JP2004115656A - Method for producing thermoplastic resin composite material mixed with frp recyclate - Google Patents
Method for producing thermoplastic resin composite material mixed with frp recyclate Download PDFInfo
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- JP2004115656A JP2004115656A JP2002281121A JP2002281121A JP2004115656A JP 2004115656 A JP2004115656 A JP 2004115656A JP 2002281121 A JP2002281121 A JP 2002281121A JP 2002281121 A JP2002281121 A JP 2002281121A JP 2004115656 A JP2004115656 A JP 2004115656A
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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
Description
【０００１】
【発明の属する技術分野】
本発明は、繊維強化複合材料（ＦＲＰ）のマテリアルリサイクルに係り、ＦＲＰリサイクレート〔第１成分〕とポリエチレン又はポリプロピレン〔第２成分〕と、表面処理剤〔第３成分〕とを配合して混練複合化することにより、耐衝撃性に優れた再生材料を得るためのＦＲＰリサイクレートを配合した熱可塑性樹脂複合材料の製造方法に関する。
【０００２】
【従来の技術】
ＦＲＰは単に樹脂のみでなく繊維などと組み合わせてある、樹脂が熱硬化性であるため熱可塑性樹脂と異なり単一溶融して再成形・再利用するという可逆的方法がとれないなどの理由で、リサイクル困難な材料である。
【０００３】
現在、ＦＲＰのリサイクル法としては、▲１▼マテリアルリサイクル、▲２▼ケミカルリサイクル、▲３▼サーマルリサイクルが考えられる。
【０００４】
この他に、ＦＲＰ廃材の利用法としては、セメント原料としての利用が行われているが、安定した成分組成のＦＲＰ廃材を大量に必要とするため、中小工場で発生する程度の材料の処理には不向きである。
【０００５】
ケミカルリサイクルとしては、ボタンを打ち抜いた廃材をグリコールと反応させて樹脂分を回収・原料化することが検討されているが、高コストである上、一般のＦＲＰは強化繊維・無機充填剤などを大量に含むため効率が悪く実用化されていない。
【０００６】
サーマルリサイクルはＦＲＰ廃材を他の可燃物とともに燃焼し、燃焼熱を利用することが検討されているが、一般のＦＲＰは強化繊維・無機充填剤などを大量に含むため未燃焼分の処理が問題となり、実用化されていない上、一回きりのリサイクルであるという欠点がある。
【０００７】
リサイクルの方法としては低コストで数回繰り返しての再利用が可能なマテリアルリサイクルが望ましい。現在は、ＦＲＰの一種であるＳＭＣ成形品の充填剤としての利用のみが実用化されているが、同じＦＲＰであるため廃棄物となった時には現在と同様な問題が生じる。
【０００８】
【発明が解決しようとする課題】
ＦＲＰリサクレートを数回繰り返して再利用するためには、リサイクルによる機械的特性の低下が小さいポリオレフィン樹脂との複合化によるマテリアルリサイクルが望ましいが、ＦＲＰとポリオレフィンの親和性が小さいため、単に溶融混合しただけでは機械的特性、とりわけ耐衝撃性の著しい低下を引き起こすという問題があった。
【０００９】
本発明者らは、ポリオレフィン樹脂とＦＲＰの親和性を改善する方法について研究を重ねるなかで、ＦＲＰリサイクレート中のガラス繊維・無機充填剤の表面を覆うポリエステル樹脂とポリオレフィン樹脂の両者に親和性を有する表面処理剤を第３成分として添加することにより、機械的特性の低下を改善できることを見出した。これに関連する先行技術は今のところみあたらない。
【００１０】
本発明は上記知見（研究成果）に基づき開発された成果物のひとつであって、耐衝撃性に優れた再生材料を得るためのＦＲＰリサイクレートを配合した熱可塑性樹脂複合材料の製造方法を提供するものである。
【００１１】
【課題を解決するための手段】
課題を解決するために本発明は、ＦＲＰリサイクレートとポリオレフィン樹脂を複合して耐衝撃性に優れた再生材料を得るためのＦＲＰリサイクレートを配合した熱可塑性樹脂複合材料の製造方法であって、
ＦＲＰリサイクレート５〜４０重量部と、ポリエチレン又はポリプロピレン４０〜９４重量部と、表面処理剤１〜２０重量部とを合計１００重量部となるように固体ブレンドし、混練押出機又は熱ロールにより混練複合化することを特徴とするものである。
【００１２】
ここで、表面処理剤がエチレン−プロピレン共重合体又はエチレン−プロピレン−ジエン共重合体に対してスチレン又はメタクリル酸をグラフト重合して得られる樹脂である。グラフト率は０〜５０％である。
【００１３】
また、ＦＲＰリサイクレート５０〜９０重量部に対して上記表面処理剤１０〜５０重量部を混練押出機又は熱ロールにより混練してＦＲＰリサイクレートを５０〜９０重量％含むマスターバッチを中間生成し、該マスターバッチ１０〜８０重量部とポリエチレン又はポリプロピレン２０〜９０重量部とを合計１００重量部となるように固体ブレンドし、混練押出機又は熱ロールにより混練複合化する場合がある。
【００１４】
さらにまた、上記表面処理剤１０〜８０重量部を有機溶剤に溶解し、ＦＲＰリサイクレート５０〜９０重量部を添加して撹拌した後、メタノール中に投入して析出させ、真空脱気、加熱乾燥及び自然乾燥を施してＦＲＰリサイクレートを５０〜９０重量％含むマスターバッチを中間生成し、該マスターバッチ１０〜８０重量部とポリエチレン又はポリプロピレン２０〜９０重量部とを合計１００重量部となるように固体ブレンドし、混練押出機又は熱ロールにより混練複合化する場合がある。
【００１５】
【発明の実施の形態】
本発明の実施の形態は、上記各構成において、ＦＲＰリサイクレートは１ｍｍ以下のメッシュのふるいを通過した成分を捕集したものを用いる。また、混練押出機については、公知の二軸混練押出機が使用可能である。
【００１６】
【実施例】
本発明の一実施例について以下説明する。
【００１７】
（実施例１）
請求項１又は２記載の発明に関し、 ０．０３０ｍｍの目のふるいを通過したＦＲＰリサイクレート３０重量部に対しポリプロピレン５０重量部、表面処理剤（エチレン−プロピレン−ジエン共重合体）２０重量部を、二軸混練押出機により混練複合化し、射出成形機で成形して、熱可塑性樹脂複合材料を得た。
【００１８】
（実施例２）
請求項３記載の発明に関し、０．３ｍｍ の目のふるいを通過したＦＲＰリサイクレート９０重量部に対し表面処理剤（エチレン−プロピレン共重合体にスチレンをグラフト重合することにより得られる樹脂、グラフト率１３％）１０重量部を、ワイゼンベルグ式押出機により混練複合化してマスターバッチを作成し、マスターバッチ２５重量部とポリプロピレン７５重量部を混練複合化し、射出成形機で成形した。
【００１９】
（実施例３）
請求項４記載の発明に関し、エチレン−プロピレン共重合体にスチレンをグラフト重合することにより得られる樹脂１０重量部を２０倍量のトルエンに溶解し、 ０．０３０ｍｍの目のふるいを通過したＦＲＰリサイクレート３０重量部を加えて４時間攪拌後、トルエンの１０倍量のメタノール中に攪拌しつつ投入して樹脂とＦＲＰリサイクレートを沈殿させた後ろ過し、乾燥してマスターバッチを作成する。このマスターバッチ２０重量部とポリプロピレン８０重量部を混練複合化し、射出成形機で成形した。
【００２０】
これらの実施例について、引張強さ、弾性率、アイゾット衝撃強さを測定した結果をまとめて表１に示す。
【００２１】
【表１】
表１において、比較例１は ０．０３０ｍｍの目のふるいを通過したＦＲＰリサイクレート３０重量部に対しポリプロピレン７０重量部、比較例２は第３成分としてプロピレンとアクリル酸の共重合体（市販のＰＰ−ポリエステル樹脂用相溶化剤）、比較例３は水添ＳＥＢＳ樹脂を用い、 ０．０３０ｍｍの目のふるいを通過したＦＲＰリサイクレート３０重量部に対しポリプロピレン６０重量部、表面処理剤１０重量部を、二軸混練押出機により混練複合化し、射出成形機で成形したものである。
【００２３】
【発明の効果】
ＦＲＰのマテリアルリサイクルにおいて、最も低下しやすい機械的特性である耐衝撃性を改善する効果を奏する。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to material recycling of fiber reinforced composite material (FRP), and mixes and kneads FRP recycle [first component], polyethylene or polypropylene [second component], and surface treatment agent [third component]. The present invention relates to a method for producing a thermoplastic resin composite material containing an FRP recycle to obtain a recycled material having excellent impact resistance by compounding.
[0002]
[Prior art]
FRP is not only a resin but also combined with fibers, etc.Because the resin is thermosetting, unlike a thermoplastic resin, it can not be reversibly formed by single melting and re-forming / reusing, etc. It is difficult to recycle.
[0003]
Currently, FRP recycling methods include (1) material recycling, (2) chemical recycling, and (3) thermal recycling.
[0004]
In addition, as a method of using FRP waste material, it is used as a raw material for cement. However, since a large amount of FRP waste material having a stable component composition is required, it is necessary to treat materials generated to a degree at small and medium-sized factories. Is not suitable.
[0005]
As for chemical recycling, it has been studied to recover waste resin from raw materials punched out of buttons with glycol to recover and use it as raw material. In addition to the high cost, general FRP uses reinforcing fibers and inorganic fillers. Since it contains a large amount, it is inefficient and has not been put to practical use.
[0006]
In thermal recycling, it is considered to burn the FRP waste together with other combustibles and use the heat of combustion. However, general FRP contains a large amount of reinforcing fibers and inorganic fillers, so there is a problem in treating unburned materials. However, it has not been put to practical use and has the disadvantage that it is recycled only once.
[0007]
As a recycling method, material recycling that can be reused several times at a low cost is desirable. At present, only the use of SMC molded products, which are a type of FRP, as fillers has been put to practical use, but the same FRP causes the same problem as present when it becomes waste.
[0008]
[Problems to be solved by the invention]
In order to reuse the FRP recycle repeatedly several times, it is desirable to recycle the material by compounding a polyolefin resin with a small decrease in mechanical properties due to recycling.However, since the affinity between FRP and the polyolefin is small, the material is simply melt-mixed. However, there is a problem that mechanical properties, particularly impact resistance, are significantly reduced.
[0009]
The present inventors have been studying a method for improving the affinity between a polyolefin resin and FRP, and have found that both the polyester resin and the polyolefin resin covering the surface of the glass fiber / inorganic filler in the FRP recycle have an affinity for both. It has been found that by adding a surface treating agent having the same as the third component, a decrease in mechanical properties can be improved. No related prior art has been found so far.
[0010]
The present invention is one of the products developed based on the above findings (research results), and provides a method for producing a thermoplastic resin composite material containing FRP recycle to obtain a recycled material having excellent impact resistance. Is what you do.
[0011]
[Means for Solving the Problems]
In order to solve the problem, the present invention is a method for producing a thermoplastic resin composite material blended with FRP recycle to obtain a recycled material having excellent impact resistance by combining FRP recycle and polyolefin resin,
5 to 40 parts by weight of FRP recycle, 40 to 94 parts by weight of polyethylene or polypropylene, and 1 to 20 parts by weight of a surface treating agent are solid-blended to a total of 100 parts by weight, and kneaded by a kneading extruder or a hot roll. It is characterized by being compounded.
[0012]
Here, the surface treatment agent is a resin obtained by graft-polymerizing styrene or methacrylic acid to an ethylene-propylene copolymer or an ethylene-propylene-diene copolymer. The graft ratio is 0 to 50%.
[0013]
Further, 10 to 50 parts by weight of the surface treatment agent is kneaded by a kneading extruder or a hot roll with respect to 50 to 90 parts by weight of FRP recycle to intermediately produce a master batch containing 50 to 90% by weight of FRP recycle. In some cases, 10 to 80 parts by weight of the master batch and 20 to 90 parts by weight of polyethylene or polypropylene are solid-blended so as to make a total of 100 parts by weight, and kneaded and compounded by a kneading extruder or a hot roll.
[0014]
Furthermore, 10 to 80 parts by weight of the above surface treating agent is dissolved in an organic solvent, 50 to 90 parts by weight of FRP recycle is added, and the mixture is stirred. And subjecting it to natural drying to intermediately produce a masterbatch containing 50 to 90% by weight of FRP recycle rate, so that 10 to 80 parts by weight of the masterbatch and 20 to 90 parts by weight of polyethylene or polypropylene become 100 parts by weight in total. There is a case where the solid is blended and kneaded and compounded by a kneading extruder or a hot roll.
[0015]
BEST MODE FOR CARRYING OUT THE INVENTION
In the embodiment of the present invention, in each of the above-described configurations, the FRP recycle rate is obtained by collecting components that have passed through a sieve having a mesh of 1 mm or less. As the kneading extruder, a known twin-screw kneading extruder can be used.
[0016]
【Example】
An embodiment of the present invention will be described below.
[0017]
(Example 1)
The invention according to claim 1 or 2, wherein 50 parts by weight of polypropylene and 20 parts by weight of a surface treating agent (ethylene-propylene-diene copolymer) are added to 30 parts by weight of the FRP recycle rate passed through a 0.030 mm eye sieve. The mixture was kneaded and compounded by a twin-screw kneading extruder and molded by an injection molding machine to obtain a thermoplastic resin composite material.
[0018]
(Example 2)
According to the third aspect of the present invention, a surface treatment agent (a resin obtained by graft-polymerizing styrene onto an ethylene-propylene copolymer, and a graft ratio, based on 90 parts by weight of FRP recycle which has passed through a sieve having a size of 0.3 mm). (13%) 10 parts by weight were kneaded and compounded by a Weisenberg extruder to prepare a master batch, and 25 parts by weight of the master batch and 75 parts by weight of polypropylene were kneaded and compounded and molded by an injection molding machine.
[0019]
(Example 3)
According to the invention of claim 4, 10 parts by weight of a resin obtained by graft-polymerizing styrene to an ethylene-propylene copolymer is dissolved in 20 times the amount of toluene, and the FRP recycled through a 0.030 mm mesh sieve. After adding 30 parts by weight of the rate and stirring for 4 hours, the mixture is poured into methanol 10 times the amount of toluene with stirring to precipitate the resin and the FRP recycle rate, followed by filtration and drying to prepare a master batch. 20 parts by weight of this master batch and 80 parts by weight of polypropylene were kneaded and compounded and molded by an injection molding machine.
[0020]
Table 1 summarizes the results of measuring the tensile strength, elastic modulus, and Izod impact strength of these examples.
[0021]
[Table 1]
In Table 1, Comparative Example 1 was composed of 70 parts by weight of polypropylene with respect to 30 parts by weight of FRP recycle which passed through a sieve of 0.030 mm. Comparative Example 2 was a copolymer of propylene and acrylic acid (commercially available) as the third component. Comparative Example 3 uses hydrogenated SEBS resin, Comparative Example 3 uses 60 parts by weight of polypropylene and 30 parts by weight of a surface treatment agent for 30 parts by weight of FRP recycle which has passed through a 0.030 mm mesh sieve. Is kneaded and compounded by a twin-screw kneading extruder and molded by an injection molding machine.
[0023]
【The invention's effect】
In the material recycling of FRP, an effect of improving impact resistance, which is a mechanical property that is most likely to be reduced, is exerted.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002281121A JP3747258B2 (en) | 2002-09-26 | 2002-09-26 | Method for producing thermoplastic resin composite material containing FRP recycle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002281121A JP3747258B2 (en) | 2002-09-26 | 2002-09-26 | Method for producing thermoplastic resin composite material containing FRP recycle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004115656A true JP2004115656A (en) | 2004-04-15 |
| JP3747258B2 JP3747258B2 (en) | 2006-02-22 |
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| JP2002281121A Expired - Fee Related JP3747258B2 (en) | 2002-09-26 | 2002-09-26 | Method for producing thermoplastic resin composite material containing FRP recycle |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036883A (en) * | 2004-07-26 | 2006-02-09 | El & Chem Corp | Reclaimed frp-based thermoplastic composite composition |
| US20160024266A1 (en) * | 2013-11-22 | 2016-01-28 | Johns Manville | Fiber-containing prepregs and methods and systems of making |
| EP3842482A1 (en) * | 2019-12-23 | 2021-06-30 | Maciej Adam Dechnik | Ecological composite made of recycled thermoplastic materials and method used in its production |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724190B (en) * | 2008-10-14 | 2011-11-16 | 青岛理工大学 | Asbestos fiber reinforced thermoplastic base wood and plastic composite material and preparing method thereof |
-
2002
- 2002-09-26 JP JP2002281121A patent/JP3747258B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006036883A (en) * | 2004-07-26 | 2006-02-09 | El & Chem Corp | Reclaimed frp-based thermoplastic composite composition |
| US20160024266A1 (en) * | 2013-11-22 | 2016-01-28 | Johns Manville | Fiber-containing prepregs and methods and systems of making |
| EP3842482A1 (en) * | 2019-12-23 | 2021-06-30 | Maciej Adam Dechnik | Ecological composite made of recycled thermoplastic materials and method used in its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3747258B2 (en) | 2006-02-22 |
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