JP2016028887A - Heat-melting lamination type filament for three-dimensional printer, and method for producing the same - Google Patents
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Abstract
Description
本発明は、熱溶解積層型３次元プリンタ用フィラメント（以下、「３Ｄプリンタ用フィラメント」と記す）およびその製造方法に関する。 The present invention relates to a filament for a hot melt laminated three-dimensional printer (hereinafter referred to as “3D printer filament”) and a method for producing the same.
多品種少量生産技術として、三次元プリンタ（以下、「３Ｄプリンタ」と記す）が再注目されている。特に、熱溶解積層法を用いた熱溶解積層型３Ｄプリンタ（特許文献１参照）は、低価格化が進んでおり、家庭・オフィス用としても需要が高まっている。
すなわち、熱溶解積層型３Ｄプリンタは、予め熱可塑性樹脂をマトリックスとする樹脂組成物からなる長尺の３Ｄプリンタ用フィラメントを作製しておき、この３Ｄプリンタ用フィラメントをプリンタの押出ヘッドに供給し、押出ヘッド内でフィラメントを加熱してマトリックスの熱可塑性樹脂を溶融あるいは半溶融状態にする。そして、その後、押出ヘッドのノズル先端から溶融物あるいは半溶融物を線状に押し出し少しずつ積み上げながら冷却固化させて射出成形では金型が複雑になる、あるいは、成形できないような立体構造を有する造形物を造形できるようになっている。
As a high-mix low-volume production technology, a three-dimensional printer (hereinafter referred to as “3D printer”) is attracting attention again. In particular, a hot melt lamination type 3D printer (see Patent Document 1) using the hot melt lamination method has been reduced in price, and the demand for home and office use is also increasing.
That is, the hot melt laminated 3D printer is prepared in advance with a long filament for a 3D printer made of a resin composition having a thermoplastic resin as a matrix, and the filament for the 3D printer is supplied to the extrusion head of the printer. The filament is heated in the extrusion head to bring the matrix thermoplastic resin into a molten or semi-molten state. After that, the melt or semi-melt is extruded linearly from the nozzle tip of the extrusion head and cooled and solidified while gradually building up, making the mold complicated or difficult to mold with injection molding You can shape objects.
しかし、熱溶解積層型３Ｄプリンタは、上記のように３Ｄプリンタ用フィラメントを溶融あるいは半溶融状態にして押出ヘッドのノズル先端から線状に押し出しながら積層する手法を採用している関係上、３Ｄプリンタ用フィラメントに使用できる材料は限られ、用途に制限があるのが現状である。また、マトリックス樹脂にフィラーと呼ばれる添加物を加える、あるいは二種類以上の樹脂をブレンドするといった、３Ｄプリンタ用フィラメントの高機能化は未だ図られていない。 However, the hot melt lamination type 3D printer employs the method of laminating the filament for 3D printer in the molten or semi-molten state and extruding it linearly from the tip of the nozzle of the extrusion head as described above. The materials that can be used for filaments are limited, and there are currently limited applications. In addition, enhancement of the function of the filament for 3D printers such as adding an additive called filler to the matrix resin or blending two or more kinds of resins has not been achieved yet.
本発明は、上記事情に鑑みて、従来の３Ｄプリンタ用フィラメントの可撓性などの取り扱い性や造形性を損なうことなく、フィラーの添加により熱可塑性マトリックス樹脂だけでは得られない所望の機能が備わった造形物を得ることができる熱溶解積層型３Ｄプリンタ用フィラメントおよびその製造方法を提供することを目的としている。 In view of the above circumstances, the present invention has a desired function that cannot be obtained only by a thermoplastic matrix resin by adding a filler without impairing handling properties such as flexibility of a filament for a conventional 3D printer and molding properties. It is an object of the present invention to provide a filament for a hot melt laminated 3D printer and a method for manufacturing the same.
上記目的を達成するために、本発明にかかる３Ｄプリンタ用フィラメントは、熱可塑性を有するマトリックス樹脂と、この熱可塑性を有するマトリックス樹脂中に分散された機能性ナノフィラーを含む機能性樹脂組成物によって形成されていることを特徴としている。 In order to achieve the above object, a filament for 3D printer according to the present invention comprises a functional resin composition comprising a thermoplastic matrix resin and functional nanofillers dispersed in the thermoplastic matrix resin. It is characterized by being formed.
本発明において、熱可塑性を有するマトリックス樹脂としては、熱可塑性樹脂、熱可塑性樹脂エラストマー、ゴムなどが挙げられ、具体的には、アクリロニトリル−ブチレン−スチレン共重合体樹脂（ＡＢＳ樹脂）、ポリ乳酸（ＰＬＡ） 樹脂、ポリアミド（ＰＡ）樹脂、ポリプロピレン（ＰＰ）樹脂、ポリエチレン（ＰＥ）樹脂、ポリカーボネート（ＰＣ）樹脂、ポリ塩化ビニル、アクリル樹脂、ポリスチレン（ＰＳ）樹脂、ポリエチレンテレフタレート（ＰＥＴ）やポリブチレンテレフタレート（ＰＢＴ）などのポリエステル樹脂、ポリウレタン樹脂、ポリフェニレンエーテル樹脂、ポリアセタール樹脂、ポリフェニレンサルファイド樹脂、フッ素樹脂、ポリアミドイミド樹脂、ポリエーテルスルホン樹脂、ポリスルホン樹脂、液晶ポリマー、ポリアリレート樹脂、ポリエーテルイミド樹脂、ポリエーテルエーテルケトン（ＰＥＥＫ）などの芳香族ポリエーテルケトン樹脂などの熱可塑性樹脂だけでなく、エチレン−プロピレン−ジエンゴム（ＥＰＤＭ）などの熱可塑性樹脂エラストマーやゴム、これらの樹脂のアロイが挙げられ、中でもＡＢＳ樹脂、ＰＬＡ、ＰＡ、ＰＰ、ＰＥ、ＰＣ、ＰＥＴなどが好適である。 In the present invention, examples of the matrix resin having thermoplasticity include thermoplastic resins, thermoplastic resin elastomers, and rubbers. Specifically, acrylonitrile-butylene-styrene copolymer resin (ABS resin), polylactic acid ( PLA) resin, polyamide (PA) resin, polypropylene (PP) resin, polyethylene (PE) resin, polycarbonate (PC) resin, polyvinyl chloride, acrylic resin, polystyrene (PS) resin, polyethylene terephthalate (PET) and polybutylene terephthalate Polyester resins such as (PBT), polyurethane resins, polyphenylene ether resins, polyacetal resins, polyphenylene sulfide resins, fluororesins, polyamideimide resins, polyethersulfone resins, polysulfone resins, liquid crystal polymers -Not only thermoplastic resins such as aromatic polyetherketone resins such as polyarylate resin, polyetherimide resin and polyetheretherketone (PEEK), but also thermoplastic elastomers such as ethylene-propylene-diene rubber (EPDM) Examples thereof include rubber and alloys of these resins. Among them, ABS resin, PLA, PA, PP, PE, PC, PET and the like are preferable.
機能性ナノフィラーとしては、例えば、カーボンナノチューブ（ＣＮＴ）、カーボンナノファイバー（ＣＮＦ）、カーボンブラック（ＣＢ）、グラフェン、銀や銅などの金属ナノ粒子、ナノクレイ、セルロースナノファイバー、シリカナノ粒子などが挙げられる。 Examples of functional nanofillers include carbon nanotubes (CNT), carbon nanofibers (CNF), carbon black (CB), graphene, metal nanoparticles such as silver and copper, nanoclays, cellulose nanofibers, and silica nanoparticles. It is done.
上記ＣＮＴ、ＣＮＦ、ＣＢ、グラフェンは、配合によって造形物の導電性を高めたり、熱伝導性を高めたり、引張強さや弾性率を高めたりすることができる。グラフェンは、配合によってガス透過性を減少させることもできる。
また、ＣＮＴとしては、特に限定されないが、多層カーボンナノチューブが好ましい。
The CNTs, CNFs, CBs, and graphenes can increase the electrical conductivity of the shaped product, increase the thermal conductivity, and increase the tensile strength and elastic modulus by blending. Graphene can also reduce gas permeability by blending.
Further, the CNT is not particularly limited, but a multi-walled carbon nanotube is preferable.
金属ナノ粒子は、配合によって造形物の導電性を高めたり、衝撃強度を高めたりすることができる。
セルロースナノファイバーは、添加によって造形物の引張強さや弾性率を高めたり、ガス透過性を減少させたりすることができる。
シリカナノ粒子は、添加によって造形物の引張強さや弾性率を高めることができる。
The metal nanoparticles can increase the conductivity of the molded article or increase the impact strength by blending.
Cellulose nanofibers can increase the tensile strength and elastic modulus of the shaped article or reduce the gas permeability when added.
Silica nanoparticles can increase the tensile strength and elastic modulus of a shaped article by addition.
ナノクレイは、配合によって造形物の引張強さや弾性率を高めたり、ガス透過性を減少させたりすることができるとともに、耐燃性および耐薬品性の改善を図ることができる。
ナノクレイとしては、特に限定されないが、モンモリロナイト、スメクタイト、イライト、セピオライト、アレルバルダイト、アメサイト、ヘクトライト、タルク、フルオロへクトライト、サポナイト、バイデライト、ノントロナイト、ステベンサイト、ベントナイト、マイカ、フルオロマイカ、バーミキュライト、フルオロバーミキュライト、ハロイサイトなどの層状ケイ酸塩化合物のナノ粒子、これらのナノ粒子表面を有機分子によって化学修飾したものなどが挙げられ、モンモリロナイト、ベントナイトが好ましい。
Nanoclay can increase the tensile strength and elastic modulus of a shaped article, reduce gas permeability, and improve flame resistance and chemical resistance by blending.
Although it is not particularly limited as nanoclay, montmorillonite, smectite, illite, sepiolite, allelevaldite, amesite, hectorite, talc, fluorohectorite, saponite, beidellite, nontronite, stevensite, bentonite, mica, fluoro Examples include nanoparticles of layered silicate compounds such as mica, vermiculite, fluorovermiculite, and halloysite, and those obtained by chemically modifying the surface of these nanoparticles with organic molecules. Montmorillonite and bentonite are preferred.
また、本発明において、上記機能性ナノフィラーは、どの方向を測定しても一般的な概念である100nm以下になっているものだけではなく、例えば、長さや幅がミクロンサイズであっても直径や厚さが100nm以下のナノサイズであるものも含まれる。 Further, in the present invention, the functional nanofiller is not limited to the general concept of 100 nm or less, which is a general concept regardless of which direction is measured. Also included are nano-sizes with a thickness of 100 nm or less.
熱可塑性を有する樹脂と機能性ナノフィラーの配合割合は、機能性ナノフィラーが配合されていない従来のフィラメントの可撓性などの取り扱い性を損なうことなく所望の機能を発現できれば、特に限定されないが、熱可塑性を有する樹脂１００重量部に対して機能性ナノフィラーが５重量部以下とすることが好ましく、０．５重量部以下とすることがより好ましい。
また、機能性樹脂組成物中に配合される機能性ナノフィラーは、１種でも構わないが、複数種類の機能性ナノフィラーを他の機能性ナノフィラーの機能付与の妨げとならない範囲で配合するようにしても構わない。
さらに、上記機能性樹脂組成物には、機能性ナノフィラーの機能付与の妨げとならない、また、フィラメントの造形性を阻害しない範囲で、必要に応じて、顔料、紫外線吸収剤、酸化防止剤、難燃剤などの他の添加剤を添加配合するようにしても構わない。
The blending ratio of the thermoplastic resin and the functional nanofiller is not particularly limited as long as the desired function can be expressed without impairing the handleability such as flexibility of a conventional filament in which the functional nanofiller is not blended. The functional nanofiller is preferably 5 parts by weight or less, more preferably 0.5 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin.
Moreover, the functional nanofiller to be blended in the functional resin composition may be one kind, but a plurality of types of functional nanofillers are blended within a range that does not hinder the functionalization of other functional nanofillers. It doesn't matter if you do.
Furthermore, in the functional resin composition, as long as it does not hinder the functional imparting of the functional nanofiller, and does not hinder the formability of the filament, as necessary, pigments, ultraviolet absorbers, antioxidants, You may make it mix | blend other additives, such as a flame retardant.
本発明にかかるフィラメントの製造方法は、混練によって熱可塑性を有するマトリックス樹脂中に機能性ナノフィラーが分散状態に配合されたフィラメント形成用機能性樹脂組成物を押出機でフィラメント形状に連続的に押し出すことを特徴としている。
なお、熱可塑性を有する樹脂と機能性ナノフィラーの混練は、超臨界二酸化炭素存在下で行うことが好ましい。
In the method for producing a filament according to the present invention, a functional resin composition for forming a filament in which a functional nanofiller is dispersed in a matrix resin having thermoplasticity by kneading is continuously extruded into a filament shape by an extruder. It is characterized by that.
The kneading of the thermoplastic resin and the functional nanofiller is preferably performed in the presence of supercritical carbon dioxide.
また、上記フィラメント形成用機能性樹脂組成物は、熱可塑性を有するマトリックス樹脂中に機能性ナノフィラーが高濃度で配合された機能性マスターバッチを作製したのち、
この機能性マスターバッチと、熱可塑性を有するマトリックス樹脂ペレットを混練押出機に投入し、混練押出機で混練して、所望割合の機能性ナノフィラーが配合された状態にして押し出して得ることが好ましい。
In addition, the functional resin composition for forming a filament is a functional masterbatch in which a functional nanofiller is blended at a high concentration in a matrix resin having thermoplasticity.
It is preferable that the functional masterbatch and the matrix resin pellets having thermoplasticity are put into a kneading extruder, kneaded with a kneading extruder, and extruded in a state where a desired ratio of functional nanofillers is blended. .
本発明にかかる３Ｄプリンタ用フィラメントは、以上のように、熱可塑性を有するマトリックス樹脂と、この熱可塑性を有するマトリックス樹脂中に分散された機能性ナノフィラーを含む機能性樹脂組成物によって形成されているので、マトリックス樹脂中に機能性ナノフィラーを少量配合するだけで、高機能化されたものとなる。
そして、少量の機能性ナノフィラーを配合するだけで高機能化できるので、機能性ナノフィラーが従来の３Ｄプリンタ用フィラメントの可撓性などの取り扱い性を阻害することがなく、また、得られる造形物の表面状態にも影響を与えることがない。
As described above, the filament for 3D printer according to the present invention is formed by a functional resin composition including a matrix resin having thermoplasticity and functional nanofillers dispersed in the matrix resin having thermoplasticity. Therefore, only a small amount of the functional nanofiller is added to the matrix resin, so that it becomes highly functional.
And since it can be highly functionalized only by blending a small amount of functional nanofiller, the functional nanofiller does not hinder the handling properties such as the flexibility of the filament for the conventional 3D printer, and the obtained molding It does not affect the surface condition of objects.
以下に、本発明の３Ｄプリンタ用フィラメントを、その実施の形態をあらわす図面を参照しつつ説明する。
図１は、本発明にかかる３Ｄプリンタ用フィラメントの１つの実施の形態の断面を拡大して模式的にあらわしている。
Below, the filament for 3D printers of this invention is demonstrated, referring drawings showing the embodiment.
FIG. 1 schematically shows an enlarged cross section of one embodiment of a filament for a 3D printer according to the present invention.
図１に示すように、この３Ｄプリンタ用フィラメント１は、熱可塑性を有するマトリックス樹脂２中に、機能性ナノフィラーであるＣＮＴ３が分散混合された機能性樹脂組成物から形成されている。
したがって、マトリックス樹脂中にＣＮＴを少量配合するだけで、導電性を高いものとすることができる。
As shown in FIG. 1, the filament 1 for a 3D printer is formed from a functional resin composition in which CNT3, which is a functional nanofiller, is dispersed and mixed in a matrix resin 2 having thermoplasticity.
Therefore, the conductivity can be increased only by mixing a small amount of CNT in the matrix resin.
そして、少量のＣＮＴを添加するだけで導電性を高めることができるので、ＣＮＴが従来の３Ｄプリンタ用フィラメントの可撓性などの取り扱い性を阻害することがない。しかも、ＣＮＴが得られる造形物の表面状態にも影響を与えることがない。
また、上記３Ｄプリンタ用フィラメント１を用いれば、従来の熱溶融積層型の３Ｄプリンタ（図示せず）を用いて全体が導電性の高い造形物を得ることができる。さらに、複数の押出ヘッドを備えた３Ｄプリンタの１つの押出ヘッドに上記３Ｄプリンタ用フィラメント１をセットし、他の押出ヘッドに従来のフィラメントをセットして、一部が導電性に優れ、残部が導電性の低い造形物を微細かつ容易に作製することができる。
And since electroconductivity can be improved only by adding a small amount of CNT, CNT does not impair the handleability of the conventional 3D printer filament, such as flexibility. Moreover, it does not affect the surface state of the shaped object from which CNTs are obtained.
If the filament 1 for a 3D printer is used, it is possible to obtain a molded article having a high conductivity as a whole using a conventional hot-melt lamination type 3D printer (not shown). Furthermore, the 3D printer filament 1 is set on one extrusion head of a 3D printer having a plurality of extrusion heads, and the conventional filament is set on the other extrusion head. A shaped article with low conductivity can be finely and easily produced.
〔ＣＮＴ入りＰＰ複合材料の評価〕
（マスターバッチＡの作製）
熱可塑性を有する樹脂としてのＰＰ（プライムポリマー社製プライムポリプロJ108M、引張強さ：36MPa 弾性率：2.28GPa）ペレット（以下、「ＰＰペレット」と記す）１００重量部に機能性ナノフィラーとしてのＣＮＴ（NANOCYL社製NANOCYLTM NC 7000、平均長さ１．５μｍ、平均径９．５ｎｍ、カーボン純度９０％）５．２６重量部（＝５重量％）を噛み合い型同方向回転二軸押出機（Coperion社製 ZSK18、最大回転数1200rpm、スクリュ直径18mm、スクリュ部の長さLとスクリュ径Dの比率Ｌ／Ｄ=40）に投入し、回転数450rpm、供給量2.25kg/h、温度200℃で混練押し出し、直径約3mm、長さ約5mmのペレット状をしたマスターバッチＡを得た。
なお、スクリュは、混練ゾーンが主に図３に示すニーディングディスクによって構成された図２（ａ）に示すニーディングスクリュを用いた。
[Evaluation of PP composite material with CNT]
(Preparation of master batch A)
PP as a resin having thermoplasticity (Prime Polypro J108M manufactured by Prime Polymer Co., Ltd., tensile strength: 36 MPa, elastic modulus: 2.28 GPa) pellets (hereinafter referred to as “PP pellets”) 100 parts by weight as CNTs as functional nanofillers (NANOCYL TM NC 7000, average length 1.5 μm, average diameter 9.5 nm, carbon purity 90%) 5.26 parts by weight (= 5% by weight) meshing type co-rotating twin screw extruder (Coperion Company ZSK18, maximum rotation speed 1200rpm, screw diameter 18mm, screw length L and screw diameter D ratio L / D = 40), rotation speed 450rpm, supply amount 2.25kg / h, temperature 200 ℃ A master batch A in the form of pellets having a diameter of about 3 mm and a length of about 5 mm was obtained by kneading and extrusion.
In addition, the kneading | mixing zone used the kneading screw shown to Fig.2 (a) by which the kneading zone was mainly comprised by the kneading disc shown in FIG.
（マスターバッチＢの作製）
スクリュとして、混練ゾーンが主に図４に示すミキシングディスクによって構成された図２（ｂ）に示すミキシングスクリュを用いた以外はマスターバッチＡと同様にしてマスターバッチＢを得た。
(Preparation of master batch B)
As a screw, a master batch B was obtained in the same manner as the master batch A except that the mixing screw shown in FIG. 2B in which the kneading zone was mainly composed of the mixing disc shown in FIG. 4 was used.
（マスターバッチＣの作製）
スクリュとして、混練ゾーンが主に図５に示すブリスタディスクによって構成された図２（ｃ）に示すブリスタスクリュを用いた以外はマスターバッチＡと、同様にしてマスターバッチＣを得た。
(Preparation of master batch C)
A master batch C was obtained in the same manner as the master batch A except that the blister task screw shown in FIG. 2 (c) in which the kneading zone was mainly composed of the blister disk shown in FIG. 5 was used as the screw.
（複合材料サンプルの作製）
得られる複合材料サンプルのＣＮＴ混合割合が、0.75重量％、1.0重量％、1.5重量％、2.0重量％、2.5重量％、3.0重量％となる割合で上記ＰＰペレットと、マスターバッチＡ〜Ｃのそれぞれを、マスターバッチＢの作製に用いた図２（ｂ）に示すミキシングスクリュをセットした上記噛み合い型同方向回転二軸押出機に投入し、マスターバッチＢの作製と同じ条件において押出機内で混練したのち混練物を押し出すことによってＣＮＴ混合割合が、0.75重量％、1.0重量％、1.5重量％、2.0重量％、2.5重量％、3.0重量％の複合材料サンプルをそれぞれ得た。
(Production of composite material sample)
Each of the PP pellets and the master batches A to C is mixed at a ratio of 0.75 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt% of the obtained composite material sample. Is put into the meshing type co-rotating twin screw extruder set with the mixing screw shown in FIG. 2B used for the production of the master batch B, and kneaded in the extruder under the same conditions as the production of the master batch B. Thereafter, the kneaded product was extruded to obtain composite material samples having CNT mixing ratios of 0.75 wt%, 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, and 3.0 wt%, respectively.
上記で得た各複合材料サンプル，上記マスターバッチＡ〜Ｃ、上記ＰＰペレットを、それぞれヒートプレス(河中産業株式会社製HP200 HB)を用いて厚さ２mmの適当な大きさに圧延（プレス速度は3mm/min、荷重は100kN）した。そして、得られた圧延物を60mm角に裁断して、厚さ2mm、縦60mm、横60mmの体積抵抗率用サンプル板をそれぞれ２枚ずつ得た。 Each of the composite material samples obtained above, the master batches A to C, and the PP pellets were rolled to an appropriate size of 2 mm in thickness using a heat press (HP200 HB manufactured by Kawanaka Sangyo Co., Ltd.) 3mm / min, load was 100kN). Then, the obtained rolled product was cut into 60 mm squares, and two sample plates for volume resistivity each having a thickness of 2 mm, a length of 60 mm, and a width of 60 mm were obtained.
各複合材料サンプル、上記マスターバッチＡ〜Ｃ、上記ＰＰペレットから形成された各２枚の体積抵抗率用サンプル板の抵抗Ｒ[Ω]を１枚５箇所ずつ、計１０箇所で測定した。
なお、抵抗Ｒは、抵抗率計（三菱化学アナリテック社製、ロレスタＧＰ、４端子４探針法）の４本の針状の電極を直線上に置き、外側の二探針間に一定電流を流し、内側の二探針間に生じる電位差を測定することによって求めた。
そして、得られた抵抗Ｒ[Ω]から、以下の定義式（１）を用いて体積抵抗率ρv[Ω・cm]を求めた。
式中、ｔ[cm]は試料の厚さ、RCFは補正係数である。
The resistance R [Ω] of each of the two sample plates for volume resistivity formed from each composite material sample, the master batches A to C, and the PP pellets was measured at 10 locations in total, 10 locations.
The resistance R is a constant current between the two outer probes, with four needle-shaped electrodes of a resistivity meter (Mitsubishi Chemical Analytech, Loresta GP, 4-terminal 4-probe method) placed on a straight line. And the potential difference generated between the two inner probes was measured.
Then, from the obtained resistance R [Ω], the volume resistivity ρv [Ω · cm] was obtained using the following definition formula (1).
In the equation, t [cm] is the thickness of the sample, and RCF is a correction coefficient.
図６は、各スクリュ構成によるＣＮＴの重量分率毎に上記体積抵抗率ρvの中央値をプロットしたグラフである。
図６から、ＣＮＴ/ＰＰ複合材料は、ＣＮＴが0.7〜0.9重量％付近でパーコレーション現象が起きることがわかる。
FIG. 6 is a graph in which the median value of the volume resistivity ρv is plotted for each CNT weight fraction by each screw configuration.
From FIG. 6, it can be seen that the percolation phenomenon occurs in the CNT / PP composite material when the CNT is around 0.7 to 0.9% by weight.
また、図６から、ブリスタスクリュ＞ミキシングスクリュ＞ニーディングスクリュの構成順に少ないＣＮＴの添加量でパーコレーションが発生していることがわかるとともに、体積抵抗率ρvは、パーコレーション発生以降は100〜102 Ω・cmの間で落ち着きそうであることがわかる。
なお、一般的に体積抵抗率ρvが101〜108 Ω・cmの樹脂は導電性樹脂(帯電防止、回路基板の保護)、10-2〜100 Ω・cmの樹脂は電磁波シールド材(各種輻射電波の遮断、金属部品の樹脂化)として用途が考えられている。
In addition, it can be seen from FIG. 6 that percolation occurs with a small amount of added CNTs in the order of the composition of the Bliss task screw> mixing screw> kneading screw, and the volume resistivity ρv is 10 0 to 10 2 after the percolation occurs. It can be seen that it seems to settle between Ω · cm.
Incidentally, generally resin volume resistivity ρv is 10 1 ~10 8 Ω · cm is conductive resin (antistatic protection of the circuit board), 10 -2 ~10 0 Ω · cm resins electromagnetic wave shielding material ( Applications are being considered for blocking various types of radiated radio waves and making metal parts resin.
さらに、図６に示すように、ブリスタスクリュとニーディングスクリュではパーコレーション発生に約０．２重量%のＣＮＴ添加量の違いが出ている。このことから、例えば、体積抵抗率104 Ω・cmの導電性樹脂を作製する場合、ブリスタスクリュを用いれば、ニーディングスクリュと比べてＣＮＴの添加量を５分の４程度に抑えられると考えられる。 Further, as shown in FIG. 6, a difference in the amount of CNT added of about 0.2% by weight occurs in the generation of percolation between the bristle screw and the kneading screw. From this, for example, when producing a conductive resin having a volume resistivity of 10 4 Ω · cm, it is considered that the use of a Bliss task screw can reduce the amount of CNT added to about 4/5 compared to a kneading screw. It is done.
図７は、マスターバッチＡ〜Ｃのそれぞれを用いて作製したＣＮＴが１．０重量％である複合材料サンプル板の体積抵抗率の平均値と標準偏差とを比較したグラフである。
図７から、ブリスタスクリュ＞ミキシングスクリュ＞ニーディングスクリュの構成順に同量のＣＮＴの添加量で導電性がよくなるとともに、体積抵抗率のばらつきが少なくなることがわかる。
FIG. 7 is a graph comparing the average value and the standard deviation of the volume resistivity of the composite material sample plate having 1.0% by weight of CNT produced using each of the master batches A to C.
From FIG. 7, it can be seen that the conductivity is improved and the variation in the volume resistivity is reduced with the same amount of CNT added in the order of the configuration of Bliss task screw> Mixing screw> Kneading screw.
また、上記マスターバッチＡ〜Ｃのそれぞれからミクロトーム(日本ミクロトーム研究所社製 RMD-5 型)を用い薄さ100nm の薄片を作製し、光学顕微鏡により光を透過させて観察を行った。倍率は150倍で、各条件につき画像6枚の撮影をした。
その結果、ブリスタスクリュ＞ミキシングスクリュ＞ニーディングスクリュの順にＣＮＴの分散状態が良好になっていることがわかった。すなわち、このことから、押出条件が同じ場合、ＣＮＴの分散性においてミキシングとブリスタのスクリュ形状の方がニーディングの形状より優れていると言える。また、ミキシングディスクおよびブリスタディスクと、ニーディングディスクの形状を比較すると、大きな違いの１つに伸長流動が発生するかという点がある。そして伸長流動の点ではブリスタディスクは特に優れているので、ＣＮＴの分散には伸長の流れが重要になってくると考えられる。
Moreover, a 100-nm thin piece was produced from each of the master batches A to C using a microtome (RMD-5 type, manufactured by Japan Microtome Laboratories Co., Ltd.), and observation was performed by transmitting light with an optical microscope. The magnification was 150x, and six images were taken for each condition.
As a result, it was found that the dispersion state of CNTs was improved in the order of Bliss task screw> mixing screw> kneading screw. In other words, when the extrusion conditions are the same, it can be said that mixing and blister screw shape are superior to kneading shape in dispersibility of CNTs. Further, when the shapes of the mixing disk and blister disk are compared with the kneading disk, one of the major differences is whether or not elongation flow occurs. And since the blister disk is particularly excellent in terms of elongation flow, it is considered that the elongation flow becomes important for the dispersion of CNTs.
図８に、上記マスターバッチＣから得られたＣＮＴの添加量が1.0重量％である複合材料サンプルのＴＥＭ写真を示す。
図８から、ＣＮＴがマトリックス樹脂中に細かく分散していることがわかる。
FIG. 8 shows a TEM photograph of a composite material sample in which the amount of CNT added from the master batch C is 1.0% by weight.
FIG. 8 shows that CNTs are finely dispersed in the matrix resin.
（実施例１）
上記マスターバッチＣから得られたＣＮＴの添加量が1.0重量％である複合材料サンプルをペレット化し、このペレットを用いて３Ｄプリンタ用のフィラメント押出機（Noztek社製 "The Pro ABS and PLA Filament Extruder for 3D Printers"）によって、フィラメント径1.75mmのＣＮＴ入りフィラメントＡ−１を作製した。押出条件は、シリンダ温度190℃とし、フィラメントの巻取りにはフィラメント巻取機（Noztek社製 "Filament Winder"）を用いた。
得られたＣＮＴ入りフィラメントＡ−１を造形材料とし、熱溶解積層方式の３Ｄプリンタ（オープンキューブ社製、SCOOVO X9）を用いて、厚さ2mm、縦60mm、横60mmの板状造形物サンプルＡ−１を作製した。
Example 1
The composite material sample obtained from the masterbatch C with an addition amount of CNT of 1.0% by weight is pelletized, and the pellet is used to produce a filament extruder for 3D printer ("The Pro ABS and PLA Filament Extruder for Noztek"). 3D Printers ") produced a CNT-containing filament A-1 having a filament diameter of 1.75 mm. The extrusion conditions were a cylinder temperature of 190 ° C., and a filament winder (“Filament Winder” manufactured by Noztek) was used for winding the filament.
Using the obtained CNT-containing filament A-1 as a modeling material, a plate-shaped model sample A having a thickness of 2 mm, a length of 60 mm, and a width of 60 mm was obtained using a hot melt lamination type 3D printer (manufactured by OpenCube, SCOOVO X9). -1 was produced.
（比較例１）
上記ＰＰペレットを用いて上記フィラメント押出機によって、フィラメント径1.75mmのフィラメントＢ−１を作製した。
このフィラメントＢ−１を造形材料とし、上記実施例１と同様の熱溶解積層方式の３Ｄプリンタを用いて、厚さ2mm、縦60mm、横60mmの板状造形物サンプルＢ−１を作製した。
(Comparative Example 1)
Filament B-1 having a filament diameter of 1.75 mm was produced using the PP pellet by the filament extruder.
Using this filament B-1 as a modeling material, a plate-shaped model sample B-1 having a thickness of 2 mm, a length of 60 mm, and a width of 60 mm was prepared using a 3D printer of the same hot melt lamination method as in Example 1 above.
上記実施例１および比較例１で得られた板状造形物サンプルＡ−１と板状造形物サンプルＢ−１の表面状態を比較したところ、板状造形物サンプルＡ−１と板状造形物サンプルＢ−１は、表面状態はほとんど変わりがなかった。
また、上記実施例１板状造形物サンプルＡ−１の体積抵抗率ρvを上記と同様の方法で測定したところ、板状造形物サンプルＡ−１は、体積抵抗率ρvが、上記複合材料サンプルとほとんど変わらなかった。
When the surface states of the plate-shaped object sample A-1 and the plate-shaped object sample B-1 obtained in Example 1 and Comparative Example 1 were compared, the plate-shaped object sample A-1 and the plate-shaped object sample were compared. Sample B-1 had almost no change in surface condition.
Further, when the volume resistivity ρv of the plate-shaped object sample A-1 in Example 1 was measured by the same method as described above, the plate-shaped object sample A-1 had a volume resistivity ρv of the composite material sample. It was almost the same.
このことからＣＮＴは少量の配合で、高い導電性を付与できるとともに、得られる造形物も添加していない従来のフィラメントと同様の表面状態の造形物が得られると考えられる。
また、本発明のフィラメントを用いて３Ｄプリンタによって造形した造形物が、フィラメントの原材料となるフィラメント用複合材料と同様の導電性を備えたものとなることがわかる。
From this, it is considered that CNT can give a high conductivity with a small amount of blending, and a shaped article having the same surface state as a conventional filament to which the obtained shaped article is not added.
Moreover, it turns out that the modeling thing modeled by 3D printer using the filament of this invention is provided with the same electroconductivity as the composite material for filaments used as the raw material of a filament.
〔モンモリロナイト入りＥＰＤＭ複合材料の評価〕
（サンプルＤ−１の作製）
上記噛み合い型同方向回転二軸押出機（Coperion社製 ZSK18、最大回転数1200rpm、スクリュ直径18mm、スクリュ部の長さLとスクリュ径Dの比率L/D=40）にＥＰＤＭ（The Dow Chemical company 製（型番4760P）、組成はエチレン67.5%、プロピレン27.5%、ジエン 5.0%である。融点は95℃）と表面に有機化処理を施したモンモリロナイト（Southern Clay Products 製 有機変性モンモリロナイトClosite15）を重量比で９０：１０の割合で投入し、回転数150rpm、供給量1.0kg/h、温度100℃で混練し、混練物を押し出すことによってモンモリロナイト入りＥＰＤＭ複合材料のサンプルＤ−１を得た。型温度は160℃、比エネルギーは0.728kWh/kgであった。
[Evaluation of EPDM composite material containing montmorillonite]
(Preparation of sample D-1)
The above mesh type co-rotating twin screw extruder (Coperion ZSK18, maximum rotation speed 1200rpm, screw diameter 18mm, screw length L to screw diameter D ratio L / D = 40) EPDM (The Dow Chemical company (Model No. 4760P), composition is ethylene 67.5%, propylene 27.5%, diene 5.0%. Melting point is 95 ° C) and organically modified montmorillonite (Organic modified montmorillonite Closite15 from Southern Clay Products) in weight ratio Was added at a ratio of 90:10, kneaded at a rotation speed of 150 rpm, a supply rate of 1.0 kg / h and a temperature of 100 ° C., and the kneaded product was extruded to obtain a sample D-1 of an EPDM composite material containing montmorillonite. The mold temperature was 160 ° C and the specific energy was 0.728kWh / kg.
（サンプルＤ−２の作製）
図９に示すスクリュ構成の同方向回転二軸混練押出機（日本製鋼所社製同方向回転二軸混練押出機TEX30α）にＥＰＤＭ（The Dow Chemical company 製（型番4760P）、組成はエチレン67.5%、プロピレン27.5%、ジエン 5.0%である。融点は95℃）と表面に有機化処理を施したモンモリロナイト（Southern Clay Products 製 有機変性モンモリロナイトClosite15）を重量比で９０：１０の割合で投入し、回転数100rpm、供給量3.89kg/h、温度100℃、0.3kg/hの超臨界二酸化炭素の存在下で混練し、混練物を押し出すことによってモンモリロナイト入り複合材料のサンプルＤ−２を得た。なお、二酸化炭素濃度は7.8％、バレル圧は8.9MPa、型温度は194℃、比エネルギーは0.779kWh/kgであった。
(Preparation of sample D-2)
The screw configuration shown in FIG. 9 is the same direction rotating twin-screw kneading extruder (Nihon Steel Works Co., Ltd., same-direction rotating twin-screw kneading extruder TEX30α), EPDM (manufactured by The Dow Chemical company (model number 4760P)) Propylene is 27.5% and diene is 5.0%. Melting point is 95 ° C) and montmorillonite (Organic modified montmorillonite Closite15 manufactured by Southern Clay Products) whose surface has been organically treated is added at a ratio of 90:10 by weight, and the rotation speed A composite sample D-2 containing montmorillonite was obtained by kneading in the presence of supercritical carbon dioxide at 100 rpm, a supply rate of 3.89 kg / h, a temperature of 100 ° C., and 0.3 kg / h, and extruding the kneaded material. The carbon dioxide concentration was 7.8%, the barrel pressure was 8.9 MPa, the mold temperature was 194 ° C, and the specific energy was 0.779 kWh / kg.
（サンプルＤ−３の作製）
図９に示すスクリュ構成の同方向回転二軸混練押出機（日本製鋼所社製同方向回転二軸混練押出機TEX30α）にＥＰＤＭ（The Dow Chemical company 製（型番4760P）、組成はエチレン67.5%、プロピレン27.5%、ジエン 5.0%である。融点は95℃）と表面に有機化処理を施したモンモリロナイト（Southern Clay Products 製 有機変性モンモリロナイトClosite15）を重量比で９０：１０の割合で投入し、回転数150rpm、供給量3.89kg/h、温度100℃、0.3 kg/hの超臨界二酸化炭素の存在下で混練し、混練物を押し出すことによってモンモリロナイト入り複合材料のサンプルＤ−３を得た。なお、二酸化炭素濃度は7.8％、バレル圧は7.7MPa、型温度は227℃、比エネルギーは1.013kWh/kgであった。
(Preparation of sample D-3)
The screw configuration shown in FIG. 9 is the same direction rotating twin-screw kneading extruder (Nihon Steel Works Co., Ltd., same-direction rotating twin-screw kneading extruder TEX30α), EPDM (manufactured by The Dow Chemical company (model number 4760P)) Propylene is 27.5% and diene is 5.0%. Melting point is 95 ° C) and montmorillonite (Organic modified montmorillonite Closite15 manufactured by Southern Clay Products) whose surface has been organically treated is added at a ratio of 90:10 by weight, and the rotation speed Kneading was performed in the presence of supercritical carbon dioxide at 150 rpm, supply rate of 3.89 kg / h, temperature of 100 ° C. and 0.3 kg / h, and the kneaded product was extruded to obtain a sample D-3 of a composite material containing montmorillonite. The carbon dioxide concentration was 7.8%, the barrel pressure was 7.7 MPa, the mold temperature was 227 ° C., and the specific energy was 1.013 kWh / kg.
上記サンプルＤ−１〜Ｄ−３の引張強さ、破断伸び、１００％モジュラスを以下のようにして測定し、ＥＰＤＭのみの場合と比較してその結果を表１に示した。
また、引張強さと１００％モジュラスの測定結果を、図１０に対比して示すとともに、破断伸びの測定結果を図１１に対比して示した。
The tensile strength, breaking elongation, and 100% modulus of the samples D-1 to D-3 were measured as follows, and the results are shown in Table 1 in comparison with the case of EPDM alone.
The measurement results of tensile strength and 100% modulus are shown in comparison with FIG. 10, and the measurement results of elongation at break are shown in comparison with FIG.
（引張強さ、破断伸び、１００％モジュラスの測定）
各サンプルを2枚重ねで、150mm×150mmのサイズになるように金型内に並べ、80℃で5分間プレスして厚み2mmのシートに成形し、得られたシートを打ち抜いて、図１２に示すJIS3号ダンベル試験片をそれぞれ得た。
得られた試験片のそれぞれについて、引張速度500mm/min、24℃における引張強さ、破断伸び、100%モジュラスを、万能試験機（島津製作所社製Auto graph（AG-100kN））を用いて求めた。
なお、測定はサンプル毎に５回行い、５つの結果の内、最大値と最小値を省き、他の３つの値の平均値を求めた。
また、上記万能試験機によって求まるのは、引張力(N)である。引張強度は単位面積あたりの引張力から求められるが、実際、試験片に収縮が起こっているため、その時々の荷重を試験片の断面積で割った値が真応力となるが、断面積の測定は容易ではない。そこで本試験では、最大荷重を初期断面積で割った値を用いた。
(Measurement of tensile strength, elongation at break, 100% modulus)
Each sample is stacked in two pieces and arranged in a mold so as to have a size of 150 mm x 150 mm, pressed at 80 ° C for 5 minutes to form a sheet with a thickness of 2 mm, and the obtained sheet is punched out. The JIS No. 3 dumbbell specimens shown were obtained.
For each of the obtained test pieces, the tensile strength at 500 mm / min, the tensile strength at 24 ° C, the elongation at break, and the 100% modulus were obtained using a universal testing machine (Auto graph (AG-100kN) manufactured by Shimadzu Corporation). It was.
The measurement was performed five times for each sample, and the maximum value and the minimum value were omitted from the five results, and the average value of the other three values was obtained.
Also, what is obtained by the universal testing machine is the tensile force (N). The tensile strength is obtained from the tensile force per unit area, but since the test piece is actually shrinking, the value obtained by dividing the load at that time by the cross-sectional area of the test piece is the true stress. Measurement is not easy. Therefore, in this test, a value obtained by dividing the maximum load by the initial cross-sectional area was used.
表１、図１０、図１１に示すように、引張強さ、破断伸び、１００％モジュラスは、モンモリロナイトを配合することによって向上するとともに、超臨界二酸化炭素存在下で混練し、混練物を押し出すようにすると、より向上することがわかる。 As shown in Table 1, FIG. 10, and FIG. 11, the tensile strength, elongation at break, and 100% modulus are improved by blending montmorillonite, and are kneaded in the presence of supercritical carbon dioxide to extrude the kneaded product. It turns out that it will improve more if it is.
（モンモリロナイトの分散状態）
上記引張強さ、破断伸び、１００％モジュラスの測定と同様にして得た2mm厚のシートを15mm×15mmの大きさに切りとり、Ｘ線回折用試験片を得た。
この試験片のＸ線回折パターンをＸ線回折装置（リガク社製RINT 2500)を用いて測定し、
その結果を図１３に示した。Ｘ線回折結果ピークサーチは、リガク社製の粉末Ｘ線回折パターン総合解析ソフトJADE6.0 を使用した。
図１３に示すように、超臨界二酸化炭素下で作製したサンプルＤ−２、３の回折ピークはそれぞれ3.0°、2.6°付近に現れている。一方、サンプルＤ−１の回折ピークは3.5°付近であり、これらを比較すると、前者は後者に比べ低角度側にピークが存在することがわかる。これは超臨界二酸化炭素により、層間間隔が拡がっていることを示す。また、スクリュ回転数が150rpmで作製したサンプルＤ−３は、サンプルＤ−２よりさらに拡がっているため、高いスクリュ回転数により発生する高せん断力により層間挿入が進行したと考えられる。
(Dispersed state of montmorillonite)
A 2 mm thick sheet obtained in the same manner as in the measurement of the tensile strength, breaking elongation, and 100% modulus was cut into a size of 15 mm × 15 mm to obtain a test piece for X-ray diffraction.
The X-ray diffraction pattern of this test piece was measured using an X-ray diffractometer (RINT 2500 manufactured by Rigaku Corporation),
The results are shown in FIG. For X-ray diffraction result peak search, powder X-ray diffraction pattern comprehensive analysis software JADE6.0 manufactured by Rigaku Corporation was used.
As shown in FIG. 13, the diffraction peaks of Samples D-2 and 3 prepared under supercritical carbon dioxide appear in the vicinity of 3.0 ° and 2.6 °, respectively. On the other hand, the diffraction peak of sample D-1 is around 3.5 °, and comparing these, it can be seen that the former has a peak on the lower angle side than the latter. This indicates that the interlayer spacing is widened by supercritical carbon dioxide. In addition, sample D-3 produced at a screw rotation speed of 150 rpm is further expanded than sample D-2, and therefore it is considered that interlayer insertion has progressed due to the high shear force generated by the high screw rotation speed.
〔ベントナイト入りポリアミド樹脂複合材料の評価〕
上記噛み合い型同方向回転二軸押出機（Coperion社製 ZSK18、最大回転数1200rpm、スクリュ直径18mm、スクリュ部の長さLとスクリュ径Dの比率L/D=40）にポリアミド樹脂（宇部興産社製UBEナイロン）と、有機変性処理を施した有機変性ベントナイト（ホージュン社製S-BEN)を重量比で９７:３の割合で投入し、回転数150rpm、供給量2.25kg/h、温度230℃で混練し、混練物を押し出すとともに、ノズルから出てきた試料を直接採取し、粉砕機でペレット化してサンプルペレットを得た。有機変性ベントナイトは水分を吸収しやすいため、予め80℃で12 時間乾燥したものを使用した。
得られたサンプルペレットを用い射出成形機（東洋機械金属社製射出成形機(PLASTR ET−40V)によって図１４に示すダンベル試験片(JIS K 7054)Ｅ−１を成形した。
射出条件は、スクリュ回転速度150rpm、射出圧150MPa、背圧5.0MPa、保圧30MPa、シリンダ温度230℃、射出速度50mm/sec、保圧時間15 sec、冷却時間25 sec、金型温度（冷却中の温度)50℃とした。
[Evaluation of bentonite-containing polyamide resin composite]
The above mesh type co-rotating twin screw extruder (Coperion ZSK18, maximum rotation speed 1200rpm, screw diameter 18mm, screw length L to screw diameter D ratio L / D = 40) and polyamide resin (Ube Industries) UBE nylon) and organically modified bentonite (S-BEN manufactured by Hojun Co., Ltd.) with an organic modification treatment are introduced at a weight ratio of 97: 3, rotation speed 150 rpm, supply rate 2.25 kg / h, temperature 230 ° C Kneaded to extrude the kneaded material, and the sample from the nozzle was directly collected and pelletized with a pulverizer to obtain sample pellets. Since the organically modified bentonite easily absorbs moisture, it was previously dried at 80 ° C. for 12 hours.
Using the obtained sample pellets, a dumbbell test piece (JIS K 7054) E-1 shown in FIG. 14 was molded by an injection molding machine (Toyo Machine Metal Co., Ltd. injection molding machine (PLASTR ET-40V)).
Injection conditions are: screw rotation speed 150rpm, injection pressure 150MPa, back pressure 5.0MPa, holding pressure 30MPa, cylinder temperature 230 ℃, injection speed 50mm / sec, holding pressure 15sec, cooling time 25sec, mold temperature (during cooling) The temperature was 50 ° C.
得られたダンベル試験片Ｅ−１と、ポリアミド樹脂（宇部興産社製UBEナイロン）のみを用いてダンベル試験片Ｅ−１と同様にして射出成形したダンベル試験片Ｅ−２の引張強さ、弾性率をそれぞれ測定しその結果を表２に示した。
なお、測定には、引張試験には島津製作所社製Auto graph（AG-100kN）を用いた。弾性率測定のため、島津製作所社製差動トランス式伸び計ST-50-10-10も合わせて用いた。試験は、作製した試験片を上記の装置で、JIS 規格K7161に従い、引張速度1mm/min、20℃における引張強さおよび弾性率を求めた。引張試験は１つの条件につき、９回実施した。そして、９回の結果の内、上位２つの値と下位２つの値を省き、他の５つの値の平均値を求めた。本試験では、引張強度として最大荷重を初期断面積で割った値を用いた。
Tensile strength and elasticity of dumbbell specimen E-2 injection-molded in the same manner as dumbbell specimen E-1 using only the obtained dumbbell specimen E-1 and polyamide resin (UBE nylon manufactured by Ube Industries). The rates were measured and the results are shown in Table 2.
For the measurement, an auto graph (AG-100kN) manufactured by Shimadzu Corporation was used for the tensile test. A differential transformer extensometer ST-50-10-10 manufactured by Shimadzu Corporation was also used for measuring the elastic modulus. In the test, the tensile strength and the elastic modulus at 20 ° C. were determined for the prepared test piece using the above-mentioned apparatus in accordance with JIS standard K7161 at a tensile speed of 1 mm / min. Ten tensile tests were carried out 9 times per condition. Of the nine results, the upper two values and the lower two values were omitted, and an average value of the other five values was obtained. In this test, the value obtained by dividing the maximum load by the initial cross-sectional area was used as the tensile strength.
上記表２から、ベントナイトの添加により、引張強さおよび弾性率が向上することがわかる。 From Table 2 above, it can be seen that the addition of bentonite improves the tensile strength and elastic modulus.
〔モンモリロナイト入りＰＰ複合材料の変性低分子量ポリオレフィン系樹脂改質剤（ＭＡＰＰ）の添加評価〕
上記噛み合い型同方向回転二軸押出機（Coperion社製 ZSK18、最大回転数1200rpm、スクリュ直径18mm、スクリュ部の長さLとスクリュ径Dの比率Ｌ／Ｄ=40）に、ＰＰ（プライムポリマー社製プライムポリプロJ108M）と、ＭＡＰＰ（三洋化成社製ユーメックス1001）と、表面に有機化処理を施したモンモリロナイト（Southern Clay Products 製 有機変性モンモリロナイトClosite15）を投入し、回転数300rpm、供給量1.4kg/h、温度180℃で混練押出して、ノズルから出てきた試料を直接採取し、粉砕機でペレット化して以下の表３に示す配合比のサンプルＦ−１〜Ｆ−６のサンプルペレットをそれぞれ作製した。
[Additional evaluation of modified low molecular weight polyolefin resin modifier (MAPP) of PP composite material containing montmorillonite]
The above-mentioned meshing type co-rotating twin screw extruder (Coperion ZSK18, maximum rotation speed 1200rpm, screw diameter 18mm, screw part length L to screw diameter D ratio L / D = 40), PP (Prime Polymer Co., Ltd.) Prime Polypro J108M), MAPP (Yumex 1001 manufactured by Sanyo Kasei Co., Ltd.), and Montmorillonite (Organic Modified Montmorillonite Closite15 manufactured by Southern Clay Products) whose surface has been organically treated are supplied at a rotational speed of 300 rpm and a supply amount of 1.4 kg / h. Kneading and extruding at a temperature of 180 ° C., directly collecting the sample coming out of the nozzle and pelletizing with a pulverizer to produce sample pellets of samples F-1 to F-6 having the blending ratios shown in Table 3 below did.
射出成形機（東洋機械金属社製射出成形機PLASTR ET−40V)によって、上記Ｆ−１〜Ｆ−６のそれぞれのサンプルペレットを用いて図１４に示すダンベル試験片(JIS K 7054) Ｆ−１〜Ｆ−６を成形した。 なお、射出条件は、スクリュ回転速度150 rpm、射出圧150MPa、背圧5.0MPa、保圧30MPa、シリンダ温度180℃、射出速度50mm/sec、保圧時間15 sec、冷却時間25 sec、金型温度(冷却中の温度) 50℃とした。 Dumbbell test piece (JIS K 7054) F-1 shown in FIG. 14 using each of the sample pellets F-1 to F-6 by an injection molding machine (injection molding machine PLASTR ET-40V manufactured by Toyo Kikai Kogyo Co., Ltd.) ~ F-6 was molded. The injection conditions are: screw rotation speed 150 rpm, injection pressure 150 MPa, back pressure 5.0 MPa, holding pressure 30 MPa, cylinder temperature 180 ° C, injection speed 50 mm / sec, holding pressure 15 sec, cooling time 25 sec, mold temperature (Temperature during cooling) The temperature was 50 ° C.
上記のようにして得られたダンベル試験片Ｆ−１〜Ｆ−６のそれぞれについて以下のようにして相対係数を求め、図１５に示した。
図１５に示すように、ＭＡＰＰの添加量の増加に伴って弾性率が向上することがわかる。
また、射出成形体サンプルＦ−１〜Ｆ−６の引張強さの相対強さを図１５に示した。
図１６に示すように、引張強さは、ＭＡＰＰの添加量が３〜６重量％でピークを示し、その後緩やかに低下して行くことがわかる。
The relative coefficient was calculated | required as follows about each of the dumbbell test pieces F-1 to F-6 obtained as mentioned above, and it showed in FIG.
As shown in FIG. 15, it can be seen that the modulus of elasticity improves as the amount of MAPP added increases.
Moreover, the relative strength of the tensile strength of the injection molded body samples F-1 to F-6 is shown in FIG.
As shown in FIG. 16, it can be seen that the tensile strength shows a peak when the added amount of MAPP is 3 to 6% by weight and then gradually decreases.
〔ＣＮＴ入りＰＬＡ複合材料の評価１〕
（マスターバッチＧの作製）
熱可塑性を有する樹脂としてのＰＬＡ（Zhejiong Hisun Biomaterials社製REVODE110）ペレット（以下、「ＰＬＡペレット」と記す）１００重量部に機能性ナノフィラーとしてのＣＮＴ（NANOCYL社製NANOCYLTM NC 7000、平均長さ１.５μｍ、平均径９.５ｎｍ、カーボン純度９０％）５.２６重量部（＝５重量％）を噛み合い型同方向回転二軸押出機（Coperion社製 ZSK18、最大回転数1200rpm、スクリュ直径18mm、スクリュ部の長さLとスクリュ径Dの比率Ｌ／Ｄ=40）に投入し、回転数150rpm、供給量4.5kg/h、温度180℃で混練押し出し、ペレット状のマスターバッチＧ (直径約3mm、長さ約5mm)を得た。
なお、スクリュは、混練ゾーンが主に図１７に示すブリスタディスクによって構成された図１８に示すブリスタスクリュを用いた。また、加水分解防止のため、ＰＬＡペレットは混錬実験前に80℃で24時間乾燥させた。
[Evaluation of PLA composite material containing CNT 1]
(Preparation of master batch G)
PLA as a resin having thermoplasticity (REVODE110 manufactured by Zhejiong Hisun Biomaterials) (hereinafter referred to as “PLA pellet”) 100 parts by weight CNT as a functional nanofiller (NANOCYL TM NC 7000 manufactured by NANOCYL, average length) 1.5μm, average diameter 9.5nm, carbon purity 90%) 5.26 parts by weight (= 5% by weight) meshing type co-rotating twin screw extruder (Coperion ZSK18, maximum rotation speed 1200rpm, screw diameter 18mm , Put into the length L of the screw part and the ratio L / D = 40 of the screw diameter D, knead and extrude at a rotation speed of 150 rpm, a supply rate of 4.5 kg / h, and a temperature of 180 ° C. 3 mm and a length of about 5 mm).
In addition, the screw task screw shown in FIG. 18 in which the kneading zone was mainly constituted by the blister disk shown in FIG. 17 was used as the screw. In order to prevent hydrolysis, PLA pellets were dried at 80 ° C. for 24 hours before the kneading experiment.
（サンプルペレットＧ−１の作製）
得られる複合材料サンプルのＣＮＴ混合割合が、1.0重量％となる割合で上記ＰＬＡペレットと、マスターバッチＧを、マスターバッチＧの作製に用いた図１８に示すブリスタスクリュをセットした上記噛み合い型同方向回転二軸押出機に投入し、回転数150rpm、供給量4.5kg/h、温度180℃で混練し、混練物を押し出すことによって、ＣＮＴ混合割合が、1.0重量％のＣＮＴ入りＰＬＡ複合材料サンプルペレットＧ−１を得た。
（サンプルペレットＧ−２の作製）
得られる複合材料サンプルのＣＮＴ混合割合が、2.0重量％となる割合で上記ＰＬＡペレットと、マスターバッチＧを、マスターバッチＧの作製に用いた図１８に示すブリスタスクリュをセットした上記噛み合い型同方向回転二軸押出機に投入し、回転数150rpm、供給量4.5kg/h、温度180℃で混練し、混練物を押し出すことによって、ＣＮＴの添加割合が、2.0重量％のＣＮＴ入りＰＬＡ複合材料サンプルペレットＧ−２を得た。
(Preparation of sample pellet G-1)
The mesh type same direction in which the PLA pellet and master batch G are used in the production of the master batch G and the bristle screw shown in FIG. Placing into a rotary twin screw extruder, kneading at a rotation speed of 150 rpm, supply rate of 4.5 kg / h, temperature of 180 ° C., and extruding the kneaded product, a CNT-containing PLA composite material sample pellet with a CNT mixing ratio of 1.0 wt% G-1 was obtained.
(Preparation of sample pellet G-2)
The mesh type same direction in which the PLA pellet and the master batch G are used in the production of the master batch G and the bristle screw shown in FIG. Placing into a rotary twin screw extruder, kneading at a rotation speed of 150 rpm, a supply rate of 4.5 kg / h, and a temperature of 180 ° C., and extruding the kneaded product, a CNT-containing PLA composite material sample with a CNT addition ratio of 2.0 wt% Pellet G-2 was obtained.
（サンプルペレットＧ−３の作製）
上記ＰＬＡペレットを上記マスターバッチＧと同様に図１８に示すブリスタスクリュをセットした上記噛み合い型同方向回転二軸押出機に投入して混練し、混練物を押し出すことによって得た混練ペレットを作製し、この混練ペレットを80℃で2.5時間乾燥させたのち、さらに図１８に示すブリスタスクリュをセットした上記噛み合い型同方向回転二軸押出機に投入して混練し、混練物を押し出すことによって比較用サンプルペレットＧ−３を得た。
(Preparation of sample pellet G-3)
As with the master batch G, the PLA pellets were put into the meshing type co-rotating twin screw extruder set with the bristle screw shown in FIG. 18 and kneaded, and the kneaded pellets obtained by extruding the kneaded material were produced. The kneaded pellets were dried at 80 ° C. for 2.5 hours, and then put into the meshing type co-rotating twin-screw extruder shown in FIG. 18 and kneaded, and the kneaded product was extruded for comparison. Sample pellet G-3 was obtained.
上記のようにして得られたサンプルペレットＧ−１〜Ｇ−３を、80℃で24時間乾燥させたのち、乾燥したサンプルペレットＧ−１およびＧ−３をそれぞれ用い、射出成形機（東洋機械金属社製射出成形機PLASTR ET−40V)によって図１４に示す形状のダンベル試験片Ｇ−１〜Ｇ−３をそれぞれ得た。
射出条件は、スクリュ回転速度100rpm、射出圧150MPa、背圧4.0MPa、保圧70MPa、シリンダ温度200℃、射出速度50mm/sec、保圧時間30 sec、冷却時間60sec、金型温度40℃とした。
The sample pellets G-1 to G-3 obtained as described above were dried at 80 ° C. for 24 hours, and then the dried sample pellets G-1 and G-3 were respectively used. Dumbbell test pieces G-1 to G-3 having the shape shown in FIG. 14 were obtained by an injection molding machine PLASTR ET-40V, manufactured by Metal Corporation.
The injection conditions were: screw rotation speed 100rpm, injection pressure 150MPa, back pressure 4.0MPa, holding pressure 70MPa, cylinder temperature 200 ℃, injection speed 50mm / sec, holding pressure 30sec, cooling time 60sec, mold temperature 40 ℃ .
得られたダンベル試験片の引張強さ、弾性率、破断伸びを、JIS K7161に従って、万能試験機（島津製作所社製Auto graph（AG-100kN））および伸び計（島津製作所社製差動トランス式伸び計ST-50-10-10）を用いて求め、その結果を表４に示した。
なお、引張試験は１つの条件につき９回実施し、９回の結果の内、上位２つの値と下位２つの値を省き、残りの５つの値の平均値を求めた。また、本試験では、引張強さとして最大荷重を初期断面積で割った値を用いた。
The tensile strength, elastic modulus, and elongation at break of the obtained dumbbell specimens were measured according to JIS K7161. Universal testing machine (Auto graph (AG-100kN) manufactured by Shimadzu Corporation) and extensometer (differential transformer type manufactured by Shimadzu Corporation) Table 4 shows the results obtained by using an extensometer ST-50-10-10).
The tensile test was performed nine times for one condition, and the upper two values and the lower two values were omitted from the nine results, and the average value of the remaining five values was obtained. In this test, the value obtained by dividing the maximum load by the initial cross-sectional area was used as the tensile strength.
上記表４から、マトリックス樹脂としてのＰＬＡにＣＮＴを配合することによって、引張強さおよび弾性率が低下しないことがわかる。 From Table 4 above, it can be seen that the tensile strength and elastic modulus are not lowered by blending CNT with PLA as a matrix resin.
上記ダンベル試験片Ｇ−１およびダンベル試験片Ｇ−３のそれぞれから横30mm、縦20mm、厚み4mmの体積抵抗率用サンプル板Ｇ−１、Ｇ−３を５枚ずつ作製し、各５枚の体積抵抗率用サンプル板Ｇ−１、Ｇ−３の中心の抵抗Ｒ[Ω]を１枚１箇所ずつ抵抗率計（三菱化学アナリテック社製、ハイレスタUP、URSプローブ）を用いて測定し、上記定義式（１）を用いて体積抵抗率ρv［Ω・cm］を求めた。測定方式は定電圧印加／漏洩電流測定方式で、RCFの値は0.273、リミッタ電圧は10V、測定時間は10秒とした。
また、上記ダンベル試験片Ｘ−２から、直径25mm、厚さ1.5mmの体積抵抗率用円形サンプル板Ｇ−２を５枚作製し、５枚の体積抵抗率用サンプル板Ｇ−２のそれぞれについて各１箇所ずつ抵抗率計（三菱化学アナリテック社製、ロレスタＧＰ、４端子４探針法、ASPプローブ）を用いて測定し、上記定義式（１）を用いて体積抵抗率ρｖを求めた。
RCFの値は3.362、リミッタ電圧は10V、測定時間は5秒とした。
From each of the dumbbell test piece G-1 and the dumbbell test piece G-3, five volume resistivity sample plates G-1 and G-3 each having a width of 30 mm, a length of 20 mm, and a thickness of 4 mm were prepared. Measure the resistance R [Ω] at the center of each of the volume resistivity sample plates G-1 and G-3 one by one using a resistivity meter (manufactured by Mitsubishi Chemical Analytech, Hiresta UP, URS probe). The volume resistivity ρv [Ω · cm] was determined using the above definition formula (1). The measurement method was a constant voltage application / leakage current measurement method. The RCF value was 0.273, the limiter voltage was 10 V, and the measurement time was 10 seconds.
Further, from the dumbbell test piece X-2, five volume resistivity circular sample plates G-2 having a diameter of 25 mm and a thickness of 1.5 mm were prepared, and each of the five volume resistivity sample plates G-2 was prepared. Each one was measured using a resistivity meter (Mitsubishi Chemical Analytech Co., Ltd., Loresta GP, 4-terminal 4-probe method, ASP probe), and the volume resistivity ρv was determined using the above definition formula (1). .
The RCF value was 3.362, the limiter voltage was 10 V, and the measurement time was 5 seconds.
求められた体積抵抗率用サンプル板Ｇ−２とＧ−３の体積抵抗率ρvの平均値を求め、その結果を対比して、表５に示した。
なお、体積抵抗率ρvの平均値は、それぞれ求められた５つの体積抵抗率の上下１つずつの値を省き、残りの３つの値を平均して求めた。
The average values of the volume resistivity ρv of the obtained volume resistivity sample plates G-2 and G-3 were obtained, and the results were compared with each other and shown in Table 5.
The average value of the volume resistivity ρv was obtained by omitting the upper and lower values of the five obtained volume resistivity values and averaging the remaining three values.
上記表５から、ＣＮＴを配合することによって導電性が高くなることがわかる。 From Table 5 above, it can be seen that the conductivity is increased by adding CNT.
上記体積抵抗率用サンプル板Ｇ−１、Ｇ−３と同じようにして得られた横30mm、縦20mm、厚み4mmの摩擦係数測定用サンプル板Ｇ−１、Ｇ−３のそれぞれについて、摩擦係数および表面粗さを以下のようにして求めた。 For each of the friction coefficient measurement sample plates G-1 and G-3 having a width of 30 mm, a length of 20 mm and a thickness of 4 mm obtained in the same manner as the volume resistivity sample plates G-1 and G-3, the friction coefficient The surface roughness was determined as follows.
（摩擦係数）
摩擦係数測定用サンプル板Ｇ−１、Ｇ−３を摩擦摩耗試験機（レスカ社製FRICTION PLAYER FPR 2000）にセットし、測定パラメータ（荷重：1N、回転半径：3.5mm、測定間隔：0.2s、回転数：27.2837rpm、線速度：1cm/s 、目標摺動距離：144m、測定時間：4時間、応力比：1.61719、常温、相手材：SUJ2（高炭素クロム軸受鋼鋼材））でピンオンディスク法により摩耗摩擦試験を行い、摩擦摩耗試験機の応力検出器から値を読み取り、摩擦力を[応力検出器の値/応力比]より算出した。そして、[摩擦力/荷重値]より摩擦係数値を算出した。
(Coefficient of friction)
Friction coefficient measurement sample plates G-1 and G-3 were set on a friction and wear tester (Resca FRICTION PLAYER FPR 2000), and measurement parameters (load: 1 N, turning radius: 3.5 mm, measurement interval: 0.2 s, Rotational speed: 27.2837 rpm, linear velocity: 1 cm / s, target sliding distance: 144 m, measurement time: 4 hours, stress ratio: 1.61719, normal temperature, mating material: SUJ2 (high carbon chromium bearing steel)) pin-on-disk The wear friction test was conducted by the method, the value was read from the stress detector of the friction wear tester, and the friction force was calculated from [value of stress detector / stress ratio]. Then, a friction coefficient value was calculated from [friction force / load value].
（表面粗さ）
摩擦係数測定用サンプル板Ｇ−１、Ｇ−３の摺動面をレーザー顕微鏡（キーエンス社製形状測定レーザマイクロスコープ VK-X210）を用いて画像解析し、各試料3箇所ずつの表面粗さRaの値を得て、その平均値を求めた。
(Surface roughness)
The sliding surfaces of the friction coefficient measurement sample plates G-1 and G-3 are subjected to image analysis using a laser microscope (shape measurement laser microscope VK-X210 manufactured by Keyence Corporation), and the surface roughness Ra of each of the three samples is measured. Was obtained, and the average value was obtained.
上記のようにして求めた摩擦係数と、表面粗さを表６に対比して示した。 The friction coefficient obtained as described above and the surface roughness are shown in comparison with Table 6.
すなわち、表６から、ＣＮＴを1重量%配合することにより、ＣＮＴを配合しない場合に比べ、飛躍的に表面摩耗量が減ると言える（実物の目視によっても、大いに差が見られた）。 That is, it can be said from Table 6 that the amount of surface wear is drastically reduced by blending 1% by weight of CNTs compared to the case of not blending CNTs (a great difference was also seen by visual inspection of the actual product).
〔ＣＮＴ入りＰＬＡ複合材料の評価２〕
（マスターバッチＨの作製）
熱可塑性を有する樹脂としてのＰＬＡ（Zhejiong Hisun Biomaterials社製REVODE110）ペレット（以下、「ＰＬＡペレット」と記す）１００重量部に機能性ナノフィラーとしてのＣＮＴ（NANOCYL社製NANOCYLTM NC 7000、平均長さ１.５μｍ、平均径９.５ｎｍ、カーボン純度９０％）５.２６重量部（＝５重量％）を噛み合い型同方向回転二軸押出機（Coperion社製 ZSK18、最大回転数1200rpm、スクリュ直径18mm、スクリュ部の長さLとスクリュ径Dの比率Ｌ／Ｄ=40）に投入し、回転数150rpm、供給量3.0kg/h、温度180-220℃で混練押し出し、ペレット状のマスターバッチＨ (直径約3mm、長さ約5mm)を得た。
なお、スクリュは、混練ゾーンが主に図３に示すニーディングディスクによって構成された、図１９に示すニーディングスクリュを用いた。また、加水分解防止のため、ＰＬＡペレットは混錬実験前に90℃で3時間真空乾燥させた。
[Evaluation of PLA composite material with CNT 2]
(Preparation of masterbatch H)
PLA as a resin having thermoplasticity (REVODE110 manufactured by Zhejiong Hisun Biomaterials) (hereinafter referred to as “PLA pellet”) 100 parts by weight CNT as a functional nanofiller (NANOCYL TM NC 7000 manufactured by NANOCYL, average length) 1.5μm, average diameter 9.5nm, carbon purity 90%) 5.26 parts by weight (= 5% by weight) meshing type co-rotating twin screw extruder (Coperion ZSK18, maximum rotation speed 1200rpm, screw diameter 18mm , Put into the ratio L / D = 40) of the length L of the screw part and the screw diameter D, knead and extrude at a rotation speed of 150 rpm, a supply rate of 3.0 kg / h, and a temperature of 180-220 ° C., and a pellet-like masterbatch H ( About 3 mm in diameter and about 5 mm in length).
As the screw, the kneading screw shown in FIG. 19 in which the kneading zone was mainly constituted by the kneading disk shown in FIG. 3 was used. In order to prevent hydrolysis, PLA pellets were vacuum dried at 90 ° C. for 3 hours before the kneading experiment.
（射出成形を用いたサンプルＨ−１の作製）
上記のようにして得られたマスターバッチＨを、80℃で24時間乾燥させたのち、乾燥したマスターバッチＨを用い、射出成形機（東洋機械金属社製射出成形機PLASTR ET−40V)によって図１４に示す形状のダンベル試験片Ｈをそれぞれ得た。
射出条件は、スクリュ回転速度100rpm、射出圧150MPa、背圧4.0MPa、保圧70MPa、シリンダ温度200℃、射出速度50mm/sec、保圧時間30 sec、冷却時間60sec、金型温度40℃とした。
上記ダンベル試験片Ｈから横30mm、縦20mm、厚み4mmのサンプル板Ｈ−１を５枚作製した。
(Production of sample H-1 using injection molding)
After the master batch H obtained as described above was dried at 80 ° C. for 24 hours, the dried master batch H was used to make a drawing with an injection molding machine (an injection molding machine PLASTR ET-40V manufactured by Toyo Kikai Co., Ltd.). Dumbbell test pieces H having the shape shown in FIG. 14 were obtained.
The injection conditions were: screw rotation speed 100rpm, injection pressure 150MPa, back pressure 4.0MPa, holding pressure 70MPa, cylinder temperature 200 ℃, injection speed 50mm / sec, holding pressure 30sec, cooling time 60sec, mold temperature 40 ℃ .
Five sample plates H-1 having a width of 30 mm, a length of 20 mm, and a thickness of 4 mm were prepared from the dumbbell test piece H.
（モノフィラメントＨの作製）
得られたマスターバッチＨを3Dプリンタ用のフィラメント押出機（Noztek社製 "The Noztek Pro ABS and PLA Filament Extruder for 3D Printers"）に投入し、フィラメント径：1.75mmの３Ｄプリンタ用モノフィラメントＨを得た。押出条件は、シリンダ温度210℃とし、フィラメントの巻取りにはフィラメント巻取機（Noztek社製 "Filament Winder"）を用いた。
(Production of monofilament H)
The obtained master batch H was charged into a filament extruder for 3D printers (“The Noztek Pro ABS and PLA Filament Extruder for 3D Printers” manufactured by Noztek) to obtain a monofilament H for a 3D printer having a filament diameter of 1.75 mm. . The extrusion conditions were a cylinder temperature of 210 ° C., and a filament winder (“Filament Winder” manufactured by Noztek) was used for winding the filament.
（３Ｄプリンタ成形を用いたサンプルＨ−２の作製）
つぎに、上記のようにして得られたモノフィラメントＨを用い、熱溶解積層方式３Ｄプリンタ（オープンキューブ社製SCOOVO X9)によって、縦30mm×横20mm×厚さ4mmのサンプル板Ｈ−２を５枚作製した。
プリント条件は、ノズル温度260℃、ヒートベッド温度80℃、層高さ0.4mm、密度100％、造形速度15mm/sとした。
(Production of sample H-2 using 3D printer molding)
Next, using the monofilament H obtained as described above, five sample plates H-2 of 30 mm in length, 20 mm in width, and 4 mm in thickness are obtained using a hot melt lamination type 3D printer (SCOOVO X9 manufactured by OpenCube). Produced.
The printing conditions were a nozzle temperature of 260 ° C., a heat bed temperature of 80 ° C., a layer height of 0.4 mm, a density of 100%, and a modeling speed of 15 mm / s.
上記サンプル板Ｈ−１、Ｈ−２の抵抗Ｒ[Ω]をアナログテスターを用いて測定した。測定方法は、＋、−の両端子を共に表面、かつ任意の距離で接地させることで各サンプル板の最小抵抗値を読み取り、その結果を表７に示した。 The resistance R [Ω] of the sample plates H-1 and H-2 was measured using an analog tester. In the measurement method, the minimum resistance value of each sample plate was read by grounding both the + and-terminals on the surface and at an arbitrary distance, and the results are shown in Table 7.
上記表７から、射出成形品より、３Ｄプリンタ成形品の方が、表面抵抗を小さくすることができ、例えば、電磁波シールド材、電子デバイス用部品、誘導加熱を利用した発熱部品等への応用が期待できると考えられる。 From Table 7 above, the surface resistance of the 3D printer molded product can be made smaller than that of the injection molded product. For example, it can be applied to electromagnetic shielding materials, electronic device components, heat generating components using induction heating, etc. It can be expected.
本発明のフィラメントは、熱溶解積層方式の３Ｄプリンタを用いて、高機能性を備えた造形物を作製するのに好適である。 The filament of the present invention is suitable for producing a model having high functionality using a hot melt lamination type 3D printer.
１ フィラメント
２ 熱可塑性を有するマトリックス樹脂
３ ＣＮＴ（機能性ナノフィラー）
1 Filament 2 Thermoplastic matrix resin 3 CNT (functional nanofiller)
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| JP6153680B1 (en) * | 2016-03-18 | 2017-06-28 | スターライト工業株式会社 | Modeling material for 3D printer, manufacturing method thereof, and three-dimensional modeled object |
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000053871A (en) * | 1998-08-07 | 2000-02-22 | Toray Ind Inc | Resin composition and its preparation |
| JP2002535177A (en) * | 1999-02-01 | 2002-10-22 | ロウエンダール イクストルージョン エンジニアリング，インコーポレイテッド | Screw extruder with improved dispersion mixing element |
| JP2005138422A (en) * | 2003-11-06 | 2005-06-02 | Shinshu Tlo:Kk | Three-dimensional shaping apparatus and yarn-like material |
| JP2009056781A (en) * | 2007-09-03 | 2009-03-19 | Yokohama National Univ | Shaping method of fine structure |
| WO2012107991A1 (en) * | 2011-02-07 | 2012-08-16 | 大陽日酸株式会社 | Composite resinous particles, method of producing composite resinous particles, composite resin molded body, and method of producing same |
| JP2012526885A (en) * | 2009-05-12 | 2012-11-01 | アルケマ フランス | Fiber substrate, method for producing the fiber substrate, and use thereof |
| WO2013129659A1 (en) * | 2012-03-02 | 2013-09-06 | 日立マクセル株式会社 | Method for producing molded body, method for producing molded body having plating film, method for producing resin pellets, molded foam having plating film, foam injection molding method, nozzle unit, and injection molding apparatus |
| WO2013180848A1 (en) * | 2012-05-30 | 2013-12-05 | General Electric Company | Secondary structures for aircraft engines and processes therefor |
| WO2014072148A1 (en) * | 2012-11-09 | 2014-05-15 | Evonik Industries Ag | Use and production of coated filaments for extrusion-based 3d printing processes |
| WO2015019212A1 (en) * | 2013-08-09 | 2015-02-12 | Kimberly-Clark Worldwide, Inc. | Polymeric material for three-dimensional printing |
| WO2015037574A1 (en) * | 2013-09-11 | 2015-03-19 | 東レ株式会社 | Material for fused-deposition-type three-dimensional modeling, and filament for fused-deposition-type 3d printing device |
| WO2015109141A1 (en) * | 2014-01-17 | 2015-07-23 | Lubrizol Advanced Materials, Inc. | Methods of using thermoplastic polyurethanes in fused deposition modeling and systems and articles thereof |
| WO2015130401A2 (en) * | 2013-12-26 | 2015-09-03 | Texas Tech University System | Microwave-induced localized heating of cnt filled polymer composites for enhanced inter-bead diffusive bonding of fused filament fabricated parts |
| WO2015182681A1 (en) * | 2014-05-29 | 2015-12-03 | 日本合成化学工業株式会社 | Support for laminate shaping and laminate shaped article using same, and method for manufacturing laminate shaped article |
-
2015
- 2015-07-13 JP JP2015139592A patent/JP6860774B2/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000053871A (en) * | 1998-08-07 | 2000-02-22 | Toray Ind Inc | Resin composition and its preparation |
| JP2002535177A (en) * | 1999-02-01 | 2002-10-22 | ロウエンダール イクストルージョン エンジニアリング，インコーポレイテッド | Screw extruder with improved dispersion mixing element |
| JP2005138422A (en) * | 2003-11-06 | 2005-06-02 | Shinshu Tlo:Kk | Three-dimensional shaping apparatus and yarn-like material |
| JP2009056781A (en) * | 2007-09-03 | 2009-03-19 | Yokohama National Univ | Shaping method of fine structure |
| JP2012526885A (en) * | 2009-05-12 | 2012-11-01 | アルケマ フランス | Fiber substrate, method for producing the fiber substrate, and use thereof |
| WO2012107991A1 (en) * | 2011-02-07 | 2012-08-16 | 大陽日酸株式会社 | Composite resinous particles, method of producing composite resinous particles, composite resin molded body, and method of producing same |
| WO2013129659A1 (en) * | 2012-03-02 | 2013-09-06 | 日立マクセル株式会社 | Method for producing molded body, method for producing molded body having plating film, method for producing resin pellets, molded foam having plating film, foam injection molding method, nozzle unit, and injection molding apparatus |
| WO2013180848A1 (en) * | 2012-05-30 | 2013-12-05 | General Electric Company | Secondary structures for aircraft engines and processes therefor |
| WO2014072148A1 (en) * | 2012-11-09 | 2014-05-15 | Evonik Industries Ag | Use and production of coated filaments for extrusion-based 3d printing processes |
| WO2015019212A1 (en) * | 2013-08-09 | 2015-02-12 | Kimberly-Clark Worldwide, Inc. | Polymeric material for three-dimensional printing |
| WO2015037574A1 (en) * | 2013-09-11 | 2015-03-19 | 東レ株式会社 | Material for fused-deposition-type three-dimensional modeling, and filament for fused-deposition-type 3d printing device |
| WO2015130401A2 (en) * | 2013-12-26 | 2015-09-03 | Texas Tech University System | Microwave-induced localized heating of cnt filled polymer composites for enhanced inter-bead diffusive bonding of fused filament fabricated parts |
| WO2015109141A1 (en) * | 2014-01-17 | 2015-07-23 | Lubrizol Advanced Materials, Inc. | Methods of using thermoplastic polyurethanes in fused deposition modeling and systems and articles thereof |
| WO2015182681A1 (en) * | 2014-05-29 | 2015-12-03 | 日本合成化学工業株式会社 | Support for laminate shaping and laminate shaped article using same, and method for manufacturing laminate shaped article |
Non-Patent Citations (1)
| Title |
|---|
| SHOFNER, M. L. ET AL.: "Nanofiber-Reinforced Polymers Prepared by Fused Deposition Modeling", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 89, JPN6020007423, 2003, pages 3081 - 3090, XP002376649, ISSN: 0004326582 * |
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