JP2011161835A - Production process of lignocellulosic filler, lignocellulosic filler produced by the process, lignocellulose-thermoplastic resin composite using the lignocellulosic filler, and molding using the lignocellulose-thermoplastic resin composite - Google Patents
Production process of lignocellulosic filler, lignocellulosic filler produced by the process, lignocellulose-thermoplastic resin composite using the lignocellulosic filler, and molding using the lignocellulose-thermoplastic resin composite Download PDFInfo
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Abstract
Description
本発明は、リグノセルロース・熱可塑性樹脂複合材料の製造に際し、樹脂との相溶性が良く、リグノセルロース充填材の比率を高めても成形時の流動性や、成形品の物性に優れたリグノセルロース系充填材およびその製造方法及び、そのリグノセルロース系充填材を用いた樹脂複合材料及び成形体に関する。 In the production of a lignocellulose / thermoplastic resin composite material, the present invention has good compatibility with the resin, and even when the ratio of the lignocellulose filler is increased, the lignocellulose has excellent flowability during molding and physical properties of the molded product. The present invention relates to a resin filler, a manufacturing method thereof, and a resin composite material and a molded body using the lignocellulose filler.
木材を粉砕して細粒化したものを充填材として用い、ポリエチレンやポリプロピレン、ポリ塩化ビニル等の熱可塑性樹脂と複合化した材料は、既に製品化され、市場に流通している。これは、木材・プラスチック成形複合体（略称『混練型ＷＰＣ』）と呼ばれている。
かかる木材・プラスチック複合体に木材を充填材として用いる理由は、耐熱性を上げる、強度を改善することのほか、樹脂に木質感を与える、原料コストを削減すること等にある。しかし、木材を始めとするリグノセルロース系材料は元来親水性で、一方樹脂は疎水性であり、いわば、水と油の関係にある。
A material obtained by pulverizing and finely pulverizing wood as a filler and composited with a thermoplastic resin such as polyethylene, polypropylene, and polyvinyl chloride has already been commercialized and distributed in the market. This is called a wood / plastic molding composite (abbreviated as “kneading type WPC”).
The reason for using wood as a filler in such a wood / plastic composite is to increase heat resistance, improve strength, give wood texture to the resin, reduce raw material costs, and the like. However, lignocellulosic materials such as wood are inherently hydrophilic, while the resin is hydrophobic, so to speak, it has a relationship between water and oil.
両者のなじみをよくするためには、親水性を持たせた樹脂（以下、相溶化剤という) を用いるのが有効である。マレイン酸変性のポリプロピレンはその代表である。実際の製品にあっても、リグノセルロース系充填材と熱可塑性樹脂の他、相溶化剤を若干添加しているが、相溶化剤は高価であるので、コスト面から添加量が限られる。したがって、リグノセルロース系充填材の添加量にも制約があり、実用上はリグノセルロース系充填材５０〜６０％、樹脂４０〜５０％が限度であった。この割合を超えてリグノセルロース系充填材を用いると、成形時の流動性が悪くなるばかりか、強度や耐朽性、抗吸湿・吸水性、寸法安定性などの諸物性も低下するためである。 In order to improve the familiarity between the two, it is effective to use a hydrophilic resin (hereinafter referred to as a compatibilizing agent). Maleic acid-modified polypropylene is a representative example. Even in an actual product, a small amount of a compatibilizer is added in addition to the lignocellulosic filler and the thermoplastic resin. However, since the compatibilizer is expensive, the amount of addition is limited from the viewpoint of cost. Therefore, the amount of lignocellulosic filler added is also limited, and the practical limits were 50-60% lignocellulosic filler and 40-50% resin. When the lignocellulose filler is used in excess of this ratio, not only the fluidity at the time of molding is deteriorated, but also various physical properties such as strength, decay resistance, anti-hygroscopicity / water absorption, and dimensional stability are lowered.
リグノセルロース系充填材の比率を６０％以上に高めるためには、リグノセルロース系充填材を疎水化して、熱可塑性樹脂との相溶性を改善することが有効と考えられる。実際、薬剤を使ってリグノセルロース系充填材を化学修飾して、疎水化する試みが、以下に示すように、実験的にはいくつか行われている。 In order to increase the ratio of the lignocellulosic filler to 60% or more, it is considered effective to improve the compatibility with the thermoplastic resin by hydrophobizing the lignocellulosic filler. In fact, several attempts have been made experimentally as shown below to chemically modify lignocellulosic fillers using chemicals to make them hydrophobic.
たとえば、特開平１０−３２９１０９（特許文献１）では、リグノセルロース系充填材を多塩基酸無水物によりエステル化することで疎水化させている。それを用いた成形品の曲げ強度は無処理のリグノセルロース系充填材を用いたときよりも顕著に優れており、また、成形性も良い旨の記載がある。 For example, in JP-A-10-329109 (Patent Document 1), a lignocellulose filler is hydrophobized by esterification with a polybasic acid anhydride. There is a description that the bending strength of a molded product using the same is remarkably superior to that when an untreated lignocellulosic filler is used, and the moldability is also good.
岐阜県生活技術研究所の研究報告（１９９９年、２９−３２ページ）（非特許文献１）には、リグノセルロース系充填材をアリル化およびアセチル化した結果についての記載があるが、これらの化学修飾により、樹脂との複合材料にあっては、抗吸湿性等の物性が改善できたとされている。 The research report of Life Technology Research Institute in Gifu Prefecture (1999, pp. 29-32) (Non-Patent Document 1) describes the results of allylation and acetylation of lignocellulosic fillers. It is said that physical properties such as anti-hygroscopic property can be improved in the composite material with resin by modification.
さらには、第５９回日本木材学会（２００９年、松本市）において、京都府立大学の関雅子氏、中嶋聖充氏、古田裕三氏、大越誠氏は、リグノセルロース系充填材をアセチル化したときのポリプロピレンとの混練性について、また、近畿大学の橋本孝氏、高谷政広氏、岡本忠氏は、リグノセルロース系充填材のアセチル化が、成形品の強度、吸水性等の物性に及ぼす影響について発表している。そのときの要旨は、第５９回日本木材学会大会研究発表要旨集収録ＣＤに収められており、それぞれ「口頭発表Ｃ１５−１６１５」（非特許文献２）、「ポスター発表ＰＩ０２１」（非特許文献３）の整理番号が付けられている。これらによると、リグノセルロース系充填材をアセチル化することで、混練性が改善できることおよび、強度性能が向上することや、吸水性が抑制できることなどが記載されている。 Furthermore, at the 59th Annual Meeting of the Wood Society of Japan (2009, Matsumoto City), Masako Seki, Seimitsu Nakajima, Yuzo Furuta, and Makoto Ohkoshi from Kyoto Prefectural University acetylated lignocellulosic fillers. Regarding the kneadability of polypropylene with polypropylene, Takashi Hashimoto, Masahiro Takaya, and Tadashi Okamoto from Kinki University commented on the effects of acetylation of lignocellulosic filler on physical properties such as strength and water absorption Announcing. The abstracts at that time are included in the 59th Annual Meeting of the Wood Society of Japan Conference Presentation Summary CD, which is “Oral Presentation C15-1615” (Non-Patent Document 2) and “Poster Presentation PI021” (Non-Patent Document 3), respectively. ) Number. According to these, it is described that kneadability can be improved, strength performance can be improved, and water absorption can be suppressed by acetylating the lignocellulose filler.
このように、木質材料からなるリグノセルロース系充填材を疎水化することの効果は認められているが、このような化学修飾は、処理方法が煩雑で、コストが嵩むために実用化には至っていないのが現状である。 Thus, although the effect of hydrophobizing the lignocellulosic filler made of a wood material is recognized, such chemical modification has not been put into practical use because the treatment method is complicated and the cost increases. is the current situation.
一方、これとは全く違った考え方で、木材等のリグノセルロース系材料そのものに流動性を付与し、石油系のプラスチックに類似した成形体を得ようとする技術もある。その技術は、いずれも高温高圧の水蒸気を利用して、リグノセルロース系材料を、あるいはその一部を加水分解して低分子化させることで熱可塑性を付与するものである。 On the other hand, based on a completely different concept, there is also a technique for imparting fluidity to a lignocellulosic material itself such as wood to obtain a molded body similar to petroleum plastic. Each of these techniques imparts thermoplasticity by hydrolyzing a lignocellulosic material or a part thereof to lower the molecular weight by utilizing high-temperature and high-pressure steam.
たとえば、特許第４０８１５７９号『リグノセルロース系材料及びその利用』（特許文献２）には、水蒸気処理で熱可塑性を付与したリグノセルロースにより成形体を製造する方法が記載されている。 For example, Japanese Patent No. 4081579 “Lignocellulosic material and use thereof” (Patent Document 2) describes a method for producing a molded body from lignocellulose to which thermoplasticity is imparted by steam treatment.
特開２００７−２８３４８９号公報には、水蒸気処理で熱可塑性を与えた木質系材料を射出成形する方法が記載されている。 Japanese Patent Application Laid-Open No. 2007-283489 describes a method of injection molding a wood-based material that has been given thermoplasticity by steam treatment.
また、特許第４３７１３７３号『木質系成形体の製造方法および木質系成形体』（特許文献４）には、圧力容器中での飽和水蒸気による加圧とその後の圧力開放、すなわち爆砕処理により、木材成分を分解して流動化させ、また粘着力を付与することで、樹脂との相溶性を改善する方法が記載されている。 Japanese Patent No. 4371373 “Manufacturing method of wood-based molded body and wood-based molded body” (Patent Document 4) describes a method of applying pressure by saturated steam in a pressure vessel and subsequent pressure release, that is, explosion treatment. A method for improving the compatibility with a resin by decomposing and fluidizing components and imparting adhesive force is described.
このように、リグノセルロース系材料中に、十分な水が存在する条件下で水蒸気処理をした場合、適度に加水分解が生じ、成分が低分子化することで、リグノセルロース系材料は熱可塑性を示す。これらの技術では、熱可塑性のプラスチックを全く使わずとも、ほぼリグノセルロース系材料のみでプラスチック様の成形体ができるという長所がある反面、湿った高温の水蒸気で処理する必要があるため、高温高圧に耐えうる閉鎖系の容器が不可欠であることが実用化の支障となっている。また、加水分解により水酸基が新たに増加するため、成形体の耐水性が低下するという懸念もある。 In this way, when steam treatment is carried out under conditions where sufficient water is present in the lignocellulosic material, the lignocellulosic material becomes thermoplastic due to moderate hydrolysis and low molecular weight components. Show. These technologies have the advantage that a plastic-like molded body can be formed using almost only lignocellulosic materials without using any thermoplastic plastics, but they must be treated with moist and hot steam. The need for a closed container that can withstand this has become a hindrance to practical application. Moreover, since a hydroxyl group newly increases by hydrolysis, there also exists a concern that the water resistance of a molded object falls.
このような状況下にあって、発明者は簡便な手法により、リグノセルロース系材料をできる限り多く用いて、石油系プラスチックと遜色のない成形性、物性が発現する成形材料を作りたいと検討を重ねてきた。その方法として、一部に熱可塑性の樹脂を使い、そこにできるだけ多くのリグノセルロース系材料を充填することが、現時点では最良と考えた。それは、上述したとおり、リグノセルロースそのものに熱可塑性を付与して成形する技術ではまだ解決すべき課題が多く、リグノセルロース・熱可塑性樹脂複合材料の方が、実用化までのハードルが低いと考えたためである。 Under such circumstances, the inventor studied using a simple method to make a molding material that uses as much lignocellulosic material as possible and exhibits molding properties and physical properties comparable to petroleum plastics. It has been repeated. As a method for this, it was considered best at the present time to partially use a thermoplastic resin and fill it with as much lignocellulosic material as possible. As described above, there are still many problems to be solved in the technology of forming a thermoplastic by imparting thermoplasticity to lignocellulose itself, and the lignocellulose / thermoplastic resin composite material is considered to have lower hurdles until practical use. It is.
そこで、リグノセルロース系材料の疎水化方法について検討した。薬剤を用いる化学的な手法により木質材料を疎水化する技術については、本願発明者の一人が発明者である特許第１９６６５２７号『樹脂含浸による木材の表面硬化と寸法安定処理方法』にあるように、発明者にも十分な知見があり、また、上述したように先行技術においても、その効果が記載されているが、そのようなリグノセルロース系充填材を製造するためのコストが大きな問題であった。 Then, the hydrophobization method of lignocellulosic material was examined. As for the technique of hydrophobizing a wood material by a chemical method using a chemical, as described in Japanese Patent No. 1966527 “Method of surface hardening and dimensional stabilization of wood by resin impregnation”, one of the inventors of the present application is an inventor. The inventors also have sufficient knowledge, and as described above, the effects have been described in the prior art, but the cost for producing such a lignocellulosic filler was a big problem. It was.
木材の基礎科学（日本木材加工技術協会 関西支部編 海青社１９９５年１１月１日初版第２刷) の４８−５０ページには、木材に寸法安定性を付与する方法として、いくつかの化学的処理方法と併せて熱処理の記載があり、それは疎水化によって寸法安定性が発現すると書かれている。しかし、ここでは詳細については書かれておらず、処理条件等は不明であった。 On pages 48-50 of Basic Science of Wood (Japan Wood Processing Technology Association, Kansai Branch, Kaiseisha, November 1, 1995, second edition, second edition), some chemistry is given as a method to impart dimensional stability to wood. There is a description of heat treatment in combination with a general treatment method, which is said to exhibit dimensional stability by hydrophobization. However, the details are not described here, and the processing conditions are unknown.
木材等のリグノセルロース系材料を疎水化するには、１５０℃程度ではほとんど効果が期待できないことは経験的に分かっていた。また、それを超える温度を与えると、リグノセルロース系材料は発火する危険性があった。また、前述のとおり、高温高圧の水蒸気を用いると、かえって吸湿性が高くなることも発明者は経験的に知っていた。そこで、ほぼ閉鎖系でありながら、ダンパーからごくわずかに排気ができる加熱槽を作ることにした。なお、『ダンパーからごくわずかに排気ができる』とは、ボイラーから導入される水蒸気の量に見合う量を排気するとの意味である。すなわち、水蒸気が閉止状態にしたダンパーの隙間から漏れ出るものであるため、正確な排気量を数値化することは困難であった。 It has been empirically known that almost no effect can be expected at about 150 ° C. for hydrophobizing lignocellulosic materials such as wood. Moreover, when the temperature exceeding it was given, there was a danger that the lignocellulosic material would ignite. Further, as described above, the inventor has also empirically known that the use of high-temperature and high-pressure water vapor increases the hygroscopicity. Therefore, we decided to make a heating tank that is almost closed, but that can evacuate slightly from the damper. Note that “very little exhaust is possible from the damper” means that an amount corresponding to the amount of water vapor introduced from the boiler is exhausted. That is, since water vapor leaks from the gap between the dampers in the closed state, it has been difficult to quantify the exact displacement.
前記の加熱槽にリグノセルロース系材料を入れ、酸素を含まない加熱気体を導入し続けることで空気を排除して、リグノセルロース系材料を燃焼させることなく熱処理をすることができる。このとき、加熱槽内は常圧である。加熱気体としてはたとえば、窒素ガスや水蒸気を挙げることができる。これらの気体を導入しつつ、炉内の電気ヒータなどで所定の温度に加熱するか、あらかじめ加熱したこれらの気体を槽内に導入するか、またあるいは両者を組み合わせることでリグノセルロース系材料を加熱処理する。処理されるリグノセルロース系材料の材温が１８０℃以上３２０℃以下になるように処理槽内の温度を調整する。１８０℃未満では疎水化がほとんど進まないし、３２０℃を超える温度では疎水化は短時間で進む一方で、リグノセルロース系材料の強度低下が著しく、そのために成形体の強度にも悪影響があるからである。特に好ましい条件は、リグノセルロース系材料の材温が２００℃以上２６０℃以下である。 The lignocellulosic material can be heat treated without burning the lignocellulosic material by placing the lignocellulosic material in the heating tank and continuing to introduce the heated gas that does not contain oxygen. At this time, the inside of a heating tank is a normal pressure. Examples of the heating gas include nitrogen gas and water vapor. While introducing these gases, heat the lignocellulosic material by heating to a predetermined temperature with an electric heater in the furnace, introducing these preheated gases into the tank, or combining them. To process. The temperature in the treatment tank is adjusted so that the temperature of the lignocellulosic material to be treated is 180 ° C. or higher and 320 ° C. or lower. Hydrophobization hardly progresses below 180 ° C, while hydrophobization progresses in a short time at temperatures exceeding 320 ° C, while the strength of the lignocellulosic material is remarkably reduced, and thus the strength of the molded product is also adversely affected. is there. Particularly preferred conditions are that the material temperature of the lignocellulosic material is 200 ° C. or higher and 260 ° C. or lower.
リグノセルロース系充填材は最終的には粉体であることが必須であるが、加熱処理は粉体で行うことも可能であるし、それよりも大きな状態、たとえば板材やチップで行った後に粉砕して充填材としてもよい。 The lignocellulosic filler is ultimately required to be in powder form, but the heat treatment can also be carried out in powder form, or in a larger state, for example, after being carried out with plate material or chips. And it is good also as a filler.
あらかじめリグノセルロース系材料を入れてから加熱処理を行うバッチ式の加熱槽でも良いし、連続的に、あるいは断続的にリグノセルロース系材料を投入して、加熱槽内を移動させながら加熱処理を行う連続式の加熱槽でも良い。 A batch-type heating tank in which lignocellulosic material is put in advance and then heat-treated may be used, or the lignocellulosic material is continuously or intermittently charged and heat-treated while moving in the heating tank. A continuous heating tank may be used.
このような過熱水蒸気を用いて常圧下で行う加熱処理では、リグノセルロース系材料に当初水分があった場合、全ての水が蒸発するまで、材料の温度は１００℃を超えて上がらない。したがって、加水分解はほとんど起こらない。その一方で、熱分解が生じ、処理中にガス化したり、液体になったりして、リグノセルロース系材料からその成分の一部が分解・除去される。したがって、加熱処理前後では明らかに重量差がみられる。このとき、下式で表される重量減少率は極めて重要な意味を持ち、それが５％以上４０％以下になるように加熱処理を行うのがよい。すなわち、重量減少率が５％未満であるときには、リグノセルロース系材料の疎水化が顕著ではなく、４０％を超えると疎水化が進んでいる一方で、リグノセルロース系材料の強度低下が著しく、そのために成形体の強度にも悪影響があるからである。特に好ましい条件は、リグノセルロース系材料の重量減少率が１０％以上３０％以下である。そのときのリグノセルロース系材料には極めて高い耐朽性（木材腐朽菌に対する抵抗性) が付与されているからである。なお、重量減少率の調整は、加熱処理の温度と時間の組み合わせで行うことができる。 In the heat treatment performed under atmospheric pressure using such superheated steam, when the lignocellulosic material initially has moisture, the temperature of the material does not exceed 100 ° C. until all the water has evaporated. Therefore, hydrolysis hardly occurs. On the other hand, thermal decomposition occurs and gasifies or becomes liquid during processing, and a part of the components are decomposed and removed from the lignocellulosic material. Therefore, there is a clear weight difference before and after the heat treatment. At this time, the weight reduction rate represented by the following formula has a very important meaning, and it is preferable to perform the heat treatment so that it becomes 5% or more and 40% or less. That is, when the weight reduction rate is less than 5%, the hydrophobization of the lignocellulosic material is not remarkable, and when it exceeds 40%, the hydrophobization progresses, while the strength of the lignocellulosic material is significantly reduced. This is because the strength of the molded article is also adversely affected. A particularly preferable condition is that the weight reduction rate of the lignocellulosic material is 10% or more and 30% or less. This is because the lignocellulosic material at that time is imparted with extremely high decay resistance (resistance to wood decay fungi). The weight reduction rate can be adjusted by combining the temperature and time of the heat treatment.
このように加熱処理および粉砕を終えたリグノセルロース系充填材と、ポリエチレン、ポリプロピレンなどの熱可塑性樹脂を混練して成形原料とする。混練には樹脂ペレット製造時に用いられるペレタイザーを用いるのが至便であるが、スーパーミキサーなどの混練装置を用いてもよいし、そのような装置がない場合、所定の割合で充填材と熱可塑性樹脂を単に混合するだけでも、成形原料を調製できる。このとき、熱可塑性樹脂の一部に、マレイン酸等の付加を行い、極性を持たせた樹脂、すなわち、相溶化剤を添加してもよい。これにより、充填材と樹脂とのさらなる親和性が得られる。 The lignocellulosic filler after the heat treatment and pulverization in this way and a thermoplastic resin such as polyethylene and polypropylene are kneaded to obtain a molding raw material. For kneading, it is convenient to use a pelletizer used at the time of producing resin pellets. However, a kneading device such as a super mixer may be used. If there is no such device, a filler and a thermoplastic resin are used at a predetermined ratio. The molding raw material can be prepared by simply mixing the two. At this time, maleic acid or the like may be added to a part of the thermoplastic resin to add a polar resin, that is, a compatibilizing agent. Thereby, the further affinity of a filler and resin is acquired.
リグノセルロース系充填材と熱可塑性樹脂は、任意の割合で混練することができる。しかし、リグノセルロース系充填材の割合が５０％未満のときには、成形品の扱いが木材ではなくなり、廃棄のときの処分方法が自治体により異なるなど、不利になることが多いので、リグノセルロース系充填材の割合は５０％以上であることが望ましい。この複合材料は、処分時には木材等のリグノセルロース材料と同等と見なされる。一方、その後の押出、あるいは射出等による成形時の流動性を考えた場合、リグノセルロース系充填材の割合は９０％以下であることが望ましい。 The lignocellulosic filler and the thermoplastic resin can be kneaded at an arbitrary ratio. However, when the proportion of lignocellulosic filler is less than 50%, the treatment of molded products is not wood, and the disposal method at the time of disposal is often disadvantageous. The ratio is preferably 50% or more. This composite material is considered equivalent to a lignocellulosic material such as wood at the time of disposal. On the other hand, when considering the fluidity at the time of molding by subsequent extrusion or injection, the ratio of the lignocellulosic filler is desirably 90% or less.
このようにして調製した成形原料は、押出、射出あるいは圧縮成形により自由な形状に成形することができる。 The molding raw material thus prepared can be molded into a free shape by extrusion, injection or compression molding.
発明に係る加熱処理をすることで疎水化したリグノセルロース系充填材を用いると、無処理のリグノセルロース系充填材を用いたときに比べて、高い比率でそれを充填しても流動性が良好で、成形速度を速くすることができる、射出成形が可能になるなどメリットが多い。さらには成形時のはみ出し（バリ) が少なくなるなど、成形品の仕上がりが良くなるという効果もある。また、成形品の物性についてもその効果は顕著であり、無処理のリグノセルロース系充填材を用いたときに比べて、耐朽性や強度性能が高くなる、吸湿性や吸水性が低くなり、寸法安定性が良くなるなどの効果がある。特に、リグノセルロース系材料を高充填したときに、疎水化の効果は顕著となる。これにより、リグノセルロース系材料を５０％を超えて高充填しても、石油系プラスチックと遜色のない性能が発現する。 When the lignocellulosic filler hydrophobized by the heat treatment according to the invention is used, the fluidity is good even if it is filled at a higher ratio than when an untreated lignocellulose filler is used. Thus, there are many merits such as high molding speed and injection molding. Furthermore, there is an effect that the finished product is improved, for example, the protrusion (burr) during molding is reduced. In addition, the effect is also remarkable for the physical properties of the molded product, compared to when using untreated lignocellulosic filler, the durability and strength performance are higher, the hygroscopicity and water absorption are lower, and the dimensions There are effects such as improved stability. Particularly, when the lignocellulosic material is highly filled, the effect of hydrophobization becomes significant. Thereby, even if it is highly filled with lignocellulosic material exceeding 50%, performance comparable to petroleum-based plastics is exhibited.
以下、実施例を紹介するが、ここに記載された内容が全てではなく、これらによって本願発明が制約されるものではない。 Hereinafter, although an Example is introduced, the content described here is not all, and this invention is not restrict | limited by these.
なお、以下の実施例や比較例において、抗吸湿能（ＭＥＥ）や抗膨潤能（ＡＳＥ）は、３０℃で相対湿度が９５％の条件下での平衡時に測定した含水率および木口面の膨潤率を用いて、以下の式で表すものとする。 In the following examples and comparative examples, the anti-hygroscopic ability (MEE) and anti-swelling ability (ASE) are the moisture content measured at the time of equilibrium at 30 ° C. and the relative humidity of 95%, and the swelling of the mouth end surface. The rate is used to express the following formula.
また、以下の実施例１、実施例２では、６０℃で乾燥させた３年生のモウソウチク材ならびにスギ辺材をそれぞれリグノセルロース系材料として用いる。 Moreover, in the following Example 1 and Example 2, the 3rd graded moso-chiku material and cedar sapwood dried at 60 degreeC are used as a lignocellulosic material, respectively.
本発明の第１の実施の形態に係るリグノセルロース系充填材（実施例１）は、以下のようにして製造される。
リグノセルロース系材料の疎水化
リグノセルロース系材料としての３年生のモウソウチク材を厚さ方向には加工せずに、３０ｍｍ（Ｔ）×３５０ｍｍ（Ｌ）に切り出し、６０℃で乾燥させた後、図６に示すようなバッチ式の加熱処理槽を用い、過熱水蒸気により、２４０℃で２時間加熱処理を行う。この加熱処理によりリグノセルロース系材料としてのモウソウチク材は、２９％の重量減少があった。このモウソウチク材の材色は著しく暗色化していたが、材料の形状はほぼ元のままであることが確認された。
The lignocellulosic filler (Example 1) according to the first embodiment of the present invention is produced as follows.
Hydrophobization of lignocellulosic material 3rd grade moso bamboo as a lignocellulosic material was cut into 30 mm (T) x 350 mm (L) without being processed in the thickness direction, and dried at 60 ° C. Using a batch-type heat treatment tank as shown in FIG. 6, heat treatment is performed at 240 ° C. for 2 hours with superheated steam. This heat treatment resulted in a 29% weight loss of the moso bamboo material as the lignocellulosic material. It was confirmed that the material color of the Moso bamboo material was darkened, but the shape of the material remained almost the same.
疎水化されたリグノセルロース系材料の粉砕
次に、上記工程において過熱水蒸気による処理が施されたリグノセルロース系材料であるモウソウチク材を粗粉砕した後、ハンマーミルに０．５ｍｍの金網を付けて再粉砕した。得られた竹粉は分級することなく全てをリグノセルロース系充填材（実施例１）として用いた。
なお、粉砕されたモウソウチク材の竹粉であるリグノセルロース系充填材（実施例１）の疎水化は進行しており、無処理の３年生のモウソウチク材を粉砕した無処理竹粉の含水率は１８．４％であり、加熱処理した３年生のモウソウチク材を粉砕した、加熱処理竹粉の含水率は８．４％であった。したがって、加熱処理した３年生のモウソウチク材のＭＥＥは５４％であった。
これからも、過熱水蒸気による処理が施されたリグノセルロース系材料であるモウソウチク材を粉砕したリグノセルロース系充填材（実施例１）の疎水化が進行していることが確認できる。
Grinding of the hydrophobized lignocellulosic material Next, after roughly pulverizing the lignocellulosic material, which is a lignocellulosic material that has been treated with superheated steam in the above-mentioned process, attach a 0.5 mm wire mesh to the hammer mill and recycle. Crushed. All the obtained bamboo powder was used as a lignocellulosic filler (Example 1) without classification.
In addition, the hydrophobization of the lignocellulosic filler (Example 1), which is a ground bamboo powder of moso bamboo, has progressed, and the moisture content of the untreated bamboo powder obtained by pulverizing untreated 3-year-old moso bamboo is: The moisture content of the heat-treated bamboo powder obtained by pulverizing the heat-treated third-year moso bamboo wood was 8.4%. Therefore, the MEE of the heat-treated third-grade moso-chiku wood was 54%.
It can be confirmed from this that the hydrophobization of the lignocellulosic filler (Example 1) obtained by pulverizing Moso bamboo, which is a lignocellulosic material treated with superheated steam, can be confirmed.
このようにして製造されたリグノセルロース系充填材（実施例１）は、以下のようにしてリグノセルロース・熱可塑性樹脂複合材料（実施例１）となる。 The lignocellulose-based filler (Example 1) thus produced becomes a lignocellulose / thermoplastic composite material (Example 1) as follows.
リグノセルロース系充填材（実施例１）と熱可塑性樹脂との混練
前記過熱水蒸気処理が施された竹粉、すなわちリグノセルロース系充填材（実施例１）８０部に対して、ポリプロピレン２０部、それに相溶化剤としてマレイン酸変性ポリプロピレン２部を加え、ヘンシェルミキサーにより混練することで、リグノセルロース・熱可塑性樹脂複合材料（実施例１）となる。
なお、混練時のヘンシェルミキサーの温度はポリプロピレンの融点以上の１７０℃程度にまで上昇した。冷却後に取り出した混練物であるリグノセルロース・熱可塑性複合材料（実施例１）は、大きなかたまりであり、全体が混練中に溶融したことがうかがえた。
Kneading of lignocellulosic filler (Example 1) and thermoplastic resin Bamboo powder subjected to the superheated steam treatment, ie, 80 parts of lignocellulosic filler (Example 1), 20 parts of polypropylene, By adding 2 parts of maleic acid-modified polypropylene as a compatibilizer and kneading with a Henschel mixer, a lignocellulose / thermoplastic resin composite material (Example 1) is obtained.
In addition, the temperature of the Henschel mixer during kneading rose to about 170 ° C. above the melting point of polypropylene. The lignocellulose / thermoplastic composite material (Example 1), which was a kneaded product taken out after cooling, was a large lump, indicating that the whole melted during kneading.
このようにして得られたリグノセルロース・熱可塑性樹脂複合材料（実施例１）を粗粉砕した後、１０ｍｍの金網を付けたハンマーミルにより再粉砕し、ホットプレスによる圧縮成形試験に供した。プレス温度はポリプロピレンの融点以上の１７０℃に設定した。粉砕したリグノセルロース・熱可塑性樹脂複合材料（実施例１）約８０ｇをテフロン（登録商標）製のシートにはさみ、プレス面のクリアランスが約１ｍｍとなるように圧締した。
約５分間圧締の後、圧力を解放して観察すると、直径約３００ｍｍで厚さ約１ｍｍのプラスチック様の薄板状の成形体ができていた。圧力解放時には成形物は暖かく、極めて柔らかかったが、温度が低下して室温に近づくにつれ堅固になり、プラスチック独特の熱特性を示した。
The lignocellulose / thermoplastic resin composite material thus obtained (Example 1) was coarsely pulverized and then re-pulverized by a hammer mill with a 10 mm wire mesh, and subjected to a compression molding test using a hot press. The pressing temperature was set to 170 ° C. above the melting point of polypropylene. About 80 g of the pulverized lignocellulose / thermoplastic resin composite material (Example 1) was sandwiched between Teflon (registered trademark) sheets and pressed so that the clearance of the press surface was about 1 mm.
After pressing for about 5 minutes, when the pressure was released and observing, a plastic-like thin molded body having a diameter of about 300 mm and a thickness of about 1 mm was formed. When the pressure was released, the moldings were warm and very soft, but as the temperature decreased and approached room temperature, it became firm and exhibited the unique thermal properties of plastic.
前記リグノセルロース・熱可塑性樹脂複合材料（実施例１）を粗粉砕した後、１０ｍｍの金網を付けたハンマーミルにより再粉砕し、押出成形試験に供した。
コニカルタイプの二軸式押出成形機に、幅６０ｍｍ、厚さ１０ｍｍの形状の成形体が作製できる金型を取り付け、半固化成形により成形体を作製した。シリンダ温度を１６０℃、ダイス温度を１４０℃として、スクリュー回転速度（回転速度は押出速度に比例する) を８ｒｐｍにすることで、シリンダ内の圧力は１０ＭＰａ程度となり、良好な押出成形体（実施例１）を得ることができた。
The lignocellulose / thermoplastic resin composite material (Example 1) was coarsely pulverized and then re-pulverized by a hammer mill with a 10 mm wire mesh and subjected to an extrusion test.
A mold capable of producing a molded body having a width of 60 mm and a thickness of 10 mm was attached to a conical type biaxial extruder, and a molded body was produced by semi-solidification molding. By setting the cylinder temperature to 160 ° C., the die temperature to 140 ° C., and the screw rotation speed (rotation speed is proportional to the extrusion speed) to 8 rpm, the pressure in the cylinder becomes about 10 MPa, and a good extruded product (Example) 1) was obtained.
すなわち、このリグノセルロース・熱可塑性樹脂複合材料（実施例１）は、圧縮成形であっても、押出成形であっても良好な成形体を得ることができるものであることが確認できた。 In other words, it was confirmed that the lignocellulose / thermoplastic resin composite material (Example 1) can obtain a good molded article regardless of whether it is compression molding or extrusion molding.
上述の押出形成により得られた押出成形体（実施例１）から厚さ（１０ｍｍ）はそのままにして、２０ｍｍ角の試験材を切り出し、JIS K 1571に基づいて、その耐朽性を室内ビン試験により評価した。
その結果、オオウズラタケによる重量減少率は０．０％、カワラタケによるそれは０．０％で、極めて高い耐朽性を示した。
A 20 mm square test material was cut out from the extruded product (Example 1) obtained by the above-described extrusion forming (Example 1) as it was, and its decay resistance was determined by an indoor bin test based on JIS K 1571. evaluated.
As a result, the weight loss rate due to Prunus edulis was 0.0% and that due to Kawaratake was 0.0%, indicating extremely high decay resistance.
前記押出成形体（実施例１）を厚さ（１０ｍｍ）と幅（６０ｍｍ）はそのままにして、長さ２００ｍｍに切断して曲げ試験材とした。スパンを１５０ｍｍとして、中央集中荷重により曲げ弾性率を求めた。なお、曲げ試験機のヘッドスピードは５ｍｍ／ｍｉｎとした。その結果、５体の試験材の平均値は６．０ＧＰａ、標準偏差は０．１２ＧＰａであった。 The extruded product (Example 1) was cut into a length of 200 mm while leaving the thickness (10 mm) and width (60 mm) as it was to obtain a bending test material. The bending elastic modulus was obtained from the central concentrated load with a span of 150 mm. The head speed of the bending tester was 5 mm / min. As a result, the average value of the five test materials was 6.0 GPa, and the standard deviation was 0.12 GPa.
前記押出成形体（実施例１）を厚さ（１０ｍｍ）と幅（６０ｍｍ）はそのままにして、長さ６０ｍｍに切断して吸水試験材とした。この吸水試験材を２５℃の水中に沈め、浸漬させてから２４時間後に重量と厚さを測定し、吸水率と厚さの変化率を求めた。厚さの測定は両切り口から２０ｍｍのところの中央付近２カ所で行い、その平均値を求めた。なお、浸漬後の測定は吸水試験材の表面の水分を軽く拭き取って行った。
その結果、吸水率は１．０％、厚さ変化率は０．０％であった。
The extruded product (Example 1) was cut into a length of 60 mm while leaving the thickness (10 mm) and width (60 mm) as it was to obtain a water absorption test material. The water absorption test material was submerged in water at 25 ° C. and immersed, and the weight and thickness were measured 24 hours later to determine the rate of change in water absorption and thickness. The thickness was measured at two locations near the
As a result, the water absorption was 1.0% and the thickness change rate was 0.0%.
上述した実施例１に係るリグノセルロース系充填材の製造方法とは異なる製造方法によって製造されたリグノセルロース系充填材を用いたリグノセルロース・熱可塑性樹脂複合材料を実施例２として挙げる。 A lignocellulose / thermoplastic resin composite material using a lignocellulosic filler produced by a production method different from the production method of the lignocellulose filler according to Example 1 described above is given as Example 2.
本発明の第２の実施の形態に係るリグノセルロース系充填材は、以下のようにして製造される。
リグノセルロース系材料の疎水化
上述した実施例１のように３年生のモウソウチク材ではなく、３０ｍｍ角で長さ約３５０ｍｍに切削加工したスギ辺材をリグノセルロース系材料として使用した。
このリグノセルロース系材料としてのスギ辺材をあらかじめ６０℃で乾燥させた後、図６に示すバッチ式の加熱処理槽を用いて、過熱水蒸気により、２２０℃で２４時間加熱処理を行った。このとき加熱処理により１５．５％の重量減少があった。
The lignocellulosic filler according to the second embodiment of the present invention is produced as follows.
Hydrophobization of lignocellulosic material Sugi sapwood cut to a length of about 350 mm with a 30 mm square was used as the lignocellulosic material, instead of the 3rd grade moso bamboo material as in Example 1 described above.
The cedar sapwood as the lignocellulosic material was dried at 60 ° C. in advance, and then heat-treated at 220 ° C. for 24 hours with superheated steam using a batch-type heat treatment tank shown in FIG. At this time, there was a weight loss of 15.5% by heat treatment.
疎水化されたリグノセルロース系材料の粉砕
この過熱水蒸気による処理の後、粗粉砕した。粗粉砕されたスギ辺材をハンマーミルに０．５ｍｍの金網を付けて再粉砕して、リグノセルロース系充填材（実施例２）とする。
Grinding of the hydrophobized lignocellulosic material After the treatment with superheated steam, coarse grinding was performed. The coarsely pulverized cedar sapwood is pulverized by attaching a 0.5 mm wire mesh to a hammer mill to obtain a lignocellulosic filler (Example 2).
リグノセルロース系材料充填材（実施例２）と熱可塑性樹脂との混練
得られたスギ木粉は分級することなく全量をリグノセルロース系充填材（実施例２）として用いた。この過熱水蒸気処理が施されたリグノセルロース系充填材（実施例２）８０部に対して、熱可塑性樹脂としてのポリプロピレン２０部、それに相溶化剤としてマレイン酸変性ポリプロピレン２部を加え、ヘンシェルミキサーにより混練して、リグノセルロース・熱可塑性樹脂複合材料（実施例２）を得た。
Kneading Lignocellulosic Material Filler (Example 2) and Thermoplastic Resin The whole amount of the obtained cedar wood flour was used as a lignocellulosic filler (Example 2) without classification. To 80 parts of this superheated steam-treated lignocellulosic filler (Example 2), 20 parts of polypropylene as a thermoplastic resin and 2 parts of maleic acid-modified polypropylene as a compatibilizing agent were added, and a Henschel mixer was used. By kneading, a lignocellulose / thermoplastic resin composite material (Example 2) was obtained.
このリグノセルロース・熱可塑性樹脂複合材料（実施例２）をペレット化した後、押出成形して押出成形体（実施例２）を得た。これを用いて、上記と同様の方法で耐朽性、強度性能、吸水性および寸法安定性を評価した。
耐朽性試験の結果、過熱水蒸気処理をしたスギ木粉、すなわちリグノセルロース系充填材（実施例２）を用いたリグノセルロース・熱可塑性樹脂複合材料（実施例２）は、オオウズラタケ、カワラタケによる重量減少率がそれぞれ０．９％と０．８％であった。曲げ弾性率の平均値と標準偏差は６．８７ＧＰａ、０．２０ＧＰａであった。また、吸水率と厚さの変化率は、１．０％と０．０％であった。
The lignocellulose / thermoplastic resin composite material (Example 2) was pelletized and then extruded to obtain an extruded product (Example 2). Using this, decay resistance, strength performance, water absorption and dimensional stability were evaluated in the same manner as described above.
As a result of the decay resistance test, the cedar wood powder treated with superheated steam, that is, the lignocellulose / thermoplastic composite material (Example 2) using the lignocellulosic filler (Example 2) was reduced in weight by Oozutake and Kawaratake. The rates were 0.9% and 0.8%, respectively. The average value and standard deviation of the flexural modulus were 6.87 GPa and 0.20 GPa. The rate of change in water absorption and thickness was 1.0% and 0.0%.
リグノセルロース系材料としての気乾状態にあるスギチップ（全乾重量換算２５ｋｇ）を、ほぼ閉鎖系でありながら、ダンパーからごくわずかに排気ができる連続式の加熱処理槽内に、１時間あたり約７ｋｇを投入して、２４０℃に調整した加熱処理槽内をスクリューにより順次送り、加熱処理槽に滞留すること約１時間かけて過熱水蒸気による加熱処理をした後、生蒸気で空気を置換した貯蔵槽で１５０℃以下になるまで冷却した。
このとき、加熱処理後のチップの全乾重量は約２０ｋｇであり、加熱処理により２０％の重量減少があった。このチップと無処理チップを実施例１と同条件、すなわち３０℃で相対湿度９５％の条件下で平衡になるまで調湿したところ、無処理チップの含水率が２０．２％であったのに対して、加熱処理チップのそれは１１．２％であり、これからＭＥＥを求めると４４．６％となり、実施例１で用いたバッチ式の加熱槽と同等の疎水化が、連続式の装置でもできることが明らかになった。
About 7 kg per hour in a continuous heat treatment tank that can exhaust the cedar chips (25 kg in terms of total dry weight) in an air-dried state as a lignocellulosic material in a closed system, but with very little exhaust from the damper. , And the heat treatment tank adjusted to 240 ° C. is sequentially sent with a screw and stays in the heat treatment tank. After the heat treatment with superheated steam over about 1 hour, the storage tank is replaced with live steam. And cooled to 150 ° C. or lower.
At this time, the total dry weight of the chip after the heat treatment was about 20 kg, and there was a 20% weight reduction due to the heat treatment. The moisture content of the untreated chip was 20.2% when this chip and the untreated chip were conditioned until they were equilibrated under the same conditions as in Example 1, ie, 30 ° C. and 95% relative humidity. On the other hand, that of the heat-treated chip is 11.2%, and when MEE is calculated from this, it becomes 44.6%, and the hydrophobization equivalent to the batch-type heating tank used in Example 1 is possible even in the continuous apparatus. It became clear that we could do it.
ところで、処理温度と時間が、耐朽性や吸湿性に与える影響について詳細な検討を行うために、耐朽性の評価には２０ｍｍ（Ｔ）×２０ｍｍ（Ｒ）×１０ｍｍ（Ｌ）、吸湿性の評価には３０ｍｍ（Ｔ）×３０ｍｍ（Ｒ）×１０ｍｍ（Ｌ）に切削加工したスギ辺材試験材を用いた。
このスギ辺材試験材をほぼ閉鎖系でありながら、ダンパーからごくわずかに排気ができるバッチ式の加熱処理槽内にそれぞれが密着しないように入れ、過熱水蒸気により槽内の空気を置換して、材温を２００〜２６０℃、所定温度に達した後の加熱時間を０．５〜７２時間として処理を行い、過熱水蒸気処理に伴う重量減少率を、前記式１により求めた。過熱水蒸気処理の条件とそれに伴う重量減少率との関係を図１に示す。
図１から判明するように、処理温度が高くなるほど、また、処理時間が長くなるほど、スギ辺材試験材の重量減少率は大きくなった。特に、処理温度はスギ辺材試験材の重量減少率に極めて大きな影響を及ぼし、２００℃、７２時間の処理で発現する重量減少率は、２２０℃では約８時間、２４０℃では２時間、２６０℃では３０分以内に得られた。
By the way, in order to conduct a detailed study on the influence of the treatment temperature and time on the decay resistance and hygroscopicity, the evaluation of the decay resistance is 20 mm (T) × 20 mm (R) × 10 mm (L). A cedar sap material test material cut into 30 mm (T) × 30 mm (R) × 10 mm (L) was used.
This cedar sapwood test material is placed in a batch-type heat treatment tank that can be exhausted slightly from the damper while being a nearly closed system, and the air in the tank is replaced with superheated steam, The material temperature was 200 to 260 ° C., the heating time after reaching the predetermined temperature was 0.5 to 72 hours, and the weight reduction rate associated with the superheated steam treatment was determined by the
As can be seen from FIG. 1, the weight reduction rate of the cedar sapwood test material increased as the processing temperature increased and the processing time increased. In particular, the treatment temperature has a great influence on the weight reduction rate of the cedar sapwood test material, and the weight reduction rate developed by the treatment at 200 ° C. for 72 hours is about 8 hours at 220 ° C., 2 hours at 240 ° C., 260 It was obtained within 30 minutes at ° C.
耐朽性は、JIS K 1571に基づき、木材腐朽菌としてオオウズラタケならびにカワラタケを用いて、室内ビン試験により評価した。試験前後にスギ辺材試験材の全乾重量を測定して、腐朽による重量減少率を求めた。図２には、過熱水蒸気処理に伴う重量減少率と、木材腐朽菌による重量減少率との関係を示した。
過熱水蒸気処理によって、腐朽による重量減少が明らかに少なくなる、すなわち、耐朽性が高くなった。特に、過熱水蒸気処理時の重量減少率が１０％を超えると、木材腐朽菌による重量減少が数％以下になり、極めて高い耐朽性を示した。図２によると、加熱温度や加熱時間の如何に関わらず、過熱水蒸気処理に伴う重量減少率が高くなるほど耐朽性が発現することが分かった。
Based on JIS K 1571, the decay resistance was evaluated by an indoor bottle test using Oozuratake and Kawaratake as wood decay fungi. The total dry weight of the cedar sapwood test material was measured before and after the test to determine the weight reduction rate due to decay. FIG. 2 shows the relationship between the weight reduction rate associated with the superheated steam treatment and the weight reduction rate due to wood decay fungi.
The superheated steam treatment clearly reduced the weight loss due to decay, i.e. increased resistance to decay. In particular, when the weight reduction rate during the superheated steam treatment exceeded 10%, the weight reduction due to the wood-rotting fungi became several percent or less, indicating extremely high decay resistance. According to FIG. 2, it was found that the decay resistance is expressed as the weight reduction rate associated with the superheated steam treatment increases regardless of the heating temperature and the heating time.
吸湿性と寸法安定性の評価は前記と同様に行った。図３には過熱水蒸気処理に伴う重量減少率と、式２により求めたＭＥＥならびに、式３により求めたＡＳＥとの関係を示した。
過熱水蒸気処理によって、ＭＥＥは明らかに高くなった。ＭＥＥの計算式からも分かるように、これは過熱水蒸気処理に伴って平衡含水率が低下すること、すなわち、疎水化が進んでいることを意味している。図３によると、処理に伴う重量減少率が５％以下ではＭＥＥが２０％以下であり、疎水化はあまり顕著ではないが、それを超えると疎水化は顕著となり、特に、１０％を超えると平衡含水率は無処理時のほぼ半分に、すなわちＭＥＥは約５０となり、疎水化が顕著となった。
また、加熱処理に伴い寸法安定性も改善された。加熱処理に伴う重量減少率が５％のときＡＳＥは約４０％、重量減少率が１０％ではＡＳＥは５０％に達し、顕著に寸法安定性が改善した。このときも、加熱温度や加熱時間の如何に関わらず、過熱水蒸気処理に伴う重量減少率が高くなるほど、疎水化と寸法安定化が発現することが分かった。
このように、過熱水蒸気処理に伴う重量減少率は、リグノセルロース系材料の疎水化の程度などの物性に関して、極めて重要な意味を持つことが明らかになった。また、水蒸気を使った加熱であっても、常圧下での過熱水蒸気による処理では、特許第４０８１５７９号や特開２００７−２８３４８９号公報などの先行技術に示された高温高圧下でのそれとは全く異なり、疎水化が進行することが明らかになった。
Hygroscopicity and dimensional stability were evaluated in the same manner as described above. FIG. 3 shows the relationship between the weight reduction rate associated with the superheated steam treatment, the MEE determined by
The superheated steam treatment clearly increased the MEE. As can be seen from the calculation formula of MEE, this means that the equilibrium moisture content decreases with the superheated steam treatment, that is, the hydrophobization is progressing. According to FIG. 3, MEE is 20% or less when the weight reduction rate due to the treatment is 5% or less, and the hydrophobization is not so remarkable, but when it exceeds that, the hydrophobization becomes prominent, especially when it exceeds 10%. The equilibrium water content was about half that of the untreated state, that is, the MEE was about 50, and the hydrophobization became remarkable.
Also, dimensional stability was improved with the heat treatment. When the weight reduction rate due to the heat treatment is 5%, the ASE reaches about 40%, and when the weight reduction rate is 10%, the ASE reaches 50%, and the dimensional stability is remarkably improved. Also at this time, it was found that the higher the weight reduction rate associated with the superheated steam treatment, the higher the hydrophobicity and the dimensional stability, regardless of the heating temperature and the heating time.
Thus, it became clear that the weight reduction rate accompanying superheated steam treatment has a very important meaning with respect to physical properties such as the degree of hydrophobicity of the lignocellulosic material. Further, even with heating using steam, the treatment with superheated steam under normal pressure is completely different from that under high temperature and high pressure shown in prior arts such as Japanese Patent No. 4081579 and Japanese Patent Application Laid-Open No. 2007-283489. In contrast, it became clear that the hydrophobization proceeds.
上述した２０ｍｍ（Ｔ）×２０ｍｍ（Ｒ）×１０ｍｍ（Ｌ）のスギ辺材試験材の他に、スギ、ヒノキ、ベイマツ、ベイツガとアルダーの心材、それに３年生のモウソウチクを試験材として重量減少率等を調べた。
モウソウチク材は、厚さ方向には加工せずに、３０ｍｍ（Ｔ）×１０ｍｍ（Ｌ）に切り出した。上記と同様に、２００〜２６０℃で２〜８時間の過熱水蒸気処理を行い、過熱水蒸気処理に伴う重量減少率を、前記式１により求めた。続いて、JIS K 1571に基づく室内ビン試験により、その耐朽性を評価した。図４には、過熱水蒸気処理をした際に生じる重量減少率と、木材腐朽菌による重量減少率との関係を示した。オオウズラタケでは過熱水蒸気処理時の重量減少率と木材腐朽菌による重量減少率との関係が、樹種により若干異なったが、いずれにしても、過熱水蒸気処理によりある程度の重量減少が生じたときには、高い耐朽性が付与できることが明らかになった。
In addition to the above-mentioned 20 mm (T) × 20 mm (R) × 10 mm (L) cedar sapwood test materials, the weight reduction rate using cedar, cypress, bay pine, baitsuga and alder heartwood, and 3rd grade Mosouchiku as test materials Etc. were investigated.
The Moso bamboo material was cut into 30 mm (T) × 10 mm (L) without being processed in the thickness direction. In the same manner as described above, the superheated steam treatment was performed at 200 to 260 ° C. for 2 to 8 hours, and the weight reduction rate associated with the superheated steam treatment was determined by the
さらに、３０ｍｍ（Ｔ）×３０ｍｍ（Ｒ）×８０ｍｍ（Ｌ）に切削加工したスギ辺材試験材を用いて、上記と同様の方法で過熱水蒸気処理を行い、処理に伴う重量減少率を、前記式１により求めた。
過熱水蒸気処理が施されたスギ辺試験材を粗粉砕した後、ハンマーミルに０．５ｍｍの金網を付けて再粉砕した。得られた木粉は分級することなく全量を用いて、成分分析を行った。全乾重量に換算して８ｇを精秤して、円筒濾紙に入れ、ソックスレー抽出器を用いてエタノール・ベンゼン混液（体積比１：２）にて、抽出液が透明になるまで抽出を行った。抽出液を１０５℃で乾燥させて、エタノール・ベンゼン可溶分を求めた。
続いて、１０５℃で全乾状態にした抽出後の木粉４ｇを精秤して、環流冷却管を付けた三角フラスコに入れ、３００ｍｌの蒸留水を用いて、４時間熱水抽出を行った。
抽出後の木粉を１０５℃で乾燥させて、抽出前後の重量差から熱水可溶分を求めた。
両抽出を終えた全乾状態の木粉１ｇを５０ｍｌビーカーに入れ、７２％硫酸１５ｍｌを加えて、時折かき混ぜながら室温にて４時間加水分解した。
さらに、その全量を５７０ｍｌの熱水を用いて１リットル容の三角フラスコに移して、３％に希釈された硫酸で環流しながら煮沸することで、４時間加水分解を続けた。その結果得られた残渣を１Ｇ３のガラスフィルターで濾過して、１０５℃で乾燥させて秤量し、酸不溶分を求めた。
なお、この処理で酸に可溶になった量も計算により求めた。通常の木材分析法では、この酸不溶分は、リグノセルロース系材料におけるリグニン成分、一方、酸可溶分はヘミセルロースやセルロースなど、細胞壁を構成している多糖類と定義されている。分析結果は、図５に示すとおりで、過熱水蒸気処理によって、抽出成分（エタノール・ベンゼン可溶分と熱水可溶分の合計量) は若干増加する程度で、ほとんど変化がないと言って良い。
一方、酸不溶分（リグニン) は明らかに増加し、酸可溶分（多糖体) は減少した。おそらくはセルロースよりも熱に弱いヘミセルロースが主に熱分解された結果と推定できる。木材等のリグノセルロース系材料において、リグニンは疎水性であり、ヘミセルロースは最も親水性であることは一般的に知られていることで、この分析結果から、過熱水蒸気処理にあって、リグノセルロース系材料が疎水化する理由は、リグニンの占める割合の増加と、ヘミセルロースの占める割合の減少であることが裏付けられた。また、後述する比較例においても示すように、飽和水蒸気による高温高圧での加熱処理では抽出成分が著しく増加し、リグニンはむしろ微減するなど、常圧下での過熱水蒸気処理とは大きく異なり、両者が全く別の処理であることが裏付けられた。
Furthermore, using a cedar sap material test material cut to 30 mm (T) × 30 mm (R) × 80 mm (L), a superheated steam treatment is performed in the same manner as described above, and the weight reduction rate associated with the treatment is It was determined by
The cedar edge test material subjected to the superheated steam treatment was coarsely pulverized, and then re-pulverized by attaching a 0.5 mm wire mesh to a hammer mill. The obtained wood flour was subjected to component analysis using the whole amount without classification. 8 g in terms of total dry weight was precisely weighed, placed in a cylindrical filter paper, and extracted with an ethanol / benzene mixture (volume ratio 1: 2) using a Soxhlet extractor until the extract became transparent. . The extract was dried at 105 ° C. to determine the ethanol / benzene solubles.
Subsequently, 4 g of the extracted wood flour that had been completely dried at 105 ° C. was precisely weighed, placed in an Erlenmeyer flask equipped with a reflux condenser, and subjected to hot water extraction using 300 ml of distilled water for 4 hours. .
The wood powder after extraction was dried at 105 ° C., and the hot water soluble content was determined from the weight difference before and after extraction.
After completion of both extractions, 1 g of completely dried wood flour was put into a 50 ml beaker, 15 ml of 72% sulfuric acid was added, and the mixture was hydrolyzed at room temperature for 4 hours with occasional stirring.
Further, the whole amount was transferred to a 1 liter Erlenmeyer flask using 570 ml of hot water and boiled while refluxing with sulfuric acid diluted to 3% to continue hydrolysis for 4 hours. The resulting residue was filtered through a 1G3 glass filter, dried at 105 ° C. and weighed to determine the acid insoluble content.
In addition, the amount which became soluble in the acid by this treatment was also obtained by calculation. In a normal wood analysis method, this acid-insoluble component is defined as a lignin component in a lignocellulosic material, while the acid-soluble component is defined as a polysaccharide constituting the cell wall, such as hemicellulose or cellulose. The analysis result is as shown in FIG. 5, and it can be said that the extraction component (total amount of ethanol / benzene soluble component and hot water soluble component) is slightly increased by the superheated steam treatment, and there is almost no change. .
On the other hand, acid-insoluble matter (lignin) was clearly increased and acid-soluble matter (polysaccharide) was decreased. Probably, it can be presumed that hemicellulose, which is weaker to heat than cellulose, was mainly pyrolyzed. In lignocellulosic materials such as wood, it is generally known that lignin is hydrophobic and hemicellulose is the most hydrophilic. From this analysis result, in the superheated steam treatment, lignocellulose It was confirmed that the reason why the material becomes hydrophobic is an increase in the proportion of lignin and a decrease in the proportion of hemicellulose. In addition, as shown in a comparative example described later, in the heat treatment with saturated steam at a high temperature and high pressure, the extracted components are significantly increased, and lignin is rather slightly reduced. It was proved that it was a completely different treatment.
次に、上述した実施例１及び実施例２の比較対照例となる比較例について説明する。 Next, a comparative example serving as a comparative example of the above-described Example 1 and Example 2 will be described.
まず、チップ状にした３年生のモウソウチク（全乾重量換算１５ｋｇ) に対して、含水率が１００％になるように水を加えて（全乾重量の竹材と水との重量比が１：１）、オートクレーブを用いて飽和水蒸気で、２００℃で１５分間の加熱（蒸煮) 処理を行った。このとき、竹チップは形状がかなりくずれており、また、相当量の水分を含み、維管束部分は繊維状に、その他の部分は粘土状になっていた。全体を６０℃で送風乾燥した後、ハンマーミルに０．５ｍｍの金網を付けて粉砕することで、リグノセルロース系充填材（比較例１）とした。このリグノセルロース系充填材（比較例１）を用いて、実施例４と同様にＭＥＥを求めたところ、−１９％（蒸煮処理竹粉の含水率２２．０％、無処理竹粉の含水率１８．４％）となり、疎水化とは逆に親水化が進んでいることが確認された。 First, water is added to a chip-like third-year moso-chiku (15 kg in terms of total dry weight) so that the water content becomes 100% (weight ratio of bamboo to water in the total dry weight is 1: 1). ), Heating (steaming) for 15 minutes at 200 ° C. with saturated steam using an autoclave. At this time, the shape of the bamboo chip was considerably deformed, and it contained a considerable amount of moisture. The vascular part was in the form of fibers and the other part was in the form of clay. The whole was blown and dried at 60 ° C., and then ground with a 0.5 mm wire mesh attached to a hammer mill to obtain a lignocellulosic filler (Comparative Example 1). Using this lignocellulose-based filler (Comparative Example 1), MEE was determined in the same manner as in Example 4. As a result, -19% (moisture content of steamed bamboo flour 22.0%, moisture content of untreated bamboo flour) 18.4%), and it was confirmed that the hydrophilization was progressing contrary to the hydrophobization.
なお、上述のように親水化が進んだ原因としては、次に示す実験とその結果を踏まええて、以下のことが考えられる。
気乾状態にあるスギチップ（全乾重量換算１５ｋｇ）に対して、含水率が１００％になるように水を加えて（全乾重量のスギ材と水との重量比が１：１）、オートクレーブを用いて飽和水蒸気で、１９０℃で２０分間の加熱（蒸煮) 処理を行った。このとき、過熱水蒸気を用いた解放系での処理とは異なり、スギチップはかなり解繊が進んでおり、また十分な水分を含んでいた。全体を６０℃での送風乾燥の後、ハンマーミルに０．５ｍｍの金網を付けて粉砕し、この木粉全量を用いて、成分分析を行った。
その結果、抽出成分（エタノール・ベンゼン可溶分と熱水可溶分の合計量) は、処理前の４．７％から２０．０％に増加する一方で、リグニンは処理前の３１．５％から２９．９％に微減、多糖類は６３．７％から５０．１％に減少することが明らかになった。多糖類の減少分と、抽出成分の増加分がほぼ同じであり、それは主には多糖類が加水分解により低分子化して、水などに可溶な糖類が生成した結果と推定された。
このように、飽和水蒸気による湿った状態での加熱では、疎水性のリグニンの含有率に変化がないか、むしろ減少することと、リグノセルロース系材料の細胞壁を構成する多糖類が低分子化して水酸基が増え、より一層親水性となったことが、比較例１の結果が示すように、材料全体の親水性が増した理由と推定された。
In addition, the following can be considered as a cause of progressing hydrophilicity as mentioned above based on the experiment and the result shown below.
Add water to the air-dried cedar chips (15 kg in terms of total dry weight) so that the moisture content is 100% (the weight ratio of cedar wood to water in the total dry weight is 1: 1), then autoclave Was heated (steamed) at 190 ° C. for 20 minutes with saturated steam. At this time, unlike the treatment in the open system using superheated steam, the cedar chips were considerably defibrated and contained sufficient water. The whole was blown and dried at 60 ° C., crushed by attaching a 0.5 mm wire mesh to a hammer mill, and component analysis was performed using the whole amount of the wood powder.
As a result, the extraction component (total amount of soluble components of ethanol / benzene and hot water) increased from 4.7% before treatment to 20.0%, while lignin was 31.5% before treatment. It was found that the polysaccharide decreased slightly from 2% to 29.9% and the polysaccharide decreased from 63.7% to 50.1%. The decrease in the polysaccharide and the increase in the extracted component were almost the same, which was presumed to be mainly the result of the polysaccharide being hydrolyzed to lower the molecular weight to produce a saccharide soluble in water and the like.
In this way, heating in a moist state with saturated water vapor does not change or rather decreases the content of hydrophobic lignin, and the polysaccharides constituting the cell wall of the lignocellulosic material are reduced in molecular weight. It was estimated that the hydrophilicity of the whole material increased as the result of the comparative example 1 showed that the hydroxyl group increased and became more hydrophilic.
この蒸煮処理竹粉の粉砕物をリグノセルロース系充填材（比較例１）として８０部、それにポリプロピレン２０部と、相溶化剤としてマレイン酸変性ポリプロピレン２部を加え、ヘンシェルミキサーにより混練した。このとき、ヘンシェルミキサーの温度はポリプロピレンの融点である１７０℃程度にまで上昇した。冷却後に取り出したとき、ポリプロピレンの樹脂ペレットは混練中に溶融して、混練後にはその形状が明らかではなかったが、リグノセルロース・熱可塑性樹脂複合材料（比較例１）全体としては粉状であり、混練物全体が溶融した形跡はなかった。 80 parts of the pulverized product of the steamed bamboo powder as a lignocellulose filler (Comparative Example 1), 20 parts of polypropylene and 2 parts of maleic acid-modified polypropylene as a compatibilizer were added and kneaded by a Henschel mixer. At this time, the temperature of the Henschel mixer rose to about 170 ° C., which is the melting point of polypropylene. When taken out after cooling, the polypropylene resin pellets melted during the kneading and the shape was not clear after the kneading, but the lignocellulose / thermoplastic resin composite material (Comparative Example 1) as a whole was powdery. There was no evidence that the entire kneaded material was melted.
また、６０℃で乾燥させた３年生のモウソウチク材を粗粉砕の後、ハンマーミルに０．５ｍｍの金網を付けて再粉砕して、リグノセルロース系充填材（比較例２）とした。このリグノセルロース系充填材（比較例２）は分級することなく全てを充填材として用いた。
このリグノセルロース系充填材（比較例２）８０部に対して、ポリプロピレン２０部、それに相溶化剤としてマレイン酸変性ポリプロピレン２部を加え、ヘンシェルミキサーにより混練した。このとき、ヘンシェルミキサーの温度はポリプロピレンの融点である１７０℃程度にまで上昇した。冷却後に取り出したとき、ポリプロピレンの樹脂ペレットは混練中に溶融して、混練後にはその形状が明らかではなかった。また、混練物の一部は小さな固まりとなっていて、一部には溶融した形跡が認められたが、混練物全体が均一に溶融するには至らなかった。
Further, after the coarsely pulverized 3-year-old moso-chiku material dried at 60 ° C., a 0.5 mm wire mesh was attached to a hammer mill and re-pulverized to obtain a lignocellulosic filler (Comparative Example 2). All the lignocellulosic fillers (Comparative Example 2) were used as fillers without classification.
To 80 parts of this lignocellulose-based filler (Comparative Example 2), 20 parts of polypropylene and 2 parts of maleic acid-modified polypropylene as a compatibilizer were added and kneaded with a Henschel mixer. At this time, the temperature of the Henschel mixer rose to about 170 ° C., which is the melting point of polypropylene. When taken out after cooling, the polypropylene resin pellets melted during kneading and the shape was not clear after kneading. Moreover, a part of the kneaded product was a small lump and a trace of melting was observed in a part, but the whole kneaded product was not melted uniformly.
６０℃で乾燥させた３年生のモウソウチク材を粗粉砕の後、ハンマーミルに０．５ｍｍの金網を付けて再粉砕した。得られた竹粉は分級することなく全てをリグノセルロース系充填材（比較例３）として用いた。
このリグノセルロース系充填材（比較例３）８０部に対して、ポリプロピレン２０部、それに相溶化剤としてマレイン酸変性ポリプロピレン２部を加え、ヘンシェルミキサーにより混練した後、押出成形により押出成形体（比較例３）を得た。
After roughly pulverizing the 3rd grade moso-chiku material dried at 60 ° C., it was pulverized by attaching a 0.5 mm wire mesh to a hammer mill. All the obtained bamboo powder was used as a lignocellulosic filler (Comparative Example 3) without classification.
To 80 parts of this lignocellulose-based filler (Comparative Example 3), 20 parts of polypropylene and 2 parts of maleic acid-modified polypropylene as a compatibilizing agent were added and kneaded with a Henschel mixer, and then extruded to give an extruded product (comparison) Example 3) was obtained.
比較例３で得られたリグノセルロース・熱可塑性樹脂複合材料（比較例３）をペレット化してホットプレスによる圧縮成形試験に供した。プレス温度はポリプロピレンの融点である１７０℃に設定した。混練物約８０ｇをテフロン（登録商標）製のシートにはさみ、プレス面のクリアランスが約１ｍｍとなるように圧締した。約５分間圧締の後、圧力を解放して観察したが、圧締の前と後とで、リグノセルロース・熱可塑性樹脂複合材料（比較例３）の形状に大きな変化はなく、プラスチック様の薄板状成形体を得ることはできなかった。 The lignocellulose / thermoplastic resin composite material (Comparative Example 3) obtained in Comparative Example 3 was pelletized and subjected to a compression molding test using a hot press. The pressing temperature was set to 170 ° C., which is the melting point of polypropylene. About 80 g of the kneaded material was sandwiched between Teflon (registered trademark) sheets and pressed so that the clearance of the press surface was about 1 mm. After pressing for about 5 minutes, the pressure was released and observed, but there was no significant change in the shape of the lignocellulose / thermoplastic composite (Comparative Example 3) before and after pressing. A thin plate-like molded body could not be obtained.
比較例３で得た押出成形体（比較例３）に対して、実施例１や実施例２と同一条件下で耐朽性、曲がり試験、吸水率、厚み変化率を測定した。 For the extruded product obtained in Comparative Example 3 (Comparative Example 3), the decay resistance, bending test, water absorption rate, and thickness change rate were measured under the same conditions as in Example 1 and Example 2.
すなわち、上述した押出成形で成形された押出成形体（比較例３）を厚さ（１０ｍｍ）はそのままにして、２０ｍｍ角の試験材を切り出し、実施例１のリグノセルロース・熱可塑性樹脂複合材料（実施例１）に行ったのと同一条件で、JIS K 1571に基づいて、その耐朽性を室内ビン試験により評価した。その結果、オオウズラタケ、カワラタケによる重量減少率は、それぞれ３．０％と２．１％であった。 That is, a 20 mm square test material was cut out while keeping the thickness (10 mm) of the extruded product (Comparative Example 3) formed by the above-described extrusion molding, and the lignocellulose / thermoplastic resin composite material of Example 1 ( Under the same conditions as in Example 1), the decay resistance was evaluated by an indoor bottle test based on JIS K 1571. As a result, the weight loss rates due to Prunus edulis and Kawaratake were 3.0% and 2.1%, respectively.
また、前記押出成形体（比較例３）を厚さ（１０ｍｍ）と幅（６０ｍｍ）はそのままにして、長さ２００ｍｍに切断して曲げ試験材とした。その結果、５体の押出成形体（比較例４）の平均値は４．８７ＧＰａ、標準偏差は０．１６ＧＰａであった。 Further, the extruded product (Comparative Example 3) was cut into a length of 200 mm while leaving the thickness (10 mm) and width (60 mm) as it was to obtain a bending test material. As a result, the average value of the five extruded products (Comparative Example 4) was 4.87 GPa, and the standard deviation was 0.16 GPa.
さらに、前記押出成形体（比較例３）を厚さ（１０ｍｍ）と幅（６０ｍｍ）はそのままにして、長さ６０ｍｍに切断して吸水試験材とした。その結果、押出成形体（比較例４）の吸水率は２．０％、厚さ変化率は１．０％であった。 Further, the extruded molded body (Comparative Example 3) was cut into a length of 60 mm while leaving the thickness (10 mm) and width (60 mm) as they were to obtain a water absorption test material. As a result, the extruded product (Comparative Example 4) had a water absorption rate of 2.0% and a thickness change rate of 1.0%.
６０℃で乾燥させたスギ辺材を粗粉砕の後、ハンマーミルに０．５ｍｍの金網を付けて再粉砕した。得られたスギ木粉は分級することなく全てをリグノセルロース系充填材（比較例４）として用いた。
このリグノセルロース系充填材（比較例４）８０部に対して、ポリプロピレン２０部、それに相溶化剤としてマレイン酸変性ポリプロピレン２部を加え、ヘンシェルミキサーにより混練した後、押出成形により押出成形体（比較例４）を得た。
この押出成形体（比較例４）に対して耐朽性の評価、強度性能の評価、吸水性および寸法安定性の評価を行った。耐朽性試験の結果、複合材料のオオウズラタケ、カワラタケによる重量減少率はそれぞれ３．３％と１．０％であった。曲げ弾性率とその標準偏差はそれぞれ６．０２ＧＰａ、０．５０ＧＰａであった。また、吸水率と厚さの変化率はそれぞれ、２．０％と１．０％であった。
The cedar sapwood dried at 60 ° C. was coarsely pulverized and then re-pulverized by attaching a 0.5 mm wire mesh to a hammer mill. All obtained cedar wood flour was used as a lignocellulosic filler (Comparative Example 4) without classification.
To 80 parts of this lignocellulosic filler (Comparative Example 4), 20 parts of polypropylene and 2 parts of maleic acid-modified polypropylene as a compatibilizer were added and kneaded with a Henschel mixer, and then extruded to give an extruded product (comparison) Example 4) was obtained.
The extruded product (Comparative Example 4) was evaluated for decay resistance, strength performance, water absorption and dimensional stability. As a result of the decay resistance test, the weight loss rates of the composite material due to Prunus edulis and Kawaratake were 3.3% and 1.0%, respectively. The flexural modulus and its standard deviation were 6.02 GPa and 0.50 GPa, respectively. Further, the water absorption rate and the rate of change in thickness were 2.0% and 1.0%, respectively.
比較例１で示した蒸煮処理をしたモウソウチク材を粉砕して得られたリグノセルロース系充填材（比較例１）や、比較例３で示した６０℃で乾燥させたモウソウチク材を粉砕して得られたリグノセルロース系充填材（比較例３）を充填材として用いたとき、シリンダ温度１７０℃、ダイス温度１５０℃に設定し、押出し成形を試みたが、スクリューの回転速度を３ｒｐｍ以上にすると、同装置のシリンダの許容最大圧力２５ＭＰａに近づいた。そこで、スクリューの回転速度３ｒｐｍ以下として成形品を得たが、成形体の表面はざらついていて、成形状態は良好ではなかった。
この結果からも、実施例１に示すように、リグノセルロース系充填材を加熱処理して疎水化することで、リグノセルロース・熱可塑性樹脂複合材料全体の流動性が高まり、成形速度を２倍以上にまで高めても、良好な成形体が得られることが分かった。
Obtained by pulverizing lignocellulosic filler (Comparative Example 1) obtained by pulverizing steamed Moso bamboo material shown in Comparative Example 1 and Moso bamboo material dried at 60 ° C. shown in Comparative Example 3 When the obtained lignocellulosic filler (Comparative Example 3) was used as a filler, the cylinder temperature was set to 170 ° C. and the die temperature was set to 150 ° C., and extrusion molding was attempted, but when the screw rotation speed was 3 rpm or more, The permissible maximum pressure of the apparatus cylinder was approaching 25 MPa. Therefore, a molded product was obtained with a screw rotation speed of 3 rpm or less, but the surface of the molded body was rough and the molded state was not good.
Also from this result, as shown in Example 1, the lignocellulose-based filler is heat treated to be hydrophobized so that the fluidity of the entire lignocellulose / thermoplastic resin composite material is increased and the molding speed is doubled or more. It has been found that a good molded product can be obtained even when the thickness is increased to 1.
すなわち、本発明の実施例１、実施例２及び比較例３、比較例４に係るリグノセルロース・熱可塑性複合材料の耐朽性、曲げ試験結果、吸水率等は以下のようになる。 That is, the durability, the bending test result, the water absorption rate, etc. of the lignocellulose / thermoplastic composite materials according to Examples 1, 2 and 3 and 4 of the present invention are as follows.
実施例１（過熱蒸気処理竹充填材を用いた樹脂複合体）
オオウズラダケによる重量減少率 ０．０％
カワラタケによる重量減少率 ０．０％
曲げ試験 平均値 ６．０ＧＰａ
標準偏差 ０．１２ＧＰａ
吸水率 ０．１％
厚さ変化率 ０．０％
Example 1 (resin composite using superheated steam-treated bamboo filler)
0.0% reduction in weight due to Prunus
Weight loss rate by Kawaratake 0.0%
Bending test average value 6.0 GPa
Standard deviation 0.12 GPa
Water absorption rate 0.1%
Thickness change rate 0.0%
実施例２（過熱蒸気処理スギ充填材を用いた樹脂複合体）
オオウズラタケによる重量減少率 ０．９％
カワラタケによる重量減少率 ０．８％
曲げ試験 平均値 ６．８７ＧＰａ
標準偏差 ０．２０ＧＰａ
吸水率 １．０％
厚さ変化率 ０．０％
Example 2 (resin composite using superheated steam-treated cedar filler)
0.9% reduction in weight due to giant crabs
Weight loss rate by Kawaratake 0.8%
Bending test average value 6.87 GPa
Standard deviation 0.20 GPa
Water absorption 1.0%
Thickness change rate 0.0%
比較例３（無処理竹充填材を用いた樹脂複合体）
オオウズラタケによる重量減少率 ３．０％
カワラタケによる重量減少率 ２．１％
曲げ試験 平均値 ４．８７ＧＰａ
標準偏差 ０．１６ＧＰａ
吸水率 ２．０％
厚さ変化率 １．０％
Comparative Example 3 (resin composite using untreated bamboo filler)
3.0% weight loss due to Prunus
Weight loss rate by Kawaratake 2.1%
Bending test average value 4.87 GPa
Standard deviation 0.16 GPa
Water absorption 2.0%
Thickness change rate 1.0%
比較例４（無処理スギ充填材を用いた樹脂複合体）
オオウズラタケによる重量減少率 ３．３％
カワラタケによる重量減少率 １．０％
曲げ試験 平均値 ６．０２ＧＰａ
標準偏差 ０．５０ＧＰａ
吸水率 ２．０％
厚さ変化率 １．０％
Comparative Example 4 (resin composite using untreated cedar filler)
Weight loss rate due to Prunus vulgaris 3.3%
Weight loss rate by Kawaratake 1.0%
Bending test average value 6.02 GPa
Standard deviation 0.50 GPa
Water absorption 2.0%
Thickness change rate 1.0%
すなわち、本発明に係る実施例１や実施例２に係るリグノセルロース系充填材を用いることで、リグノセルロース・熱可塑性樹脂複合材料のリグノセルロース系充填材の割合を従来よりもきわめて高く設定しても、高い流動性および優れた物性を得ることができることが確認できた。 That is, by using the lignocellulosic filler according to Example 1 or Example 2 of the present invention, the ratio of lignocellulosic filler of the lignocellulose / thermoplastic resin composite material is set to be extremely higher than before. It was also confirmed that high fluidity and excellent physical properties can be obtained.
Claims (12)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013176922A (en) * | 2012-02-29 | 2013-09-09 | Dai Ichi High Frequency Co Ltd | Processing method and processing device of lignocellulose material |
| JP2018161802A (en) * | 2017-03-27 | 2018-10-18 | 奈良県 | Method of manufacturing highly durable wood |
| CN110396247A (en) * | 2018-04-24 | 2019-11-01 | 佛吉亚内饰工业公司 | Composite material and preparation method and use and vehicle part and preparation method thereof |
| WO2023058088A1 (en) * | 2021-10-04 | 2023-04-13 | 国立大学法人京都大学 | Lignocellulose solution, molded article, and production methods therefor |
| US11691312B2 (en) | 2016-01-27 | 2023-07-04 | National Institute Of Advanced Industrial Science And Technology | Method of molding plant-based material and molded body |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009132094A (en) * | 2007-11-30 | 2009-06-18 | Toray Ind Inc | Manufacturing process of natural fiber board, and natural fiber board |
| JP2011152679A (en) * | 2010-01-26 | 2011-08-11 | Panasonic Electric Works Co Ltd | Method for producing woody board and woody board |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009132094A (en) * | 2007-11-30 | 2009-06-18 | Toray Ind Inc | Manufacturing process of natural fiber board, and natural fiber board |
| JP2011152679A (en) * | 2010-01-26 | 2011-08-11 | Panasonic Electric Works Co Ltd | Method for producing woody board and woody board |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013176922A (en) * | 2012-02-29 | 2013-09-09 | Dai Ichi High Frequency Co Ltd | Processing method and processing device of lignocellulose material |
| US11691312B2 (en) | 2016-01-27 | 2023-07-04 | National Institute Of Advanced Industrial Science And Technology | Method of molding plant-based material and molded body |
| JP2018161802A (en) * | 2017-03-27 | 2018-10-18 | 奈良県 | Method of manufacturing highly durable wood |
| CN110396247A (en) * | 2018-04-24 | 2019-11-01 | 佛吉亚内饰工业公司 | Composite material and preparation method and use and vehicle part and preparation method thereof |
| CN110396247B (en) * | 2018-04-24 | 2023-08-08 | 佛吉亚内饰工业公司 | Composite material, method for producing same, use thereof, vehicle component, and method for producing same |
| WO2023058088A1 (en) * | 2021-10-04 | 2023-04-13 | 国立大学法人京都大学 | Lignocellulose solution, molded article, and production methods therefor |
| WO2023058662A1 (en) * | 2021-10-04 | 2023-04-13 | 株式会社ダイセル | Lignocellulose solution and shaped article, and production method therefor |
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