JP2019059026A - Molding material - Google Patents
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- JP2019059026A JP2019059026A JP2017183212A JP2017183212A JP2019059026A JP 2019059026 A JP2019059026 A JP 2019059026A JP 2017183212 A JP2017183212 A JP 2017183212A JP 2017183212 A JP2017183212 A JP 2017183212A JP 2019059026 A JP2019059026 A JP 2019059026A
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本発明は造形材料に関し、特に材料押出型の付加製造法による３Ｄプリンター用の造形材料に関する。 The present invention relates to a build material, and in particular to a build material for 3D printers by additive manufacturing method of material extrusion type.
３ＤＣＡＤの作図データや３Ｄスキャンデータを基に立体（３次元のオブジェクト）を造形する３Ｄプリンターは、近年急速に普及している。３Ｄプリンターは付加製造装置の一種であり、手法や用いる造形材料によって、光造形、粉末焼結造形、材料押出型造形等の種類がある。近年、特に個人向けにおいては、低価格の材料押出型３Ｄプリンターが普及してきている。 In recent years, 3D printers that form three-dimensional objects (three-dimensional objects) based on 3D CAD drawing data and 3D scan data are rapidly spreading. The 3D printer is a type of additive manufacturing device, and there are types such as optical shaping, powder sinter shaping, and material extrusion type shaping, depending on the method and the modeling material used. In recent years, low-cost material extrusion type 3D printers have become widespread, particularly for individuals.
材料押出型３Ｄプリンターのための造形材料としては、一般にストランド状の形態のものが用いられており、これはフィラメントなどと呼称されている。材料押出型３Ｄプリンターでは、造形材料をプーリーで押出ヘッドへ送り込み、押出ヘッドに付設されたヒーターで造形材料を融解する。押出ヘッドはコンピュータでプログラム化した描画プロセスに従って造形テーブル上を動きながら、押し出された溶融物を造形テーブルに押し付けるように積層し、所望の形状の造形物を得る仕組みである。そのため、造形物の側面には積層ピッチごとに縞状の積層痕が残る場合が多い。 As a forming material for a material extrusion type 3D printer, one in a strand form is generally used, and this is called a filament or the like. In the material extrusion type 3D printer, a build material is fed to an extrusion head by a pulley, and the build material is melted by a heater attached to the extrusion head. The extrusion head is a mechanism for laminating the extruded melt so as to press it against the modeling table while moving on the modeling table according to a computer-programmed drawing process, to obtain a molded article having a desired shape. Therefore, in many cases, stripe-like lamination marks are left on the side surface of the shaped article for each lamination pitch.
造形材料に使用される素材としては、ＡＢＳ（アクリロニトリル・ブタジエン・スチレン）とポリ乳酸の二種が主流である。たとえばポリ乳酸については、特許文献１に開示がある。環境性、安全性、低反り性などの観点ではポリ乳酸が有利である。 As a material used for a modeling material, ABS (acrylonitrile butadiene styrene) and two types of polylactic acid are in use. For example, polylactic acid is disclosed in Patent Document 1. Polylactic acid is advantageous in terms of environment, safety, low warpage, and the like.
ところで、造形物表面の積層痕が好ましくない用途においては、造形物に対して研磨や薬剤処理などの表面仕上げが行われるが、表面仕上げ性ではポリ乳酸はＡＢＳに劣る。そのため、表面仕上げ性を向上したポリ乳酸製の造形材料が望まれている。特に薬剤に浸漬または噴霧するなどにより表面加工する手法が簡便であり、この手法で好適に処理できることが望まれている。 By the way, in applications where lamination marks on the surface of a shaped object are not preferable, surface finishing such as polishing or chemical treatment is performed on the shaped object, but polylactic acid is inferior to ABS in surface finishability. Therefore, a modeling material made of polylactic acid with improved surface finish is desired. In particular, a method of surface processing by immersion or spraying in a drug is simple and it is desired that the method can be suitably processed by this method.
本発明は、材料押出型の付加製造に用いる造形材料であって、環境性、安全性、低反り性などポリ乳酸特有の性能を維持しつつ、造形後に表面仕上げの施し易い造形材料を提供することを技術的な課題とする。 The present invention is a shaped material used for additive production of a material extrusion type, and provides a shaped material that is easy to be subjected to surface finish after shaping while maintaining the performance peculiar to polylactic acid such as environmental property, safety and low warping property. To be a technical issue.
本発明は、上記課題を解決するものであり、材料押出型の付加製造に用いる造形材料であって、ポリ乳酸系樹脂とポリ酢酸ビニル樹脂とを混合状態で含有し、ポリ乳酸系樹脂とポリ酢酸ビニル樹脂との混合比率が、質量分率にて、ポリ乳酸系樹脂：ポリ酢酸ビニル樹脂＝９５：５〜７５：２５であることを特徴とする。 The present invention solves the above-mentioned problems, and is a forming material used for additive production of material extrusion type, containing a polylactic acid resin and a polyvinyl acetate resin in a mixed state, and a polylactic acid resin and a poly It is characterized in that the mixing ratio with the vinyl acetate resin is, in mass fraction, polylactic acid-based resin: polyvinyl acetate resin = 95: 5 to 75:25.
本発明の造形材料によれば、ストランド状の形態であることが好適である。 According to the build material of the present invention, it is preferred that it is in the form of a strand.
本発明の造形方法は、上記の造形材料を用いて造形を行い、得られた造形品の表面を薬剤処理および、または研磨処理することにより、前記表面の平滑性を向上させることを特徴とする。 The shaping method of the present invention is characterized by performing shaping using the above-mentioned shaping material, and treating the surface of the obtained shaped article with a drug treatment and / or polishing to improve the smoothness of the surface. .
本発明の造形材料によれば、ポリ乳酸系樹脂とポリ酢酸ビニル樹脂とを混合状態で含有し、ポリ乳酸系樹脂とポリ酢酸ビニル樹脂との混合比率が、質量分率にて、ポリ乳酸系樹脂：ポリ酢酸ビニル樹脂＝９５：５〜７５：２５であるため、環境性、安全性、低反り性などポリ乳酸特有の性能を維持しつつ、造形後に表面仕上げを施し易い。また本発明の造形方法によれば、上記の造形材料を用いて造形を行い、得られた造形品の表面を薬剤処理および、または研磨処理することにより、前記表面の平滑性を向上させるため、平滑性に優れた造形品を得ることができる。このため本発明によれば、微細な造形での表現力向上や、樹脂型として使用した際の積層痕の転写抑制が期待できる。 According to the molding material of the present invention, the polylactic acid-based resin and the polyvinyl acetate resin are contained in a mixed state, and the mixing ratio of the polylactic acid-based resin and the polyvinyl acetate resin is, by mass fraction, the polylactic acid-based resin Resin: Polyvinyl acetate resin = 95: 5 to 75:25, and therefore, it is easy to apply surface finish after shaping while maintaining the performance peculiar to polylactic acid such as environmental property, safety and low warping property. Further, according to the shaping method of the present invention, the surface of the obtained shaped article is treated with a drug and / or polished to improve the smoothness of the surface by performing the shaping using the above-mentioned shaping material. A shaped article excellent in smoothness can be obtained. Therefore, according to the present invention, it is possible to expect improvement in expressiveness in fine modeling and suppression of transfer of lamination marks when used as a resin mold.
本発明の造形材料は、ポリ乳酸系樹脂を主成分として構成される。ポリ乳酸系樹脂は、光学異性体であるＬ−乳酸とＤ−乳酸とを含有する重合体またはこれらの共重合体である。例えば、Ｌ−乳酸を主体としＤ−乳酸の含有量を４モル％以下としたものを用いるとよい。ポリ乳酸系樹脂におけるＤ−乳酸の含有量とは、ポリ乳酸樹脂を構成する総乳酸単位のうち、Ｄ−乳酸単位が占める割合（モル％）をいう。例えば、Ｄ−乳酸の含有量が１．０モル％のポリ乳酸系樹脂の場合、このポリ乳酸系樹脂は、Ｄ−乳酸単位が占める割合が１．０モル％であり、Ｌ−乳酸単位が占める割合が９９．０モル％である。 The molding material of the present invention is composed mainly of a polylactic acid-based resin. The polylactic acid-based resin is a polymer containing L-lactic acid which is an optical isomer and D-lactic acid, or a copolymer of these. For example, it is good to use what used L-lactic acid as a main, and made content of D-lactic acid 4 mol% or less. The content of D-lactic acid in the polylactic acid-based resin means the ratio (mol%) of the D-lactic acid unit to the total lactic acid units constituting the polylactic acid resin. For example, in the case of a polylactic acid-based resin in which the content of D-lactic acid is 1.0 mol%, in the polylactic acid-based resin, the proportion of the D-lactic acid unit is 1.0 mol%, and the L-lactic acid unit is The proportion is 99.0 mol%.
ポリ乳酸系樹脂には他の共重合単位が加わっていてもよく、たとえばグリコール酸、カプロラクトン、エチレングリコールなどを共重合することができる。共重合の構造は、ブロック共重合、ランダム共重合、グラフト共重合など、特に限定されない。 Other copolymerized units may be added to the polylactic acid-based resin, and for example, glycolic acid, caprolactone, ethylene glycol and the like can be copolymerized. The structure of copolymerization is not particularly limited, such as block copolymerization, random copolymerization, graft copolymerization and the like.
本発明の造形材料は、主としてポリ乳酸系樹脂とポリ酢酸ビニル樹脂とが混合したものである。 The molding material of the present invention is mainly a mixture of a polylactic acid-based resin and a polyvinyl acetate resin.
ポリ酢酸ビニル樹脂は、重合度が５００〜２，０００程度のものが好ましい。重合度が低すぎると、液状となって、ポリ乳酸系樹脂とブレンドした後にブリードアウトする恐れがある。反対に重合度が高すぎると、ポリ乳酸系樹脂との均一な分散が難しくなる。 The polyvinyl acetate resin preferably has a degree of polymerization of about 500 to 2,000. If the degree of polymerization is too low, it may become liquid and bleed out after blending with the polylactic acid-based resin. On the other hand, if the degree of polymerization is too high, uniform dispersion with the polylactic acid resin becomes difficult.
ポリ酢酸ビニル樹脂には他の共重合単位が加わっていてもよく、たとえばエチレン、エチレングリコール、ビニルアルコール、塩化ビニル、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステルなどを共重合単位として含んでいてもよい。共重合の構造は、ブロック共重合、ランダム共重合、グラフト共重合など、特に限定されない。 Other copolymerized units may be added to the polyvinyl acetate resin, and for example, ethylene, ethylene glycol, vinyl alcohol, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester, etc. are contained as copolymerized units. It may be. The structure of copolymerization is not particularly limited, such as block copolymerization, random copolymerization, graft copolymerization and the like.
ポリ乳酸系樹脂とポリ酢酸ビニル樹脂との混合方法は、特に限定されないが、一般的な混練機を用いた溶融混練などの方法を採用できる。ポリ乳酸系樹脂とポリ酢酸ビニルの混合比率は、質量分率にて、ポリ乳酸系樹脂：ポリ酢酸ビニル樹脂＝９５：５〜７５：２５の範囲であることが必要である。ポリ酢酸ビニル樹脂の比率が低すぎると、造形物の表面仕上げ性を十分に改善することができない。またポリ酢酸ビニル樹脂の比率が高すぎると、混練後の分散状態が悪化し、フィラメント状の造形材料を製造する場合には、作製時の操業性悪化や寸法精度低下につながる。 The method of mixing the polylactic acid-based resin and the polyvinyl acetate resin is not particularly limited, but a method such as melt-kneading using a general kneader can be adopted. The mixing ratio of the polylactic acid resin and the polyvinyl acetate needs to be in the range of polylactic acid resin: polyvinyl acetate resin = 95: 5 to 75:25 in mass fraction. If the proportion of the polyvinyl acetate resin is too low, the surface finish of the shaped article can not be sufficiently improved. When the proportion of the polyvinyl acetate resin is too high, the dispersion state after kneading is deteriorated, and when manufacturing a filamentous shaped material, it leads to the deterioration of the operability at the time of preparation and the deterioration of the dimensional accuracy.
造形材料を構成する樹脂には、本発明の効果を損なわない範囲であれば、上記したポリ乳酸系樹脂およびポリ酢酸ビニル樹脂に加えて、副成分として、ポリグリコール酸、ポリ力プロラクトン、ポリブチレンサクシネ一ト、ポリエチレンサクシネート、ポリブチレンアジペートテレフタレート、ポリブチレンサクシネートテレフタレート等から選ばれる一種または二種以上の樹脂を含有してもよい。また、種々の機能性を付与する各種添加剤、機能剤、フィラー等を添加してもよい。例えばポリブチレンアジペートテレフタレートを添加すると、得られる造形材料に良好な柔軟性を付与することができ、炭素繊維を添加すると造形材料の強度や剛性を向上することができ、ワックスを添加すると造形材料作製時や付加製造時の溶融樹脂の流動性を調整することができる。 In addition to the above-mentioned polylactic acid-based resin and polyvinyl acetate resin, the resin constituting the shaping material may be polyglycolic acid, polyforce prolactone, poly as a minor component, as long as the effects of the present invention are not impaired. It may contain one or more resins selected from butylene succinate, polyethylene succinate, polybutylene adipate terephthalate, polybutylene succinate terephthalate and the like. In addition, various additives, functional agents, fillers and the like which impart various functionalities may be added. For example, when polybutylene adipate terephthalate is added, good flexibility can be imparted to the resulting shaped material, when carbon fibers are added, strength and rigidity of the shaped material can be improved, and when wax is added, shaped material preparation It is possible to adjust the fluidity of the molten resin at the time of production or at the time of additive production.
本発明の造形材料は、ストランド状の形態をしていることが好ましい。その直径は、１〜５ｍｍほどである。特に、直径１．７５ｍｍや２．８５ｍｍの造形材料は、市販の熱溶解積層法による３Ｄプリンターに適合するため好ましい。ストランド状の形態の製法は、特に限定されない。例えば、溶融押出機で押出した後、液相または気相にて冷却し、所定速度で引き取ることで、作製することができる。造形材料としての機械的物性を改善するために、ストランド状の形態の樹脂に延伸を施してもよい。また乾燥やアニーリングなどの目的で熱処理してもよい。 The shaping material of the present invention is preferably in the form of a strand. The diameter is about 1 to 5 mm. In particular, a modeling material having a diameter of 1.75 mm or 2.85 mm is preferable because it is compatible with a commercially available hot melt lamination method 3D printer. The preparation method of the strand form is not particularly limited. For example, after extruding with a melt extruder, it can be produced by cooling in a liquid phase or a gas phase and pulling at a predetermined speed. The resin in the form of strands may be stretched in order to improve the mechanical properties as a modeling material. Further, heat treatment may be performed for the purpose of drying or annealing.
本発明の造形材料を用いて３Ｄプリンターにて得られた造形品は、薬剤を用いて表面を溶解したり、表面を機械的に研磨したりすることで、その表面の平滑化処理を行うことが可能である。特に、本発明の造形材料によれば、ポリ乳酸系樹脂にポリ酢酸ビニル樹脂を所定量だけ添加したものであるために、ポリ乳酸系樹脂だけて構成された造形材料に比べて、上記した薬剤を用いた表面の溶解や、表面の機械的な研磨によって、その表面の平滑化処理を容易に行うことができる。そのための薬剤としては、メタノール、エタノール、イソプロピルアルコールなどのアルコール類、アセトン、メチルエチルケトンなどのケトン類、酢酸エチル、酢酸ブチルなどのエステル類などを、単独または複数種を混合した状態で、好ましく用いることができる。 The molded article obtained by the 3D printer using the molding material of the present invention is subjected to a smoothing treatment of the surface by dissolving the surface with a drug or mechanically polishing the surface. Is possible. In particular, according to the molding material of the present invention, since a predetermined amount of polyvinyl acetate resin is added to the polylactic acid-based resin, the above-described drug is compared to the molding material constituted of only the polylactic acid-based resin. The surface can be easily smoothed by dissolving the surface with the use or mechanical polishing of the surface. As the drug for that purpose, it is preferable to use alcohols such as methanol, ethanol, isopropyl alcohol etc., ketones such as acetone, methyl ethyl ketone etc., esters such as ethyl acetate, butyl acetate etc. singly or in a mixture of plural kinds. Can.
実施例１
ポリ乳酸系樹脂（ネイチャーワークス社製「６２０１Ｄ」、Ｌ−乳酸の含有量９８．６モル％、Ｄ−乳酸の含有量１．４モル％）９５質量％と、ポリ酢酸ビニル樹脂（デンカ社製「ＳＮ−０９Ｔ」、重合度１０００〜１１５０）５質量％とを原料とした。これらの原料を使用し、二つのシリンダーおよびダイスを１９０℃に設定した二軸混練装置（東洋製機社製）を用いて溶融混練し、押出した樹脂を２０℃の水で急冷させて引き取ることにより、直径約１．７５ｍｍのストランド状物を得た。このストランド状物を減圧乾燥して、実施例１の造形材料を得た。
Example 1
Polylactic acid resin (Natureworks "6201D", content of L-lactic acid 98.6 mol%, content of D-lactic acid 1.4 mol%) 95% by mass, polyvinyl acetate resin (Denca Corporation) "SN-09T", polymerization degree 1000-1150) 5 mass% was used as a raw material. Using these raw materials, melt kneading using a twin-screw kneader (made by Toyo Seisakusho Co., Ltd.) in which two cylinders and dies are set at 190 ° C., and the extruded resin is quenched with water at 20 ° C. Thus, a strand having a diameter of about 1.75 mm was obtained. The strand material was dried under reduced pressure to obtain the shaping material of Example 1.
実施例２
実施例１と比べて、ポリ乳酸系樹脂の割合を９０質量％に変更するとともに、ポリ酢酸ビニル樹脂の割合を１０質量％に変更した。そして、それ以外は実施例１と同様にして、実施例２の造形材料を得た。
Example 2
While changing the ratio of polylactic acid-type resin to 90 mass% compared with Example 1, the ratio of polyvinyl acetate resin was changed to 10 mass%. And the modeling material of Example 2 was obtained like Example 1 except it.
実施例３
実施例１と比べて、ポリ乳酸系樹脂の割合を８０質量％に変更するとともに、ポリ酢酸ビニル樹脂の割合を２０質量％に変更した。そして、それ以外は実施例１と同様にして、実施例３の造形材料を得た。
Example 3
While changing the ratio of polylactic acid-type resin to 80 mass% compared with Example 1, the ratio of polyvinyl acetate resin was changed to 20 mass%. And the modeling material of Example 3 was obtained like Example 1 except it.
実施例４
実施例１と比べて、ポリ乳酸系樹脂の割合を７６質量％に変更するとともに、ポリ酢酸ビニル樹脂の割合を２０質量％に変更した（ポリ乳酸：ポリ酢酸ビニル＝７９：２１（質量分率））。さらに、ポリブチレンアジペートテレフタレート樹脂（ＢＡＳＦ社製「Ｅｃｏｆｌｅｘ Ｆ Ｂｌｅｎｄ Ｃ１２００」）４重量％を添加した。そして、それ以外は実施例１と同様にして、実施例４の造形材料を得た。
Example 4
While changing the ratio of polylactic acid-type resin to 76 mass% compared with Example 1, the ratio of polyvinyl acetate resin was changed to 20 mass% (poly lactic acid: polyvinyl acetate = 79:21 (mass fraction )). Further, 4% by weight of polybutylene adipate terephthalate resin ("Ecoflex F Blend C1200" manufactured by BASF Corporation) was added. And the modeling material of Example 4 was obtained like Example 1 except it.
比較例１
実施例１と比べて、ポリ乳酸系樹脂の割合を１００質量％に変更するとともに、ポリ酢酸ビニル樹脂の割合を０質量％に変更した。すなわち、ポリ乳酸系樹脂のみを原料とした。そして、それ以外は実施例１と同様にして、比較例１の造形材料を得た。
Comparative Example 1
As compared with Example 1, while changing the ratio of polylactic acid-type resin to 100 mass%, the ratio of polyvinyl acetate resin was changed to 0 mass%. That is, only polylactic acid-based resin was used as a raw material. And except that, it carried out similarly to Example 1, and obtained the modeling material of the comparative example 1. FIG.
比較例２
実施例１と比べて、ポリ乳酸系樹脂の割合を９８質量％に変更するとともに、ポリ酢酸ビニル樹脂の割合を２質量％に変更した。そして、それ以外は実施例１と同様にして、比較例２の造形材料を得た。
Comparative example 2
While changing the ratio of polylactic acid-type resin to 98 mass% compared with Example 1, the ratio of polyvinyl acetate resin was changed to 2 mass%. And the modeling material of comparative example 2 was obtained like Example 1 except it.
比較例３
実施例１と比べて、ポリ乳酸系樹脂の割合を７０質量％に変更するとともに、ポリ酢酸ビニル樹脂の割合を３０質量％に変更した。そして、それ以外は実施例１と同様にして造形材料を得ようと試みたが、ストランド状物を安定して採取できなかった。
Comparative example 3
While changing the ratio of polylactic acid-type resin to 70 mass% compared with Example 1, the ratio of polyvinyl acetate resin was changed to 30 mass%. And although it tried to obtain a modeling material like Example 1 except it, the strand-like thing was not able to be extracted stably.
フィラメント加工性
実施例１〜４および比較例１〜３の造形材料を採取する際の操業性を、下記の指標で◎、○、×の３段階に評価した。
Filament processability
The operability at the time of collecting the forming materials of Examples 1 to 4 and Comparative Examples 1 to 3 was evaluated in three stages of ◎, 、, and × with the following index.
◎ ： 吐出がきわめて安定しており、工程通過性も優秀であった。 :: The discharge was extremely stable, and the process passability was also excellent.
○ ： 吐出または工程通過性が良好であった。 :: Ejection or process passability was good.
× ： 吐出および／または工程通過性に不良が見られた。 X: Defective discharge and / or processability was observed.
表面仕上げ試験
３Ｄプリンター「Ｍｏｍｅｎｔ（Ｍｏｍｅｎｔ社製）」を用いて、積層ピッチを０．２ｍｍに設定し、処理温度１９０℃で造形した試験片（６３ｍｍ×２０ｍｍ×２ｍｍ）を、密閉空間中で、アセトンが蒸散している雰囲気下にて、それぞれ２４℃で１２時間置き、試験片表面の平滑化を下記の指標で◎、○、×の３段階に評価した。
Surface Finishing Test A test piece (63 mm × 20 mm × 2 mm) formed at a processing temperature of 190 ° C., with a lamination pitch of 0.2 mm, using a 3D printer “Moment (manufactured by Moment)”, in a closed space, Each of the samples was placed at 24 ° C. for 12 hours in an atmosphere in which acetone is transpirationed, and the smoothing of the surface of the test piece was evaluated in three stages of ◎, 、, and × with the following index.
◎ ： 表面の凹凸が目立たず、十分平滑に仕上がった。 ◎: The surface unevenness was not noticeable and finished sufficiently smooth.
○ ： 表面の凹凸が緩和し、平滑になった。 ○: The surface irregularities were relaxed and smooth.
× ： 表面の凹凸が殆ど変っておらず、表面仕上げできていなかった。 X: The surface irregularities were hardly changed, and the surface was not finished.
評価結果は、下表のとおりである。適度な量のポリ酢酸ビニル樹脂を添加することにより、フィラメント加工性を維持しながら、表面仕上げ性を併せ持った造形材料を得ることができた。ポリ酢酸ビニル樹脂の添加量が少ないと表面仕上げ性が十分には得られず、添加量が多いとフィラメント加工時の操業性が悪化してしまった。 The evaluation results are as shown in the table below. By adding an appropriate amount of polyvinyl acetate resin, it was possible to obtain a shaped material having surface finishability while maintaining filament processability. When the addition amount of the polyvinyl acetate resin is small, the surface finish can not be sufficiently obtained, and when the addition amount is large, the operability at the time of filament processing is deteriorated.
特に、実施例４の造形材料およびこれを用いて造形した試験片は、ポリブチレンアジペートテレフタレート樹脂を適量添加したものであったため、実施例３のものに比べて柔軟化しており、手で曲げたところ実施例３のものと比較して弾力性があり割れ難いものであった。 In particular, since the molding material of Example 4 and the test piece formed using this were those obtained by adding an appropriate amount of polybutylene adipate terephthalate resin, they are softened as compared with those of Example 3, and were bent by hand. By the way, compared with the thing of Example 3, it was elastic and was hard to be broken.
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| JP2008222873A (en) * | 2007-03-13 | 2008-09-25 | Taiyo Kagaku Kk | Molded and coated article and method for producing molded and coated article |
| 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 |
| CN105985615A (en) * | 2015-02-13 | 2016-10-05 | 汉达精密电子(昆山)有限公司 | Polylactic acid composite material and its product |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008222873A (en) * | 2007-03-13 | 2008-09-25 | Taiyo Kagaku Kk | Molded and coated article and method for producing molded and coated article |
| 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 |
| CN105985615A (en) * | 2015-02-13 | 2016-10-05 | 汉达精密电子(昆山)有限公司 | Polylactic acid composite material and its product |
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