JP2006036883A - Reclaimed frp-based thermoplastic composite composition - Google Patents

Reclaimed frp-based thermoplastic composite composition Download PDF

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JP2006036883A
JP2006036883A JP2004217458A JP2004217458A JP2006036883A JP 2006036883 A JP2006036883 A JP 2006036883A JP 2004217458 A JP2004217458 A JP 2004217458A JP 2004217458 A JP2004217458 A JP 2004217458A JP 2006036883 A JP2006036883 A JP 2006036883A
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frp
composite composition
regenerated
waste
fluid composite
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Takahiro Okamoto
隆宏 岡本
Isamu Tokuyama
勇 徳山
Yasumochi Hamada
泰以 濱田
Asami Nakai
朝美 仲井
Keisuke Fukuoka
敬介 福岡
Yasuhiko Hirao
康彦 平尾
Shigeki Toshima
茂喜 戸島
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El & Chem Corp
TRUST KK
Kurimoto Kasei Kogyo KK
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El & Chem Corp
TRUST KK
Kurimoto Kasei Kogyo KK
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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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
    • 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

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reclaimed FRP-based thermoplastic composite composition obtained by utilizing a waste FRP, having heat flow characteristics moldable by a general-purpose molding method of a resin material such as an injection molding method and an extrusion molding method, providing an FRP-reclaimed product keeping the sufficient mechanical properties even when the mixed proportion of the waste FRP is ≥50 pts. wt. and effective for practical application of the material recycle of the waste FRP. <P>SOLUTION: The reclaimed FRP-based thermoplastic composite composition is obtained by mixing a pulverized waste FRP with a polyolefin-based resin and a functional binder comprising a copolymer or terpolymer having an epoxy group in the main chain of the polymer to form a chemical bond at the interface of the waste FRP and the polyolefin-based resin, and compounding the mixture by melting and kneading. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、浴槽をはじめ船舶、タンク、建設資材、自動車など産業上幅広く使用されているＦＲＰ（Fiber Reinforced Plastic：繊維強化複合プラスチック材料）のマテリアルリサイクル技術（不用物を選別回収してその素材、部材毎に再加工してもう一度新しい商品や包材として再利用する技術）に関する。特に、射出成形法、押出成形法といった樹脂材料の汎用成形法に好適な再生ＦＲＰ系熱流動性複合組成物に関するものである。   In the present invention, FRP (Fiber Reinforced Plastic) is widely used in industries such as bathtubs, ships, tanks, construction materials, and automobiles. Technology for reworking each member and reusing it as a new product or packaging material). In particular, the present invention relates to a regenerated FRP-based heat-fluid composite composition suitable for general-purpose molding methods of resin materials such as injection molding and extrusion molding.

ＦＲＰは、ガラス繊維や炭素繊維などの無機繊維又はアラミド繊維などの有機繊維を不飽和ポリエステル樹脂、エポキシ樹脂、フェノール樹脂、ウレタン樹脂などのバインダー樹脂により固化した複合材料であり、軽量性、高剛性、耐薬品性、耐熱性などの優れた特性を有する先進材料である。
近年の環境に対する意識の高まりと共に、資源有効利用法（改正リサイクル法）の施行により、ＦＲＰ製品についても３Ｒ：Reduce(減量)，Reuse(再使用)，Recycle(再生利用)に配慮した設計などの対応が義務づけられ、ＦＲＰ製品のリサイクルは避けて通れない問題となっている。 FRP is a composite material in which inorganic fibers such as glass fibers and carbon fibers, or organic fibers such as aramid fibers are solidified with a binder resin such as unsaturated polyester resin, epoxy resin, phenol resin, urethane resin, and is lightweight and highly rigid. Advanced material with excellent properties such as chemical resistance and heat resistance.
Along with the recent increase in environmental awareness, the implementation of the Effective Resource Utilization Law (Revised Recycling Law), FRP products, such as 3R: Reduce, Reuse, Recycle (recycle) design, etc. Response is required, and recycling of FRP products is an unavoidable problem.

しかしながら、ＦＲＰは、バインダー樹脂として硬化性樹脂を含む複合材料であり、ポリプロピレンやポリエチレン、ポリスチレンなどの一般的な熱可塑性樹脂とは異なる性質を有しているため、前記熱可塑性樹脂と同様に、粉砕後、加熱溶融して再成形・再利用することができず、マテリアルリサイクルが困難なものである。
そのため、廃棄ＦＲＰについては、一部のＦＲＰ製品メーカーが自社工程内廃棄物を破砕後、セメントキルンで処理してセメント原料として再資源化したり、細かく粉砕してＦＲＰの一種であるＳＭＣ(Sheet Molding Compound)の充填材として再使用するなどの取り組みを行ってはいるものの、大部分は埋立処分されているのが実情である。 However, FRP is a composite material containing a curable resin as a binder resin, and has properties different from general thermoplastic resins such as polypropylene, polyethylene, and polystyrene. After crushing, it cannot be remelted and reused by heating and melting, and material recycling is difficult.
For this reason, some FRP product manufacturers crush their in-process wastes and process them with cement kilns to recycle them as cement raw materials, or finely pulverize them to produce SMC (Sheet Molding). Although efforts are being made to re-use it as a compound (compound) filler, most of it has been disposed of in landfills.

一方で、近年、産業廃棄物の埋立用地の新規確保も困難を極めており、埋立処分場の残余年数は全国平均で３.９年、首都圏においては１.２年と厳しい状況にあるとの報告もあり、廃棄ＦＲＰの有効的なマテリアルリサイクル技術の確立が切望されている。   On the other hand, in recent years, it has become extremely difficult to secure new land for industrial waste, and the remaining years of landfill sites are 3.9 years on average nationwide and 1.2 years in the Tokyo metropolitan area. There is a report, and establishment of effective material recycling technology of waste FRP is eagerly desired.

これら現状を鑑みて、廃棄ＦＲＰの致命的な欠点である燃焼カロリーの低さを補うために、ポリプロピレンやポリエチレンなどの高燃焼カロリーの廃棄樹脂と混合して熱回収するサーマルリサイクルや、廃棄ＦＲＰに含まれる熱硬化性のバインダー樹脂をグリコールなどで分解・融解させた後、蒸留してモノマーとして再利用するケミカルリサイクルなどのリサイクル方法が検討されている。   In view of these current conditions, in order to compensate for the low burned calories, which is a fatal drawback of waste FRP, thermal recycling that recovers heat by mixing with waste resin of high burned calories such as polypropylene and polyethylene, and waste FRP A recycling method such as chemical recycling in which the thermosetting binder resin contained is decomposed and melted with glycol or the like and then distilled and reused as a monomer has been studied.

しかしながら、前記サーマルリサイクルは、リサイクルにおける最終手段であって、われわれの目指している資源循環型社会においては、廃棄物を複数回にわたって再製品化・再使用（マテリアルリサイクル）させて、再生において物性の保持が困難となった後に、最終的サーマルリサイクルにより熱回収されることが望まれる。また、前記ケミカルリサイクルは、大掛かりな設備や高額な加工コストを要すると共に、無機物を多く含むため樹脂製分の回収率が低く、リサイクル効率がよくないという問題がある。   However, the thermal recycling is a last resort in recycling, and in the resource recycling society we are aiming for, waste can be remanufactured and reused multiple times (material recycling), and the physical properties in recycling can be improved. It is desired that the heat is recovered by final thermal recycling after the holding becomes difficult. In addition, the chemical recycling requires large-scale equipment and expensive processing costs, and has a problem that the recovery rate of the resin product is low because it contains a lot of inorganic substances, and the recycling efficiency is not good.

このような状況の下で、廃棄ＦＲＰの粉砕物にポリプロピレンなどのポリオレフィン系樹脂と表面処理剤とを添加して加熱溶融混練することにより、一般的な熱可塑性樹脂と同様に、加熱プレス成形や射出成形が可能な熱可塑性樹脂複合材料を製造する廃棄ＦＲＰのリサイクル方法が提唱されている。（特許文献１参照）
ＦＲＰの粉砕物は、無機充填材に比べてポリオレフィン系樹脂との界面での親和性が低く、前記廃棄ＦＲＰの混合比が高くなると樹脂複合組成物の機械的特性が低下されることから、このものでは、廃棄ＦＲＰとオレフィン系樹脂と共に両者間の親和性を改善する表面処理剤を混合することにより機械的特性の低下の防止を図っている。
特開２００４−１１５６５６号公報 Under such circumstances, by adding a polyolefin-based resin such as polypropylene and a surface treatment agent to the pulverized waste FRP and heating and kneading the mixture, heat press molding or A recycling method of waste FRP for producing a thermoplastic resin composite material capable of injection molding has been proposed. (See Patent Document 1)
The pulverized product of FRP has a lower affinity at the interface with the polyolefin-based resin than the inorganic filler, and when the mixing ratio of the waste FRP is increased, the mechanical properties of the resin composite composition are lowered. In the present invention, deterioration of mechanical properties is prevented by mixing a surface treatment agent that improves the affinity between the waste FRP and the olefin resin.
JP 2004-115656 A

しかしながら、上記熱可塑性樹脂複合材料を製造方法においては、廃棄ＦＲＰの混合比は最大でも４０重量部であり、ポリオレフィン系樹脂に廃棄ＦＲＰの微粉砕物が充填材的に海島状分散された組成となっており、製造される熱可塑性樹脂複合材料の物性はマトリックス（海島状分散の海の部分）であるポリオレフィン系樹脂の物性に大きく依存するものとなっている。（特許文献１,請求項１参照）
そのため、廃棄ＦＲＰを含んでいる点で環境に配慮した材料ではあるが、主材とするポリオレフィン系樹脂材料の一種と考えられ、廃棄ＦＲＰをマテリアルリサイクルした再生品であるとは言いがたいものがある。実際、環境型商品の一つの指標である「エコマーク」による類似類型商品の認定基準において、再生材料の使用割合が５０〜６０重量部以上であることを基準とするものが多く、廃棄ＦＲＰの再生品であるために、廃棄ＦＲＰの使用割合が５０重量部以上であることが必要とされる可能性が高いと考えられる。 However, in the method for producing the thermoplastic resin composite material, the mixing ratio of the waste FRP is 40 parts by weight at the maximum, and a composition in which the finely pulverized waste FRP is dispersed in a polyolefin resin as a sea island Thus, the physical properties of the thermoplastic resin composite material to be produced largely depend on the physical properties of the polyolefin resin that is a matrix (sea part of sea-island dispersion). (See Patent Document 1 and Claim 1)
Therefore, although it is an environmentally friendly material in that it contains waste FRP, it is considered a kind of polyolefin resin material as the main material, and it is difficult to say that it is a recycled product that is material recycled from waste FRP. is there. In fact, many of the certification criteria for similar products based on the “Eco Mark”, which is one of the indicators for environmental products, are based on the usage rate of recycled materials being 50-60 parts by weight or more. Since it is a recycled product, it is highly likely that the usage rate of the waste FRP is required to be 50 parts by weight or more.

また、上記熱可塑性樹脂複合材料を製造方法では、予め廃棄ＦＲＰと表面処理剤とを溶融混練により複合化してマスターバッチを中間生成させた後、前記マスターバッチとポリオレフィン系樹脂とを機械的に溶融混練して複合化することにより、廃棄ＦＲＰの混合比が５０重量部以上の熱可塑性樹脂複合材料を製造する方法が開示されているが（特許文献１，請求項３参照）、機械的な溶融混練を２回も行うから熱可塑性樹脂複合材料の製造コストが高くなると共に、熱可塑性樹脂複合材料の劣化（機械的強度，弾性力など物性の低下）を招く恐れがある。   In the method for producing the thermoplastic resin composite material, waste FRP and a surface treatment agent are combined in advance by melt-kneading to form a master batch, and then the master batch and the polyolefin resin are mechanically melted. Although a method for producing a thermoplastic resin composite material having a mixing ratio of waste FRP of 50 parts by weight or more by kneading and compounding is disclosed (see Patent Document 1 and Claim 3), mechanical melting is disclosed. Since kneading is performed twice, the manufacturing cost of the thermoplastic resin composite material increases, and the thermoplastic resin composite material may be deteriorated (deterioration of physical properties such as mechanical strength and elastic force).

本発明は、上記事情を鑑みてなされたものであり、廃棄ＦＲＰを利用した再生ＦＲＰ系複合組成物において、射出成形法や押出成形法などの樹脂材料の汎用成形法により成形可能な熱流動特性を有し、且つ、廃棄ＦＲＰの混合比を５０重量部以上とする場合にもＦＲＰ再生品として十分な機械的物性を維持できるようにすることにより、廃棄ＦＲＰのマテリアルリサイクルの実用化に有効な再生ＦＲＰ系熱流動性複合組成物を提供することを課題とする。   The present invention has been made in view of the above circumstances, and in a recycled FRP-based composite composition using waste FRP, heat flow characteristics that can be molded by a general-purpose molding method of a resin material such as an injection molding method or an extrusion molding method. In addition, even when the mixing ratio of waste FRP is 50 parts by weight or more, it is effective for practical use of material recycling of waste FRP by maintaining sufficient mechanical properties as a recycled FRP product. It is an object of the present invention to provide a regenerated FRP heat-fluid composite composition.

上記課題を達成するために、本発明は、『粉砕した廃棄ＦＲＰと、ポリオレフィン系樹脂と、前記廃棄ＦＲＰとポリオレフィン系樹脂との界面において化学結合を生成する官能性結合剤とを混合し、溶融混練により複合化させた再生ＦＲＰ系熱流動性複合組成物であって、前記官能性結合剤は、高分子主鎖中にエポキシ基を有するコポリマー又はターポリマーであること』を特徴とするものである。
これによれば、粉砕された廃棄ＦＲＰに、熱流動特性を与えるための粘結材としてポリロプロピレンなどのポリオレフィン系熱可塑性樹脂と、廃棄ＦＲＰの構成成分である繊維及びバインダー樹脂と前記ポリオレフィン系樹脂との界面において化学結合を生成する反応性の高いエポキシ基を有する官能性結合剤とを混合して溶融混練することにより、親和性の低い廃棄ＦＲＰとポリオレフィン系樹脂の界面相互間に強固な化学結合が生成される。
したがって、廃棄ＦＲＰの混合比が５０重量部以上を占める組成とする場合にも、成形時に熱可塑性樹脂の溶融流動特性における無機質の均一分散化が進み、無機質の不均一化による成形品の機械的強度のバラツキが抑えられるから、成形品としての機械的物性が著しく低下されることがなく、曲げ強度や引張強度などの静的荷重に対する機械的強度や弾性に優れたＦＲＰ再生品を得ることができる。 In order to achieve the above-mentioned object, the present invention is to mix and melt a pulverized waste FRP, a polyolefin resin, and a functional binder that generates a chemical bond at the interface between the waste FRP and the polyolefin resin. A regenerated FRP-based heat-fluid composite composition obtained by compounding by kneading, wherein the functional binder is a copolymer or terpolymer having an epoxy group in the polymer main chain. is there.
According to this, a polyolefin-based thermoplastic resin such as polypropylene as a binder for imparting heat flow characteristics to the pulverized waste FRP, fibers and binder resins that are constituents of the waste FRP, and the polyolefin-based material By mixing and melting and kneading a functional binder having a highly reactive epoxy group that generates a chemical bond at the interface with the resin, the interface between the waste FRP having a low affinity and the polyolefin resin is strong. A chemical bond is generated.
Therefore, even when the composition ratio of the waste FRP occupies 50 parts by weight or more, the uniform dispersion of the inorganic material in the melt flow characteristics of the thermoplastic resin proceeds at the time of molding, and the mechanical properties of the molded product due to the non-uniform inorganic material Since variation in strength is suppressed, mechanical properties as a molded product are not significantly reduced, and an FRP recycled product having excellent mechanical strength and elasticity against static loads such as bending strength and tensile strength can be obtained. it can.

『前記廃棄ＦＲＰを５０〜７０重量部と、前記ポリオレフィン系樹脂を１５〜４５重量部と、前記官能性結合剤を５〜１５重量部とを合計を１００重量部となるように混合した』ものによれば、廃棄ＦＲＰを主材とするＦＲＰの再生品を容易に製造することができるからマテリアルリサイクルの実用化に有効である。
さらに、『前記ポリオレフィン系樹脂は、再生材料又は再生材料とバージン材料との混合材料である』ものでは、１００％バージン材料のポリオレフィン系樹脂を用いる組成物よりも再生材料の使用割合が大きいから、リサイクル効率及び環境志向性が高い。また、再生材料は、バージン材料よりも材料コストが小さいからＦＲＰ再生品の製造コストが低減される。 “50 to 70 parts by weight of the waste FRP, 15 to 45 parts by weight of the polyolefin resin, and 5 to 15 parts by weight of the functional binder are mixed to a total of 100 parts by weight” According to the above, since it is possible to easily manufacture a recycled product of FRP mainly composed of waste FRP, it is effective for practical use of material recycling.
Furthermore, in the case where “the polyolefin resin is a recycled material or a mixed material of a recycled material and a virgin material”, the usage ratio of the recycled material is larger than the composition using a polyolefin resin of 100% virgin material, High recycling efficiency and environmental orientation. Further, since the recycled material has a lower material cost than the virgin material, the manufacturing cost of the FRP recycled product is reduced.

『前記官能性結合剤は、不飽和カルボン酸グリシジルエステルを含有するコポリマー、又は、不飽和カルボン酸グリシジルエステル−エチレン系不飽和エステル化合物を含有するターポリマーからなる』ものが好ましく、具体的には、前記不飽和カルボン酸グリシジルエステルとしては、グリシジルメタクリレート，グリシジルアクリレート，イタコン酸ジグリシジルエステル，ブテントリカルボン酸グリシジルエステル，ｐ−スチレンカルボン酸グリシジルエステルなどが挙げられる。また、エチレン系不飽和エステル化合物としては、アクリル酸メチル，アクリル酸エチル，アクリル酸ｎ−プロピル，アクリル酸イソプロピル，アクリル酸ｎ−ブチル，アクリル酸ｔ−ブチル，アクリル酸イソブチル，メタクリル酸メチル，メタクリル酸エチル，メタクリル酸ブチル，酢酸ビニル，プロピオン酸ビニルなどが挙げられる。   "The functional binder is preferably composed of a copolymer containing an unsaturated carboxylic acid glycidyl ester or a terpolymer containing an unsaturated carboxylic acid glycidyl ester-ethylenically unsaturated ester compound", specifically Examples of the unsaturated carboxylic acid glycidyl ester include glycidyl methacrylate, glycidyl acrylate, itaconic acid diglycidyl ester, butenetricarboxylic acid glycidyl ester, and p-styrene carboxylic acid glycidyl ester. Examples of the ethylenically unsaturated ester compound include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, methacrylic acid. Examples include ethyl acetate, butyl methacrylate, vinyl acetate, and vinyl propionate.

特に、『前記官能性結合剤が、エチレン−グリシジルメタクリレートコポリマー、エチレン−グリシジルメタクリレート−酢酸ビニルターポリマー、エチレン−グリシジルメタクリレート−アクリル酸メチルターポリマーよりなる群から選択される』ものがより好ましい。   In particular, “the functional binder is selected from the group consisting of ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate terpolymer, ethylene-glycidyl methacrylate-methyl acrylate terpolymer” is more preferable.

本発明によれば、廃棄ＦＲＰと熱流動性を有するポリオレフィン系樹脂の界面相互間を反応性の高いエポキシ基を有する官能性結合剤が強固に化学結合することにより、汎用成形法により成形可能な熱流動特性と、廃棄ＦＲＰの混合比が高い場合にも成形品として十分な機械的物性とを有しているから、本発明の再生ＦＲＰ系熱流動性複合組成物を用いることにより、曲げ強度や引張強度などの静的荷重に対する機械的強度や弾性に優れたＦＲＰ再生品を容易に成形することができる。
そのため、従来例として挙げた廃棄ＦＲＰのリサイクル方法に比べて成形容易性や再生コスト、再生材料のリサイクル効率などの点において優れており、廃棄ＦＲＰのマテリアルリサイクルの実用化に有効である。 According to the present invention, a functional binder having a highly reactive epoxy group is firmly bonded between the interfaces of the waste FRP and the polyolefin resin having thermal fluidity, and thus can be molded by a general-purpose molding method. Since it has sufficient mechanical properties as a molded product even when the mixing ratio of the waste FRP is high, the bending strength is obtained by using the regenerated FRP-based heat fluid composite composition of the present invention. FRP recycled products having excellent mechanical strength and elasticity against static loads such as tensile strength and tensile strength can be easily formed.
For this reason, it is excellent in terms of ease of molding, recycling cost, recycling efficiency of recycled materials, and the like, compared to the recycling method of waste FRP mentioned as the conventional example, and is effective for practical use of material recycling of waste FRP.

以下に、本発明実施の形態について説明する。
本発明に係る再生ＦＲＰ系熱流動性複合組成物の実施の形態は、粉砕した廃棄ＦＲＰを主材、ポリオレフィン系樹脂材を副材とし、エポキシ基を有する官能性結合剤を混合し、均質になるように機械的に溶融混練させて複合化したものである。
前記ポリオレフィン系樹脂は、バージン材料に限られるものではなく、材料コストの節減の観点からも再生材料又はバージン材料と再生材料との混合材料を用いることが好ましい。 Hereinafter, embodiments of the present invention will be described.
In the embodiment of the regenerated FRP heat fluid composite composition according to the present invention, the pulverized waste FRP is used as a main material, the polyolefin resin material is used as a secondary material, and a functional binder having an epoxy group is mixed and homogeneously mixed. Thus, it is mechanically melted and kneaded to form a composite.
The polyolefin resin is not limited to a virgin material, and it is preferable to use a recycled material or a mixed material of a virgin material and a recycled material from the viewpoint of saving material costs.

より具体的には、前記廃棄ＦＲＰを５０〜７０重量部と、前記ポリオレフィン系樹脂１５〜４５重量部と、官能性結合剤を５〜１５重量部とを、合計１００重量部となるように混合させた複合組成物とすることにより、これを用いた成形品は廃棄ＦＲＰの使用割合が５０重量部以上となるからＦＲＰ再生品として、再生樹脂製品に対して明確な位置づけが可能となる点で好ましい。   More specifically, 50 to 70 parts by weight of the waste FRP, 15 to 45 parts by weight of the polyolefin-based resin, and 5 to 15 parts by weight of a functional binder are mixed so that the total amount becomes 100 parts by weight. By using the composite composition, the molded product using the composite composition has a usage rate of the waste FRP of 50 parts by weight or more, so that it can be clearly positioned as a recycled resin product as a recycled FRP product. preferable.

前記官能性結合剤は、高分子主鎖中にエポキシ基を有し、前記高分子自体が常温でゴム弾性を有する低ガラス転移温度を持つコポリマー又はターポリマーとすることが好適であり、特に、エチレン−グリシジルメタクリレートコポリマー、エチレン−グリシジルメタクリレート−アクリル酸メチルターポリマー、エチレン−グリシジルメタクリレート−酢酸ビニルターポリマーから選択されるものが好ましい。   The functional binder is preferably a copolymer or terpolymer having an epoxy group in a polymer main chain, the polymer itself having a low glass transition temperature having rubber elasticity at room temperature, Preferred are those selected from ethylene-glycidyl methacrylate copolymers, ethylene-glycidyl methacrylate-methyl acrylate terpolymers, ethylene-glycidyl methacrylate-vinyl acetate terpolymers.

前記再生ＦＲＰ系熱流動性複合組成物には、各種のエラストマーをさらに混合することもできる。具体的には、前記エラストマーとしては、粘結材としてポリオレフィン系樹脂を用いる場合の官能性結合剤との相溶化の観点から、ＳＥＢＳ（スチレンエチレンブチレンスチレンブロック共重合体），ＳＥＰＳ（スチレンエチレンプロピレンスチレンブロック共重合体），ＳＥＰ（スチレンエチレンプロピレンブロック共重合体），ＳＥＥＰＳ（スチレンエチレンエチレンプロピレンスチレン共重合体）などのスチレン系熱可塑性エラストマーが好適であり、特に、ＳＥＢＳ（スチレンエチレンブチレンスチレンブロック共重合体）又はＳＥＰＳ（スチレンエチレンプロピレンスチレンブロック共重合体）から洗濯されるのが好ましい。   Various elastomers can be further mixed into the regenerated FRP heat-fluid composite composition. Specifically, as the elastomer, SEBS (styrene ethylene butylene styrene block copolymer), SEPS (styrene ethylene propylene) are used from the viewpoint of compatibilization with a functional binder when a polyolefin resin is used as a binder. Styrenic thermoplastic elastomers such as styrene block copolymer), SEP (styrene ethylene propylene block copolymer), and SEEPS (styrene ethylene ethylene propylene styrene copolymer) are suitable. In particular, SEBS (styrene ethylene butylene styrene block). Copolymer) or SEPS (styrene ethylene propylene styrene block copolymer).

前記エラストマーは、バージン材料料に限られるものではなく、材料コストの観点から再生材料又はバージン材料と再生材料との混合材料を用いることが好ましい。また、前記エラストマーを混合する場合には、前記官能性結合剤とエラストマーとの合計重量部が５〜２０重量部となるように混合するのが好ましい。   The elastomer is not limited to a virgin material material, and it is preferable to use a recycled material or a mixed material of a virgin material and a recycled material from the viewpoint of material cost. Moreover, when mixing the said elastomer, it is preferable to mix so that the total weight part of the said functional binder and an elastomer may be 5-20 weight part.

廃棄ＦＲＰの粉砕物は５ｍｍ以下のメッシュのふるいを通過したものを用いる。
再生ＦＲＰ系熱流動性複合組成物の製造には、加熱溶融混練押出機又は加熱ニーダー機として公知の単軸もしくは二軸加熱溶融混練押出機が使用可能であり、必要に応じて材料供給部に加熱ニーダー機が併設された構成のものであってもよい。 The waste FRP pulverized material that has passed through a mesh screen of 5 mm or less is used.
In the production of the regenerated FRP-based heat-fluid composite composition, a known single-screw or biaxial heat-melt kneading extruder can be used as a heat-melt kneading extruder or a heat kneader machine. The thing of the structure by which the heating kneader machine was adjoined may be sufficient.

（実施例１）
廃棄ＦＲＰを粉砕して５ｍｍメッシュのふるいを通過した廃棄ＦＲＰの粉砕物を６０重量部と、粘結材として再生ポリプロピレン樹脂を３５重量部と、官能性結合剤としてエチレン−グリシジルメタクリレートコポリマー（ＥＧＭＡ）を５重量部とを均一に混合したものを、前記加熱ニーダー機併設型単軸溶融混練押出機により溶融混練、複合化させて再生ＦＲＰ系熱流動性複合組成物を製造した。この再生ＦＲＰ系熱流動性複合組成物を用いて、射出成形機でJIS規格 K7113に従った引張試験用ダンベル型1号試験片に成形した。 (Example 1)
60 parts by weight of the waste FRP pulverized after passing through a 5 mm mesh screen, 35 parts by weight of recycled polypropylene resin as a binder, and ethylene-glycidyl methacrylate copolymer (EGMA) as a functional binder A remixed FRP-based heat-fluid composite composition was produced by uniformly mixing 5 parts by weight of the mixture with a heating kneader-equipped uniaxial melt-kneading extruder. Using this regenerated FRP-based heat-fluid composite composition, it was molded into a dumbbell type No. 1 test piece for tensile testing according to JIS standard K7113 by an injection molding machine.

（実施例２）
廃棄ＦＲＰを粉砕して５ｍｍメッシュのふるいを通過した廃棄ＦＲＰの粉砕物を６０重量部と、粘結材として再生ポリプロピレン樹脂を３０重量部と、官能性結合剤としてエチレン−グリシジルメタクリレートコポリマー（ＥＧＭＡ）を５重量部と、再生エラストマー樹脂としてＳＥＰＳを５重量部とを均一に混合したものを加熱ニーダー機併設型単軸溶融混練押出機により溶融混練、複合化させて再生ＦＲＰ系熱流動性複合組成物を製造した。この再生ＦＲＰ系熱流動性複合組成物を用いて、射出成形機でJIS規格 K7113に従った引張試験用ダンベル型1号試験片に成形した。 (Example 2)
60 parts by weight of the waste FRP pulverized after passing through a 5 mm mesh screen, 30 parts by weight of recycled polypropylene resin as a binder, and ethylene-glycidyl methacrylate copolymer (EGMA) as a functional binder 5 parts by weight and 5 parts by weight of SEPS as a regenerated elastomer resin are uniformly mixed with a single kneading and kneading extruder equipped with a heating kneader and combined to produce a regenerated FRP thermal fluid composite composition The thing was manufactured. Using this regenerated FRP-based heat-fluid composite composition, it was molded into a dumbbell type No. 1 test piece for tensile testing according to JIS standard K7113 by an injection molding machine.

（比較例１）
廃棄ＦＲＰを粉砕して５ｍｍメッシュのふるいを通過した廃棄ＦＲＰの粉砕物を４０重量部と、粘結材として再生ポリプロピレン樹脂を６０重量部とを均一に混合したものを加熱ニーダー機併設型単軸溶融混練押出機により溶融混練、複合化させて再生ＦＲＰ系熱流動性複合組成物を製造した。この再生ＦＲＰ系熱流動性複合組成物を用いて、射出成形機でJIS規格 K7113に従った引張試験用ダンベル型1号試験片に成形した。 (Comparative Example 1)
A uniaxial heating kneader equipped with 40 parts by weight of the waste FRP pulverized and passed through a 5 mm mesh sieve and 60 parts by weight of recycled polypropylene resin as a binder A regenerated FRP heat fluid composite composition was produced by melt-kneading and compounding with a melt-kneading extruder. Using this regenerated FRP-based heat-fluid composite composition, it was molded into a dumbbell type No. 1 test piece for tensile testing according to JIS standard K7113 by an injection molding machine.

（比較例２）
廃棄ＦＲＰを粉砕して５ｍｍメッシュのふるいを通過した廃棄ＦＲＰの粉砕物を５０重量部と、粘結材として再生ポリプロピレン樹脂を５０重量部とを均一に混合したものを加熱ニーダー機併設型単軸溶融混練押出機により溶融混練、複合化させて再生ＦＲＰ系熱流動性複合組成物を製造した。この再生ＦＲＰ系熱流動性複合組成物を用いて、射出成形機でJIS規格 K7113に従った引張試験用ダンベル型1号試験片に成形した。 (Comparative Example 2)
A single shaft equipped with a heating kneader machine that uniformly mixes 50 parts by weight of the pulverized waste FRP after pulverizing the waste FRP and passed through a 5 mm mesh sieve and 50 parts by weight of recycled polypropylene resin as a binder. A regenerated FRP heat fluid composite composition was produced by melt-kneading and compounding with a melt-kneading extruder. Using this regenerated FRP-based heat-fluid composite composition, it was molded into a dumbbell type No. 1 test piece for tensile testing according to JIS standard K7113 by an injection molding machine.

（比較例３）
廃棄ＦＲＰを粉砕して５ｍｍメッシュのふるいを通過した廃棄ＦＲＰの粉砕物を６０重量部と、粘結材として再生ポリプロピレン樹脂４０重量部とを均一に混合したものを加熱ニーダー機併設型単軸溶融混練押出機により溶融混練、複合化させて再生ＦＲＰ系熱流動性複合組成物を製造した。この再生ＦＲＰ系熱流動性複合組成物を用いて、射出成形機でJIS規格 K7113に従った引張試験用ダンベル型1号試験片に成形した。 (Comparative Example 3)
Uniform fusion of heating kneader with a mixture of 60 parts by weight of the waste FRP pulverized and passed through a 5 mm mesh sieve and 40 parts by weight of recycled polypropylene resin as a binder A regenerated FRP-based heat-fluid composite composition was produced by melt-kneading and compounding with a kneading extruder. Using this regenerated FRP-based heat-fluid composite composition, it was molded into a dumbbell type No. 1 test piece for tensile testing according to JIS standard K7113 by an injection molding machine.

（比較例４）
上述の実施例ならびに比較例の検証において、粘結材として供した再生ポリプロピレン樹脂を用いて、射出成形機でJIS規格 K7113に従った引張試験用ダンベル型1号試験片に成形した。 (Comparative Example 4)
In the verification of the above-described Examples and Comparative Examples, the recycled polypropylene resin provided as a binder was molded into a dumbbell type No. 1 test piece for tensile test according to JIS standard K7113 using an injection molding machine.

これらの実施例ならびに比較例により得られたダンベル型一号試験片について、引張強度、引張弾性率、曲げ強度、曲げ弾性率、破断伸び、アイゾッド衝撃強度を測定した結果を表１に示している。   Table 1 shows the results of measuring the tensile strength, tensile elastic modulus, bending strength, bending elastic modulus, elongation at break, and Izod impact strength of the dumbbell type No. 1 test pieces obtained in these Examples and Comparative Examples. .

Figure 2006036883
Figure 2006036883

上記実験結果より、本発明の再生ＦＲＰ系熱流動性複合組成物を用いた廃棄ＦＲＰを主材とするマテリアルリサイクルの結果物であるＦＲＰ再生品：実施例１〜３は、機械的物性面において、比較例４のポリプロピレン樹脂の成形品に比べて引張強度や衝撃強度については低下が見られるものの、曲げ強度や各種弾性率については大きく向上されており、特に、剛性はアクリルニトリル−スチレン共重合樹脂（ＡＳ樹脂）や中衝撃ポリスチレン樹脂（ＭＩＰＳ樹脂）に準ずる高い値を示しており、相対的にみて成形品としての機械的物性は維持されていることが分かる。また、官能性結合剤を用いることなく廃棄ＦＲＰと再生ポリプロピレン樹脂とを溶融混練した比較例１〜３と比べても、引張強度，引張弾性率，各種弾性率が向上されていることが分かる。
これより、本発明の再生ＦＲＰ系熱流動性複合組成物によれば、廃棄ＦＰＲの混合比が５０重量部以上となる場合にも成形品として十分な機械的物性を備えたＦＰＲ再生品を成形することが可能である。 From the above experimental results, FRP recycled products that are the result of material recycling using waste FRP as a main material using the recycled FRP heat-fluid composite composition of the present invention: Examples 1 to 3 are in terms of mechanical properties. Although the tensile strength and impact strength are reduced as compared with the molded product of the polypropylene resin of Comparative Example 4, the bending strength and various elastic moduli are greatly improved. In particular, the rigidity is an acrylonitrile-styrene copolymer. It shows a high value according to resin (AS resin) and medium impact polystyrene resin (MIPS resin), and it can be seen that the mechanical properties as a molded product are maintained relatively. It can also be seen that the tensile strength, tensile elastic modulus, and various elastic moduli are improved as compared with Comparative Examples 1 to 3 in which waste FRP and recycled polypropylene resin are melt-kneaded without using a functional binder.
Thus, according to the recycled FRP-based heat-fluid composite composition of the present invention, an FPR recycled product having sufficient mechanical properties as a molded product is formed even when the mixing ratio of waste FPR is 50 parts by weight or more. Is possible.

また、前述の実施の形態において汎用の射出成形により成形しているが、本発明の再生ＦＲＰ系熱流動性複合組成物は、従来の廃棄ＦＲＰのリサイクル方法のように加熱プレス成形などの特殊な成形法のみに頼らず、汎用の射出成形や押出成形などの一般的な樹脂成形法により容易にＦＲＰ再生品を成形することができる点において、従来のリサイクル方法よりも、廃棄ＦＲＰのマテリアルリサイクルにおいて実用性が高いものである。
Further, in the above-described embodiment, it is molded by general-purpose injection molding. However, the regenerated FRP-based heat-fluid composite composition of the present invention is a special method such as hot press molding as in the conventional recycling method of waste FRP. In the material recycling of waste FRP rather than the conventional recycling method, the FRP recycled product can be easily molded by general resin molding methods such as general-purpose injection molding and extrusion molding, without relying only on the molding method. It is highly practical.

Claims (6)

粉砕した廃棄ＦＲＰと、ポリオレフィン系樹脂と、前記廃棄ＦＲＰとポリオレフィン系樹脂との界面において化学結合を生成する官能性結合剤とを混合し、溶融混練により複合化させた再生ＦＲＰ系熱流動性複合組成物であって、
前記官能性結合剤は、高分子主鎖中にエポキシ基を有するコポリマー又はターポリマーであることを特徴とする再生ＦＲＰ系熱流動性複合組成物。 Recycled FRP thermal fluid composite obtained by mixing pulverized waste FRP, polyolefin resin, and a functional binder that generates a chemical bond at the interface between the waste FRP and polyolefin resin, and combining them by melt kneading A composition comprising:
The regenerated FRP heat fluid composite composition, wherein the functional binder is a copolymer or terpolymer having an epoxy group in a polymer main chain. 請求項１に記載の再生ＦＲＰ系熱流動性複合組成物において、
前記廃棄ＦＲＰを５０〜７０重量部と、前記ポリオレフィン系樹脂を１５〜４５重量部と、前記官能性結合剤を５〜１５重量部とを合計を１００重量部となるように混合したことを特徴とする再生ＦＲＰ系熱流動性複合組成物。 In the regenerated FRP-based heat fluid composite composition according to claim 1,
50 to 70 parts by weight of the waste FRP, 15 to 45 parts by weight of the polyolefin-based resin, and 5 to 15 parts by weight of the functional binder are mixed so that the total amount becomes 100 parts by weight. A regenerated FRP-based heat-fluid composite composition. 請求項１又は２に記載の再生ＦＲＰ系熱流動性複合組成物において、
前記ポリオレフィン系樹脂は、再生材料又は再生材料とバージン材料との混合材料であることを特徴とするＦＲＰ系熱流動性複合組成物。 In the regenerated FRP-based heat fluid composite composition according to claim 1 or 2,
The FRP thermal fluid composite composition, wherein the polyolefin resin is a recycled material or a mixed material of a recycled material and a virgin material. 請求項１から３のいずれかに記載の再生ＦＲＰ系熱流動性複合組成物において、
前記官能性結合剤は、不飽和カルボン酸グリシジルエステルを含有するコポリマー、又は、不飽和カルボン酸グリシジルエステル−エチレン系不飽和エステル化合物を含有するターポリマーからなることを特徴とする再生ＦＲＰ系熱流動性複合組成物。 In the regenerated FRP heat-fluid composite composition according to any one of claims 1 to 3,
The functional binder comprises a copolymer containing an unsaturated carboxylic acid glycidyl ester, or a terpolymer containing an unsaturated carboxylic acid glycidyl ester-ethylenically unsaturated ester compound. Composite composition. 請求項１から４のいずれかに記載の再生ＦＲＰ系熱流動性複合組成物において、
前記官能性結合剤が、エチレン−グリシジルメタクリレートコポリマー、エチレン−グリシジルメタクリレート−酢酸ビニルターポリマー、エチレン−グリシジルメタクリレート−アクリル酸メチルターポリマーよりなる群から選択されることを特徴とする再生ＦＲＰ系熱流動性複合組成物。 In the regenerated FRP-based heat fluid composite composition according to any one of claims 1 to 4,
The regenerative FRP-based heat flow characterized in that the functional binder is selected from the group consisting of ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate terpolymer, ethylene-glycidyl methacrylate-methyl acrylate terpolymer. Composite composition. 請求項１から５のいずれかに記載の再生ＦＲＰ系熱流動性複合組成物を用いてなる成形品。   A molded article using the regenerated FRP-based heat-fluid composite composition according to any one of claims 1 to 5.
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Publication number Priority date Publication date Assignee Title
CN106220956A (en) * 2016-08-03 2016-12-14 江苏锐康新材料科技有限公司 Utilize imitation wood section bar and the preparation technology thereof of glass fiber reinforced plastic wastes regeneration preparation
CN115558231A (en) * 2022-10-17 2023-01-03 南京斯贝尔复合材料仪征有限公司 FRP (fiber reinforced plastic) section composite material and preparation method thereof

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CN106220956A (en) * 2016-08-03 2016-12-14 江苏锐康新材料科技有限公司 Utilize imitation wood section bar and the preparation technology thereof of glass fiber reinforced plastic wastes regeneration preparation
CN115558231A (en) * 2022-10-17 2023-01-03 南京斯贝尔复合材料仪征有限公司 FRP (fiber reinforced plastic) section composite material and preparation method thereof

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