JP2021014518A - Method for recycling and recovering reinforcement material from reinforced composite material - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Reinforced Plastic Materials (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
Description
本発明は、強化複合材料から強化材を再生回収する方法に関する。 The present invention relates to a method for regenerating and recovering a reinforcing material from a reinforced composite material.
強化複合材料とは、母材である樹脂に、炭素繊維、ガラス繊維、炭素繊維、ガラス繊維、金属繊維、有機系高強度繊維等の強化材を複合化して成形される材料である。その特徴は強度が高く、鉄等の金属に比べて軽いことである。その特徴を活かして、エネルギー効率の向上に大きく貢献する素材として、一部の自動車や航空機等に加え、風車のブレード等にも利用され始めている。強化材の１つである炭素繊維の生産量は、２０１５年の６万トンから２０２０年の１４万トンへ、５年間で２倍以上の増大が予想されている。炭素繊維はまず、石油からアクリロニトリルという化学物質を合成し、それを糸にしたアクリル繊維を製造する。そして、数千度という高温で炭化処理することによって炭素繊維が製造される。炭素繊維はそのまま使われる事もあるが、多くは連続繊維や不織布、チョップド等様々な形態に加工され、更に様々な種類の樹脂と複合することにより、強化複合材料の１つである炭素繊維強化プラスチック（ＣＦＲＰ）として使用されている。 The reinforced composite material is a material formed by compounding a reinforcing material such as carbon fiber, glass fiber, carbon fiber, glass fiber, metal fiber, and organic high-strength fiber with a resin as a base material. Its characteristics are high strength and lighter than metals such as iron. Taking advantage of its characteristics, it has begun to be used for wind turbine blades in addition to some automobiles and aircraft as a material that greatly contributes to the improvement of energy efficiency. The production of carbon fiber, which is one of the reinforcing materials, is expected to more than double in five years from 60,000 tons in 2015 to 140,000 tons in 2020. For carbon fiber, first, a chemical substance called acrylonitrile is synthesized from petroleum, and acrylic fiber is manufactured using the chemical substance as a thread. Then, carbon fiber is produced by carbonizing at a high temperature of several thousand degrees. Carbon fiber is sometimes used as it is, but most are processed into various forms such as continuous fiber, non-woven fabric, and chopped, and by further combining with various types of resin, carbon fiber reinforcement, which is one of the reinforced composite materials, is reinforced. It is used as plastic (CFRP).
炭素繊維強化プラスチックは、強い、硬い、錆びない、腐らない等優れた材料特性を持っているが、それ故に廃棄方法が課題である。一般的なプラスチックは容易に燃焼させることができるが、炭素繊維は高度にグラファイト化された構造であるため燃えにくい。したがって、国内では炭素繊維強化プラスチックの端材や廃材は産業廃棄物として粉砕後、埋め立て処分されている。粉砕されて、埋め立て処分された炭素繊維は、生分解されずに海洋プラスチック汚染の原因物質となってしまう。 Carbon fiber reinforced plastics have excellent material properties such as strength, hardness, rust resistance, and non-rotation, but the disposal method is therefore an issue. General plastics can be easily burned, but carbon fibers have a highly graphitized structure and are difficult to burn. Therefore, in Japan, carbon fiber reinforced plastic scraps and waste materials are crushed as industrial waste and then landfilled. Carbon fibers that have been crushed and landfilled are not biodegraded and become a causative agent of marine plastic pollution.
そこで、使用後の強化複合材料から強化材を分離回収し、再利用する方法が提案されている。
例えば、低酸素状態で５００〜７００℃の高温で炭素繊維強化プラスチックを処理することで、母材である樹脂成分を熱分解させて炭素繊維のみを回収する方法である。また、二段階熱分解法という技術も開発された。その技術は、一段階目である程度まで樹脂成分を熱分解し、そこから可燃性ガスを回収する。そのガスを加熱用の燃焼ガスとして活用することで、燃料の消費を低減する。その後、二段階目で再び熱分解し、繊維表面に残った樹脂成分を熱分解して除去する方法である（例えば、特許文献１参照。）。
Therefore, a method has been proposed in which the reinforcing material is separated and recovered from the used reinforcing composite material and reused.
For example, it is a method of recovering only carbon fibers by thermally decomposing the resin component which is the base material by treating the carbon fiber reinforced plastic at a high temperature of 500 to 700 ° C. in a low oxygen state. In addition, a technique called a two-step pyrolysis method was also developed. The technology thermally decomposes the resin component to some extent in the first step and recovers the flammable gas from it. By utilizing the gas as a combustion gas for heating, fuel consumption is reduced. After that, it is thermally decomposed again in the second step, and the resin component remaining on the fiber surface is thermally decomposed and removed (see, for example, Patent Document 1).
また、過熱水蒸気を利用する方法も提案されている。過熱水蒸気とは飽和蒸気を更に過熱することにより、ある圧力において飽和温度以上の蒸気温度を持つ水蒸気のことである。この過熱水蒸気を用いて、母材である樹脂成分を効率よく熱分解させて炭素繊維のみを回収する方法である（例えば、特許文献２参照。）。 In addition, a method using superheated steam has also been proposed. Superheated steam is steam that has a steam temperature equal to or higher than the saturation temperature at a certain pressure by further heating the saturated steam. This is a method of efficiently thermally decomposing a resin component which is a base material by using this superheated steam to recover only carbon fibers (see, for example, Patent Document 2).
また、特定の有機溶剤に樹脂成分を溶解させる手法も提案されている。処理温度が１００〜１５０℃という低温であることと、ウェットプロセスなので樹脂の残存がないために、回収した炭素繊維の強度が低下しないことが特徴である（例えば、非特許文献１参照。）。 In addition, a method of dissolving the resin component in a specific organic solvent has also been proposed. It is characterized in that the treatment temperature is as low as 100 to 150 ° C. and that the strength of the recovered carbon fibers does not decrease because there is no residual resin because it is a wet process (see, for example, Non-Patent Document 1).
更に、メタノールを８ＭＰａ以上の高圧装置に入れることで、超臨界状態にして樹脂を溶解する方法も提案されている。この方法も処理温度が２４０℃程度と比較的低温のため、回収した炭素繊維の強度は低下しないことが特徴である（例えば、特許文献３参照。）。 Further, a method of dissolving the resin in a supercritical state by putting methanol in a high-pressure device of 8 MPa or more has been proposed. This method is also characterized in that the strength of the recovered carbon fibers does not decrease because the treatment temperature is relatively low, about 240 ° C. (see, for example, Patent Document 3).
炭素繊維強化プラスチックの現実における活用方法は、連続繊維から中間基材であるプリプレグや織物として加工され、それと母材である熱硬化性樹脂又は熱可塑性樹脂と組み合わせて製造される強化複合材料がほとんどである。しかし、特許文献１〜３に記載の方法では、再生強化材は繊維長数ｃｍの長繊維、又は繊維長数ｍｍの短繊維として回収されることが多く、活用方法に制限があった。非特許文献１に提案されている常圧溶解法は、溶解できる樹脂がＰＥＴ等のポリエステル系に限られるため、処理できる炭素繊維強化プラスチックに制限がある。熱可塑性樹脂を用いた炭素繊維強化プラスチックは、使用される樹脂の種類が豊富で、ＰＥＴ（ポリエステル）、ＰＰ（ポリプロピレン）、ＰＥＥＫ（ポリエーテルエーテルケトン）、ＰＡ（ポリアミド）等多岐にわたっている。しかし、それらを一目で見分けることは難しい。専用の機器を用いて分析することは可能だが、回収した炭素繊維強化プラスチックの部品を一つずつ分析して選別することは現実的ではない。そこで、全ての繊維強化プラスチックに適応可能であり、かつ強化材が連続繊維として再生できることができれば、その活用方法は大きく広がり、再生強化材が余ることなく循環型社会の実現につながる。
強化材を連続繊維として再生する部材としては、例えば、水素タンクやＣＮＧ圧力タンク等が挙げられる。これら圧力タンクは、耐衝撃性や耐擦傷性を向上し、更に外部との電気絶縁性を付与するために、炭素繊維強化プラスチックで成形されたタンクの外周部にガラス繊維強化プラスチックで覆っている。また、バルブやタンク内部にアルミニウムが使用されていることが多い。
このような部材にも適応でき、かつ強化材を連続繊維状態で再生できる技術が求められている。
Most of the practical uses of carbon fiber reinforced plastics are reinforced composite materials that are processed from continuous fibers as intermediate base materials such as prepregs and textiles, and are manufactured in combination with the base material, thermosetting resin or thermoplastic resin. Is. However, in the methods described in Patent Documents 1 to 3, the recycled reinforcing material is often recovered as long fibers having a fiber length of several cm or short fibers having a fiber length of several mm, and there are restrictions on the utilization method. In the atmospheric dissolution method proposed in Non-Patent Document 1, since the resin that can be dissolved is limited to polyester-based resins such as PET, there is a limitation on the carbon fiber reinforced plastic that can be treated. Carbon fiber reinforced plastics using thermoplastic resins have a wide variety of resins used, such as PET (polyester), PP (polypropylene), PEEK (polyetheretherketone), and PA (polyamide). However, it is difficult to distinguish them at a glance. Although it is possible to analyze using a dedicated device, it is not realistic to analyze and sort the recovered carbon fiber reinforced plastic parts one by one. Therefore, if it can be applied to all fiber reinforced plastics and the reinforcing material can be regenerated as continuous fiber, the utilization method will be greatly expanded, and it will lead to the realization of a recycling-oriented society without surplus recycled reinforcing material.
Examples of the member that regenerates the reinforcing material as continuous fibers include a hydrogen tank and a CNG pressure tank. In order to improve impact resistance and scratch resistance, and to provide electrical insulation to the outside, these pressure tanks are covered with glass fiber reinforced plastic on the outer periphery of the tank molded of carbon fiber reinforced plastic. .. In addition, aluminum is often used inside valves and tanks.
There is a need for a technique that can be applied to such members and that the reinforcing material can be regenerated in a continuous fiber state.
上述した従来提案されている技術は、下記のような問題点を有している。
特許文献１に提案されている熱分解法を、炭素繊維強化プラスチックとガラス繊維強化プラスチックからなる構造材料に適応した場合、ガラス繊維やアルミニウムが溶融してペースト状になってしまい、強化複合材料から強化材を分離回収することができない。また、特許文献１では、熱分解のため、樹脂の熱分解ガスの毒性という課題がある。熱硬化性炭素繊維強化プラスチックの主要な樹脂であるエポキシ樹脂は、熱分解によってガン原生物質の疑いがあるビスフェノールＡが生成するため、注意を要する。また、回収した炭素繊維の強度が７０〜８０％に低下してしまうことである。これは、高温処理をすることによって炭素繊維の表面に微小なクラックが入ってしまうためである。更に、炭素繊維は樹脂と複合化して炭素繊維強化プラスチックに加工する際、繊維に表面処理をして樹脂との親和性を上げる必要がある。熱分解法で回収した炭素繊維は、表面に発生したクラックと樹脂の残渣のために、表面処理を阻害してしまう。そのため、熱分解法で回収した炭素繊維を用いて炭素繊維強化プラスチックを製造した場合、炭素繊維自体の強度低下に加えて、更に７０〜８０％の強度低下が発生してしまう。
The above-mentioned conventionally proposed techniques have the following problems.
When the thermal decomposition method proposed in Patent Document 1 is applied to a structural material composed of carbon fiber reinforced plastic and glass fiber reinforced plastic, the glass fiber and aluminum are melted into a paste, and the reinforced composite material is used. Reinforcement material cannot be separated and recovered. Further, in Patent Document 1, there is a problem of toxicity of the thermal decomposition gas of the resin due to thermal decomposition. Epoxy resin, which is the main resin of thermosetting carbon fiber reinforced plastic, requires caution because bisphenol A, which is suspected to be a cancer protozoan, is produced by thermal decomposition. In addition, the strength of the recovered carbon fibers is reduced to 70 to 80%. This is because the carbon fiber surface is cracked by the high temperature treatment. Further, when the carbon fiber is combined with the resin and processed into a carbon fiber reinforced plastic, it is necessary to surface-treat the fiber to improve the affinity with the resin. The carbon fibers recovered by the thermal decomposition method hinder the surface treatment due to the cracks generated on the surface and the resin residue. Therefore, when a carbon fiber reinforced plastic is produced using the carbon fibers recovered by the thermal decomposition method, the strength of the carbon fibers themselves is further reduced by 70 to 80%.
特許文献２に提案されている過熱水蒸気法を、炭素繊維強化プラスチックとガラス繊維強化プラスチックからなる構造材料に適応した場合、前述の熱分解法と同様にガラス繊維やアルミニウムが溶融してペースト状になってしまい、強化複合材料から強化材を分離回収することができない。また、前述の熱分解法と同様に高温処理をすることによって、回収した炭素繊維の強度が低下してしまう。また、熱分解の効率を向上するためにロータリーキルンを用いているが、装置に入れることができる大きさにする必要があるため、処理する炭素繊維強化プラスチックを粉砕しなくてはならない。そのため、連続繊維状の炭素繊維を回収することができず、再び母材と複合化するためには強化材を中間基材に加工する際に不織布やフィラー等一部の形状に限られてしまい、そのために再加工された強化複合材料の用途も限定されてしまう。 When the superheated steam method proposed in Patent Document 2 is applied to a structural material composed of carbon fiber reinforced plastic and glass fiber reinforced plastic, the glass fibers and aluminum are melted into a paste as in the above-mentioned thermal decomposition method. Therefore, the reinforcing material cannot be separated and recovered from the reinforced composite material. Further, the strength of the recovered carbon fibers is lowered by performing the high temperature treatment in the same manner as the above-mentioned thermal decomposition method. Also, although rotary kilns are used to improve the efficiency of thermal decomposition, the carbon fiber reinforced plastics to be treated must be crushed because they must be large enough to fit in the equipment. Therefore, continuous fibrous carbon fibers cannot be recovered, and in order to recomposite with the base material, the reinforcing material is limited to some shapes such as non-woven fabric and filler when it is processed into an intermediate base material. Therefore, the use of the reprocessed reinforced composite material is also limited.
非特許文献１に提案されている常圧溶解法は、溶解できる樹脂がＰＥＴ等のポリエステル系に限られるため、処理できる炭素繊維強化プラスチックに制限がある。熱可塑性樹脂を用いた炭素繊維強化プラスチックは、使用される樹脂の種類が豊富で、ＰＥＴ（ポリエステル）、ＰＰ（ポリプロピレン）、ＰＥＥＫ（ポリエーテルエーテルケトン）、ＰＡ（ポリアミド）等多岐にわたっている。しかし、それらを一目で見分けることは難しい。専用の機器を用いて分析することは可能だが、回収した炭素繊維強化プラスチックの部品を一つずつ分析して選別することは現実的ではない。 In the atmospheric dissolution method proposed in Non-Patent Document 1, since the resin that can be dissolved is limited to polyester-based resins such as PET, there is a limitation on the carbon fiber reinforced plastic that can be treated. Carbon fiber reinforced plastics using thermoplastic resins have a wide variety of resins used, such as PET (polyester), PP (polypropylene), PEEK (polyetheretherketone), and PA (polyamide). However, it is difficult to distinguish them at a glance. Although it is possible to analyze using a dedicated device, it is not realistic to analyze and sort the recovered carbon fiber reinforced plastic parts one by one.
特許文献３に提案されている超臨界法は、高圧装置が非常に高コストになることと、大
型化が難しく実用的ではない。
上述したように、従来提案されている強化複合材料からの強化材の分離回収方法は、処理できる強化複合材料の種類に制限がある方法や、回収した強化材の強度低下や粉砕による形状変化がある方法のため、強化複合材料へ再び活用する際にその複合化の方法や強化複合材料の用途に制限がある。また、処理する構造材の組み合わせによっては、強化材を分離回収できない場合が発生する。
The supercritical method proposed in Patent Document 3 is not practical because the high-voltage device becomes very expensive and it is difficult to increase the size.
As described above, the conventionally proposed methods for separating and recovering the reinforcing material from the reinforced composite material include a method in which the types of the reinforced composite material that can be processed are limited, and the shape of the recovered reinforcing material is reduced due to a decrease in strength or crushing. Due to certain methods, there are restrictions on the method of compounding and the use of the reinforced composite when reusing it as a reinforced composite. In addition, depending on the combination of structural materials to be treated, the reinforcing material may not be separated and recovered.
本発明は、上記問題点に鑑みてなされたものであり、母材の種類によらず、強化複合材料から連続繊維の状態で強化材を再生することできる、強化複合材料からの強化材の再生回収方法を提供することを目的とする。 The present invention has been made in view of the above problems, and the reinforcing material can be regenerated in the state of continuous fibers from the reinforcing composite material regardless of the type of the base material. Regeneration of the reinforcing material from the reinforcing composite material. The purpose is to provide a collection method.
本発明者は、上記課題を解決するために鋭意検討した結果、特定の強化複合材料から強化材を再生回収する方法により、上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventor has found that the above object can be achieved by a method of regenerating and recovering a reinforcing material from a specific reinforcing composite material, and has completed the present invention.
すなわち本発明は、以下の通りである。
〔１〕
母材と強化材とを含む強化複合材料から、強化材を再生回収する方法であって、
ａ）前記強化複合材料を、処理溶液により、母材と強化材とに分解する工程、
ｃ）強化材を芯材に巻き取る工程、
を含み、
前記処理溶液が、ケトン系、アルコール系、アミド系、エーテル系、炭化水素系の溶媒を含まないことを特徴とする、強化複合材料から強化材を再生回収する方法。
〔２〕
前記ａ）工程が、
ａ１）硫酸溶液を電気分解することにより酸化性活性種を含む処理溶液を得る工程、
ａ２）前記処理溶液に、前記強化複合材料を浸漬して、母材と強化材とに分解する工程、を含む、〔１〕記載の強化複合材料から強化材を再生回収する方法。
〔３〕
前記ａ）工程と前記ｃ）工程との間に
ｂ）前記強化材を洗浄、乾燥する工程、
を含む、〔１〕又は〔２〕記載の強化複合材料から強化材を再生回収する方法。
〔４〕
前記強化材が、炭素繊維、ガラス繊維、及び金属繊維からなる群から選ばれる少なくとも１種から構成される、〔１〕ないし〔３〕のいずれか１つに記載の強化複合材料から強化材を再生回収する方法。
〔５〕
〔１〕ないし〔４〕のいずれか１つに記載の方法で再生回収した強化材と、母材とを複合化することを特徴とする、強化複合材料の製造方法。
That is, the present invention is as follows.
[1]
A method of reclaiming and recovering a reinforcing material from a reinforcing composite material containing a base material and a reinforcing material.
a) A step of decomposing the reinforced composite material into a base material and a reinforced material with a treatment solution.
c) The process of winding the reinforcing material around the core material,
Including
A method for regenerating and recovering a reinforcing material from a reinforcing composite material, wherein the treatment solution does not contain a ketone-based, alcohol-based, amide-based, ether-based, or hydrocarbon-based solvent.
[2]
The step a)
a1) A step of obtaining a treatment solution containing an oxidizing active species by electrolyzing a sulfuric acid solution,
a2) The method for regenerating and recovering a reinforcing material from the reinforcing composite material according to [1], which comprises a step of immersing the reinforcing composite material in the treatment solution and decomposing it into a base material and a reinforcing material.
[3]
Between the steps a) and c) b) the step of cleaning and drying the reinforcing material,
A method for regenerating and recovering a reinforcing material from the reinforcing composite material according to [1] or [2], which comprises.
[4]
The reinforcing material is obtained from the reinforcing composite material according to any one of [1] to [3], wherein the reinforcing material is composed of at least one selected from the group consisting of carbon fiber, glass fiber, and metal fiber. How to reclaim and collect.
[5]
A method for producing a reinforced composite material, which comprises combining a reinforcing material regenerated and recovered by the method according to any one of [1] to [4] and a base material.
本発明によれば、連続繊維の状態で強化材を再生することできる、強化複合材料からの強化材の再生回収方法を提供することができる。 According to the present invention, it is possible to provide a method for regenerating and recovering a reinforcing material from a reinforcing composite material, which can regenerate the reinforcing material in the state of continuous fibers.
以下、本発明を実施するための形態（以下、「本実施形態」という。）について詳細に説明する。なお、本発明は以下の記載に限定されるものではなく、その要旨の範囲内で種々変形して実施できる。
初めに、本実施形態の強化材の再生回収方法において用いられる強化複合材料について記載する。
Hereinafter, embodiments for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following description, and can be modified in various ways within the scope of the gist thereof.
First, the reinforced composite material used in the method for regenerating and recovering the reinforcing material of the present embodiment will be described.
本実施形態の強化複合材料から強化材を再生回収する方法は、母材と強化材とを含む強化複合材料から、強化材を再生回収する方法であって、
ａ）前記強化複合材料を、処理溶液により、母材と強化材とに分解する工程、
ｃ）強化材を芯材に巻き取る工程、
を含む。前記処理溶液は、ケトン系、アルコール系、アミド系、エーテル系、炭化水素系の溶媒を含まないことが好ましい。
本明細書において、母材と強化材とに分解する上記工程は、母材と強化材とに分離する工程であり、「分解工程」と称する場合がある。また、強化材を芯材に巻き取る工程を、「巻き取り工程」と称する場合がある。
図１は、本実施形態の強化複合材料から強化材を再生回収する方法を示す説明図である。分解工程において、強化複合材料を母材と強化材とに分解し、巻き取り工程において、上記分解工程で回収した強化材を芯材に巻き取る。
The method of regenerating and recovering the reinforcing material from the reinforced composite material of the present embodiment is a method of regenerating and recovering the reinforcing material from the reinforced composite material including the base material and the reinforcing material.
a) A step of decomposing the reinforced composite material into a base material and a reinforced material with a treatment solution.
c) The process of winding the reinforcing material around the core material,
including. The treatment solution preferably does not contain a ketone-based, alcohol-based, amide-based, ether-based, or hydrocarbon-based solvent.
In the present specification, the above-mentioned step of decomposing into a base material and a reinforcing material is a step of separating the base material and the reinforcing material, and may be referred to as a "decomposition step". Further, the process of winding the reinforcing material around the core material may be referred to as a "winding process".
FIG. 1 is an explanatory diagram showing a method of regenerating and recovering a reinforcing material from the reinforcing composite material of the present embodiment. In the decomposition step, the reinforced composite material is decomposed into a base material and a reinforcing material, and in the winding step, the reinforcing material recovered in the above decomposition step is wound around the core material.
〔強化複合材料〕
上記強化複合材料とは、樹脂等の母材中に繊維等の異種材料である強化材を複合化することによって、強度が向上された材料である。複合化の手法は、特に限定されることなく、水素結合や分子間力等の相互作用を利用する手法であってよく、分散、付着、接着、吸着、担持、配置等としてよい。上記強化複合材料は、母材（例えば、後述の樹脂）と強化材とを含む原料を成形（例えば、射出成形、圧縮成形等）した材料としてよい。例えば、複数の強化複合材料を、直接積層した、又は接着剤層等の他の層を介して積層した積層体であってもよい。
強化複合材料は、母材、強化材、その他の添加剤等を含んでよい。
[Reinforced composite material]
The reinforced composite material is a material whose strength is improved by compounding a reinforcing material which is a different material such as fiber in a base material such as resin. The method of compounding is not particularly limited, and may be a method that utilizes interactions such as hydrogen bonds and intermolecular forces, and may be dispersion, adhesion, adhesion, adsorption, support, arrangement, or the like. The reinforced composite material may be a material obtained by molding (for example, injection molding, compression molding, etc.) a raw material containing a base material (for example, a resin described later) and a reinforcing material. For example, it may be a laminate in which a plurality of reinforced composite materials are directly laminated or laminated via another layer such as an adhesive layer.
The reinforced composite material may include a base material, a reinforcing material, other additives and the like.
〔強化材〕
上記強化材とは、強化複合材料の母材となるマトリックス樹脂に複合化又は分散される材料のことで、炭素繊維、ガラス繊維、金属繊維等が挙げられる。
上記強化材は、一種を単独で又は複数を組み合わせて用いることができる。
[Reinforcement material]
The reinforcing material is a material that is composited or dispersed in a matrix resin that is a base material of the reinforcing composite material, and examples thereof include carbon fiber, glass fiber, and metal fiber.
The above-mentioned reinforcing material may be used alone or in combination of two or more.
炭素繊維とは、アクリル繊維又はピッチ（石油、石炭、コールタール等の副生成物）を原料に高温で炭化して作った繊維のことである。
ガラス繊維とは、ガラスを融解、牽引して繊維状にしたものである。
金属繊維とは、塑性加工（圧延等）のほか、溶融紡糸法、ＣＶＤ法等により、ステンレス、アルミニウム、鉄、ニッケル、銅等の金属を糸状に加工したものである。
Carbon fiber is a fiber made by carbonizing acrylic fiber or pitch (a by-product of petroleum, coal, coal tar, etc.) at a high temperature.
Glass fiber is made by melting and pulling glass into fibers.
The metal fiber is formed by processing a metal such as stainless steel, aluminum, iron, nickel, and copper into a thread shape by a melt spinning method, a CVD method, or the like, in addition to plastic working (rolling, etc.).
これらの繊維は連続繊維や不織布等の中間基材に加工されて母材と複合化される。
連続繊維とは、すべての繊維が互いに平行に並んでいる一方向層の形態で用いられる長繊維のことで、編んだり、織ったりして用いることができる。また、一方向層を様々な方向に積層することで擬似等方性や直交性、異方性のある板をつくることができる。
不織布とは、繊維を織らずに絡み合わせたシート状のものである。不織布は繊維を熱・機械的又は化学的な作用によって接着又は絡み合わせることで布にしたものを指す。
These fibers are processed into an intermediate base material such as continuous fibers or non-woven fabrics and composited with the base material.
The continuous fiber is a long fiber used in the form of a unidirectional layer in which all the fibers are arranged in parallel with each other, and can be used by knitting or weaving. Further, by laminating the unidirectional layers in various directions, a plate having pseudo isotropic property, orthogonality, and anisotropy can be produced.
The non-woven fabric is a sheet-like material that is entwined without weaving fibers. Nonwoven fabric refers to a cloth made by adhering or entwining fibers by thermal, mechanical or chemical action.
上記強化複合材料中の上記強化材の含有量としては、強化複合材料を１００質量％として、１０〜８０質量％であることが好ましい。好適には、下限は、１５質量％以上、２０質量％以上であり、また、好適には、上限は、７５質量％以下、７０質量％以下である。 The content of the reinforcing material in the reinforcing composite material is preferably 10 to 80% by mass, with the reinforcing composite material as 100% by mass. Preferably, the lower limit is 15% by mass or more and 20% by mass or more, and preferably, the upper limit is 75% by mass or less and 70% by mass or less.
〔母材〕
上記母材とは、強化複合材料のマトリックスとして用いられる樹脂のことで、熱可塑性樹脂又は熱硬化性樹脂が用いられる。
上記母材は、一種を単独で又は複数を組み合わせて用いることができる。
[Base material]
The base material is a resin used as a matrix of a reinforced composite material, and a thermoplastic resin or a thermosetting resin is used.
The base material may be used alone or in combination of two or more.
熱可塑性樹脂とは、ガラス転移温度又は融点まで加熱することによって軟らかくなり、目的の形に成形できる樹脂を指す。一般的に、熱可塑性樹脂は、切削・研削等の機械加工がしにくい事が多く、加温し軟化したところで金型に押し込み、冷し固化させて最終製品とする射出成形加工等が広く用いられている。例として、ポリエチレン、ポリプロピレン、ポリスチレン、ＡＢＳ樹脂、塩化ビニル樹脂、メタクリル酸メチル樹脂、ナイロン、フッ素樹脂、ポリカーボネート、ポリエステル樹脂等が挙げられる。 Thermoplastic resin refers to a resin that becomes soft by heating to the glass transition temperature or melting point and can be molded into a desired shape. In general, thermoplastic resins are often difficult to machine such as cutting and grinding, and are widely used for injection molding, etc., where they are pushed into a mold when heated and softened, cooled and solidified to make a final product. Has been done. Examples thereof include polyethylene, polypropylene, polystyrene, ABS resin, vinyl chloride resin, methyl methacrylate resin, nylon, fluororesin, polycarbonate, polyester resin and the like.
熱硬化性樹脂とは、加熱すると重合を起こして高分子の網目構造を形成し、硬化して元に戻らなくなる樹脂を指す。使用に際しては、流動性を有するレベルの比較的低分子の樹脂を所定の形状に整形し、その後加熱等により反応させて硬化させる。接着剤やパテでＡ液（基剤）とＢ液（硬化剤）を混ぜて使うタイプがあるが、これは熱硬化性樹脂のエポキシ樹脂で、混合により重合反応が起こっている。熱硬化性樹脂は硬くて熱や溶剤に強い。例として、フェノール樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、ポリウレタン等が挙げられる。 Thermosetting resin refers to a resin that polymerizes when heated to form a polymer network structure that cures and cannot be restored. At the time of use, a relatively low-molecular-weight resin having a fluidity level is shaped into a predetermined shape, and then reacted by heating or the like to be cured. There is a type in which liquid A (base) and liquid B (curing agent) are mixed and used with an adhesive or putty, but this is a thermosetting resin epoxy resin, and a polymerization reaction occurs due to the mixing. Thermosetting resins are hard and resistant to heat and solvents. Examples include phenolic resins, epoxy resins, unsaturated polyester resins, polyurethanes and the like.
上記強化複合材料中の上記母材の含有量としては、強化材を１００質量部として、２０〜９０質量部であることが好ましい。好適には、下限は、２５質量部以上、３０質量部以上であり、また、好適には、上限は、８５質量部以下、８０質量部以下である。 The content of the base material in the reinforced composite material is preferably 20 to 90 parts by mass with the reinforced material as 100 parts by mass. Preferably, the lower limit is 25 parts by mass or more and 30 parts by mass or more, and preferably, the upper limit is 85 parts by mass or less and 80 parts by mass or less.
〔その他の添加剤〕
その他の添加剤としては、特に限定されず、難燃剤、熱安定剤、酸化防止剤、光吸収剤、離型剤、滑剤、各種安定剤、帯電防止剤、染顔料や、上述の複合化において用いられる各種反応剤等が挙げられる。
上記強化複合材料中の上記その他の添加剤の含有量としては、強化複合材料を１００質量％として、０．０１質量％以上、８０質量％以下としてよい。
[Other additives]
Other additives are not particularly limited, and include flame retardants, heat stabilizers, antioxidants, light absorbers, mold release agents, lubricants, various stabilizers, antistatic agents, dye pigments, and the above-mentioned composites. Examples thereof include various reactants used.
The content of the other additives in the reinforced composite material may be 0.01% by mass or more and 80% by mass or less, with the reinforced composite material being 100% by mass.
〔構造材料〕
構造材料とは、母材と強化材とを含む強化複合材料に、異なる樹脂材料や異なる強化複合材料が接着されて構成されている材料を指す。構造例を図２に示す。
例えば、水素タンクは、耐衝撃性や耐擦傷性を向上し、更に外部との電気絶縁性を付与するために、炭素繊維強化プラスチックで成形されたタンクの外周部にガラス繊維強化プラスチックで覆っている。また、バルブやタンク内部にアルミニウムが使用されていることが多い。
[Structural material]
The structural material refers to a material formed by adhering different resin materials or different reinforced composite materials to a reinforced composite material including a base material and a reinforcing material. A structural example is shown in FIG.
For example, in a hydrogen tank, in order to improve impact resistance and scratch resistance, and to provide electrical insulation with the outside, the outer periphery of the tank molded of carbon fiber reinforced plastic is covered with glass fiber reinforced plastic. There is. In addition, aluminum is often used inside valves and tanks.
（分解工程）
上記分解工程は、処理溶液を用いるものが好ましく、電解硫酸法を用いるものがより好ましい。上記分解工程は、加熱、加圧等しながら行ってもよい。
(Disassembly process)
The decomposition step preferably uses a treatment solution, and more preferably an electrolytic sulfuric acid method. The decomposition step may be carried out while heating, pressurizing or the like.
上記処理溶液は、ケトン系、アルコール系、アミド系、エーテル系、炭化水素系の溶媒を含まない。
上記処理溶液は、母材の種類によらず強化材を連続繊維の状態で一層効率よく回収することができる観点から、硫酸系の溶媒を含んでいてもよい。上記硫酸系の溶媒としては、硫酸と過酸化水素との混合溶媒（例えば、硫酸／過酸化水素の質量割合が３／１〜７／１である混合溶媒）、電解硫酸法により得られる溶液等が挙げられる。中でも、過酸化水素等の他の溶媒を添加することなく使用できて硫酸が再利用可能であり、より効率的に母材を分解できる観点から、電解硫酸法により得られる溶液が好ましい。
上記処理溶液は、母材を一層効率よく分解できる観点から、処理溶液１００質量％に対して硫酸系の溶媒を３０〜９５質量％含むことが好ましく、５０〜８０質量％含むことがより好ましい。また、上記処理溶液は、硫酸系の溶媒と水とからなる溶液であってもよく、硫酸系の溶媒のみからなる溶液であってもよい。また上記処理溶液は、塩酸、硝酸、過酸化水素やペルオキソ硫酸のような過酸化物を含んでいてもよい。
The treatment solution does not contain ketone, alcohol, amide, ether, or hydrocarbon solvents.
The treatment solution may contain a sulfuric acid-based solvent from the viewpoint that the reinforcing material can be recovered more efficiently in the state of continuous fibers regardless of the type of the base material. Examples of the sulfuric acid-based solvent include a mixed solvent of sulfuric acid and hydrogen peroxide (for example, a mixed solvent having a mass ratio of sulfuric acid / hydrogen peroxide of 3/1 to 7/1), a solution obtained by an electrolytic sulfuric acid method, and the like. Can be mentioned. Among them, a solution obtained by the electrolytic sulfuric acid method is preferable from the viewpoint that it can be used without adding another solvent such as hydrogen peroxide, sulfuric acid can be reused, and the base material can be decomposed more efficiently.
From the viewpoint of more efficiently decomposing the base material, the treatment solution preferably contains 30 to 95% by mass of a sulfuric acid-based solvent, and more preferably 50 to 80% by mass, based on 100% by mass of the treatment solution. Further, the treatment solution may be a solution composed of a sulfuric acid-based solvent and water, or may be a solution composed of only a sulfuric acid-based solvent. Further, the above-mentioned treatment solution may contain peroxides such as hydrochloric acid, nitric acid, hydrogen peroxide and peroxosulfuric acid.
上記電解硫酸法とは、硫酸溶液を電気分解することにより得られた酸化性活性種を含む処理溶液に、母材と強化材とからなる強化複合材料を浸漬することにより、上記母材が水と二酸化炭素等に分解し、分解後の分解物が上記処理溶液に溶解され、その後、上記強化材を上記処理溶液から取り出す方法である。特に、強化材の分解を一層抑制し、再生回収前の強化複合材料に含まれる強化材の平均繊維長さにより近い長さの強化材を再生回収できる観点から、電解硫酸法が好ましい。 The electrolytic sulfuric acid method is a method in which a reinforcing composite material composed of a base material and a reinforcing material is immersed in a treatment solution containing an oxidizing active species obtained by electrolyzing a sulfuric acid solution, whereby the base material becomes water. This is a method in which the decomposition product is dissolved in the treatment solution, and then the reinforcing material is taken out from the treatment solution. In particular, the electrolytic sulfuric acid method is preferable from the viewpoint of further suppressing the decomposition of the reinforcing material and regenerating and recovering the reinforcing material having a length closer to the average fiber length of the reinforcing material contained in the reinforcing composite material before regeneration and recovery.
酸化性活性種とは、所定電流、所定電圧にて硫酸溶液を電気分解すること等で生成されるものであり、具体的には、ヒドロキシラジカルやペルオキソ硫酸、ペルオキソ二硫酸等である。 The oxidative active species is produced by electrolyzing a sulfuric acid solution at a predetermined current and a predetermined voltage, and specifically, hydroxyl radical, peroxosulfuric acid, peroxodisulfuric acid and the like.
具体的には、本実施形態の強化材の再生回収方法は、
ａ）母材と強化材からなる強化複合材料を、処理溶液により、母材と強化材とに分解する工程、
ｃ）強化材を芯材に巻き取る工程、
を含む。
Specifically, the method for regenerating and recovering the reinforcing material of the present embodiment is
a) A process of decomposing a reinforced composite material consisting of a base material and a reinforcing material into a base material and a reinforcing material with a treatment solution.
c) The process of winding the reinforcing material around the core material,
including.
上記硫酸溶液は、硫酸（Ｈ2ＳＯ4）と水（Ｈ2Ｏ）とからなる溶液である。硫酸溶液中に含まれる硫酸の濃度は３０〜９５質量％が好ましく、さらに好ましくは５０〜８０質量％である。硫酸の濃度が３０質量％未満の場合は、強化複合材料の母材を分解するために必要な酸化性活性種の量を得ることができず、母材の分解に長時間を要する。なお、濃度９８質量％等の９５％超の濃硫酸においても、電気分解の方法を工夫しさえすれば酸化性活性種を生成させることは可能ではあるが、電気分解の際において電流が流れにくいことから酸化性活性種の生成量が極端に低下したり、電気分解に使用する電極の寿命が極端に短くなったりすることから好ましくはない。 The sulfuric acid solution is a solution composed of sulfuric acid (H 2 SO 4 ) and water (H 2 O). The concentration of sulfuric acid contained in the sulfuric acid solution is preferably 30 to 95% by mass, more preferably 50 to 80% by mass. If the concentration of sulfuric acid is less than 30% by mass, the amount of oxidatively active species required for decomposing the base material of the reinforced composite material cannot be obtained, and it takes a long time to decompose the base material. Even with concentrated sulfuric acid having a concentration of 98% by mass or more of more than 95%, it is possible to generate an oxidizing active species only by devising the method of electrolysis, but it is difficult for an electric current to flow during electrolysis. Therefore, it is not preferable because the amount of oxidizing active species produced is extremely reduced and the life of the electrode used for electrolysis is extremely shortened.
なお、電気分解した酸化性活性種を含む処理溶液に濃硫酸や塩酸、硝酸を加えてもよい。また、処理溶液に過酸化水素やペルオキソ硫酸のような過酸化物を添加してもよい。この場合、強化複合材の母材の分解速度を速める効果が得られる。 Concentrated sulfuric acid, hydrochloric acid, and nitric acid may be added to the treatment solution containing the electrolyzed oxidizing active species. Further, a peroxide such as hydrogen peroxide or peroxosulfate may be added to the treatment solution. In this case, the effect of accelerating the decomposition rate of the base material of the reinforced composite material can be obtained.
硫酸溶液の電気分解では、白金電極やカーボン電極等が使用できるが、濃度の高い硫酸溶液の電気分解にあっては、耐久性の面から、金属板表面に薄膜状にダイヤモンドコーティングされたいわゆるダイヤモンド電極を用いることができる。硫酸溶液の電気分解装置としては、ダイヤモンド電極を用いた隔膜式の電解セルを用いることが好ましい。 Platinum electrodes, carbon electrodes, etc. can be used for electrolysis of sulfuric acid solution, but for electrolysis of high-concentration sulfuric acid solution, so-called diamond with a thin diamond coating on the surface of the metal plate from the viewpoint of durability. Electrodes can be used. As the electrolyzer for the sulfuric acid solution, it is preferable to use a diaphragm type electrolytic cell using a diamond electrode.
電気分解の通電条件（例えば、ダイヤモンド電極の場合の通電条件）は、電流密度を０．０１〜１０Ａ／ｃｍ2（好ましくは１〜１０Ａ／ｃｍ2）、電圧０．１〜３００Ｖ（好ましくは１００〜２００Ｖ）であればよいが、電極の種類、硫酸溶液の硫酸濃度、硫酸溶液の液量等によって適宜変更される。 The energization conditions for electrolysis (for example, energization conditions for a diamond electrode) are a current density of 0.01 to 10 A / cm 2 (preferably 1 to 10 A / cm 2 ) and a voltage of 0.1 to 300 V (preferably 100). ~ 200V), but it is appropriately changed depending on the type of electrode, the sulfuric acid concentration of the sulfuric acid solution, the amount of the sulfuric acid solution, and the like.
なお、電気分解は、閉鎖系にて行うことが好ましく、閉鎖した硫酸溶液循環系にて、所定量の硫酸溶液を循環させながら行うことが好ましい。循環方法としては、ポンプ等を利用して電極面に対して平行方向に５０ｍＬ／分以上の流量で通液する方法、電気分解によって発生するガスの流れに従って対流させる自然循環による方法でもよい。 The electrolysis is preferably carried out in a closed system, and is preferably carried out while circulating a predetermined amount of sulfuric acid solution in a closed sulfuric acid solution circulation system. The circulation method may be a method of passing a liquid at a flow rate of 50 mL / min or more in a direction parallel to the electrode surface using a pump or the like, or a method of natural circulation in which convection is performed according to the flow of gas generated by electrolysis.
電気分解の処理時間は、硫酸溶液の量、硫酸濃度、硫酸溶液の流量、通電条件等によって適宜変更されるが、硫酸溶液１Ｌ当たり０．５〜１０時間処理することが酸化性活性種を効率的に生成させる点で好ましい。 The treatment time for electrolysis is appropriately changed depending on the amount of sulfuric acid solution, sulfuric acid concentration, flow rate of sulfuric acid solution, energization conditions, etc., but treatment for 0.5 to 10 hours per 1 L of sulfuric acid solution is efficient for oxidizing active species. It is preferable in that it is generated as a target.
陰極液及び陽極液に硫酸溶液を用いて電解する硫酸電解方法の場合は、両極に濃度の異なる硫酸を用いてもよい。特に、本実施形態では、濃度の高い硫酸を電気分解して得られた酸化性活性種を含む硫酸溶液が強化複合材料の母材の分解を促進する上で有効であることから、陽極側の硫酸濃度を高くし、陰極側の硫酸濃度を低くすることが電極の寿命を長くする上で好ましい。 In the case of the sulfuric acid electrolysis method in which a sulfuric acid solution is used for the cathode solution and the anode solution, sulfuric acid having different concentrations may be used for both electrodes. In particular, in the present embodiment, the sulfuric acid solution containing the oxidizing active species obtained by electrolyzing high-concentration sulfuric acid is effective in accelerating the decomposition of the base material of the reinforced composite material. It is preferable to increase the sulfuric acid concentration and decrease the sulfuric acid concentration on the cathode side in order to prolong the life of the electrode.
硫酸溶液の電気分解するための電源としては、考えられる様々な装置類から電気を調達することが可能であるが、太陽電池のようないわゆる再生可能エネルギーより生成された電気を用いることが好ましい。また、電気分解で発生した水素（陰極より発生）と酸素（陽極より発生）を回収して、発電や熱に変換することもできる。 As a power source for electrolyzing the sulfuric acid solution, electricity can be procured from various conceivable devices, but it is preferable to use electricity generated from so-called renewable energy such as a solar cell. It is also possible to recover hydrogen (generated from the cathode) and oxygen (generated from the anode) generated by electrolysis and convert them into power generation or heat.
得られた酸化性活性種を含む硫酸溶液を、強化複合材料の母材を分解させるための処理槽に供給する方式としては、ポンプ等で電解装置から連続して処理槽に供給する方式（連続式）、閉ざされた系内で硫酸溶液を循環させて電気分解処理後に系内から処理溶液を採取し、処理槽に処理溶液を供給する方式（バッチ式）のいずれでもよい。また、採取された処理溶液を加熱又は冷却、加圧できる装置を組み合わせてもよい。 As a method of supplying the obtained sulfuric acid solution containing the oxidizing active species to the treatment tank for decomposing the base material of the reinforced composite material, a method of continuously supplying the sulfuric acid solution from the electrolytic device to the treatment tank by a pump or the like (continuously). Either the formula) or the method (batch type) in which the sulfuric acid solution is circulated in the closed system, the treatment solution is collected from the system after the electrolysis treatment, and the treatment solution is supplied to the treatment tank. Further, an apparatus capable of heating, cooling, or pressurizing the collected treatment solution may be combined.
なお、強化複合材料を処理した後の処理溶液は繰り返し使用することができるため、回収して濃度調節し、再度酸化性活性種を生成させるための電気分解を行うための硫酸溶液として再利用することができる。 Since the treated solution after treating the reinforced composite material can be used repeatedly, it is recovered, adjusted in concentration, and reused as a sulfuric acid solution for electrolysis to generate an oxidizing active species again. be able to.
酸化性活性種を含む処理溶液は、強化複合材料の母材の分解を高めるために加熱することが好ましい。加熱温度は処理溶液の沸点にも関係するが、好ましくは１００℃以上の温度で加熱して使用することが強化複合材料の母材を効率的に短期間に分解する上で好ましい。加熱温度は、硫酸溶液の沸点以下の温度でもよく、大気圧又は不活性ガス下で加熱される。なお、処理溶液の加熱の際、加圧あるいは減圧下で行ってもよい。 The treatment solution containing the oxidatively active species is preferably heated to enhance the decomposition of the base material of the reinforced composite. Although the heating temperature is related to the boiling point of the treatment solution, it is preferable to heat it at a temperature of 100 ° C. or higher for use in order to efficiently decompose the base material of the reinforced composite material in a short period of time. The heating temperature may be a temperature equal to or lower than the boiling point of the sulfuric acid solution, and is heated under atmospheric pressure or an inert gas. When heating the treatment solution, it may be carried out under pressure or reduced pressure.
上記処理溶液は、母材と強化材とをより効率的に分解し、連続繊維状態の強化材が得やすくなる観点から、強化複合材料の質量１ｋｇに対して、０．０５〜５０Ｌの割合で用いることが好ましく、０．１〜１０Ｌの割合で用いることがより好ましい。
また、連続繊維状態の強化材が得やすくなる観点から、上記分解工程に用いる強化複合材料は、切断等の前処理を行わないことが好ましい。
上記強化複合材料が積層体である場合、各層毎に、複数の段階を分けて処理をしてもよい。各段階の処理溶液は、同じ溶液を用いてもよいし異なる溶液を用いてもよい。また、各段階の処理条件は、同じであってもよいし異なっていてもよい。また、各段階後に強化材を巻き取ってもよいし、全ての層の処理が終わった後に、まとめて強化材を巻き取ってもよい。
The above-mentioned treatment solution decomposes the base material and the reinforcing material more efficiently, and from the viewpoint of making it easier to obtain the reinforcing material in the continuous fiber state, the ratio of 0.05 to 50 L to 1 kg of the mass of the reinforcing composite material. It is preferable to use it, and it is more preferable to use it in a ratio of 0.1 to 10 L.
Further, from the viewpoint that a reinforcing material in a continuous fiber state can be easily obtained, it is preferable that the reinforcing composite material used in the decomposition step is not subjected to pretreatment such as cutting.
When the reinforced composite material is a laminated body, each layer may be treated in a plurality of steps. As the treatment solution of each stage, the same solution may be used or different solutions may be used. Further, the processing conditions at each stage may be the same or different. Further, the reinforcing material may be wound up after each stage, or the reinforcing material may be wound up collectively after the treatment of all the layers is completed.
（巻き取り工程）
強化複合材料の強化材を連続繊維として回収するために、母材を分解することによって強化材の一部を取り出して芯に括り付けて、更に母材を分解しながら強化材を巻き取ることによって再生することができる。
(Winding process)
In order to recover the reinforcing material of the reinforced composite material as continuous fibers, a part of the reinforcing material is taken out by disassembling the base material and tied to the core, and the reinforcing material is wound while further disassembling the base material. Can be played.
その際、強化材を水洗したり乾燥したりしてもよい。強化材を巻き取る前に水洗や乾燥してもよいし、巻き取った後で水洗や乾燥してもよい。上記分解工程と上記巻き取り工程との間に、上記強化材を洗浄、乾燥する工程を設けてもよい。 At that time, the reinforcing material may be washed with water or dried. The reinforcing material may be washed and dried before being wound up, or may be washed and dried after being wound up. A step of cleaning and drying the reinforcing material may be provided between the disassembling step and the winding step.
（強化材、中間基材、強化複合材料）
上述の本実施形態の強化材の再生回収方法を用いて製造される、強化材、中間基材、強化複合材料の詳細について、以下に記載する。
(Reinforcing material, intermediate base material, reinforced composite material)
Details of the reinforcing material, the intermediate base material, and the reinforced composite material produced by using the method for regenerating and recovering the reinforcing material of the present embodiment described above will be described below.
上述の本実施形態の強化材の再生回収方法により再生したとき、再生した強化材の強度が再生する前の強化材の強度の８０％以上であり、かつ強化材の再生前後での形状保持率が９０％以上であることが好ましい。
また、上述の本実施形態の強化材の再生回収方法により再生したとき、再生した強化材の強度が再生する前の強化材の強度の９０％以上であり、かつ強化材の再生前後での形状保持率が８０％以上であることが好ましい。
なお、強化材の強度は、後述の実施例に記載の方法で測定されるものをいう。また、再生前後での形状保持率は、後述の実施例に記載の方法で測定されるものをいう。
When regenerated by the method for regenerating and recovering the reinforcing material of the present embodiment, the strength of the regenerated reinforcing material is 80% or more of the strength of the reinforcing material before regeneration, and the shape retention rate before and after the regeneration of the reinforcing material. Is preferably 90% or more.
Further, when regenerated by the method for regenerating and recovering the reinforcing material of the present embodiment, the strength of the regenerated reinforcing material is 90% or more of the strength of the reinforcing material before regeneration, and the shape before and after the regeneration of the reinforcing material. The retention rate is preferably 80% or more.
The strength of the reinforcing material is measured by the method described in Examples described later. The shape retention rate before and after regeneration is measured by the method described in Examples described later.
さらに、上述の本実施形態の強化材の再生回収方法により再生したとき、再生した強化材の強度が、再生する前の強化材の強度の９０％以上であり、かつ強化材の再生前後での形状保持率が９０％以上であることがより好ましい。 Further, when regenerated by the method for regenerating and recovering the reinforcing material of the present embodiment, the strength of the regenerated reinforcing material is 90% or more of the strength of the reinforcing material before regeneration, and before and after the regeneration of the reinforcing material. It is more preferable that the shape retention rate is 90% or more.
上述の本実施形態の強化材の再生回収方法により再生した強化材を適宜加工して、中間基材を作製してよい。上記中間基材は、再生した強化材を含む連続繊維からなる、プリプレグ、織物、不織布、ラミネート又はペレットとしてよい。 An intermediate base material may be prepared by appropriately processing the reinforcing material regenerated by the method for regenerating and recovering the reinforcing material of the present embodiment described above. The intermediate substrate may be a prepreg, a woven fabric, a non-woven fabric, a laminate or pellets made of continuous fibers containing a regenerated reinforcing material.
樹脂等の母材中に、上述の再生した強化材や上述の中間基材を複合化することによって、再生した強化複合材料を作製してよい。 A regenerated reinforced composite material may be produced by combining the above-mentioned regenerated reinforcing material and the above-mentioned intermediate base material in a base material such as a resin.
本実施形態において、上述の方法を用いて強化複合材料を再生したとき、再生した強化材した強化材を用いて再生した強化複合材料の強度が、再生する前の強化材を用いて作製した強化複合材料の強度の６５％以上であることが好ましく、より好ましくは７０％以上であり、さらに好ましくは７５％以上であり、また、９５％以下であることが好ましく、より好ましくは８０％以下である。
なお、強化複合材料の強度は、後述の実施例に記載の方法で測定されるものをいう。
In the present embodiment, when the reinforced composite material is regenerated by using the above method, the strength of the reinforced composite material regenerated using the regenerated reinforcing material is the strength produced by using the reinforcing material before regeneration. The strength of the composite material is preferably 65% or more, more preferably 70% or more, further preferably 75% or more, and preferably 95% or less, more preferably 80% or less. is there.
The strength of the reinforced composite material is measured by the method described in Examples described later.
上述の本実施形態の強化材の再生回収方法により再生したとき、再生回収した強化材の平均繊維長さが、再生回収する前の強化複合材料に含まれる強化材の平均繊維長さ１００％に対して、５０％以上であることが好ましく、８０％以上であることがより好ましい。 When regenerated by the method for regenerating and recovering the reinforcing material of the present embodiment described above, the average fiber length of the reinforced material regenerated and recovered becomes 100% of the average fiber length of the reinforcing material contained in the reinforcing material before being regenerated and recovered. On the other hand, it is preferably 50% or more, and more preferably 80% or more.
（強化複合材料の製造方法）
本実施形態の強化複合材料の製造方法は、上述の本実施形態の強化材の再生回収方法により回収した強化材と、母材とを複合化して製造する方法である。上記母材は、新たな母材としてよい。
上記強化複合材料の製造方法は、例えば、
ａ）母材と強化材からなる強化複合材料を、処理溶液により、母材と強化材とに分解する工程、
ｃ）強化材を芯材に巻き取る工程、
を含む。
(Manufacturing method of reinforced composite material)
The method for producing the reinforced composite material of the present embodiment is a method of combining the reinforced material recovered by the above-described method for regenerating and recovering the reinforced material of the present embodiment and the base material. The base material may be used as a new base material.
The method for producing the reinforced composite material is, for example,
a) A process of decomposing a reinforced composite material consisting of a base material and a reinforcing material into a base material and a reinforcing material with a treatment solution.
c) The process of winding the reinforcing material around the core material,
including.
（強化複合材料の循環型社会を実現する方法）
強化複合材料の循環型社会を実現する方法は、上述の本実施形態の強化複合材料の処理方法を用いるものである。
再生する前の上記強化複合材料としては、輸送機器、建設材料、電子部品等の材料を用いてよく、例えば、航空機、自動車、宇宙船、船舶、及び汽車からなる群から選ばれる少なくとも１つの輸送機器に含まれる強化複合材料を使用し、再生した上記強化複合材料を再び上記輸送機器に使用するものとしてよい。
(How to realize a recycling-oriented society of reinforced composite materials)
The method for realizing a recycling-oriented society of the reinforced composite material is to use the above-described method for treating the reinforced composite material of the present embodiment.
As the reinforced composite material before regeneration, materials such as transportation equipment, construction materials, and electronic parts may be used, and for example, at least one transportation selected from the group consisting of aircraft, automobiles, spacecraft, ships, and trains. The reinforced composite material contained in the equipment may be used, and the regenerated reinforced composite material may be used again in the transportation equipment.
以下、具体的な実施例、比較例を挙げて本発明を説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.
実施例、比較例においては以下の方法により測定及び評価を行った。 In the examples and comparative examples, measurements and evaluations were carried out by the following methods.
＜強化材の強度比＞
強化材の強度を以下の方法にて測定した。
万能引っ張り試験機（株式会社島津製作所製ＥＺ ＴＥＳＴ−５Ｎ）を用いて２３℃、引っ張り速度：１．５ｍｍ／分にて長さ方向の強度を測定した。強度としては任意の８０個の強化材の平均を用いた。
強化材の強度比（％）は、下記式にて算出した。
強化材の強度比（％）＝１００×（強化複合材料から再生回収した強化材の強度／再生回収前の強化複合材料に含まれる強化材の強度）
<Strength ratio of reinforcing material>
The strength of the reinforcing material was measured by the following method.
The strength in the length direction was measured at 23 ° C. and a tensile speed of 1.5 mm / min using a universal tensile tester (EZ TEST-5N manufactured by Shimadzu Corporation). As the strength, the average of any 80 reinforcing materials was used.
The strength ratio (%) of the reinforcing material was calculated by the following formula.
Strength ratio of reinforcing material (%) = 100 × (strength of reinforcing material reclaimed from reinforced composite material / strength of reinforcing material contained in reinforced composite material before recycling and recovery)
＜形状保持率＞
形状保持率の算出は、走査型プローブ顕微鏡（株式会社島津製作所製 ＳＰＭ−９７００）を用いて、強化材の直径を測定し、再生前後での直径の比率を計算することによって、行った。
強化材の幅方向の直径を測定した。直径としては任意の１０個の強化材の平均を用いた。
形状保持率（％）は、下記式にて算出した。
形状保持率（％）＝１００×（強化複合材料から再生回収した強化材の直径／再生回収前の強化複合材料に含まれる強化材の直径）
<Shape retention rate>
The shape retention rate was calculated by measuring the diameter of the reinforcing material using a scanning probe microscope (SPM-9700 manufactured by Shimadzu Corporation) and calculating the diameter ratio before and after regeneration.
The diameter of the reinforcing material in the width direction was measured. As the diameter, the average of 10 arbitrary reinforcing materials was used.
The shape retention rate (%) was calculated by the following formula.
Shape retention rate (%) = 100 x (diameter of the reinforcing material reclaimed from the reinforced composite material / diameter of the reinforcing material contained in the reinforced composite material before regeneration and recovery)
［実施例１］
再生回収する強化複合材料として、図２に示す構造の水素タンクを用いた。上記水素タンクは、外部の強化複合材料の強化材Ａ１がガラス繊維：ＲＳ４４０ ＲＲ−５２０（日東紡績株式会社製）、内部の強化複合材料の強化材Ａ２が炭素繊維：トレカＴ７００ＳＣ−１２Ｋ−５０Ｃ（東レ株式会社製）の積層体である。
上記２つの強化複合材料をそれぞれフィラメントワインダー（旭化成エンジニアリング社製）を用い、母材としてエポキシ樹脂を用いて作製した後、１５０℃、３０分間で硬化することで水素タンクを作製した。
強化複合材料からの強化材の再生回収方法は、電解硫酸法を用いた。
具体的には、電極面積７００ｃｍ2のダイヤモンド電極を用い、電極を水冷しながら、隔膜式の電解セル内で濃度６０％の硫酸水溶液を電気分解して酸化性活性種を含む処理溶液を作製した。１回で電気分解する処理溶液（硫酸水溶液）の量は１０Ｌであった。電流は３〜１０Ａ／ｃｍ2、電圧は１７０〜２００Ｖ、処理時間は１２０分であった。電界は、閉鎖系で、電気分解によって発生するガスの流れに従って滞留させて自然循環させながら行った。
作製した酸化性活性種を含む処理溶液６０Ｌに、水素タンク１本（１２０ｋｇ）を処理溶液に浸漬した。
１段階目として１５０℃、５時間で外部の強化複合材料を浸漬処理し、外部の強化複合材料の母材を分解して強化材Ａ１を、芯に連続繊維として巻き取り、水洗、乾燥して、分離回収した。
その後、２段階目に１５０℃、５時間で内部の強化複合材料を浸漬処理し、内部の強化複合材料の母材を分解した。
分離した強化材Ａ２を芯に連続繊維として巻き取り、水洗して、乾燥した。
巻き取り後の強化材Ａ１の強度比は９０％以上であった。また、巻き取り後の強化材Ａ２の強度比は９０％以上であった。
巻き取り後の強化材Ａ１の形状保持率は９０％以上であった。また、巻き取り後の強化材Ａ２の形状保持率は９０％以上であった。
巻き取り後の強化材Ａ１の平均繊維長さは、再生回収前の強化複合材料に含まれる強化材Ａ１の平均繊維長さ１００％に対して、９０％であった。また、巻き取り後の強化材Ａ２の平均繊維長さは、再生回収前の強化複合材料に含まれる強化材Ａ２の平均繊維長さ１００％に対して、９０％であった。強化材Ａ１及びＡ２は、何れも連続繊維状態で再生回収できた。なお、平均繊維長さは、任意の８０個の強化材の延在方向長さの平均値とした。
[Example 1]
A hydrogen tank having the structure shown in FIG. 2 was used as the reinforced composite material to be regenerated and recovered. In the above hydrogen tank, the reinforcing material A1 of the external reinforcing composite material is glass fiber: RS440 RR-520 (manufactured by Nitto Spinning Co., Ltd.), and the reinforcing material A2 of the internal reinforcing composite material is carbon fiber: Treca T700SC-12K-50C ( It is a laminated body of Toray Industries, Inc.).
A hydrogen tank was prepared by preparing each of the above two reinforced composite materials using a filament winder (manufactured by Asahi Kasei Engineering Co., Ltd.) and using an epoxy resin as a base material, and then curing at 150 ° C. for 30 minutes.
The electrolytic sulfuric acid method was used as a method for regenerating and recovering the reinforcing material from the reinforced composite material.
Specifically, a diamond electrode having an electrode area of 700 cm 2 was used, and while the electrode was water-cooled, a sulfuric acid aqueous solution having a concentration of 60% was electrolyzed in a diaphragm type electrolytic cell to prepare a treatment solution containing an oxidizing active species. .. The amount of the treatment solution (sulfuric acid aqueous solution) to be electrolyzed at one time was 10 L. The current was 3-10 A / cm 2 , the voltage was 170-200 V, and the processing time was 120 minutes. The electric field was carried out in a closed system while being retained and naturally circulated according to the flow of gas generated by electrolysis.
One hydrogen tank (120 kg) was immersed in the prepared treatment solution 60 L containing the oxidatively active species.
As the first step, the external reinforcing composite material is immersed at 150 ° C. for 5 hours, the base material of the external reinforcing composite material is decomposed, and the reinforcing material A1 is wound around the core as continuous fibers, washed with water, and dried. , Separated and recovered.
Then, in the second step, the inner reinforced composite material was immersed at 150 ° C. for 5 hours to decompose the base material of the inner reinforced composite material.
The separated reinforcing material A2 was wound around the core as continuous fibers, washed with water, and dried.
The strength ratio of the reinforcing material A1 after winding was 90% or more. The strength ratio of the reinforcing material A2 after winding was 90% or more.
The shape retention rate of the reinforcing material A1 after winding was 90% or more. Further, the shape retention rate of the reinforcing material A2 after winding was 90% or more.
The average fiber length of the reinforcing material A1 after winding was 90% with respect to 100% of the average fiber length of the reinforcing material A1 contained in the reinforcing composite material before regeneration and recovery. The average fiber length of the reinforcing material A2 after winding was 90% with respect to 100% of the average fiber length of the reinforcing material A2 contained in the reinforcing composite material before regeneration and recovery. Both the reinforcing materials A1 and A2 could be regenerated and recovered in the continuous fiber state. The average fiber length was the average value of the lengths of any 80 reinforcing materials in the extending direction.
［実施例２］
実施例１と同様の方法で、強化複合材料の母材を分解した。分離した強化材Ａ２を、水洗して、乾燥した後に芯に巻き取ることによって連続繊維の強化材Ａ１及びＡ２を再生した。
再生した強化材Ａ１及びＡ２の強度比は９０％以上であった。
再生した強化材Ａ１及びＡ２の形状保持率は９０％以上であった。
巻き取り後の強化材Ａ１及びＡ２の平均繊維長さは、再生回収前の強化複合材料に含まれる強化材の平均繊維長さ１００％に対して、９０％であり、連続繊維状態で再生回収できた。
[Example 2]
The base material of the reinforced composite material was decomposed in the same manner as in Example 1. The separated reinforcing materials A2 were washed with water, dried, and then wound around a core to regenerate the reinforcing materials A1 and A2 of continuous fibers.
The strength ratio of the regenerated reinforcing materials A1 and A2 was 90% or more.
The shape retention rate of the regenerated reinforcing materials A1 and A2 was 90% or more.
The average fiber length of the reinforcing materials A1 and A2 after winding is 90% with respect to the average fiber length of 100% of the reinforcing material contained in the reinforcing composite material before regeneration and recovery, and is recycled and recovered in a continuous fiber state. did it.
［実施例３］
再生回収する強化複合材料として、図２に示す構造の水素タンクを用いた。上記水素タンクは、外部の強化複合材料の強化材Ａ１がガラス繊維：ＲＳ４４０ ＲＲ−５２０（日東紡績株式会社製）、内部の強化複合材料の強化材Ａ２が炭素繊維：トレカＴ７００ＳＣ−１２Ｋ−５０Ｃ（東レ株式会社製）の積層体である。
上記２つの強化複合材料をそれぞれフィラメントワインダー（旭化成エンジニアリング社製）を用い、母材としてポリアミド樹脂（２０ｗｔ％ジメチルスルホキシド溶液）を用いて作製した後、１５０℃、３０分間で乾燥することで水素タンクを作製した。
得られた水素タンクを実施例１と同様の方法で、強化複合材料の母材を分解した。分離した強化材Ａ２を、水洗して、乾燥した後に芯に巻き取ることによって連続繊維の強化材Ａ１及びＡ２を再生した。
再生した強化材Ａ１及びＡ２の強度比は９０％以上であった。
再生した強化材Ａ１及びＡ２の形状保持率は９０％以上であった。
巻き取り後の強化材Ａ１及びＡ２の平均繊維長さは、再生回収前の強化複合材料に含まれる強化材の平均繊維長さ１００％に対して、９０％であり、連続繊維状態で再生回収できた。
[Example 3]
A hydrogen tank having the structure shown in FIG. 2 was used as the reinforced composite material to be regenerated and recovered. In the above hydrogen tank, the reinforcing material A1 of the external reinforcing composite material is glass fiber: RS440 RR-520 (manufactured by Nitto Spinning Co., Ltd.), and the reinforcing material A2 of the internal reinforcing composite material is carbon fiber: Treca T700SC-12K-50C ( It is a laminated body of Toray Industries, Inc.).
Each of the above two reinforced composite materials is prepared using a filament winder (manufactured by Asahi Kasei Engineering Co., Ltd.) and a polyamide resin (20 wt% dimethyl sulfoxide solution) as a base material, and then dried at 150 ° C. for 30 minutes to form a hydrogen tank. Was produced.
The obtained hydrogen tank was used in the same manner as in Example 1 to decompose the base material of the reinforced composite material. The separated reinforcing materials A2 were washed with water, dried, and then wound around a core to regenerate the reinforcing materials A1 and A2 of continuous fibers.
The strength ratio of the regenerated reinforcing materials A1 and A2 was 90% or more.
The shape retention rate of the regenerated reinforcing materials A1 and A2 was 90% or more.
The average fiber length of the reinforcing materials A1 and A2 after winding is 90% with respect to the average fiber length of 100% of the reinforcing material contained in the reinforcing composite material before regeneration and recovery, and is recycled and recovered in a continuous fiber state. did it.
［実施例４］
再生回収する強化複合材料として、図２に示す構造の水素タンクを用いた。上記水素タンクは、外部の強化複合材料の強化材Ａ１がガラス繊維：ＲＳ４４０ ＲＲ−５２０（日東紡績株式会社製）、内部の強化複合材料の強化材Ａ２が炭素繊維：トレカＴ７００ＳＣ−１２Ｋ−５０Ｃ（東レ株式会社製）の積層体である。
上記２つの強化複合材料をそれぞれフィラメントワインダー（旭化成エンジニアリング社製）を用い、母材としてフェノール樹脂を用いて作製した後、２００℃、３０分間で硬化することで水素タンクを作製した。
得られた水素タンクを実施例１と同様の方法で、強化複合材料の母材を分解した。分離した強化材Ａ２を、水洗して、乾燥した後に芯に巻き取ることによって連続繊維の強化材Ａ１及びＡ２を再生した。
再生した強化材Ａ１及びＡ２の強度比は９０％以上であった。
再生した強化材Ａ１及びＡ２の形状保持率は９０％以上であった。
巻き取り後の強化材Ａ１及びＡ２の平均繊維長さは、再生回収前の強化複合材料に含まれる強化材の平均繊維長さ１００％に対して、９０％であり、連続繊維状態で再生回収できた。
[Example 4]
A hydrogen tank having the structure shown in FIG. 2 was used as the reinforced composite material to be regenerated and recovered. In the above hydrogen tank, the reinforcing material A1 of the external reinforcing composite material is glass fiber: RS440 RR-520 (manufactured by Nitto Spinning Co., Ltd.), and the reinforcing material A2 of the internal reinforcing composite material is carbon fiber: Treca T700SC-12K-50C ( It is a laminated body of Toray Industries, Inc.).
A hydrogen tank was prepared by preparing each of the above two reinforced composite materials using a filament winder (manufactured by Asahi Kasei Engineering Co., Ltd.) and using a phenol resin as a base material, and then curing at 200 ° C. for 30 minutes.
The obtained hydrogen tank was used in the same manner as in Example 1 to decompose the base material of the reinforced composite material. The separated reinforcing materials A2 were washed with water, dried, and then wound around a core to regenerate the reinforcing materials A1 and A2 of continuous fibers.
The strength ratio of the regenerated reinforcing materials A1 and A2 was 90% or more.
The shape retention rate of the regenerated reinforcing materials A1 and A2 was 90% or more.
The average fiber length of the reinforcing materials A1 and A2 after winding is 90% with respect to the average fiber length of 100% of the reinforcing material contained in the reinforcing composite material before regeneration and recovery, and is recycled and recovered in a continuous fiber state. did it.
［実施例５］
再生回収する強化複合材料として、図２に示す構造の水素タンクを用いた。上記水素タンクは、外部の強化複合材料の強化材Ａ１がガラス繊維：ＲＳ４４０ ＲＲ−５２０（日東紡績株式会社製）、内部の強化複合材料の強化材Ａ２が炭素繊維：トレカＴ７００ＳＣ−１２Ｋ−５０Ｃ（東レ株式会社製）の積層体である。
上記２つの強化複合材料をそれぞれフィラメントワインダー（旭化成エンジニアリング社製）を用い、母材としてエポキシ樹脂を用いて作製した後、１５０℃、３０分間で硬化することで水素タンクを作製した。
強化複合材料からの強化材の再生回収方法は、硫酸／過酸化水素混合液法を用いた。
具体的には、過酸化水素水に６０ｗｔ％硫酸を１００℃以下に冷却しながらゆっくりと添加し、硫酸／過酸化水素が３／１とした。
作製した酸化性活性種を含む処理溶液６０Ｌに、水素タンク１本（１２０ｋｇ）を処理溶液に浸漬した。
１段階目として１５０℃、１５時間で外部の強化複合材料を浸漬処理し、外部の強化複合材料の母材を分解して強化材Ａ１を、芯に連続繊維として巻き取り、水洗、乾燥して、分離回収した。
その後、２段階目に１５０℃、１５時間で内部の強化複合材料を浸漬処理し、内部の強化複合材料の母材を分解した。
分離した強化材Ａ２を芯に連続繊維として巻き取り、水洗して、乾燥した。
巻き取り後の強化材Ａ１の強度比は９０％以上であった。また、巻き取り後の強化材Ａ２の強度比は９０％以上であった。
巻き取り後の強化材Ａ１の形状保持率は９０％以上であった。また、巻き取り後の強化材Ａ２の形状保持率は９０％以上であった。
巻き取り後の強化材Ａ１の平均繊維長さは、再生回収前の強化複合材料に含まれる強化材Ａ１の平均繊維長さ１００％に対して、９０％であった。また、巻き取り後の強化材Ａ２の平均繊維長さは、再生回収前の強化複合材料に含まれる強化材Ａ２の平均繊維長さ１００％に対して、９０％であった。強化材Ａ１及びＡ２は、何れも連続繊維状態で再生回収できた。なお、平均繊維長さは、任意の８０個の強化材の延在方向長さの平均値とした。
[Example 5]
A hydrogen tank having the structure shown in FIG. 2 was used as the reinforced composite material to be regenerated and recovered. In the above hydrogen tank, the reinforcing material A1 of the external reinforcing composite material is glass fiber: RS440 RR-520 (manufactured by Nitto Spinning Co., Ltd.), and the reinforcing material A2 of the internal reinforcing composite material is carbon fiber: Treca T700SC-12K-50C ( It is a laminated body of Toray Industries, Inc.).
A hydrogen tank was prepared by preparing each of the above two reinforced composite materials using a filament winder (manufactured by Asahi Kasei Engineering Co., Ltd.) and using an epoxy resin as a base material, and then curing at 150 ° C. for 30 minutes.
A sulfuric acid / hydrogen peroxide mixed solution method was used as a method for regenerating and recovering the reinforcing material from the reinforced composite material.
Specifically, 60 wt% sulfuric acid was slowly added to the hydrogen peroxide solution while cooling to 100 ° C. or lower to reduce the amount of sulfuric acid / hydrogen peroxide to 3/1.
One hydrogen tank (120 kg) was immersed in the prepared treatment solution 60 L containing the oxidatively active species.
As the first step, the external reinforcing composite material is immersed at 150 ° C. for 15 hours, the base material of the external reinforcing composite material is decomposed, and the reinforcing material A1 is wound around the core as continuous fibers, washed with water, and dried. , Separated and recovered.
Then, in the second step, the inner reinforced composite material was immersed at 150 ° C. for 15 hours to decompose the base material of the inner reinforced composite material.
The separated reinforcing material A2 was wound around the core as continuous fibers, washed with water, and dried.
The strength ratio of the reinforcing material A1 after winding was 90% or more. The strength ratio of the reinforcing material A2 after winding was 90% or more.
The shape retention rate of the reinforcing material A1 after winding was 90% or more. Further, the shape retention rate of the reinforcing material A2 after winding was 90% or more.
The average fiber length of the reinforcing material A1 after winding was 90% with respect to 100% of the average fiber length of the reinforcing material A1 contained in the reinforcing composite material before regeneration and recovery. The average fiber length of the reinforcing material A2 after winding was 90% with respect to 100% of the average fiber length of the reinforcing material A2 contained in the reinforcing composite material before regeneration and recovery. Both the reinforcing materials A1 and A2 could be regenerated and recovered in the continuous fiber state. The average fiber length was defined as the average value of the lengths of any 80 reinforcing materials in the extending direction.
［比較例１］
強化複合材料は実施例１と同様の水素タンクを用いた。
強化複合材料からの強化材の分離回収方法は、熱分解法を用いた。
具体的には、作製した強化複合材料を燃焼炉に入れて、１段階目として窒素雰囲気下、６００℃、５時間処理することによって外部の強化複合材料の母材を熱分解して強化材Ａ１の分離回収を試みたが、強化材Ａ１のガラス繊維が溶融してペースト状になってしまったため、強化材Ａ２を分離回収することができなかった。
[Comparative Example 1]
As the reinforced composite material, the same hydrogen tank as in Example 1 was used.
As a method for separating and recovering the reinforcing material from the reinforced composite material, a thermal decomposition method was used.
Specifically, the prepared reinforced composite material is placed in a combustion furnace and treated in a nitrogen atmosphere at 600 ° C. for 5 hours as the first step to thermally decompose the base material of the external reinforced composite material to reinforce the material A1. However, the reinforcing material A2 could not be separated and recovered because the glass fibers of the reinforcing material A1 were melted into a paste.
Claims (5)
ａ）前記強化複合材料を、処理溶液により、母材と強化材とに分解する工程、
ｃ）強化材を芯材に巻き取る工程、
を含み、
前記処理溶液が、ケトン系、アルコール系、アミド系、エーテル系、炭化水素系の溶媒を含まないことを特徴とする、強化複合材料から強化材を再生回収する方法。 A method of reclaiming and recovering a reinforcing material from a reinforcing composite material containing a base material and a reinforcing material.
a) A step of decomposing the reinforced composite material into a base material and a reinforced material with a treatment solution.
c) The process of winding the reinforcing material around the core material,
Including
A method for regenerating and recovering a reinforcing material from a reinforcing composite material, wherein the treatment solution does not contain a ketone-based, alcohol-based, amide-based, ether-based, or hydrocarbon-based solvent.
ａ１）硫酸溶液を電気分解することにより酸化性活性種を含む処理溶液を得る工程、
ａ２）前記処理溶液に、前記強化複合材料を浸漬して、母材と強化材とに分解する工程、を含む、請求項１記載の強化複合材料から強化材を再生回収する方法。 The step a)
a1) A step of obtaining a treatment solution containing an oxidizing active species by electrolyzing a sulfuric acid solution,
a2) The method for regenerating and recovering a reinforcing material from the reinforcing composite material according to claim 1, which comprises a step of immersing the reinforcing composite material in the treatment solution and decomposing it into a base material and a reinforcing material.
ｂ）前記強化材を洗浄、乾燥する工程、
を含む、請求項１又は２記載の強化複合材料から強化材を再生回収する方法。 Between the steps a) and c) b) the step of cleaning and drying the reinforcing material,
A method for regenerating and recovering a reinforcing material from the reinforcing composite material according to claim 1 or 2.
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