preferably 30% or more. Since the water-based emulsion is a self-emulsifying type, it does not contain extra components such as surfactants, and does not impair the physical properties of the composite material when made into a composite material, and has excellent strength even when using recovered carbon fibers. It is suitable because a composite material can be obtained.
　特許文献２に記載の炭素繊維複合材料（ＣＦＲＰ廃材等の）を酸化雰囲気で加熱処理し、その後陽極酸化して、炭素繊維複合材料に含まれる樹脂分から炭素繊維を分離回収することで得られるリサイクル炭素繊維であって、陽極酸化後に分離回収された炭素繊維は湿潤状態である。回収炭素繊維の水分率は分離回収方法にもよるが、例えば、３０％以上である。そのため、この湿潤状態の炭素繊維をそのまま工程（１）の（Ｂ）の方法に用いることが、製造工程の簡素化と、炭素繊維が湿潤状態にあるので、水系自己乳化型エマルジョンとの馴染みが良好で、熱可塑性ウレタン樹脂との炭素繊維間の接着及び炭素繊維の被覆が良好に行われ、最終的に得られる複合材料の強度が向上することから好ましい。 Recycling obtained by heat-treating a carbon fiber composite material (such as CFRP waste material) described in Patent Document 2 in an oxidizing atmosphere, then anodizing, and separating and recovering the carbon fiber from the resin contained in the carbon fiber composite material Carbon fibers that are separated and recovered after anodization are in a wet state. The moisture content of the recovered carbon fiber is, for example, 30% or more although it depends on the separation and recovery method. Therefore, using this wet carbon fiber as it is in the method of (B) in step (1) simplifies the production process, and because the carbon fiber is in a wet state, it is compatible with an aqueous self-emulsifying emulsion. It is preferable because adhesion between carbon fibers with a thermoplastic urethane resin and coating of carbon fibers are performed well, and the strength of the composite material finally obtained is improved.
　もちろん新品のカットした炭素繊維単独又は特許文献２記載の回収炭素繊維の混合物であっても良い。新品のカットした炭素繊維を用いる場合、工程（１）の（Ａ）の方法に用いるか、または、新品のカットした炭素繊維を常法により湿潤化した後に工程（１）の（Ｂ）の方法に用いることもできる。 Of course, it may be a new cut carbon fiber alone or a mixture of recovered carbon fibers described in Patent Document 2. When a new cut carbon fiber is used, it is used in the method (A) of the step (1), or after the new cut carbon fiber is wetted by a conventional method, the method of the step (1) (B) It can also be used.
　ここで用いる熱可塑性ウレタン樹脂は、乾燥した後、250℃以上の耐熱性を有する熱可塑性フィルムを形成するものであることが好ましい。水系エマルジョンの粒子径は、単糸直径が約５～１０μmの炭素繊維の間に含浸できるという観点から、例えば、０．０１～０．１μｍの範囲が好ましい。 It is preferable that the thermoplastic urethane resin used here forms a thermoplastic film having a heat resistance of 250 ° C. or higher after drying. The particle size of the water-based emulsion is preferably in the range of 0.01 to 0.1 μm, for example, from the viewpoint that it can be impregnated between carbon fibers having a single yarn diameter of about 5 to 10 μm.
　熱可塑性ウレタン樹脂は、工程（２）における加熱において、熱可塑性樹脂と共に溶融し、熱可塑性樹脂と適度に混和し、得られる複合材料の強度向上に寄与できるという観点から、ガラス転移温度が、例えば、４０℃以上の範囲であることが適当であり、さらに好ましくは、８０℃以上の範囲である。 From the viewpoint that the thermoplastic urethane resin can be melted together with the thermoplastic resin in the heating in the step (2) and appropriately mixed with the thermoplastic resin to contribute to the improvement of the strength of the resulting composite material, the glass transition temperature is, for example, The temperature is preferably in the range of 40 ° C. or higher, more preferably in the range of 80 ° C. or higher.
　熱可塑性ウレタン樹脂は、材質には特に制限はなく、例えば、無黄変エステル系、無黄変エステル・エーテル系、無黄変カーボネート系、又は芳香族イソシアネート系の水系ウレタン樹脂を挙げることができる。上記ガラス転移温度及びエマルジョンの粒子径を有する熱可塑性ウレタン樹脂の水系自己乳化型エマルジョンは、例えば、第一工業製薬のスーパーフレックスシリーズが市販品として入手が可能である。 The material of the thermoplastic urethane resin is not particularly limited, and examples thereof include a non-yellowing ester-based, a non-yellowing ester / ether-based, a non-yellowing carbonate-based, or an aromatic isocyanate-based water-based urethane resin. . A water-based self-emulsifying emulsion of a thermoplastic urethane resin having the glass transition temperature and the particle size of the emulsion can be obtained as a commercial product, for example, from Daiichi Kogyo Seiyaku Superflex series.
　エマルジョンの使用量は、炭素繊維１００質量部に対して、エマルジョンを固形分で例えば、５～１５質量部の範囲で用いることが、リサイクル炭素繊維を用いた場合でも、炭素繊維間の接着及び表面の被覆による熱可塑性樹脂との接着性を良好にし、優れた機械的強度を有する複合材料が得られるという観点から適当である。５質量部未満では、単糸間の空隙を樹脂で完全に埋めることが難しく、力学特性の優れた複合材料を得ることが難しくなる傾向がある。１５質量部を超えても、それ以上の力学特性の優れた複合材料は得られない傾向がある。 The amount of the emulsion used is such that the emulsion is used in a solid content of, for example, 5 to 15 parts by mass with respect to 100 parts by mass of the carbon fiber, even when recycled carbon fiber is used. This is suitable from the viewpoint of improving the adhesiveness to the thermoplastic resin by coating and obtaining a composite material having excellent mechanical strength. If it is less than 5 parts by mass, it is difficult to completely fill the voids between the single yarns with resin, and it tends to be difficult to obtain a composite material having excellent mechanical properties. Even if it exceeds 15 parts by mass, there is a tendency that a composite material having more excellent mechanical properties cannot be obtained.
　工程（１）で得られる不織布は、目付が１００ｇ～２０００ｇ/ｍ２の範囲であることが好ましい。目付が１００ｇ／ｍ２以下では複合材料の生産性が低いので本発明の経済効果が乏しくなる傾向がある。逆に、２０００ｇ／ｍ２以上では、不織布化が技術的に難しくなる傾向があり、不織布化した後の乾燥にも時間がかかるので、経済性が低下する傾向がある。 The nonwoven fabric obtained in the step (1) preferably has a basis weight in the range of 100 g to 2000 g / m 2 . If the basis weight is 100 g / m 2 or less, the productivity of the composite material is low, so the economic effect of the present invention tends to be poor. On the other hand, if it is 2000 g / m 2 or more, it tends to be technically difficult to make a nonwoven fabric, and it takes time for drying after making the nonwoven fabric, so that the economy tends to decrease.
　熱可塑性ウレタン樹脂で接着及び被覆された不織布は、工程（２）に供する前に加熱乾燥することが好ましい。加熱乾燥は、熱可塑性ウレタン樹脂の熱的特性を考慮し、炭素繊維が良好に接着及び被覆されることを考慮して、適宜決定することができる。例えば、１００～１６０℃の範囲で、乾燥することができる。乾燥方法としては、例えば、熱風乾燥、熱板乾燥、赤外線乾燥などを挙げることができる。乾燥後、加圧して平板化することが好ましい。乾燥後の不織布は含水率が５％以下、好ましくは１％（ほぼ絶乾）であることが好ましい。 The nonwoven fabric bonded and coated with the thermoplastic urethane resin is preferably heat-dried before being subjected to the step (2). The heat drying can be appropriately determined in consideration of the thermal characteristics of the thermoplastic urethane resin and the good adhesion and coating of the carbon fibers. For example, it can be dried in the range of 100 to 160 ° C. Examples of the drying method include hot air drying, hot plate drying, and infrared drying. It is preferable to flatten by pressurization after drying. The dried nonwoven fabric has a moisture content of 5% or less, preferably 1% (almost absolutely dry).
　工程（２）では、工程（１）で得た不織布の少なくとも１枚とマトリックス部材としての熱可塑性樹脂シートの少なくとも１枚を交互に積層し、次いで加熱して繊維強化熱可塑性樹脂複合材料を得る。工程（２）で用いる熱可塑性樹脂シートは、複合材料のマトリックス部材を構成するものである。マトリックス部材として用いられる熱可塑性樹脂としては、特に限定されないが、充填用の熱可塑性ウレタン樹脂との接着力の高い熱可塑性樹脂が好ましい。熱可塑性ウレタン樹脂の熱分解温度以下で溶融する合成樹脂が好ましい。具体的には、ナイロン、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエーテルスルホン等を使用することが出来る。 In step (2), at least one nonwoven fabric obtained in step (1) and at least one thermoplastic resin sheet as a matrix member are alternately laminated, and then heated to obtain a fiber-reinforced thermoplastic resin composite material. . The thermoplastic resin sheet used in the step (2) constitutes a matrix member of a composite material. Although it does not specifically limit as a thermoplastic resin used as a matrix member, The thermoplastic resin with high adhesive force with the thermoplastic urethane resin for filling is preferable. A synthetic resin that melts below the thermal decomposition temperature of the thermoplastic urethane resin is preferred. Specifically, nylon, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or the like can be used.
　不織布の少なくとも１枚とマトリックス部材としての熱可塑性樹脂シートの少なくとも２枚を交互に積層する。好ましくは、不織布の両面を熱可塑性樹脂シートが被覆するように挟み込む。即ち、不織布ｎ枚に対して、熱可塑性樹脂シートｎ＋１枚を交互に積層する。熱可塑性樹脂シートの厚みは、不織布の目付に応じて、さらには、複合材料における不織布とマトリックス部材としての熱可塑性樹脂との所望の質量比に応じて適宜決定することができる。不織布とマトリックス部材としての熱可塑性樹脂との質量比は、特に制限はないが、不織布１００質量部に対して、マトリックス部材としての熱可塑性樹脂１０～１０００質量部の範囲とすることができ、好ましくは２５～４００質量部の範囲である。繊維と樹脂の割合は特に限定はないが、繊維の体積含有率が２０～８０％が好ましい。２０％以下であると、複合材料としての力学特性が低く、適用する意味が少ない。８０％を越えると、力学特性が逆に低下する場合がある。 At least one non-woven fabric and at least two thermoplastic resin sheets as a matrix member are alternately laminated. Preferably, the nonwoven fabric is sandwiched so that both sides of the nonwoven fabric are covered with the thermoplastic resin sheet. That is, n + 1 thermoplastic resin sheets are alternately laminated on n nonwoven fabrics. The thickness of the thermoplastic resin sheet can be appropriately determined according to the basis weight of the nonwoven fabric and further according to a desired mass ratio between the nonwoven fabric in the composite material and the thermoplastic resin as the matrix member. The mass ratio between the nonwoven fabric and the thermoplastic resin as the matrix member is not particularly limited, but can be in the range of 10 to 1000 parts by mass of the thermoplastic resin as the matrix member with respect to 100 parts by mass of the nonwoven fabric. Is in the range of 25 to 400 parts by weight. The ratio of the fiber and the resin is not particularly limited, but the fiber volume content is preferably 20 to 80%. If it is 20% or less, the mechanical properties as a composite material are low, and there is little meaning to apply. If it exceeds 80%, the mechanical properties may deteriorate.
　得られた積層物は加熱して繊維強化熱可塑性樹脂複合材料を得る。加熱の際には積層物の両面から加圧することが好ましい。加熱温度は、熱可塑性樹脂シートを構成する熱可塑性樹脂の熱可塑性（溶融温度）を考慮して適宜決定することができる。さらに加圧の圧力は、加熱温度及びその温度における熱可塑性樹脂の粘度等を考慮して適宜決定できる。平板化した不織布の最上面と不織布と熱可塑性樹脂フィルムを交互に配置し、加熱・加圧して一体化させて、繊維強化熱可塑性樹脂複合材料を製造することができる。 The obtained laminate is heated to obtain a fiber reinforced thermoplastic resin composite material. It is preferable to apply pressure from both sides of the laminate during heating. The heating temperature can be appropriately determined in consideration of the thermoplasticity (melting temperature) of the thermoplastic resin constituting the thermoplastic resin sheet. Furthermore, the pressure of pressurization can be appropriately determined in consideration of the heating temperature and the viscosity of the thermoplastic resin at that temperature. The uppermost surface of the flattened nonwoven fabric, the nonwoven fabric, and the thermoplastic resin film are alternately arranged and integrated by heating and pressurization to produce a fiber-reinforced thermoplastic resin composite material.
　以下、本発明を実施例に基づいて更に詳細に説明する。但し、実施例は本発明の例示であって、本発明は実施例に限定される意図ではない。 Hereinafter, the present invention will be described in more detail based on examples. However, the examples are illustrative of the present invention, and the present invention is not intended to be limited to the examples.
実施例１－１（リサイクル炭素繊維の場合）
（１）引用文献２を参考に回収したＣＦＲＰを２０ｍｍに切断した後、空気雰囲気３７５℃で１時間加熱し、マトリックス樹脂の大部分を除去した。ついで、０．２規定の硫酸水溶液に浸漬し、１２Ｖで３分間陽極酸化した。
（２）回収した塊状の炭素繊維を水洗、脱水処理し、水分率を５０％の回収炭素繊維を得た。これを常法に従って繊維目付重量が３６０ｇ／ｍ２（水分率５０％）の不織布を作成した。
（３）これに、第一工業製薬(株)製の無黄変型エーテル系自己乳化タイプポリウレタンエマルジョン液「スーパーフレックス１３０」の固形分３６ｇ／ｍ２に相当する量を均一に付与し、金網上で１２０℃の熱風で２時間乾燥した。乾燥後、金網から外し、板状の厚さ０．２ｍｍのシートを得た。 Example 1-1 (in the case of recycled carbon fiber)
(1) The CFRP collected with reference to the cited document 2 was cut to 20 mm and then heated at 375 ° C. for 1 hour to remove most of the matrix resin. Subsequently, it was immersed in a 0.2 N aqueous sulfuric acid solution and anodized at 12 V for 3 minutes.
(2) The collected massive carbon fibers were washed with water and dehydrated to obtain recovered carbon fibers having a moisture content of 50%. A nonwoven fabric having a fiber weight per unit area of 360 g / m 2 (water content 50%) was prepared according to a conventional method.
(3) A uniform amount corresponding to a solid content of 36 g / m 2 of the non-yellowing ether-based self-emulsifying type polyurethane emulsion “Superflex 130” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. And dried with hot air at 120 ° C. for 2 hours. After drying, the sheet was removed from the wire mesh to obtain a plate-like sheet having a thickness of 0.2 mm.
（４）このシート７枚と０．２ｍｍの厚さの積水成形工業(株)製のポリプロピレンシートＰ８１３４の８枚を交互に重ね、２００℃に加熱した河中産業(株)製のホットプレスで５分間加熱してポリプロピレンシートを溶融させたのち、６ＭＰａの圧力に１０分間保持した。その後、圧力を保持したまま５０℃に降温した。金型を解体し、サイズ３０ｃｍ角で、厚さ３ｍｍの板状複合材を得た。
（５）これをダイヤモンドカッターで切り出し、下記形状の試験片を作成し、ＪＩＳ７１１５-1986に従って、引張試験を実施し、結果を表１に示した。
＜引張試験＞　１号試験片　ＪＩＳ７１１５-19866.1.1(1)に記載 (4) Seven sheets of this sheet and eight sheets of polypropylene sheet P8134 manufactured by Sekisui Molding Industries Co., Ltd. having a thickness of 0.2 mm were alternately stacked and heated with a hot press manufactured by Kawanaka Sangyo Co., Ltd. heated to 200 ° C. After the polypropylene sheet was melted by heating for 5 minutes, the pressure was kept at 6 MPa for 10 minutes. Thereafter, the temperature was lowered to 50 ° C. while maintaining the pressure. The mold was disassembled to obtain a plate-shaped composite material having a size of 30 cm square and a thickness of 3 mm.
(5) This was cut out with a diamond cutter, a test piece having the following shape was prepared, a tensile test was carried out according to JIS 7115-1986 , and the results are shown in Table 1.
<Tensile test> No. 1 test piece JIS7115-1986 described in 6.1.1 (1)
実施例１－２
　実施例１－１の（１）と同様にして回収した塊状の炭素繊維を水洗、脱水処理し、水分率を５０％の回収炭素繊維を得た。これに、第一工業製薬(株)製の無黄変型エーテル系自己乳化タイプポリウレタンエマルジョン液「スーパーフレックス１３０」の固形分３６ｇ／ｍ２に相当する量を添加し、これから常法に従って繊維目付重量が３６０ｇ／ｍ２（水分率５０％）の不織布を作成した。次いで、金網上で１２０℃の熱風で２時間乾燥した。乾燥後、金網から外し、板状の厚さ０．２ｍｍのシートを得た。このシートを実施例１－１の（４）と同様の手順で板状複合材を得た。実施例１－１の板状複合材とほぼ同等のコンポジット引張強度を得た。 Example 1-2
Collected carbon fibers recovered in the same manner as in Example 1-1 (1) were washed with water and dehydrated to obtain recovered carbon fibers having a moisture content of 50%. To this, an amount corresponding to a solid content of 36 g / m 2 of a non-yellowing ether-based self-emulsifying type polyurethane emulsion “Superflex 130” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was added. Produced a non-woven fabric of 360 g / m 2 (water content 50%). Next, it was dried with hot air at 120 ° C. for 2 hours on a wire mesh. After drying, the sheet was removed from the wire mesh to obtain a plate-like sheet having a thickness of 0.2 mm. A plate-like composite material was obtained from this sheet in the same procedure as in Example 1-1 (4). A composite tensile strength almost equivalent to that of the plate-like composite material of Example 1-1 was obtained.
実施例２－１（通常の不織布製法）
（１）直径が7ミクロンの１２０００本の単糸からなる連続炭素繊維３６０ｇを長さ２０ｍｍにカットし、アニオン系界面活性剤を溶解させた水に分散させた。
（２）上記分散液を１００ｃｍ角の金網に濾過し、湿潤状態の不織布（乾燥状態での繊維目付：３６０ｇ/ｍ２）を得た。金網ごとプレスし、水分率を５０％とした。 Example 2-1 (Normal Nonwoven Fabrication Method)
(1) 360 g of continuous carbon fibers composed of 12,000 single yarns having a diameter of 7 microns were cut into a length of 20 mm and dispersed in water in which an anionic surfactant was dissolved.
(2) The dispersion was filtered through a 100 cm square wire mesh to obtain a wet nonwoven fabric (fiber basis weight in a dry state: 360 g / m 2 ). The whole wire mesh was pressed to make the moisture content 50%.
（３）これに、第一工業製薬(株)製の無黄変型エーテル系自己乳化タイプポリウレタンエマルジョン液「スーパーフレックス１３０」の固形分３６ｇを均一に付与し、１２０℃の熱風で２時間乾燥した。乾燥後、金網から外し、熱プレスし板状の不織布（厚さ：０．２ｍｍ）を得た。 (3) A solid content of 36 g of a non-yellowing ether-based self-emulsifying type polyurethane emulsion liquid “Superflex 130” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was uniformly applied thereto and dried with hot air at 120 ° C. for 2 hours. . After drying, it was removed from the wire mesh and hot pressed to obtain a plate-like nonwoven fabric (thickness: 0.2 mm).
（４）３０ｃｍ角に切断した板状の不織布７枚と０．２ｍｍの厚さの積水成形工業(株)製のポリプロピレンシート８枚を上下に金枠の中に重ね、実施例１－１の（４）と同様の手順で、サイズ３０ｃｍ角で、厚さ３ｍｍの板状複合材を得た。
（５）これをダイヤモンドカッターで切りだし、実施例１－１と同様の形状の試験片を作成し、ＪＩＳ７１１５-1986に従って、引張試験を実施した。 (4) Seven plate-shaped nonwoven fabrics cut into 30 cm square and eight polypropylene sheets of 0.2 mm thickness made by Sekisui Molding Industry Co., Ltd. In the same procedure as (4), a plate-shaped composite material having a size of 30 cm square and a thickness of 3 mm was obtained.
(5) This was cut out with a diamond cutter, a test piece having the same shape as in Example 1-1 was prepared, and a tensile test was performed according to JIS 7115-1986 .
実施例２－２
　実施例１－１の（１）と同様にして得た、アニオン系界面活性剤を溶解させた水に炭素繊維を分散させた分散液に、第一工業製薬(株)製の無黄変型エーテル系自己乳化タイプポリウレタンエマルジョン液「スーパーフレックス１３０」の固形分３６ｇを添加し、１００ｃｍ角の金網に濾過し、湿潤状態の不織布（乾燥状態での繊維目付：３６０ｇ/ｍ２）を得た。金網ごとプレスし、水分率を５０％とした。これを１２０℃の熱風で２時間乾燥した。乾燥後、金網から外し、熱プレスし板状の不織布（厚さ：０．２ｍｍ）を得た。この不織布シートを実施例１－１の（４）と同様の手順で板状複合材を得た。実施例２－１の板状複合材とほぼ同等のコンポジット引張強度を得た。 Example 2-2
A non-yellowing ether manufactured by Daiichi Kogyo Seiyaku Co., Ltd. was used in a dispersion obtained by dispersing carbon fibers in water in which an anionic surfactant was dissolved, obtained in the same manner as in Example 1-1 (1). A solid content of 36 g of the system self-emulsifying type polyurethane emulsion liquid “Superflex 130” was added and filtered through a 100 cm square metal mesh to obtain a wet nonwoven fabric (fiber basis weight in a dry state: 360 g / m 2 ). The whole wire mesh was pressed to make the moisture content 50%. This was dried with hot air at 120 ° C. for 2 hours. After drying, it was removed from the wire mesh and hot pressed to obtain a plate-like nonwoven fabric (thickness: 0.2 mm). A plate-like composite material was obtained from this nonwoven fabric sheet by the same procedure as in Example 1-1 (4). A composite tensile strength almost equivalent to that of the plate-like composite material of Example 2-1 was obtained.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　上記表１より、ポリウレタン処理することにより、引張強度が向上する。特に、リサイクル炭素繊維から製造した複合材料は新品の炭素繊維とほぼ同等であることが確認された。 From Table 1 above, the tensile strength is improved by the polyurethane treatment. In particular, it was confirmed that the composite material produced from recycled carbon fiber was almost equivalent to new carbon fiber.
　本発明は、炭素繊維複合材料から回収した炭素繊維の有効利用に有用である。 The present invention is useful for effective utilization of carbon fibers recovered from a carbon fiber composite material.

Claims (6)

  1. （Ａ）炭素繊維を熱可塑性ウレタン樹脂の水系自己乳化型エマルジョンとともに不織布化する、又は（Ｂ）湿潤化した炭素繊維不織布に熱可塑性ウレタン樹脂の水系自己乳化型エマルジョンを添加して、熱可塑性ウレタン樹脂で接着及び被覆された炭素繊維不織布を得る工程（１）、
    工程（１）で得た不織布の少なくとも１枚とマトリックス部材としての熱可塑性樹脂シートの少なくとも１枚を交互に積層し、次いで加熱して繊維強化熱可塑性樹脂複合材料を得る工程（２）
    を含む、繊維強化熱可塑性樹脂複合材料の製造方法。     (A) Carbon fiber is made into a non-woven fabric together with a water-based self-emulsifying emulsion of a thermoplastic urethane resin, or (B) A water-based self-emulsifying emulsion of a thermoplastic urethane resin is added to a wetted carbon fiber non-woven fabric to produce a thermoplastic urethane. A step (1) of obtaining a carbon fiber nonwoven fabric bonded and coated with a resin;
    Step (2) in which at least one nonwoven fabric obtained in step (1) and at least one thermoplastic resin sheet as a matrix member are alternately laminated and then heated to obtain a fiber-reinforced thermoplastic resin composite material
    A method for producing a fiber-reinforced thermoplastic resin composite material.
  2. 前記熱可塑性ウレタン樹脂はガラス転移温度が、４０℃以上である、請求項１に記載の製造方法。 The said thermoplastic urethane resin is a manufacturing method of Claim 1 whose glass transition temperature is 40 degreeC or more.
  3. 前記熱可塑性ウレタン樹脂は、無黄変エステル系、無黄変エステル・エーテル系、無黄変カーボネート系、又は芳香族イソシアネート系の水系ウレタン樹脂であり、かつ前記エマルジョンの粒子径が０．０１～０．１μｍの範囲である、請求項１又は２に記載の製造方法。 The thermoplastic urethane resin is a non-yellowing ester-based, non-yellowing ester-ether-based, non-yellowing carbonate-based, or aromatic isocyanate-based water-based urethane resin, and the emulsion has a particle size of 0.01 to The manufacturing method of Claim 1 or 2 which is the range of 0.1 micrometer.
  4. 工程（１）において、炭素繊維１００質量部に対して、前記エマルジョンを固形分で５～１５質量部の範囲で用いる、請求項１～３のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 3, wherein in the step (1), the emulsion is used in a range of 5 to 15 parts by mass with respect to 100 parts by mass of the carbon fiber.
  5. 工程（１）において用いる炭素繊維の一部又は全部は、炭素繊維複合材料を酸化雰囲気で加熱処理し、その後陽極酸化して、炭素繊維複合材料に含まれる樹脂分から炭素繊維を分離回収することで得られる、湿潤状態の炭素繊維であり、（Ａ）では湿潤状態の炭素繊維をそのまま不織布化に用い、（Ｂ）では湿潤状態の炭素繊維を不織布として湿潤化した炭素繊維不織布を得る、請求項１～４のいずれかに記載の製造方法。 Part or all of the carbon fibers used in the step (1) are obtained by heat-treating the carbon fiber composite material in an oxidizing atmosphere, then anodizing, and separating and collecting the carbon fibers from the resin component contained in the carbon fiber composite material. The obtained carbon fiber in a wet state, wherein (A) uses the wet carbon fiber as it is for making a non-woven fabric, and (B) obtains a wet carbon fiber non-woven fabric as a non-woven fabric. 5. The production method according to any one of 1 to 4.
  6. 工程（１）で得られる不織布は、目付が１００ｇ～２０００ｇ/ｍ２の範囲である、請求項１～５のいずれかに記載の製造方法。 The production method according to any one of claims 1 to 5, wherein the nonwoven fabric obtained in the step (1) has a basis weight in a range of 100 g to 2000 g / m 2 .
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WO2023182158A1 (en) * 2022-03-22 2023-09-28 東レ株式会社 Integrated molded component and method for manufacturing integrated molded component

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JP2004011030A (en) * 2002-06-03 2004-01-15 Mitsubishi Rayon Co Ltd Chopped carbon fiber bundle, method for producing the same, aqueous sizing agent for chopped carbon fiber bundle and thermoplastic resin composition and molded product thereof
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JP2002212311A (en) * 2001-01-15 2002-07-31 Japan Vilene Co Ltd Carbon fiber-reinforced stampable sheet, method for producing the same and molded product thereof
JP2004011030A (en) * 2002-06-03 2004-01-15 Mitsubishi Rayon Co Ltd Chopped carbon fiber bundle, method for producing the same, aqueous sizing agent for chopped carbon fiber bundle and thermoplastic resin composition and molded product thereof
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