JP2011523430A - Composite containing kenaf microfiber blended with polypropylene or polylactic acid - Google Patents

Composite containing kenaf microfiber blended with polypropylene or polylactic acid Download PDF

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JP2011523430A
JP2011523430A JP2011509169A JP2011509169A JP2011523430A JP 2011523430 A JP2011523430 A JP 2011523430A JP 2011509169 A JP2011509169 A JP 2011509169A JP 2011509169 A JP2011509169 A JP 2011509169A JP 2011523430 A JP2011523430 A JP 2011523430A
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kenaf
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スビヤット
バムバング スビヤント
エウイス ヘルミアティ
デデ ヘリ ユリ ヤント
フィトリア
クルニア ウィジ プラセトヨ
イスマリ ブディマン
イスマディ
ウィングキー クルニアワン
隆嗣 稲生
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Indonesian Institute Of Sciences Lipi
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond

Abstract

本発明は、ケナフ(Hibiscus cannabinus)靭皮微繊維と、ポリプロピレン及び/又はポリ乳酸のポリマーとの混合物を含み、上記微繊維を２０〜８０重量％含有している複合材料に関する。本発明によれば、ケナフ微繊維とポリプロピレン又はポリ乳酸のマトリックスとを含む、高強度で環境にやさしい自動車構成材のための複合材料を達成できる。
【選択図】なしThe present invention relates to a composite material containing a mixture of kenaf (Hibiscus cannabinus) bast microfibers and a polymer of polypropylene and / or polylactic acid and containing 20 to 80% by weight of the microfibers. ADVANTAGE OF THE INVENTION According to this invention, the composite material for the automotive component which is high intensity | strength and which is easy to contain including the matrix of a kenaf microfiber and a polypropylene or polylactic acid can be achieved.
[Selection figure] None

Description

本発明は自動車構成材に適用するコンポジット材及びこれを生産する方法に関する。特に、本発明は、ケナフ靭皮ミクロ繊維とポリプロピレン（ＰＰ）またはポリ乳酸（ＰＬＡ）とから構成される、高強度及び環境にやさしいコンポジット材に関する。   The present invention relates to a composite material applied to automobile components and a method for producing the same. In particular, the present invention relates to a high-strength and environmentally friendly composite material composed of kenaf bast microfiber and polypropylene (PP) or polylactic acid (PLA).

クリーンな開発計画による環境品質の改良は、世界中の大部分の国中の優先的な問題である。例えば、自動車産業において、ガラス繊維、炭素及びアラミド繊維のような環境を汚染する材料を利用することが徐々に削減され、「緑色の車（Green Car）」を作るために、代わりに天然繊維が利用される。例えば、欧州連合の使用済み自動車計画では、２０１５年に、すべての新車が９５％のリサイクル可能な材料を有するべきであると要求している（Marsh 2003）。したがって、天然繊維で補強される複合体は、重要な役割を演じ、この世紀における革命的な材料となる可能性がある（Marsh 2003）。合成繊維と比較して天然繊維を使用する幾つかの効果としては、更新可能であること、生物分解性があること、リサイクル可能であること、環境及び健康に非毒性であること、より軽い密度であること、より良好な機械的特性を示すこと、器具に対して非研磨性であること、及び低い価格であることが挙げられる（Zimmermann et al. 2004, Oksman et al. 2003, Wambua et al. 2003, Mohanty et al. 2002, Leao et al. 1998）。天然繊維を利用することで、４０％まで自動車重量を低減し、グラスファイバ（３０ＧＪ／トン）と比較して天然繊維製造に要するエネルギーを低減できる（４ＧＪ／トン）。また、グラスファイバの製造により毒性ガス（例えばＣＯ２、窒素酸化物、ＳＯｘ及びダスト）が放出される（Marsh 2003）。天然繊維複合体の利用によって多くの利点が得られるが、幾つかの欠点も認識される。天然繊維は親水性という性質をもち、疎水性である高分子マトリックスと組み合わせても、相溶性が低い。天然繊維は、繊維脆化を回避するため約２００℃程度といった低温での処理が必要となる(Nakagaito et al. 2005)。この欠点を克服するため、基質中にカップリング剤を添加したり、改良された処理方法を適用したりする。 Improving environmental quality through a clean development plan is a priority issue in most countries around the world. For example, in the automotive industry, the use of environmentally polluting materials such as glass fiber, carbon and aramid fibers has been gradually reduced, and instead of using natural fibers to create a “Green Car”. Used. For example, the European Union end-of-life vehicle program requires that all new cars should have 95% recyclable materials in 2015 (Marsh 2003). Therefore, composites reinforced with natural fibers play an important role and could be a revolutionary material in this century (Marsh 2003). Some effects of using natural fibers compared to synthetic fibers are: renewable, biodegradable, recyclable, non-toxic to the environment and health, lighter density , Better mechanical properties, non-abrasive to the instrument, and low cost (Zimmermann et al. 2004, Oksman et al. 2003, Wambua et al 2003, Mohanty et al. 2002, Leao et al. 1998). By using natural fibers, the vehicle weight can be reduced to 40%, and the energy required for natural fiber production can be reduced (4 GJ / ton) compared to glass fiber (30 GJ / ton). In addition, the production of glass fibers releases toxic gases (eg CO 2 , nitrogen oxides, SO x and dust) (Marsh 2003). Although the use of natural fiber composites provides many advantages, several disadvantages are also recognized. Natural fibers have a hydrophilic property and have low compatibility even when combined with a hydrophobic polymer matrix. Natural fibers need to be treated at a low temperature of about 200 ° C. to avoid fiber embrittlement (Nakagaito et al. 2005). In order to overcome this drawback, a coupling agent is added to the substrate or an improved processing method is applied.

十分な可能性がある天然繊維の一種としてケナフ（Hibiscus cannabinus）がある。ケナフは、高さが４〜５ｍに達し、茎計が４〜５ｃｍとなる一年草であり、成長速度が速い。ケナフは一年中植えることができ、そして、いかなる高所でも育つ、収穫時間は約１２０日間である。乾燥重量基準に、本幹上の靭皮繊維含有量は２１％から３６％の範囲である。ケナフ靭皮繊維の寸法は、長さ２〜３ｍｍおよび幅１５〜２５マイクロメートルである。   One kind of natural fiber that has sufficient potential is kenaf (Hibiscus cannabinus). Kenaf is an annual grass with a height of 4 to 5 m and a stem total of 4 to 5 cm, and has a high growth rate. Kenaf can be planted all year round and grows at any height, harvest time is about 120 days. Based on dry weight, the bast fiber content on the trunk is in the range of 21% to 36%. The dimensions of kenaf bast fibers are 2-3 mm long and 15-25 micrometers wide.

ケナフ靭皮繊維を化学内容は、以下の通りである：
セルロース（４４〜６２％）、ヘミセルロース（１４〜２０％）、リグニン（６〜９％）及びペクチン（４〜５％）。 The chemical content of kenaf bast fiber is as follows:
Cellulose (44-62%), hemicellulose (14-20%), lignin (6-9%) and pectin (4-5%).

ケナフ靭皮繊維を密度は１．４７ｇ／ｃｍ３であるが、引張り強度は４７９〜１６００ＭＰａであり、ヤング率は１８．２ＧＰａである。工業に使用される原料としてケナフには十分な可能性がある。これは、収量が1ｈａにつき約１．５〜５トン（乾燥繊維換算）であるからである。ケナフは、速い光合成速度を有することを意味する１日７〜８ｃｍの速さで生育し、大量の二酸化炭素を吸収できる。それ故、地球温暖化を低減するために植えることができる。 The density of the kenaf bast fiber is 1.47 g / cm 3 , but the tensile strength is 479 to 1600 MPa, and the Young's modulus is 18.2 GPa. Kenaf has sufficient potential as a raw material used in industry. This is because the yield is about 1.5 to 5 tons (in terms of dry fiber) per ha. Kenaf grows at a rate of 7-8 cm per day, meaning it has a fast photosynthetic rate, and can absorb large amounts of carbon dioxide. Therefore it can be planted to reduce global warming.

繊維サイズは、自動車構成材のための複合体を製造する際に非常に重要な因子となる。複合体の強度を向上させるため、ミクロ原線維セルロース（MFC）のような、より小さな繊維サイズが必要とされる。米国特許２００６０１４７６９５は、１００マイクロメートル〜２０ｍｍのケナフ繊維とポリ乳酸の高分子マトリックスとを含む、ケナフ繊維強化複合体を電気および電子設備製品に使用することを記載している。   Fiber size is a very important factor in producing composites for automotive components. In order to improve the strength of the composite, smaller fiber sizes, such as microfibrillar cellulose (MFC), are required. U.S. Patent No. 20060147695 describes the use of kenaf fiber reinforced composites for electrical and electronic equipment products comprising kenaf fibers of 100 micrometers to 20 mm and a polymeric matrix of polylactic acid.

米国特許第５９７３０３５号は、樹脂（例えば熱可塑性樹脂）と、少なくとも約２重量％（より好ましくは、少なくとも約５重量％）の織地化されたセルロース系繊維又はリグノセルロース系繊維とを含む複合体に特徴を有する発明を記述している。また、この発明は、ポリエチレンと少なくとも約５０重量％の織地化されたセルロース系繊維又はリグノセルロース系繊維とを含む複合体に特徴を有する。当該複合体は、少なくとも約３，０００ｐｓｉの曲げ強度又は少なくとも約３，０００ｐｓｉを引張り強度を有している。複合体を製造する方法は、セルロース系繊維又はリグノセルロース系繊維をせん断して、織地化されたセルロース系繊維又はリグノセルロース系繊維を形成する工程と、せん断された繊維に樹脂を組み合わせる工程とを含んでいる。この方法において、回転ナイフ・カッターで繊維をせん断することが好ましい。せん断することにより、内部の繊維が実質的に曝されることになる。せん断した後、織地化されたセルロース系繊維又はリグノセルロース系繊維の少なくとも約５０％（より好ましくは、少なくとも約７０％）は、長さ／直径（Ｌ／Ｄ）比率が少なくとも５、より好ましくは少なくとも２５又は少なくとも５０となる。   US Pat. No. 5,973,035 discloses a composite comprising a resin (eg, a thermoplastic resin) and at least about 2% by weight (more preferably at least about 5% by weight) of woven cellulosic or lignocellulosic fibers. The invention having the characteristics is described. The invention is also characterized by a composite comprising polyethylene and at least about 50% by weight of woven cellulosic or lignocellulosic fibers. The composite has a flexural strength of at least about 3,000 psi or a tensile strength of at least about 3,000 psi. A method for producing a composite includes a step of shearing cellulosic fibers or lignocellulosic fibers to form a woven cellulose fiber or lignocellulosic fibers, and a step of combining a resin with the sheared fibers. Contains. In this method, it is preferable to shear the fiber with a rotary knife / cutter. By shearing, the internal fibers are substantially exposed. After shearing, at least about 50% (more preferably at least about 70%) of the woven cellulosic or lignocellulosic fibers have a length / diameter (L / D) ratio of at least 5, more preferably At least 25 or at least 50.

米国特許第４５５９３７６号は、セルロース原料又はリグノセルロース原料とプラスチックに基づく複合体の製造方法を記述する。この方法によれば、セルロース原料又はリグノセルロース原料は、複合化工程又は処理工程に先立って若しくはその最中に、加水分解前処理又は他の化学的分解処理に供される。これにより、セルロース原料又はリグノセルロース原料の粉砕及びプラスチックへの改善された分散を達成することができる。熱可塑性複合体は、加水分解前処理されたセルロース原料又はリグノセルロース原料を最大４０重量％含有する。マスターバッチ濃縮物は、加水分解前処理されたセルロース原料又はリグノセルロース原料を最大７０重量％含有するように製造される。   U.S. Pat. No. 4,559,376 describes a method for producing a composite based on a cellulose or lignocellulose raw material and a plastic. According to this method, the cellulose raw material or lignocellulose raw material is subjected to a hydrolysis pretreatment or other chemical decomposition treatment prior to or during the compounding step or treatment step. Thereby, the grinding | pulverization of a cellulose raw material or a lignocellulose raw material and the improved dispersion | distribution to a plastic can be achieved. The thermoplastic composite contains a cellulose raw material or lignocellulose raw material that has been pre-hydrolyzed, up to 40% by weight. The masterbatch concentrate is produced to contain up to 70% by weight of a cellulose raw material or lignocellulose raw material that has been pre-hydrolyzed.

米国特許第６９３９９０３号は、以下の工程：a)反応性オルガノシランを有する天然繊維の大きさを設定する工程；b)ポリオレフィン系樹脂と大きさを設定された天然繊維を混合する工程；c)前記大きさを設定された天然繊維及びポリオレフィン系樹脂の混合物に官能化ポリオレフィン・カップリング剤を添加して、複合体材料を提供する工程を含む、複合体材料を準備する方法を記述している。   US Pat. No. 6,939,903 discloses the following steps: a) setting the size of a natural fiber having a reactive organosilane; b) mixing a polyolefin-based resin with a set size of natural fiber; c) Describes a method of preparing a composite material, including the step of providing a composite material by adding a functionalized polyolefin coupling agent to the sized natural fiber and polyolefin resin mixture. .

米国特許第５９７３０３５号US Pat. No. 5,973,035 米国特許第４５５９３７６号U.S. Pat. No. 4,559,376 米国特許第６９３９９０３号US Pat. No. 6,939,903

本発明は、ケナフ微繊維及びポリプロピレン又はポリ乳酸マトリックスを含み、高強度で環境にやさしい、自動車構成材のための複合材料を取得することを目的としている。当該目的は、請求の範囲に述べられた製品及び方法により達成される。   The object of the present invention is to obtain a composite material for automotive components which contains kenaf fine fibers and polypropylene or polylactic acid matrix and is high in strength and environmentally friendly. The object is achieved by the products and methods described in the claims.

本発明は、ケナフ微繊維とポリプロピレン（ＰＰ）及び/又はポリ乳酸（ＰＬＡ）のポリマーとの混合物を含む、自動車構成材のための複合体製品に関する。   The present invention relates to a composite product for automotive components comprising a mixture of kenaf fine fibers and a polymer of polypropylene (PP) and / or polylactic acid (PLA).

ケナフ繊維は、まず第１に、パルプに加工され、そして、石のグラインダを使用してフィブリル化した。ケナフ繊維は、１０〜５０μｍの直径サイズを有して、好ましくは、ポリマーに混合される。   The kenaf fibers were first processed into pulp and fibrillated using a stone grinder. The kenaf fiber has a diameter size of 10-50 μm and is preferably mixed with the polymer.

ケナフ微繊維およびポリプロピレン（ＰＰ）の複合体は、例えば１７０〜１９０℃、５０〜７０ｒｐｍで１０〜３０分間、ミキサー（Ｌａｂｏ ｐｌａｓｔｏｍｉｌｌ）内で、顆粒のポリプロピレン（ＰＰ）と乾性パルプを混合することにより作られる。ケナフ微繊維の量は、４０〜８０重量％（複合体重量）とした。混合中、カップリング剤として無水マレイン酸ポリプロピレン（ＭＡＰＰ）を、例えば３〜１２．５重量％（複合体重量）添加することが好ましい。原料混合物は、Ｌａｂｏ ｐｌａｓｔｏｍｉｌｌから取り除かれ、テフロン製シートを有するプレート上に載置し、マット状とした。そして、その後、熱間圧縮加工に供した。熱間圧縮加工は、例えば１７０〜１９０℃で、例えば１ＭＰａの圧力で３０〜６０秒間で実行される。熱間圧縮加工の後、プレートは直ちに、例えば１ＭＰａの圧力で３〜７分間の冷間圧縮におかれる。その後、当該プレートよりボードが取り出される。   The composite of kenaf fine fiber and polypropylene (PP) is obtained by mixing granular polypropylene (PP) and dry pulp in a mixer (Labo plasticmill) for 10 to 30 minutes at 170 to 190 ° C. and 50 to 70 rpm, for example. Made. The amount of kenaf fine fiber was 40 to 80% by weight (composite weight). During mixing, it is preferable to add, for example, 3 to 12.5% by weight (complex weight) of maleic anhydride polypropylene (MAPP) as a coupling agent. The raw material mixture was removed from the Labo plastomill and placed on a plate having a Teflon sheet to form a mat. Then, it was subjected to hot compression processing. Hot compression processing is performed at 170 to 190 ° C., for example, at a pressure of 1 MPa for 30 to 60 seconds, for example. After hot pressing, the plate is immediately subjected to cold pressing for 3-7 minutes, for example at a pressure of 1 MPa. Thereafter, the board is removed from the plate.

ケナフ微繊維とポリ乳酸（ＰＬＡ）との複合体ボードは以下のようになされる。まず第１に、ＰＬＡをジクロロメタン中に溶解し、室温で撹拌する。ウェットパルプを溶解したＰＬＡに投入し、ホモジナイズされるまで撹拌する。混合中、可塑剤としてトリアセチンを例えば３〜９重量％（複合体重量）で添加することが好ましい。ケナフ微繊維の量は、３０〜６０重量％（複合体重量）とすることが好ましい。混合物は、オーブンの中で、例えば６０〜１０５℃、１２〜３６時間で乾燥される。乾燥した混合物は、例えば１６０〜１８０℃、５０〜７０ｒｐｍで１０〜３０分間、ミキサー（Ｌａｂｏ ｐｌａｓｔｏｍｉｌｌ）内で更に処理される。混合物は、取り除かれ、テフロン製シートを有するプレート上に載置し、マット状とした。そして、その後、熱間圧縮加工に供した。熱間圧縮加工は、例えば１７０〜１９０℃で、例えば１ＭＰａの圧力で３０〜６０秒間で実行される。熱間圧縮加工の後、プレートは直ちに、例えば１ＭＰａの圧力で３〜７分間の冷間圧縮におかれる。その後、当該プレートよりボードが取り出される。   A composite board of kenaf fine fibers and polylactic acid (PLA) is made as follows. First, PLA is dissolved in dichloromethane and stirred at room temperature. The wet pulp is put into the dissolved PLA and stirred until homogenized. During mixing, it is preferable to add 3-9% by weight (complex weight) of triacetin as a plasticizer. The amount of kenaf fine fiber is preferably 30 to 60% by weight (composite weight). The mixture is dried in an oven, for example at 60-105 ° C. for 12-36 hours. The dried mixture is further processed in a mixer (Labo plastmill), for example at 160-180 ° C., 50-70 rpm for 10-30 minutes. The mixture was removed and placed on a plate with a Teflon sheet to form a mat. Then, it was subjected to hot compression processing. Hot compression processing is performed at 170 to 190 ° C., for example, at a pressure of 1 MPa for 30 to 60 seconds, for example. After hot pressing, the plate is immediately subjected to cold pressing for 3-7 minutes, for example at a pressure of 1 MPa. Thereafter, the board is removed from the plate.

下記の図を使用して本発明を詳述した。   The invention has been described in detail using the following figures.

図１は、本発明に係る、ポリプロピレン（ＰＰ）とケナフ微繊維の複合体に関する調製法プロセスのフローチャートを示す。FIG. 1 shows a flow chart of a preparation process for a composite of polypropylene (PP) and kenaf fine fibers according to the present invention. 図２は、本発明に係る、ポリ乳酸（ＰＬＡ）とケナフ微繊維の複合体に関する調製法プロセスのフローチャートを示す。FIG. 2 shows a flowchart of the preparation process for a composite of polylactic acid (PLA) and kenaf microfibers according to the present invention.

まず第１に、ケナフ繊維をパルプに加工し、そして、石のグラインダを使用してフィブリル化することで、好ましくは１０〜５０μｍのサイズを有するようにし、ポリマーに混合された。   First, the kenaf fibers were processed into pulp and fibrillated using a stone grinder, preferably having a size of 10-50 μm and mixed with the polymer.

図１に従って、ケナフ微繊維およびポリプロピレン（ＰＰ）の複合体は、例えば１７０〜１９０℃、５０〜７０ｒｐｍで１０〜３０分間、ミキサー（Ｌａｂｏ ｐｌａｓｔｏｍｉｌｌ）内で、顆粒のポリプロピレン（ＰＰ）と乾性パルプを混合することにより作られた。ケナフ微繊維の量は、４０、５０、６０、７０及び８０重量％（複合体重量）とした。混合中、カップリング剤として無水マレイン酸ポリプロピレン（ＭＡＰＰ）を、３、５、７．５、１０及び１２．５重量％（複合体重量）となるように添加した。原料混合物は、Ｌａｂｏ ｐｌａｓｔｏｍｉｌｌから取り除かれ、テフロン製シートを有するプレート上に載置し、マット状とした。そして、その後、熱間圧縮加工に供した。熱間圧縮加工は、１７０〜１９０℃で、１ＭＰａの圧力で３０〜６０秒間で実行した。熱間圧縮加工の後、プレートは直ちに、１ＭＰａの圧力で３〜７分間の冷間圧縮におかれた。その後、当該プレートよりボードが取り出された。   According to FIG. 1, a composite of kenaf fine fiber and polypropylene (PP) is obtained by mixing granular polypropylene (PP) and dry pulp in a mixer (Labo plastic mill) for 10 to 30 minutes at 170 to 190 ° C. and 50 to 70 rpm, for example. Made by mixing. The amount of kenaf fine fiber was 40, 50, 60, 70 and 80% by weight (composite weight). During the mixing, maleic anhydride polypropylene (MAPP) was added as a coupling agent to 3, 5, 7.5, 10, and 12.5% by weight (complex weight). The raw material mixture was removed from the Labo plastomill and placed on a plate having a Teflon sheet to form a mat. Then, it was subjected to hot compression processing. The hot compression process was performed at 170 to 190 ° C. and a pressure of 1 MPa for 30 to 60 seconds. After hot pressing, the plate was immediately placed in cold compression for 3-7 minutes at a pressure of 1 MPa. Thereafter, the board was removed from the plate.

図２に従って、ケナフ微繊維とポリ乳酸（ＰＬＡ）との複合体ボードは以下のようになされる。まず第１に、ＰＬＡをジクロロメタン中に溶解し、室温で撹拌した。ウェットパルプと可塑剤としてのトリアセチンとを、溶解したＰＬＡに投入し、ホモジナイズされるまで撹拌した。ケナフ微繊維の量は、３０、４０、５０及び６０重量％（複合体重量）とした。添加されたトリアセチンの量は、３、５、７及び９重量％（複合体重量）とした。混合物は、オーブンの中で６０〜１０５℃、１２〜３６時間で乾燥された。乾燥した混合物は、１６０〜１８０℃、５０〜７０ｒｐｍで１０〜３０分間、ミキサー（Ｌａｂｏ ｐｌａｓｔｏｍｉｌｌ）内で更に処理された。混合物は、取り除かれ、テフロン製シートを有するプレート上に載置し、マット状とした。そして、その後、熱間圧縮加工に供した。熱間圧縮加工は、１７０〜１９０℃、１ＭＰａの圧力で３０〜６０秒間で実行された。熱間圧縮加工の後、プレートは直ちに、１ＭＰａの圧力で３〜７分間の冷間圧縮におかれた。その後、当該プレートよりボードが取り出された。   According to FIG. 2, the composite board of kenaf fine fiber and polylactic acid (PLA) is made as follows. First, PLA was dissolved in dichloromethane and stirred at room temperature. Wet pulp and triacetin as a plasticizer were added to the dissolved PLA and stirred until homogenized. The amount of kenaf fine fiber was 30, 40, 50 and 60% by weight (composite weight). The amount of triacetin added was 3, 5, 7, and 9% by weight (complex weight). The mixture was dried in an oven at 60-105 ° C. for 12-36 hours. The dried mixture was further processed in a mixer (Labo blastmill) at 160-180 ° C., 50-70 rpm for 10-30 minutes. The mixture was removed and placed on a plate with a Teflon sheet to form a mat. Then, it was subjected to hot compression processing. The hot compression processing was performed at 170 to 190 ° C. and 1 MPa for 30 to 60 seconds. After hot pressing, the plate was immediately placed in cold compression for 3-7 minutes at a pressure of 1 MPa. Thereafter, the board was removed from the plate.

得られたボードを５０ｘ１５０ｍｍの供試片に加工した。供試片の両端を１００ｍｍの幅長を有するように自由に支持した。上記幅長の中心に５０ｍｍ／分で荷重をかけ、たわみ量を測定した。そして、それぞれの供試片につき、荷重-たわみ曲線が得られた。供試片が破壊される荷重の値を最大曲げ荷重（５０ｍｍ幅における）と定義した。曲げ弾性勾配は、荷重-たわみ曲線の荷重初期での線形領域における歪み量及び曲げ荷重から計算される、１ｃｍのたわみでの曲げ荷重として定義される。試験結果を表１〜４に示した。   The obtained board was processed into a 50 × 150 mm test piece. Both ends of the test piece were freely supported so as to have a width of 100 mm. A load was applied to the center of the width length at 50 mm / min, and the amount of deflection was measured. A load-deflection curve was obtained for each specimen. The value of the load at which the specimen was broken was defined as the maximum bending load (at 50 mm width). The bending elastic gradient is defined as a bending load at a deflection of 1 cm, which is calculated from a strain amount and a bending load in the linear region at the initial stage of the load-deflection curve. The test results are shown in Tables 1-4.

Figure 2011523430
Figure 2011523430
Figure 2011523430
Figure 2011523430
Figure 2011523430
Figure 2011523430
Figure 2011523430
Figure 2011523430

上記の結果に基づいて、ケナフ微繊維及びＰＰの複合体は、５％のＭＡＰＰを添加した５０：５０の比率を有するものが好ましいといえる。一方、ケナフ微繊維及びＰＬＡの複合体は、７％のトリアセチンを添加した５０：５０の比率を有するものが好ましいといえる。   Based on the above results, it can be said that the composite of kenaf fine fiber and PP preferably has a ratio of 50:50 to which 5% MAPP is added. On the other hand, it can be said that the composite of kenaf fine fibers and PLA preferably has a ratio of 50:50 to which 7% of triacetin is added.

Claims (13)

ケナフ(Hibiscus cannabinus)靭皮微繊維と、ポリプロピレン及び/又はポリ乳酸のポリマーとの混合物を含み、上記微繊維を２０〜８０重量％含有している複合材料。   A composite material containing a mixture of kenaf (Hibiscus cannabinus) bast microfibers and a polymer of polypropylene and / or polylactic acid and containing 20 to 80% by weight of the microfibers. 上記微繊維の径が１０〜５０μｍであることを特徴とする請求項１記載の複合材料。   The composite material according to claim 1, wherein the fine fiber has a diameter of 10 to 50 μm. 上記ポリマーがポリプロピレンを有する場合、上記混合物は無水マレイン酸ポリプロピレン（MAPP）を更に含有することを特徴とする請求項１記載の複合材料。   2. The composite material according to claim 1, wherein when the polymer comprises polypropylene, the mixture further comprises maleic anhydride polypropylene (MAPP). 上記無水マレイン酸ポリプロピレン（MAPP）の含有量が３〜１２．５重量％であることを特徴とする請求項３記載の複合材料。   4. The composite material according to claim 3, wherein the content of maleic anhydride polypropylene (MAPP) is 3 to 12.5% by weight. 上記ポリマーがポリ乳酸を有する場合、上記混合物はトリアセチンを更に含有することを特徴とする請求項１記載の複合材料。   The composite material according to claim 1, wherein, when the polymer has polylactic acid, the mixture further contains triacetin. 上記トリアセチンの含有量が３〜９重量％であることを特徴とする請求項５記載の複合材料。   6. The composite material according to claim 5, wherein the content of triacetin is 3 to 9% by weight. 密度が０．８〜１．４ｇ／ｃｍ３の範囲であることを特徴とする請求項１記載の複合材料。 The composite material according to claim 1, wherein the density is in a range of 0.8 to 1.4 g / cm 3 . ケナフ(Hibiscus cannabinus)靭皮微繊維と、ポリプロピレン及び/又はポリ乳酸のポリマーとを含む複合材料の製造方法であって、
ａ）上記靭皮微繊維と上記ポリプロピレン及び/又はポリ乳酸のポリマーとを、当該微繊維が２０〜８０重量％の量で混合する工程と、
ｂ）ステップａ）の結果として得られる産物を熱間圧縮する工程と、
ｃ）ステップｂ）の結果として得られる産物を冷間圧縮する工程と
を含む製造方法。 A method for producing a composite material comprising kenaf (Hibiscus cannabinus) bast microfibers and a polymer of polypropylene and / or polylactic acid,
a) a step of mixing the bast fine fiber and the polypropylene and / or polylactic acid polymer in an amount of 20 to 80% by weight of the fine fiber;
b) hot compressing the product obtained as a result of step a);
c) cold compressing the product obtained as a result of step b). 上記微繊維の径が１０〜５０μｍであることを特徴とする請求項８記載の製造方法。   9. The production method according to claim 8, wherein the fine fiber has a diameter of 10 to 50 [mu] m. 上記ポリマーがポリプロピレンを有する場合、上記混合物は無水マレイン酸ポリプロピレン（MAPP）を更に含有することを特徴とする請求項８記載の製造方法。   9. The method according to claim 8, wherein when the polymer has polypropylene, the mixture further contains maleic anhydride polypropylene (MAPP). 上記無水マレイン酸ポリプロピレン（MAPP）の含有量が３〜１２．５重量％であることを特徴とする請求項１０記載の製造方法。   The method according to claim 10, wherein the content of the maleic anhydride polypropylene (MAPP) is 3 to 12.5% by weight. 上記ポリマーがポリ乳酸を有する場合、上記混合物はトリアセチンを更に含有することを特徴とする請求項８記載の製造方法。   9. The method according to claim 8, wherein when the polymer has polylactic acid, the mixture further contains triacetin. 上記トリアセチンの含有量が３〜９重量％であることを特徴とする請求項１２記載の製造方法。   The method according to claim 12, wherein the content of triacetin is 3 to 9% by weight.
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JP7354134B2 (en) 2018-10-03 2023-10-02 古河電気工業株式会社 Resin molded bodies and resin compositions
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