JP7347739B2 - Method for producing plant fiber reinforced resin composition - Google Patents
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Description
本発明は、植物繊維強化樹脂組成物の製造方法に関する。 The present invention relates to a method for producing a plant fiber reinforced resin composition.
セルロース等の植物繊維を配合して強度を高めた樹脂組成物は、多分野で利用されている。このような樹脂組成物は、植物繊維及び樹脂に加え、利用目的に応じて物性を改善するための添加剤を用いて製造される場合がある。例えば、特許文献１には、ゴム含有ポリマーを添加した樹脂組成物が記載されている。 BACKGROUND ART Resin compositions with increased strength by blending vegetable fibers such as cellulose are used in many fields. Such a resin composition may be manufactured using, in addition to plant fibers and resin, additives for improving physical properties depending on the purpose of use. For example, Patent Document 1 describes a resin composition to which a rubber-containing polymer is added.
特許文献１に記載の樹脂組成物に添加されるゴム含有ポリマーは、樹脂組成物の柔軟性を向上させる一方で、剛性を低下させるおそれがある。
本発明は上記事情に鑑み、添加物を用いる以外の方法で力学的物性を改善する植物繊維強化樹脂組成物の製造方法を提供することを課題とする。
The rubber-containing polymer added to the resin composition described in Patent Document 1 may improve the flexibility of the resin composition, but may reduce the rigidity.
In view of the above circumstances, it is an object of the present invention to provide a method for producing a plant fiber-reinforced resin composition that improves mechanical properties by a method other than using additives.
上記課題を解決するための具体的手段には、以下の実施態様が含まれる。
＜１＞樹脂と植物繊維とを含む混合物を、下記式（１）及び式（２）を満たす領域を備える二軸押出機を用いて混錬する工程を有する、植物繊維強化樹脂組成物の製造方法。
式（１） Ｌ１／Ｄ＝Ａ
式（２） Ｎ≧８Ａ
式（１）及び式（２）において、Ｌ１は前記領域の長さであり、Ｄは前記二軸押出機のスクリュー径であり、Ｎは前記領域に含まれる１軸あたりのニーディングディスクの数であり、Ａは５以上の数である。
＜２＞前記混合物は樹脂を５５質量％～９５質量％及び植物繊維を５質量％～４５質量％含む、＜１＞に記載の植物繊維強化樹脂組成物の製造方法。
＜３＞前記樹脂はポリオレフィン樹脂を含む、＜１＞又は＜２＞に記載の植物繊維強化樹脂組成物の製造方法。
＜４＞前記植物繊維はセルロース繊維を含む、＜１＞～＜３＞のいずれか１項に記載の植物繊維強化樹脂組成物の製造方法。
＜５＞前記二軸押出機のスクリュー長Ｌ２／スクリュー径Ｄ（Ｌ２／Ｄ）が３６以上である、＜１＞～＜４＞のいずれか１項に記載の植物繊維強化樹脂組成物の製造方法。
＜６＞前記領域は前記二軸押出機の後半部に存在する、＜１＞～＜５＞のいずれか１項に記載の植物繊維強化樹脂組成物の製造方法。
Specific means for solving the above problems include the following embodiments.
<1> Production of a plant fiber-reinforced resin composition, which includes a step of kneading a mixture containing a resin and plant fibers using a twin-screw extruder equipped with a region that satisfies the following formulas (1) and (2). Method.
Formula (1) L1/D=A
Formula (2) N≧8A
In formulas (1) and (2), L1 is the length of the region, D is the screw diameter of the twin screw extruder, and N is the number of kneading disks per shaft included in the region. and A is a number of 5 or more.
<2> The method for producing a plant fiber-reinforced resin composition according to <1>, wherein the mixture contains 55% by mass to 95% by mass of resin and 5% to 45% by mass of vegetable fibers.
<3> The method for producing a plant fiber reinforced resin composition according to <1> or <2>, wherein the resin includes a polyolefin resin.
<4> The method for producing a plant fiber reinforced resin composition according to any one of <1> to <3>, wherein the plant fibers include cellulose fibers.
<5> Production of the plant fiber reinforced resin composition according to any one of <1> to <4>, wherein the twin screw extruder has a screw length L2/screw diameter D (L2/D) of 36 or more. Method.
<6> The method for producing a plant fiber reinforced resin composition according to any one of <1> to <5>, wherein the region is present in the latter half of the twin-screw extruder.
本発明によれば、添加物を用いる以外の方法で力学的物性を改善する植物繊維強化樹脂組成物の製造方法が提供される。 According to the present invention, there is provided a method for producing a plant fiber-reinforced resin composition that improves mechanical properties by a method other than using additives.
以下、本発明を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。
本明細書において「～」を用いて示された数値範囲には、「～」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including elemental steps and the like) are not essential unless otherwise specified. The same applies to numerical values and their ranges, and they do not limit the present invention.
In this specification, the numerical range indicated using "~" includes the numerical values written before and after "~" as the minimum value and maximum value, respectively.
本開示の植物繊維強化樹脂組成物（以下、単に樹脂組成物もいう）の製造方法は、樹脂と植物繊維とを含む混合物を、下記式（１）及び式（２）を満たす領域を備える二軸押出機を用いて混錬する工程を有する。
式（１） Ｌ１／Ｄ＝Ａ
式（２） Ｎ≧８Ａ
A method for producing a plant fiber-reinforced resin composition (hereinafter also simply referred to as a resin composition) of the present disclosure includes a method for producing a plant fiber-reinforced resin composition (hereinafter also simply referred to as a resin composition), in which a mixture containing a resin and a plant fiber is mixed into two regions having a region that satisfies the following formulas (1) and (2). It has a step of kneading using a screw extruder.
Formula (1) L1/D=A
Formula (2) N≧8A
式（１）及び式（２）において、Ｌ１は前記領域の長さであり、Ｄは前記二軸押出機のスクリュー径であり、Ｎは前記領域に含まれる１軸あたりのニーディングディスクの数であり、Ａは５以上の数である。 In formulas (1) and (2), L1 is the length of the region, D is the screw diameter of the twin screw extruder, and N is the number of kneading disks per shaft included in the region. and A is a number of 5 or more.
上記方法によれば、添加物を用いる以外の方法で樹脂組成物の力学的物性を向上させることができる。その理由は必ずしも明らかではないが、下記のように考えられる。
樹脂組成物の混錬に使用する二軸押出機は、式（１）及び式（２）を満たす領域を備えている。この領域はニーディングディスクを高密度で含み、かつ一定の長さで存在している。樹脂と植物繊維との混合物がこの領域を通過することで、植物繊維の開繊性が向上して樹脂への分散性が高まる結果、樹脂組成物の力学的物性が向上すると考えられる。
According to the above method, the mechanical properties of the resin composition can be improved by a method other than using additives. Although the reason is not necessarily clear, it is thought to be as follows.
The twin-screw extruder used for kneading the resin composition is equipped with a region that satisfies formula (1) and formula (2). This area contains kneading disks at a high density and has a constant length. It is thought that when the mixture of resin and plant fiber passes through this region, the spreadability of the plant fiber is improved and the dispersibility in the resin is increased, resulting in an improvement in the mechanical properties of the resin composition.
上記方法で使用する二軸押出機の種類は特に制限されず、樹脂組成物の混練に一般的に使用される二軸押出機から選択できる。
二軸押出機のスクリュー長Ｌ２（材料の投入口から取出口までの長さ）は特に制限されず、例えば、６００ｍｍ～１６，０００ｍｍであってもよい。
二軸押出機のスクリュー径Ｄは特に制限されず、例えば、１５ｍｍ～４００ｍｍであってもよい。スクリュー径が一定でない場合は、その最小値をスクリュー径Ｄとする。
The type of twin-screw extruder used in the above method is not particularly limited, and can be selected from twin-screw extruders commonly used for kneading resin compositions.
The screw length L2 (the length from the material input port to the material output port) of the twin screw extruder is not particularly limited, and may be, for example, 600 mm to 16,000 mm.
The screw diameter D of the twin-screw extruder is not particularly limited, and may be, for example, 15 mm to 400 mm. If the screw diameter is not constant, the minimum value is taken as the screw diameter D.
混合物を充分に混練する観点からは、Ｌ２／Ｄは３６以上であることが好ましい。生産性及び混合物の劣化抑制の観点からは、Ｌ２／Ｄは１２０以下であることが好ましい。 From the viewpoint of sufficiently kneading the mixture, L2/D is preferably 36 or more. From the viewpoint of productivity and suppression of deterioration of the mixture, L2/D is preferably 120 or less.
二軸押出機における式（１）及び式（２）を満たす領域の位置は、特に制限されない。例えば、二軸押出機のスクリュー長の中央部であっても、中央部より材料の投入口に近い位置（前半部）であっても、中央部より材料の取出口に近い位置（後半部）であってもよい。植物繊維の分散効果を十分に得る観点からは、上記領域は、二軸押出機の後半部にあることが好ましい。式（１）及び式（２）を満たす領域は、１箇所に存在していても、複数箇所に分割して存在していてもよい。領域が複数箇所に分割されている場合、その合計が式（１）及び式（２）を満たしていればよい。 The position of the region satisfying formulas (1) and (2) in the twin-screw extruder is not particularly limited. For example, even if it is the center of the screw length of a twin-screw extruder, it may be a position closer to the material input port than the center (first half), or a position closer to the material output port than the center (second half). It may be. From the viewpoint of obtaining a sufficient dispersion effect of plant fibers, the above region is preferably located in the rear half of the twin-screw extruder. The region that satisfies equations (1) and (2) may exist in one location or may exist in multiple locations. When the area is divided into multiple parts, the total need only satisfy equations (1) and (2).
二軸押出機のスクリュー長Ｌ２に占める式（１）及び式（２）を満たす領域の長さＬの割合は、特に制限されない。植物繊維を充分に分散させる観点からは、上記割合は５％以上であることが好ましく、１０％以上であることがより好ましい。生産性及び樹脂組成物の劣化抑制の観点からは、上記割合は３０％以下であることが好ましく、２５％以下であることがより好ましい。 The ratio of the length L of the region satisfying formulas (1) and (2) to the screw length L2 of the twin-screw extruder is not particularly limited. From the viewpoint of sufficiently dispersing the plant fibers, the above ratio is preferably 5% or more, more preferably 10% or more. From the viewpoint of productivity and suppression of deterioration of the resin composition, the above ratio is preferably 30% or less, more preferably 25% or less.
式（１）において、Ａは５以上の数である。Ａの値が大きいほど、二軸押出機のスクリュー径に対する領域の長さが長いことを意味する。植物繊維を充分に分散させる観点からは、Ａは１０以上であっても、１５以上であってもよい。生産性及び混合物の劣化抑制の観点からは、Ａは３０以下であってもよく、２５以下であってもよい。 In formula (1), A is a number of 5 or more. The larger the value of A, the longer the length of the region relative to the screw diameter of the twin-screw extruder. From the viewpoint of sufficiently dispersing the plant fibers, A may be 10 or more, or 15 or more. From the viewpoint of productivity and suppression of deterioration of the mixture, A may be 30 or less, or may be 25 or less.
式（２）において、Ｎは上記領域に含まれるニーディングディスクの１軸あたりの数であり、Ａの８倍以上（Ｎ≧８Ａ）である。植物繊維を充分に分散させる観点からは、ＮはＡの９倍以上（Ｎ≧９Ａ）であってもよく、Ａの１０倍以上（Ｎ≧１０Ａ）であってもよい。
生産性の観点からは、ＮはＡの２０倍以下（Ｎ≦２０Ａ）であってもよく、Ａの１５倍以下（Ｎ≦１５Ａ）であってもよい。
In Equation (2), N is the number of kneading disks included in the above area per axis, and is 8 times or more of A (N≧8A). From the viewpoint of sufficiently dispersing the plant fibers, N may be 9 times or more of A (N≧9A), or 10 times or more of A (N≧10A).
From the viewpoint of productivity, N may be 20 times or less than A (N≦20A), or may be 15 times or less than A (N≦15A).
式（１）及び式（２）を満たす領域に含まれるニーディングディスクの数は、例えば、ニーディングディスクの厚み又は間隔により調節することができる。
式（１）及び式（２）を満たす領域に含まれる複数のニーディングディスクの厚み又は間隔は、一定であっても異なっていてもよい。
The number of kneading disks included in the region satisfying equations (1) and (2) can be adjusted, for example, by adjusting the thickness or spacing of the kneading disks.
The thicknesses or intervals of the plurality of kneading disks included in the region satisfying formulas (1) and (2) may be constant or different.
隣接するニーディングディスクの長軸がなす角度（ずらし角度）は特に制限されず、例えば、３０°～９０°の範囲から選択してもよい。ニーディングディスクの主面のアスペクト比（長軸の長さ／短軸の長さ）は特に制限されず、例えば、１．２～２．０の範囲から選択してもよい。 The angle (shift angle) formed by the long axes of adjacent kneading disks is not particularly limited, and may be selected from the range of 30° to 90°, for example. The aspect ratio (long axis length/short axis length) of the main surface of the kneading disk is not particularly limited, and may be selected from the range of 1.2 to 2.0, for example.
本開示の方法は、樹脂と植物繊維とを含む混合物を、式（１）及び式（２）を満たす領域を備える二軸押出機を用いて混錬する工程を有するのであれば特に制限されず、その他の条件は一般的な混練方法に準じて設定できる。例えば、混練時のシリンダー温度は１５０℃～２５０℃の範囲から選択してもよい。 The method of the present disclosure is not particularly limited as long as it includes the step of kneading a mixture containing a resin and vegetable fiber using a twin-screw extruder equipped with a region that satisfies formulas (1) and (2). , and other conditions can be set according to general kneading methods. For example, the cylinder temperature during kneading may be selected from the range of 150°C to 250°C.
混合物に含まれる樹脂の種類は特に制限されない。例えば、ポリプロピレン、ポリエチレン等のポリオレフィン樹脂、ＡＢＳ（アクリロニトリル－ブタジエン－スチレン）樹脂、アクリル樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリスチレン樹脂、ポリアミド樹脂、ポリ塩化ビニル樹脂、ポリカーボネート樹脂等の熱可塑性樹脂、及びオレフィン系エラストマー、スチレン系エラストマー、ポリアミド系エラストマー、ポリエステル系エラストマー、ポリウレタン系エラストマー等の熱可塑性エラストマーが挙げられる。これらの中でもポリオレフィン樹脂が好ましい。
混合物に含まれる樹脂は、１種のみでも２種以上であってもよい。
The type of resin contained in the mixture is not particularly limited. For example, polyolefin resins such as polypropylene and polyethylene, thermoplastic resins such as ABS (acrylonitrile-butadiene-styrene) resins, acrylic resins, polyester resins, polyurethane resins, polystyrene resins, polyamide resins, polyvinyl chloride resins, and polycarbonate resins, and olefins. Examples of thermoplastic elastomers include thermoplastic elastomers, styrene-based elastomers, polyamide-based elastomers, polyester-based elastomers, and polyurethane-based elastomers. Among these, polyolefin resins are preferred.
The number of resins contained in the mixture may be one or two or more.
樹脂としては、官能基を有するものを用いてもよい。官能基としてはカルボキシ基、無水マレイン酸等の酸無水物基、エポキシ基などが挙げられる。官能基を有する樹脂を用いることで、樹脂と植物繊維との密着性が向上する効果が期待できる。
官能基を有する樹脂を用いる場合、その量は混合物に含まれる樹脂全体の１０質量％以下であることが好ましい。
As the resin, one having a functional group may be used. Examples of the functional group include a carboxy group, an acid anhydride group such as maleic anhydride, and an epoxy group. By using a resin having a functional group, the effect of improving the adhesion between the resin and the plant fibers can be expected.
When using a resin having a functional group, the amount thereof is preferably 10% by mass or less of the total resin contained in the mixture.
植物繊維としては、セルロース繊維が挙げられる。セルロース繊維の寸法は特に制限されない。例えば、平均繊維長を１μｍ～１００μｍの範囲から選択してもよく、平均繊維径を１μｍ～５０μｍの範囲から選択してもよい。
混合物に含まれる植物繊維は、１種のみでも２種以上であってもよい。
Examples of plant fibers include cellulose fibers. The dimensions of the cellulose fibers are not particularly limited. For example, the average fiber length may be selected from the range of 1 μm to 100 μm, and the average fiber diameter may be selected from the range of 1 μm to 50 μm.
The number of plant fibers contained in the mixture may be one or two or more.
混合物に含まれる樹脂及び植物繊維の含有率は特に制限されず、樹脂組成物の利用目的等に応じて設定できる。
混合物に含まれる樹脂の含有率は、混合物全体の３０質量％～９９質量％の範囲から選択してもよく、５５質量％～９５質量％の範囲から選択してもよい。
混合物に含まれる植物繊維の含有率は、混合物全体の１質量％～７０質量％の範囲から選択してもよく、５質量％～４５質量％の範囲から選択してもよい。
The contents of the resin and vegetable fibers contained in the mixture are not particularly limited, and can be set depending on the purpose of use of the resin composition.
The content of the resin contained in the mixture may be selected from the range of 30% by mass to 99% by mass of the entire mixture, or may be selected from the range of 55% by mass to 95% by mass.
The content of plant fibers contained in the mixture may be selected from the range of 1% to 70% by weight, or may be selected from the range of 5% to 45% by weight of the entire mixture.
必要に応じ、混合物は樹脂及び植物繊維以外の成分を含んでもよい。例えば、植物繊維強化樹脂組成物の添加剤として一般的に用いられる成分を含んでもよい。
上述したように、本開示の方法で製造される樹脂組成物は、添加剤を用いる以外の方法で力学的物性が改善される。このため、例えば、樹脂組成物の何らかの物性を低下させるおそれのある成分であっても、従来の樹脂組成物に比べて使用量を増やしたり、従来の樹脂組成物には使用に適しない成分を使用することが可能になる。
混合物が樹脂及び植物繊維以外の成分を含む場合、その含有率は混合物全体の１０質量％以下であってもよい。
If necessary, the mixture may contain components other than resin and vegetable fibers. For example, it may contain components commonly used as additives for plant fiber reinforced resin compositions.
As described above, the mechanical properties of the resin composition produced by the method of the present disclosure are improved by methods other than the use of additives. For this reason, for example, even if there is a risk of deteriorating some physical properties of the resin composition, the amount used may be increased compared to conventional resin compositions, or ingredients that are unsuitable for use in conventional resin compositions may be added. becomes possible to use.
When the mixture contains components other than resin and vegetable fibers, the content may be 10% by mass or less of the entire mixture.
以下、実施例に基づいて本発明を詳細に説明する。ただし、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be explained in detail based on Examples. However, the present invention is not limited to these examples.
＜樹脂組成物の作製＞
図１～４に示す構成の二軸押出機をそれぞれ用いて実施例及び比較例の樹脂組成物を作製した。
実施例１～３では、図１～３にそれぞれ示すように、式（１）及び式（２）を満たし、かつ表１に示す条件を満たす領域（１箇所又は２箇所）が二軸押出機の後半部に存在するようにニーディングディスクを配置した。
比較例１では、図４に示すように、式（１）及び式（２）を満たす領域が存在しないようにニーディングディスクを配置した。
二軸押出機としては、株式会社日本製鋼所のＴＥＸ３０（スクリュー長／スクリュー径（Ｌ２／Ｄ）＝７７、Ｄ＝３０ｍｍ）を使用した。
<Preparation of resin composition>
Resin compositions of Examples and Comparative Examples were produced using twin-screw extruders having the configurations shown in FIGS. 1 to 4, respectively.
In Examples 1 to 3, as shown in FIGS. 1 to 3, the areas (one or two places) that satisfy formulas (1) and (2) and satisfy the conditions shown in Table 1 are in the twin screw extruder. The kneading disk was placed so that it was located in the rear half of the disk.
In Comparative Example 1, as shown in FIG. 4, the kneading disks were arranged so that there were no regions satisfying equations (1) and (2).
As a twin-screw extruder, TEX30 (screw length/screw diameter (L2/D) = 77, D = 30 mm) manufactured by Japan Steel Works, Ltd. was used.
ポリプロピレン（株式会社プライムポリマー、Ｊ１０８Ｍ）７１．７質量％、針葉樹パルプ繊維２５質量％、及び無水マレイン酸変性ポリプロピレン（Ａｄｄｉｖａｎｔ社、ポリボンド３２００）３．３質量％を、二軸押出機の投入口（図中の位置１）からポリプロピレンを３．５８５ｋｇ／ｈ、針葉樹パルプ繊維を１．２５ｋｇ／ｈ、無水マレイン酸変性ポリプロピレンを０．１６５ｋｇ／ｈの供給速度で投入し、シリンダー温度１７０℃、スクリュー回転数１３６ｒｐｍの条件で混錬して、ペレットを作製した。作製したペレットを、５ｋｇ／ｈの供給速度で二軸押出機に投入し、上記と同じ条件で混錬する工程を２回実施して、樹脂組成物を得た。 71.7% by mass of polypropylene (Prime Polymer Co., Ltd., J108M), 25% by mass of softwood pulp fiber, and 3.3% by mass of maleic anhydride-modified polypropylene (Addivant, Polybond 3200) were added to the input port of a twin-screw extruder ( From position 1) in the figure, polypropylene was fed at a feeding rate of 3.585 kg/h, softwood pulp fiber at 1.25 kg/h, and maleic anhydride-modified polypropylene at 0.165 kg/h, the cylinder temperature was 170°C, and the screw was rotating. Pellets were produced by kneading at several 136 rpm. The produced pellets were fed into a twin-screw extruder at a feed rate of 5 kg/h, and the process of kneading them under the same conditions as above was performed twice to obtain a resin composition.
＜力学的物性の評価＞
得られた樹脂組成物から、射出成型機を用いてＪＩＳ １Ａ型多目的試験片を作製し、万能型試験機（インストロン社、モデル５５６６）を用いて変位速度２ｍｍ／ｍｉｎ、支点間距離６４ｍｍの条件で曲げ試験を行い、曲げ弾性率及び曲げ強度を測定した。結果を表１に示す。
<Evaluation of mechanical properties>
A JIS 1A type multipurpose test piece was prepared from the obtained resin composition using an injection molding machine, and a multipurpose test piece of JIS 1A type was prepared using a universal testing machine (Instron, model 5566) at a displacement rate of 2 mm/min and a distance between fulcrums of 64 mm. A bending test was conducted under the following conditions, and the bending elastic modulus and bending strength were measured. The results are shown in Table 1.
表１に示すように、式（１）及び式（２）を満たす領域を備える二軸押出機を用いて得た実施例の樹脂組成物は、式（１）及び式（２）を満たす領域を備えない二軸押出機を用いて得た比較例の樹脂組成物に比べて曲げ弾性率及び曲げ強度に優れていた。 As shown in Table 1, the resin composition of the example obtained using a twin screw extruder having a region satisfying formula (1) and formula (2) has a region satisfying formula (1) and formula (2). The resin composition was superior in flexural modulus and flexural strength compared to the resin composition of the comparative example obtained using a twin-screw extruder not equipped with a twin-screw extruder.
Claims (6)
式（１） Ｌ１／Ｄ＝Ａ
式（２） Ｎ≧８Ａ
式（１）及び式（２）において、Ｌ１は前記領域の長さであり、Ｄは前記二軸押出機のスクリュー径であり、Ｎは前記領域に含まれる１軸あたりのニーディングディスクの数であり、Ａは１７．５以上の数である。 A method for producing a plant fiber-reinforced resin composition, comprising the step of kneading a mixture containing a resin and plant fibers using a twin-screw extruder equipped with a region that satisfies the following formulas (1) and (2).
Formula (1) L1/D=A
Formula (2) N≧8A
In formulas (1) and (2), L1 is the length of the region, D is the screw diameter of the twin screw extruder, and N is the number of kneading disks per shaft included in the region. and A is a number of 17.5 or more.
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|---|---|---|---|---|
| JP2007237679A (en) | 2006-03-10 | 2007-09-20 | Japan Steel Works Ltd:The | Plasticization kneading extruder for plastic raw material |
| JP2013000913A (en) | 2011-06-13 | 2013-01-07 | Asahi Kasei Chemicals Corp | Extruder and melting and kneading method using the same |
| JP2015110329A (en) | 2013-10-31 | 2015-06-18 | 東レ株式会社 | Manufacturing method for thermoplastic resin composition |
| JP2016064501A (en) | 2014-05-22 | 2016-04-28 | 国立大学法人九州工業大学 | Method for producing biomass nanofibers and method for producing biomass nanofiber-polymeric resin composite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007237679A (en) | 2006-03-10 | 2007-09-20 | Japan Steel Works Ltd:The | Plasticization kneading extruder for plastic raw material |
| JP2013000913A (en) | 2011-06-13 | 2013-01-07 | Asahi Kasei Chemicals Corp | Extruder and melting and kneading method using the same |
| JP2015110329A (en) | 2013-10-31 | 2015-06-18 | 東レ株式会社 | Manufacturing method for thermoplastic resin composition |
| JP2016064501A (en) | 2014-05-22 | 2016-04-28 | 国立大学法人九州工業大学 | Method for producing biomass nanofibers and method for producing biomass nanofiber-polymeric resin composite |
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