JP7696417B2 - Polyolefin resin composition, recycled carbon fiber reinforced resin molded body, method for producing recycled carbon fiber reinforced resin pellets, and method for producing recycled carbon fiber reinforced resin molded body - Google Patents
Polyolefin resin composition, recycled carbon fiber reinforced resin molded body, method for producing recycled carbon fiber reinforced resin pellets, and method for producing recycled carbon fiber reinforced resin molded body Download PDFInfo
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Description
本発明は、再生炭素繊維を含むポリオレフィン樹脂組成物と、再生炭素繊維強化樹脂成形体と、再生炭素繊維強化樹脂ペレットの製造方法と、再生炭素繊維強化樹脂成形体の製造方法に関する。 The present invention relates to a polyolefin resin composition containing recycled carbon fibers, a recycled carbon fiber reinforced resin molded body, a method for producing recycled carbon fiber reinforced resin pellets, and a method for producing a recycled carbon fiber reinforced resin molded body.
炭素繊維強化樹脂成形体は、軽量で高い剛性を有するため、各種の分野で使用されている。例えば、自動車や航空機の部品、ノートパソコンなどの携帯機器の筐体等に炭素繊維強化樹脂成形体は使用されている。 Carbon fiber reinforced plastic moldings are lightweight and highly rigid, and are therefore used in a variety of fields. For example, carbon fiber reinforced plastic moldings are used in automobile and aircraft parts, and housings for portable devices such as laptops.
炭素繊維強化樹脂成形体の使用量が増加するにしたがい、使用後の炭素繊維強化樹脂成形体の廃棄量も増加し、その再利用が求められている。
炭素繊維強化樹脂成形体の再利用の一つとして、廃炭素繊維強化樹脂成形体から再生炭素繊維を得る方法が提案されている。
As the amount of carbon fiber reinforced plastic moldings used increases, the amount of carbon fiber reinforced plastic moldings that are discarded after use also increases, and there is a demand for their reuse.
As one method for reusing carbon fiber reinforced resin moldings, a method for obtaining recycled carbon fibers from waste carbon fiber reinforced resin moldings has been proposed.
しかし、再生炭素繊維を使用した再生炭素繊維強化樹脂成形体は、バージン（未使用）の炭素繊維を使用した炭素繊維強化樹脂成形体と比べて物性が劣る問題があった。 However, recycled carbon fiber reinforced resin moldings made from recycled carbon fiber have inferior physical properties compared to carbon fiber reinforced resin moldings made from virgin (unused) carbon fiber.
本発明は、前記の点に鑑みなされたものであって、再生炭素繊維を使用して良好な品質の成形体を得ることができるポリオレフィン樹脂組成物、再生炭素繊維強化樹脂成形体、再生炭素繊維強化樹脂ペレットの製造方法、及び再生炭素繊維強化樹脂成形体の製造方法の提供を目的とする。 The present invention has been made in consideration of the above points, and aims to provide a polyolefin resin composition that can obtain a molded product of good quality using recycled carbon fibers, a recycled carbon fiber reinforced resin molded product, a method for producing recycled carbon fiber reinforced resin pellets, and a method for producing a recycled carbon fiber reinforced resin molded product.
第１の態様は、ポリオレフィン樹脂と、再生炭素繊維と、イミン変性ポリオレフィン樹脂とを含むポリオレフィン樹脂組成物に係る。 A first aspect relates to a polyolefin resin composition comprising a polyolefin resin, recycled carbon fibers, and an imine-modified polyolefin resin.
第２の態様は、第１の態様において、前記イミン変性ポリオレフィン樹脂は、前記再生炭素繊維の１０～５０重量％であることを特徴とする。 A second aspect is the first aspect , characterized in that the imine-modified polyolefin resin accounts for 10 to 50% by weight of the recycled carbon fibers.
第３の態様は、第１の態様または第２の態様において、前記再生炭素繊維は、前記ポリオレフィン樹脂１００重量部に対し、５～４０重量部であることを特徴とする。 A third aspect is the first or second aspect , characterized in that the recycled carbon fibers are 5 to 40 parts by weight per 100 parts by weight of the polyolefin resin.
第４の態様は、第１の態様から第３の態様の何れか一つにおいて、前記再生炭素繊維は、裁断されたチョップド再生炭素繊維、または粉砕されたミルド再生炭素繊維であることを特徴とする。 A fourth aspect is any one of the first to third aspects , characterized in that the recycled carbon fiber is chopped recycled carbon fiber or milled recycled carbon fiber.
第５の態様は、第１の態様から第４の態様の何れか一つにおいて、前記再生炭素繊維は、廃炭素繊維強化樹脂の熱分解物であることを特徴とする。 A fifth aspect is any one of the first to fourth aspects , characterized in that the recycled carbon fiber is a pyrolysis product of waste carbon fiber reinforced resin.
第６の態様は、第１の態様から第５の態様の何れか一つに記載のポリオレフィン樹脂組成物からなる再生炭素繊維強化樹脂成形体に係る。 A sixth aspect relates to a recycled carbon fiber reinforced resin molding comprising the polyolefin resin composition according to any one of the first to fifth aspects .
第７の態様は、再生炭素繊維を、ポリオレフィン樹脂とイミン変性ポリオレフィン樹脂と共に混練押出機で混練りし、該混練物を前記混練押出機から押し出してペレットにすることを特徴とする再生炭素繊維強化樹脂ペレットの製造方法に係る。 The seventh aspect relates to a method for producing recycled carbon fiber reinforced resin pellets, characterized in that recycled carbon fibers are kneaded together with a polyolefin resin and an imine-modified polyolefin resin in a kneading extruder, and the kneaded mixture is extruded from the kneading extruder to form pellets.
第８の態様は、ポリオレフィン樹脂と、再生炭素繊維と、イミン変性ポリオレフィン樹脂とを含むポリオレフィン樹脂組成物から得られた再生炭素繊維強化樹脂ペレットを用い、射出成形、押出成形、ブロー成形の何れかによって成形体を得ることを特徴とする再生炭素繊維強化樹脂成形体の製造方法に係る。 The eighth aspect relates to a method for producing a recycled carbon fiber reinforced resin molded body, characterized in that a molded body is obtained by any one of injection molding, extrusion molding, and blow molding using recycled carbon fiber reinforced resin pellets obtained from a polyolefin resin composition containing a polyolefin resin, recycled carbon fibers, and an imine-modified polyolefin resin.
本発明によって得られるポリオレフィン樹脂組成物は、ポリオレフィン樹脂と、再生炭素繊維と、イミン変性ポリオレフィン樹脂とを含むものからなるため、再生炭素繊維を使用しているにもかかわらず、良好な品質の成形体を得ることができる。 The polyolefin resin composition obtained by the present invention contains polyolefin resin, recycled carbon fiber, and imine-modified polyolefin resin, so that molded articles of good quality can be obtained despite the use of recycled carbon fiber.
以下、以下本発明における、ポリオレフィン樹脂組成物、再生炭素繊維強化樹脂成形体、再生炭素繊維強化樹脂ペレットの製造方法、及び再生炭素繊維強化樹脂成形体の製造方法について説明する。
本発明のポリオレフィン樹脂組成物は、ポリオレフィン樹脂と、再生炭素繊維と、イミン変性ポリオレフィン樹脂とを含むものからなる。
ポリオレフィン樹脂としては、ポリプロピレン樹脂、低密度ポリエチレン（ＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、エチレン－酢酸ビニル共重合体樹脂、エチレン－プロピレン共重合体、エチレン－ブテン共重合体、エチレンとメチル、エチル、プロピル若しくはブチルの各アクリル酸エステルとの共重合体、又はこれらの塩素化物、あるいはそれらの混合物、さらにはそれらとアイソタクチックポリプロピレン若しくはアタクチックポリプロピレンの混合物等を挙げることができる。特に好ましいポリオレフィン樹脂は、ポリプロピレン、ポリエチレンである。
The polyolefin resin composition, the recycled carbon fiber reinforced resin molded product, the method for producing the recycled carbon fiber reinforced resin pellets, and the method for producing the recycled carbon fiber reinforced resin molded product according to the present invention will be described below.
The polyolefin resin composition of the present invention comprises a polyolefin resin, recycled carbon fibers, and an imine-modified polyolefin resin.
Examples of polyolefin resins include polypropylene resins, low density polyethylene (LDPE), high density polyethylene (HDPE), ethylene-vinyl acetate copolymer resins, ethylene-propylene copolymers, ethylene-butene copolymers, copolymers of ethylene with methyl, ethyl, propyl or butyl acrylates, or chlorinated products thereof, or mixtures thereof, or mixtures of these with isotactic polypropylene or atactic polypropylene, etc. Particularly preferred polyolefin resins are polypropylene and polyethylene.
再生炭素繊維は、廃炭素繊維強化樹脂を加熱処理して得られる熱分解物が好ましい。廃炭素繊維強化樹脂は、炭素繊維と樹脂とからなる炭素繊維強化樹脂（ＣＦＲＰ）成形体の廃棄物である。また、廃炭素繊維強化樹脂から再生炭素繊維を得るための加熱処理は、廃炭素繊維強化樹脂を加熱して樹脂を炭化物とし、その炭化物を酸化分解して炭素繊維（再生炭素繊維）を得る処理であり、公知の処理技術である。 The recycled carbon fiber is preferably a pyrolysis product obtained by heat-treating waste carbon fiber reinforced resin. Waste carbon fiber reinforced resin is waste from carbon fiber reinforced resin (CFRP) molded bodies made of carbon fiber and resin. The heat treatment for obtaining recycled carbon fiber from waste carbon fiber reinforced resin involves heating the waste carbon fiber reinforced resin to carbonize the resin, and then oxidatively decomposing the carbonized resin to obtain carbon fiber (recycled carbon fiber), and is a well-known processing technique.
再生炭素繊維は、裁断されたチョップド再生炭素繊維（好ましくは１～１５ｍｍの長さ）、または粉砕されたミルド再生炭素繊維の何れでもよい。チョップド再生炭素繊維は、ミルド再生炭素繊維よりも、成形体の線膨張係数が小になって伸縮性が小さくなる。一方、ミルド再生炭素繊維は、チョップド再生炭素繊維よりも、成形体の外観（平滑性）が良好になる。 The recycled carbon fiber may be either chopped recycled carbon fiber (preferably 1 to 15 mm long) or milled recycled carbon fiber. Chopped recycled carbon fiber produces a molded body with a smaller linear expansion coefficient and less elasticity than milled recycled carbon fiber. On the other hand, milled recycled carbon fiber produces a molded body with a better appearance (smoothness) than chopped recycled carbon fiber.
再生炭素繊維の配合量は、ポリオレフィン樹脂１００重量部に対し、５～４０重量部が好ましく、より好ましくは５～１０重量部である。再生炭素繊維の配合量が少なすぎると成形体の剛性が低くなり、逆に多すぎると成形体の成形性が低下するようになる。また、再生炭素繊維と共にバージンの炭素繊維を併用してもよい。 The amount of recycled carbon fiber is preferably 5 to 40 parts by weight, more preferably 5 to 10 parts by weight, per 100 parts by weight of polyolefin resin. If the amount of recycled carbon fiber is too small, the rigidity of the molded body will be low, and conversely, if the amount is too large, the moldability of the molded body will decrease. Virgin carbon fiber may also be used in combination with the recycled carbon fiber.
イミン変性ポリオレフィン樹脂は、ポリオレフィンにイミノ基を多数含有しているポリイミド化合物を、ラジカル発生剤の存在下でグラフト処理することによって得られるものである。ポリイミド化合物の基となるポリオレフィンとしては、ポリエチレン、ポリプロピレン、ポリ－１－ブテン、ポリイソブチレン等が挙げられる。 Imine-modified polyolefin resins are obtained by grafting a polyimide compound, which contains many imino groups, onto a polyolefin in the presence of a radical generator. Examples of polyolefins that serve as the base for polyimide compounds include polyethylene, polypropylene, poly-1-butene, and polyisobutylene.
イミン変性ポリオレフィン樹脂をポリオレフィン樹脂組成物に配合することにより、ポリオレフィン樹脂組成物の溶融押出時におけるメルトテンションの限界速度の値が大になり、成形体の外観（成形体表面の平滑性）を良好にできる。メルトテンションの限界速度は、樹脂の溶融押出時における増速引取による破断時の最大速度であり、ＪＩＳ Ｋ７１９９に基づいて測定される。メルトテンションの限界速度の値が大きいほど、溶融体の破裂を生じ難いため、得られる成形体の表面の平滑性が良好なものになる。
イミン変性ポリオレフィン樹脂の配合量は、再生炭素繊維の１０～５０重量％が好ましい。イミン変性ポリオレフィン樹脂の配合量が少なすぎると、成形体の平滑性及び衝撃強度が悪くなる。
By blending the imine-modified polyolefin resin with the polyolefin resin composition, the melt tension limit speed value during melt extrusion of the polyolefin resin composition becomes large, and the appearance (smoothness of the surface of the molded product) of the molded product can be improved. The melt tension limit speed is the maximum speed at which the resin breaks due to accelerated take-up during melt extrusion, and is measured based on JIS K7199. The higher the melt tension limit speed value, the less likely the melt will break, and the smoother the surface of the molded product obtained will be.
The amount of the imine-modified polyolefin resin is preferably 10 to 50% by weight of the recycled carbon fiber. If the amount of the imine-modified polyolefin resin is too small, the smoothness and impact strength of the molded product will be deteriorated.
本発明のポリオレフィン樹脂組成物は、再生炭素繊維強化樹脂ペレットにされて、再生炭素繊維強化樹脂成形体の製造に用いられる。
再生炭素繊維強化樹脂ペレットの製造は、再生炭素繊維を、ポリオレフィン樹脂とイミン変性ポリオレフィン樹脂と共に、混練押出機で混練りし、該混練物をストランド状に押出し、水中冷却槽に通して冷却硬化し、ペレタイザーで切断してペレットとすることにより行うことができる。なお、樹脂のペレット化は、公知の方法である。
The polyolefin resin composition of the present invention is made into recycled carbon fiber reinforced resin pellets and used for producing recycled carbon fiber reinforced resin molded articles.
The recycled carbon fiber reinforced resin pellets can be produced by kneading the recycled carbon fibers together with the polyolefin resin and the imine-modified polyolefin resin in a kneading extruder, extruding the kneaded mixture into a strand shape, passing the strand through an underwater cooling tank to cool and harden it, and cutting the strand into pellets with a pelletizer. The resin pelletization is a known method.
本発明のポリオレフィン樹脂組成物を用いて行う再生炭素繊維強化樹脂成形体の製造は、射出成形、押出成形、ブロー成形の何れかによって行われ、成形体の用途に応じた成形方法が採用される。 The polyolefin resin composition of the present invention is used to produce recycled carbon fiber reinforced resin molded articles by injection molding, extrusion molding, or blow molding, and the molding method used is based on the intended use of the molded article.
射出成形では、前記再生炭素繊維強化樹脂ペレットを、射出成形機に投入して溶融し、その溶融樹脂を金型のキャビティ内に射出してキャビティ形状の再生炭素繊維強化樹脂成形体を形成し、その後金型から取り出す。 In injection molding, the recycled carbon fiber reinforced resin pellets are placed in an injection molding machine and melted, and the molten resin is injected into the cavity of a mold to form a cavity-shaped recycled carbon fiber reinforced resin molded body, which is then removed from the mold.
押出成形では、前記再生炭素繊維強化樹脂ペレットを、押出機に投入して溶融し、溶融樹脂をダイスから押し出してダイス形状の長尺品からなる再生炭素繊維強化樹脂成形体を形成する。 In extrusion molding, the recycled carbon fiber reinforced resin pellets are fed into an extruder and melted, and the molten resin is extruded through a die to form a recycled carbon fiber reinforced resin molded body consisting of a long die-shaped product.
ブロー成形では、前記再生炭素繊維強化樹脂ペレットを押出機に投入して溶融し、ヘッドから筒状のパリソンを押し出し、前記パリソンをブロー金型内に挟み込み、その状態でパリソン内に気体を吹き込んで金型内面形状に膨らませることにより、中空の再生炭素繊維強化樹脂成形体を形成し、その後金型から取り出す。 In blow molding, the recycled carbon fiber reinforced resin pellets are fed into an extruder and melted, and a cylindrical parison is extruded from the head. The parison is then sandwiched inside a blow mold, and gas is blown into the parison in this state to inflate it to the shape of the inner surface of the mold, forming a hollow recycled carbon fiber reinforced resin molded body, which is then removed from the mold.
なお、ブロー成形は、筒状のパリソンに代えてシート状に押し出して形成したシート状パリソンの２枚をブロー金型で挟み、２枚のシート状パリソン間に気体を吹き込んで金型内面形状に膨らませる方法でもよい。 In addition, blow molding may be performed by sandwiching two sheet-like parisons formed by extruding a sheet instead of a cylindrical parison between a blow mold and blowing gas between the two sheet-like parisons to inflate them to the shape of the inner surface of the mold.
図１の配合からなる各実施例及び各比較例のポリオレフィン樹脂組成物を、混練押出機（品名：ＫＴＸ－３０、神戸製鋼製）で溶融混練し、直径３ｍｍのストランド状で水中冷却層に押し出し、ペレタイザー（品名：ストランドカッター、タナカ社製）で長さ３～４ｍｍに切断して各実施例及び各比較例のペレットを製造した。溶融混練条件はバレルおよびダイ温度２００℃、スクリュー回転数４００ｒｐｍ、吐出量２０ｋｇ／ｈである。 The polyolefin resin composition of each Example and Comparative Example, which has the composition shown in Figure 1, was melt-kneaded in a kneading extruder (product name: KTX-30, manufactured by Kobe Steel), extruded into an underwater cooling layer in the form of a strand with a diameter of 3 mm, and cut into lengths of 3 to 4 mm using a pelletizer (product name: strand cutter, manufactured by Tanaka Co., Ltd.) to produce pellets of each Example and Comparative Example. The melt-kneading conditions were barrel and die temperatures of 200°C, screw rotation speed of 400 rpm, and discharge rate of 20 kg/h.
使用した原料を以下に示す。
・ポリエチレン：高密度ポリエチレン（ＨＤＰＥ）、品名；ハイゼックス５０００Ｈ、株式会社プライムポリマー製
・再生炭素繊維（チョップド）：廃炭素繊維強化樹脂の熱分解物からなる繊維長１０ｍｍ以下の再生炭素繊維、品名；チョップド再生ＣＦ繊維、カーボンファイバーリサイクル工業株式会社製
製
・再生炭素繊維（ミルド）：廃炭素繊維強化樹脂の熱分解物からなる平均径２５μｍの再生炭素繊維、品名；ミルド再生ＣＦ繊維、カーボンファイバーリサイクル工業株式会社製
・イミン変性ポリオレフィン樹脂：品名：アドマー（登録商標）ＩＰ、三井化学株式会社製
・酸変性ポリオレフィン樹脂：マレイン酸変性ポリオレフィン、品名；ユーメックス、三洋化成株式会社製
The raw materials used are shown below.
Polyethylene: High density polyethylene (HDPE), Product name: Hi-Zex 5000H, manufactured by Prime Polymer Co., Ltd. Recycled carbon fiber (chopped): Recycled carbon fiber with a fiber length of 10 mm or less, made of a pyrolysis product of waste carbon fiber reinforced resin, Product name: Chopped recycled CF fiber, manufactured by Carbon Fiber Recycle Industry Co., Ltd. Recycled carbon fiber (milled): Recycled carbon fiber with an average diameter of 25 μm, made of a pyrolysis product of waste carbon fiber reinforced resin, Product name: Milled recycled CF fiber, manufactured by Carbon Fiber Recycle Industry Co., Ltd. Imine-modified polyolefin resin: Product name: Admer (registered trademark) IP, manufactured by Mitsui Chemicals, Inc. Acid-modified polyolefin resin: Maleic acid-modified polyolefin, Product name: Umex, manufactured by Sanyo Chemical Co., Ltd.
各実施例及び各比較例のペレットを、押出成形機（品名：ＧＳ９０、池貝社製）に投入し、押出成形によって、外径３０ｍｍ、内径２５ｍｍからなるチューブ状の成形体を製造した。成形条件は、ダイ温度２００℃、スクリュー回転数３０ｒｐｍ、引取速度２．０ｍ／ｍｉｎである。 The pellets of each example and each comparative example were fed into an extrusion molding machine (product name: GS90, manufactured by Ikegai Co., Ltd.) and extrusion molding was performed to produce a tubular molded body with an outer diameter of 30 mm and an inner diameter of 25 mm. The molding conditions were a die temperature of 200°C, a screw rotation speed of 30 rpm, and a take-up speed of 2.0 m/min.
各実施例及び各比較例に対し、機械物性としてシャルピー衝撃強度（ノッチあり）、成形評価としてメルトテンション限界速度、線膨張係数（２０℃°→６０℃）を測定した。 For each example and comparative example, the mechanical properties, Charpy impact strength (with notch), and the melt tension limit speed and linear expansion coefficient (20°C°→60°C) were measured as molding evaluations.
シャルピー衝撃強度（ノッチあり）は、各実施例及び各比較例のペレットを、熱可塑性射出成形機に投入し、ＪＩＳ Ｋ７１１１に定められたノッチ付き試験片サンプルを作成し、そのサンプルに対してＪＩＳ Ｋ７１１１に基づいて測定した。 The Charpy impact strength (notched) was measured by feeding the pellets of each example and comparative example into a thermoplastic injection molding machine to create a notched test piece sample as specified in JIS K7111, and measuring the sample in accordance with JIS K7111.
メルトテンション限界速度は、ＪＩＳ Ｋ７１９９に基づいて測定した。測定条件は、温度２００℃ 、押出速度１０ｍ／ｍｉｎである。
メルトテンション限界速度は、樹脂の溶融押出時の増速引取による破断時の引取速度であり、限界速度の値が大きいほど、溶融樹脂の破断を生じ難いため、成形体外観（表面の平滑性）が良好になる。
メルトテンション限界速度の測定結果が９ｍ／ｍｉｎ未満の場合に、外観（表面の平滑性）評価「×」、９～１２ｍ／ｍｉｎ未満の場合に「△」、１２～１８ｍ／ｍｉｎ未満の場合に「〇」、１８ｍ／ｍｉｎ以上の場合に「◎」とした。
The melt tension limit speed was measured based on JIS K7199. The measurement conditions were a temperature of 200° C. and an extrusion speed of 10 m/min.
The melt tension limit speed is the take-up speed at which breakage occurs due to accelerated take-up during melt extrusion of a resin. The higher the limit speed, the less likely the molten resin will break, resulting in a better appearance (surface smoothness) of the molded product.
When the measurement result of the melt tension limit speed was less than 9 m/min, the appearance (surface smoothness) was evaluated as "x", when it was 9 to less than 12 m/min, it was evaluated as "△", when it was 12 to less than 18 m/min, it was evaluated as "◯", and when it was 18 m/min or more, it was evaluated as "◎".
線膨張係数の測定方法は、長さ１０００ｍｍのサンプルを２０℃の恒温槽に８時間収納した後、サンプルの長さＬｃを測定し、次に６０℃の恒温槽に８時間収納した後、サンプルの長さＬｈを測定し、その値を用いて線膨張係数＝（Ｌｈ－Ｌｃ）／［Ｌｃ（６０－２０）］の式によって線膨張係数（単位：／℃）を算出した。 The linear expansion coefficient was measured by storing a 1000 mm long sample in a thermostatic chamber at 20°C for 8 hours, measuring the length Lc of the sample, then storing it in a thermostatic chamber at 60°C for 8 hours, measuring the length Lh of the sample, and using these values to calculate the linear expansion coefficient (unit: /°C) according to the formula: linear expansion coefficient = (Lh-Lc)/[Lc(60-20)].
実施例１は、ポリエチレン１００重量部、再生炭素繊維（チョップド）１０重量部、イミン変性ポリオレフィン樹脂１重量部からなるポリオレフィン樹脂組成物の例である。
実施例１の成形体は、シャルピー衝撃強度（ノッチあり）が１０．１ＫＪ／ｍ２、メルトテンション限界速度１２．７ｍ／ｍｉｎ、外観（平滑性）「〇」、線膨張係数（２０℃→６０℃）が５．２×１０ －５ ／℃であり、十分な耐衝撃強度（シャルピー衝撃強度が十分に大きく）があり、外観の平滑性が良好で線膨張係数が十分に小さいものであった。
Example 1 is an example of a polyolefin resin composition comprising 100 parts by weight of polyethylene, 10 parts by weight of recycled carbon fiber (chopped), and 1 part by weight of imine-modified polyolefin resin.
The molded product of Example 1 had a Charpy impact strength (with notch) of 10.1 KJ/ m2 , a melt tension limit speed of 12.7 m/min, an appearance (smoothness) of "Good", and a linear expansion coefficient (20°C to 60°C) of 5.2 x 10-5 /°C, and thus had sufficient impact strength (sufficiently high Charpy impact strength), good appearance smoothness, and a sufficiently small linear expansion coefficient.
実施例２は、実施例１におけるイミン変性ポリオレフィン樹脂を３重量部に増加させ、他を実施例１と同様にした例である。
実施例２の成形体は、シャルピー衝撃強度（ノッチあり）が１６．９ＫＪ／ｍ２、メルトテンション限界速度１７．１ｍ／ｍｉｎ、外観（平滑性）「〇」、線膨張係数（２０℃→６０℃）が２．７×１０ －５ ／℃であり、実施例１よりも耐衝撃強度が大きく、外観の平滑性が良好で線膨張係数が小さいものであった。
Example 2 is an example in which the amount of the imine-modified polyolefin resin in Example 1 was increased to 3 parts by weight, and the other parts were the same as Example 1.
The molded product of Example 2 had a Charpy impact strength (with notch) of 16.9 kJ/ m2 , a melt tension limit speed of 17.1 m/min, an appearance (smoothness) of "Good", and a linear expansion coefficient (20°C → 60°C) of 2.7 × 10-5 /°C. Thus, it had greater impact strength, better appearance smoothness, and a smaller linear expansion coefficient than Example 1.
実施例３は、実施例１におけるイミン変性ポリオレフィン樹脂を５重量部に増加させ、他を実施例１と同様にした例である。
実施例３の成形体は、シャルピー衝撃強度（ノッチあり）が１６．１ＫＪ／ｍ２、メルトテンション限界速度１６．８ｍ／ｍｉｎ、外観（平滑性）「〇」、線膨張係数（２０℃→６０℃）が３．４×１０ －５ ／℃であり、実施例１よりも耐衝撃強度が大きく、外観の平滑性が良好で線膨張係数が小さいものであった。
Example 3 is an example in which the amount of the imine-modified polyolefin resin in Example 1 was increased to 5 parts by weight, and the other parts were the same as Example 1.
The molded product of Example 3 had a Charpy impact strength (with notch) of 16.1 kJ/ m2 , a melt tension limit speed of 16.8 m/min, an appearance (smoothness) of "Good", and a linear expansion coefficient (20°C → 60°C) of 3.4 × 10-5 /°C. Thus, it had greater impact strength, better appearance smoothness, and a smaller linear expansion coefficient than Example 1.
実施例４は、実施例２における再生炭素繊維（チョップド）１０重量部に代えて再生炭素繊維（ミルド）１０重量部を配合し、他を実施例２と同様にした例である。
実施例４の成形体は、シャルピー衝撃強度（ノッチあり）が２１．７ＫＪ／ｍ２、メルトテンション限界速度１８．６ｍ／ｍｉｎ、外観（平滑性）「◎」、線膨張係数（２０℃→６０℃）が８．５×１０ －５ ／℃であった。
実施例４は、実施例２の再生炭素繊維（チョップド）に代えて再生炭素繊維（ミルド）を配合した結果、実施例２よりも耐衝撃強度が大きく、外観の平滑性が良好になったが、線膨張係数については実施例２よりも大きくなった。
Example 4 is an example in which 10 parts by weight of recycled carbon fiber (milled) was used instead of 10 parts by weight of recycled carbon fiber (chopped) in Example 2, and the other parts were the same as Example 2.
The molded product of Example 4 had a Charpy impact strength (notched) of 21.7 KJ/m 2 , a melt tension limit speed of 18.6 m/min, an appearance (smoothness) of "Excellent", and a linear expansion coefficient (20°C→60°C) of 8.5×10 -5 /°C.
In Example 4, recycled carbon fiber (milled) was used instead of the recycled carbon fiber (chopped) in Example 2. As a result, the impact resistance was greater than that of Example 2 and the smoothness of the appearance was improved, but the linear expansion coefficient was greater than that of Example 2.
比較例１は、ポリエチレン１００重量部、再生炭素繊維（チョップド）１０重量部からなり、イミン変性ポリオレフィン樹脂を含まないポリオレフィン樹脂組成物の例であり、実施例１とは、イミン変性ポリオレフィン樹脂を含まないことのみで相違する。
比較例１の成形体は、シャルピー衝撃強度（ノッチあり）が７．８ＫＪ／ｍ２、メルトテンション限界速度８．６ｍ／ｍｉｎ、外観（平滑性）「×」、線膨張係数（２０℃→６０℃）が６．１×１０ －５ ／℃であった。
比較例１は、イミン変性ポリオレフィン樹脂を含まないため、イミン変性ポリオレフィン樹脂を含む実施例１と比べて、耐衝撃強度が小さく（シャルピー衝撃強度の値が小さく）、外観の平滑性が悪く、線膨張係数が大きくなった。
Comparative Example 1 is an example of a polyolefin resin composition consisting of 100 parts by weight of polyethylene and 10 parts by weight of recycled carbon fiber (chopped) and does not contain imine-modified polyolefin resin, and differs from Example 1 only in that it does not contain imine-modified polyolefin resin.
The molded product of Comparative Example 1 had a Charpy impact strength (notched) of 7.8 KJ/m 2 , a melt tension limit speed of 8.6 m/min, an appearance (smoothness) of "x", and a linear expansion coefficient (20°C→60°C) of 6.1×10 -5 /°C.
Since Comparative Example 1 did not contain the imine-modified polyolefin resin, it had lower impact strength (lower Charpy impact strength value), poorer smoothness in appearance, and a higher linear expansion coefficient than Example 1, which contained the imine-modified polyolefin resin.
比較例２は、ポリエチレン１００重量部、再生炭素繊維（チョップド）１０重量部と、酸変性ポリオレフィン樹脂３重量部からなるポリオレフィン樹脂組成物の例であり、実施例２におけるイミン変性ポリオレフィン樹脂３重量部に代えて酸変性ポリオレフィン樹脂３重量部を含む例である。
比較例２の成形体は、シャルピー衝撃強度（ノッチあり）が１０．３ＫＪ／ｍ２、メルトテンション限界速度１１．６ｍ／ｍｉｎ、外観（平滑性）「△」、線膨張係数（２０℃→６０℃）が５．６×１０ －５ ／℃であった。
比較例２は、酸変性ポリオレフィン樹脂を３重量部含むため、酸変性ポリオレフィン樹脂及びイミン変性ポリオレフィン樹脂を含まない比較例１と比べ、耐衝撃強度、外観の平滑性及び線膨張係数の全てにおいて僅かに改善されたが、イミン変性ポリオレフィン樹脂を３重量部含む実施例２と比べると、耐衝撃強度、外観の平滑性及び線膨張係数の全てについて劣っていた。
Comparative Example 2 is an example of a polyolefin resin composition consisting of 100 parts by weight of polyethylene, 10 parts by weight of recycled carbon fiber (chopped), and 3 parts by weight of acid-modified polyolefin resin, and is an example that contains 3 parts by weight of acid-modified polyolefin resin instead of the 3 parts by weight of imine-modified polyolefin resin in Example 2.
The molded product of Comparative Example 2 had a Charpy impact strength (notched) of 10.3 KJ/m 2 , a melt tension limit speed of 11.6 m/min, an appearance (smoothness) of "Δ", and a linear expansion coefficient (20°C→60°C) of 5.6×10 -5 /°C.
Comparative Example 2 contained 3 parts by weight of an acid-modified polyolefin resin, and therefore showed slight improvements in all of the impact strength, smoothness of appearance, and linear expansion coefficient compared to Comparative Example 1, which did not contain an acid-modified polyolefin resin or an imine-modified polyolefin resin. However, compared to Example 2, which contained 3 parts by weight of an imine-modified polyolefin resin, it was inferior in all of the impact strength, smoothness of appearance, and linear expansion coefficient.
比較例３は、ポリエチレン１００重量部、再生炭素繊維（チョップド）１０重量部と、酸変性ポリオレフィン樹脂５重量部からなるポリオレフィン樹脂組成物の例であり、実施例３におけるイミン変性ポリオレフィン樹脂５重量部に代えて酸変性ポリオレフィン樹脂５重量部を含む例である。
比較例３の成形体は、シャルピー衝撃強度（ノッチあり）が１０．７ＫＪ／ｍ２、メルトテンション限界速度１１．３ｍ／ｍｉｎ、外観（平滑性）「△」、線膨張係数（２０℃→６０℃）が６．２×１０ －５ ／℃であった。
比較例３は、酸変性ポリオレフィン樹脂を比較例２の３重量部から５重量部に増加させたが、耐衝撃強度、外観の平滑性及び線膨張係数の全てにおいて、比較例２と比べて殆ど変化がなく、イミン変性ポリオレフィン樹脂を５重量部含む実施例３と比べると、耐衝撃強度、外観の平滑性及び線膨張係数の全てについて劣っていた。
Comparative Example 3 is an example of a polyolefin resin composition consisting of 100 parts by weight of polyethylene, 10 parts by weight of recycled carbon fiber (chopped), and 5 parts by weight of acid-modified polyolefin resin, and is an example that contains 5 parts by weight of acid-modified polyolefin resin instead of 5 parts by weight of imine-modified polyolefin resin in Example 3.
The molded product of Comparative Example 3 had a Charpy impact strength (notched) of 10.7 KJ/m 2 , a melt tension limit speed of 11.3 m/min, an appearance (smoothness) of "△", and a linear expansion coefficient (20°C→60°C) of 6.2×10 -5 /°C.
In Comparative Example 3, the amount of acid-modified polyolefin resin was increased from 3 parts by weight in Comparative Example 2 to 5 parts by weight, but there was almost no change in impact strength, smoothness of appearance, and linear expansion coefficient compared to Comparative Example 2, and the impact strength, smoothness of appearance, and linear expansion coefficient were all inferior to Example 3, which contained 5 parts by weight of imine-modified polyolefin resin.
このように、本発明のポリオレフィン樹脂組成物、再生炭素繊維強化樹脂成形体、再生炭素繊維強化樹脂ペレットの製造方法、及び再生炭素繊維強化樹脂成形体の製造方法は、品質の良好な再生炭素繊維強化樹脂成形体を得ることができる。 In this way, the polyolefin resin composition, the method for producing recycled carbon fiber reinforced resin molded body, the method for producing recycled carbon fiber reinforced resin pellets, and the method for producing recycled carbon fiber reinforced resin molded body of the present invention can produce high-quality recycled carbon fiber reinforced resin molded body.
Claims (3)
（Ａ）ＪＩＳ Ｋ７１１１に基づくシャルピー衝撃強度（ノッチあり）が１０．１ＫＪ／ｍ２以上、
（Ｂ）ＪＩＳ Ｋ７１９９に基づくメルトテンション限界速度が、温度２００℃、押出速度１０ｍ／ｍｉｎにおいて１２ｍ／ｍｉｎ以上、
（Ｃ）以下の条件（ｉ）における線膨張係数が８．５×１０－５／℃以下、
（ｉ）長さ１０００ｍｍのサンプルを２０℃の恒温槽に８時間収納した後、サンプルの長さＬｃを測定し、次に６０℃の恒温槽に８時間収納した後、サンプルの長さＬｈを測定し、その値を用いて線膨張係数＝（Ｌｈ－Ｌｃ）／［Ｌｃ（６０－２０）］の式によって線膨張係数（単位：／℃）を算出する、
（Ｄ）前記ポリオレフィン樹脂は、低密度ポリエチレン（ＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、エチレン－酢酸ビニル共重合体樹脂、エチレン－プロピレン共重合体、エチレン－ブテン共重合体、エチレンとメチル、エチル、プロピル若しくはブチルの各アクリル酸エステルとの共重合体、低密度ポリエチレン（ＬＤＰＥ）の塩素化物、高密度ポリエチレン（ＨＤＰＥ）の塩素化物、エチレン－酢酸ビニル共重合体樹脂の塩素化物、エチレン－プロピレン共重合体の塩素化物、エチレン－ブテン共重合体の塩素化物、エチレンとメチル、エチル、プロピル若しくはブチルの各アクリル酸エステルとの共重合体の塩素化物；前記で列挙した化合物の混合物；及び前記で列挙した化合物とアイソタクチックポリプロピレン若しくはアタクチックポリプロピレンとの混合物からなる群から選択される少なくとも一つであり、前記再生炭素繊維は、前記ポリオレフィン樹脂１００重量部に対し、５～１０重量部である。 A polyolefin resin composition comprising a polyolefin resin, recycled carbon fibers, and an imine-modified polyolefin resin, and satisfying the following (D) and at least one of (A) to (C).
(A) Charpy impact strength (notched) based on JIS K7111 is 10.1 KJ / m2 or more;
(B) The melt tension limit speed based on JIS K7199 is 12 m/min or more at a temperature of 200 ° C. and an extrusion speed of 10 m/min;
(C) a linear expansion coefficient under the following condition (i) is 8.5×10 −5 /° C. or less;
(i) A sample having a length of 1000 mm is stored in a thermostatic bath at 20° C. for 8 hours, and then the length Lc of the sample is measured. Then, the sample is stored in a thermostatic bath at 60° C. for 8 hours, and the length Lh of the sample is measured. The linear expansion coefficient (unit: /° C.) is calculated using the linear expansion coefficient value according to the formula: linear expansion coefficient=(Lh-Lc)/[Lc(60-20)].
(D) The polyolefin resin is at least one selected from the group consisting of low density polyethylene (LDPE), high density polyethylene (HDPE), ethylene-vinyl acetate copolymer resin, ethylene-propylene copolymer, ethylene-butene copolymer, copolymer of ethylene and methyl, ethyl, propyl or butyl acrylate ester, chlorinated low density polyethylene (LDPE), chlorinated high density polyethylene (HDPE), chlorinated ethylene-vinyl acetate copolymer resin, chlorinated ethylene-propylene copolymer, chlorinated ethylene-butene copolymer, chlorinated copolymer of ethylene and methyl, ethyl, propyl or butyl acrylate ester; mixtures of the compounds listed above ; and mixtures of the compounds listed above with isotactic polypropylene or atactic polypropylene, and the recycled carbon fiber is 5 to 10 parts by weight relative to 100 parts by weight of the polyolefin resin.
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| JP7742216B2 (en) | 2025-09-19 |
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