JP5039549B2 - 三次元物体のための支持構造を作成するための原料 - Google Patents
三次元物体のための支持構造を作成するための原料 Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/08—Coating a former, core or other substrate by spraying or fluidisation, e.g. spraying powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/36—Feeding the material on to the mould, core or other substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/50—Shaping under special conditions, e.g. vacuum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
- B29K2055/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0008—Anti-static agents
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Description
本発明は、アディティブ法造形技術を用いた三次元物体の製造に関する。より詳細には、本発明は、所定のパターンで凝固可能な材料を堆積させることによる三次元物体の形成と、このような三次元物体を作製する際にその一部を支持するための支持構造の提供とに関する。
[発明の簡単な概要]
本発明は三次元物体を作成するための組成物に関する。この組成物は可塑剤とベースポリマーとを含む。ここで、ベースポリマーはカルボン酸を含む。また、組成物はアルカリ溶液に溶解する。
[詳細な説明]
アルカリ可溶性熱可塑性材料を採用する本発明の工程は、凝固して物体(目的物)を形成する溶融造形材を堆積させる三次元造形システムにおける使用に適用できる。
造形物を槽40内に設置する前に台座14を造形物26から取り外してもよい。または、槽40内に設置する際も台座14を造形物26に付着させたまま残してもよい。後者の場合、アルカリ可溶性発泡体等のアルカリ可溶性台座が望ましいといえる。
<アセテート>
クミルフェニルアセテート;
グリセリルトリアセテート、トリアセチン;
<アジピン酸>
アジピン酸ジブトキシエトキシエチル
アジピン酸ジブトキシエチル
アジピン酸ジイソブチル
<クエン酸>
クエン酸トリ−n−エチル;
クエン酸アセチルトリ−n−エチル;
クエン酸トリ−n−プロピル;
クエン酸アセチルトリ−n−プロピル;
クエン酸トリ−n−ブチル;
クエン酸アセチルトリ−n−ブチル;
<フタレート>
DBP、ジブチルフタレート(部分的相溶性);
BBP、ブチルベンジルフタレート(完全相溶性);
DBEP、ジブトキシエチルフタレート(部分的相溶性);
2−エチルヘキシルベンジルフタレート;
テトラメチルオキサオノノニルベンジルフタレート;
<安息香酸>
ジプロピレングリコールジベンゾエート;
ジエチレングリコールジベンゾエート;
ジプロピレングリコールジベンゾエートとジエチレングリコールジベンゾエートとの50/50混合物;
1,4−シクロヘキサンジメンタノールジベンゾエート;
グリセリルトリベンゾエート;
クミルフェニルベンゾエート;
ネオペンチルグリコールジベンゾエート;
ペンタエリスリトールテタベンゾエート;
<リン酸塩>
ブチルフェニルジフェニルホスフェート;
TCP、トリクレジルホスフェート;
2−エチルヘキシルジフェニルホスフェート;
イソデシルジフェニルホスフェート;
C12−C16アルキルジフェニルホスフェート;
イソプロピル化トリフェニルホスフェート;
<ポリグリコール>
ポリエチレングリコール;
ポリプロピレングリコール
特に好ましい可塑剤は高い熱安定性を有し、当該可塑剤としては、p−t−ブチルフェニルジフェニルホスフェート、ブチルベンジルフタレート、7−(2,6,6,8−テトラメチル−4−オキサ−3−オキソノニル)ベンジルフタレート、C7/C9アルキルベンジルフタレート、2−エチルヘキシルジフェニルホスフェート、イソデシルジフェニルホスフェートが含まれる。
<実施例>
以下、本発明を実施例の中でより具体的に説明するが、これらは例示のものとしてのみ意図され、本発明の範囲内の多数の修正形態および変形形態が当業者にとっては明らかであろう。明記する場合を除いて、以下の実施例で報告する全ての部品、パーセンテージ、比率は、重量基準であり、実施例内の全ての試薬は、ミズーリ州セントルイスのシグマアルドリッチ化学会社等の一般的な化学製品供給業者から得られ、または購入可能であり、あるいは従来からある技術によって合成されてもよい。
<実施例I>
アルカリ可溶性熱可塑性材料は、74%のベースポリマーと、26%のブチルフェニルジフェニルホスフェート可塑剤とを含有する。ベースポリマーは、メタクリル酸とメタクリル酸メチルとの高分子量および低分子量の共重合体からなる。ベースポリマーは、およそ50%の高分子量共重合体と50%の低分子量共重合体とを含有し、それぞれプラスマイナス5%である。各共重合体では、重量%比1:2のメタクリル酸とメタクリル酸メチルとを含有する。高分子量共重合体は高粘度(低メルトフロー)という特徴を有し、低分子量共重合体は低粘度(高メルトフロー)という特徴を有する。共重合体のメルトフローは、各共重合体を26重量%のブチルフェニルジフェニルホスフェート可塑剤を用いて別々に可塑化することにより計測される。可塑化された高分子量共重合体のメルトフローインデックスは、230℃での1.2キログラムの荷重下においてASTM D1238に準拠して測定すると、0.4グラム/10分から0.8グラム/10分の範囲内である。可塑化された低分子量共重合体のメルトフローインデックスは、28グラム/10分から35グラム/10分の範囲内である。結果として生じる熱可塑性組成物は、5グラム/10分から6.5グラム/10分のメルトフローインデックスと、約90℃のガラス転移温度とを有する。
<実施例II>
アルカリ可溶性可塑性材料は、79%(+/−5%)のベースポリマーと21%(+/−5%)のブチルフェニルジフェニルホスフェート可塑剤とを含有する。ベースポリマーは重量%比1:1のメタクリル酸とメタクリル酸メチルとから成り、135,000グラム/モルの分子量を有する。ベースポリマーを可塑剤に混ぜ合わせる前に、ベースポリマーは、ポリマーから水分を除去するために220℃のオーブンにおいて低圧で加熱される。10〜15時間の低圧での加熱が、ベースポリマーを乾燥させるために十分であると認められた。結果として生じた乾燥ポリマーは粒状の形態であり、可塑剤と共に周知の方法で撹拌機に供給される。結果として生じるアルカリ可溶性熱可塑性材料は、230℃での1.2キログラムの荷重下においてASTM D1238に準拠して測定したところ、5グラム/10分から6.5グラム/10分の範囲のメルトフローインデックスを有する。アルカリ可溶性熱可塑性材料のガラス転移開始温度は約101.5℃であり、ガラス転移最高温度は約111℃である。
<実施例III>
アルカリ可溶性熱可塑性材料は上述の実施例IIの場合と同じ組成物を有するが、この実施例では、水分を除去するためのベースポリマーの加熱は行われない。実施例IIの場合と同様に、アルカリ可溶性熱可塑性材料は、加工され、Stratasys FDM(登録商標)機から押し出され、そして堆積させられる。これにより、ABS熱可塑性剤で作製された造形物の支持構造が形成される。この実施例では、アルカリ可溶性熱可塑性材料が、押出ヘッドから適正量よりも多量の「滲出」を示したが、それ以外では、三次元造形に好適な特性を示した。「滲出」は組成物内に存在する水分に起因する。もし、材料ディスペンサが積極的な分離機構を有する造形システムで使用されれば、Stratasys FDM(登録商標)機内で示された「滲出」作用は生じないであろうし、この実施例IIIにかかる材料を有効に利用することができる。
<実施例IV>
可塑剤のガラス転移温度およびメルトフローインデックスへの影響を比較するために、種々の濃度の可塑剤を有する本発明のアルカリ可溶性熱可塑性材料の試料が作成された。用いられたベースポリマーおよび可塑剤は実施例Iで述べたものと同じである。表1は、実施例IV(A)〜実施例IV(M)のアルカリ可溶性熱可塑性材料の重量%濃度を示す。表に示すように、実施例ごとに可塑剤の濃度に変化を持たせた。表1は、さらに、実施例IV(A)〜実施例IV(M)のアルカリ可溶性熱可塑性材料の、対応するガラス転移温度(Tg)とメルトフローインデックス(MFI)とを示す。メルトフローインデックスは、160℃、230℃、または270℃での1.2キログラムの荷重下においてASTM D1238に準拠して試験された。
Claims (7)
- アディティブ法造形技術を用いて三次元物体のための支持構造を作成するための原料であって、
前記原料は、少なくとも1つの可塑剤と、少なくとも1つの共重合体と、を含む組成物を有し、
前記少なくとも1つの共重合体のそれぞれは、少なくとも1つのカルボン酸及び少なくとも1つのアルキルメタクリレートを含むモノマーから誘導され、
前記組成物はアルカリ水溶液に可溶であり、当該原料は、アディティブ法造形技術を用いて三次元物体に付属する支持構造を形成するようにされたフィラメント供給押出システムに受け入れられるようにフィラメントの形を有する、原料。 - 前記少なくとも1つの可塑剤は、p−t−ブチルフェニルジフェニルホスフェート;ブチルベンジルフタレート;7−(2,6,6,8−テトラメチル−4−オキサ−3−オキソノニル)ベンジルフタレート;C7/C9アルキルベンジルフタレート;2−エチルヘキシルジフェニルホスフェート;イソデシルジフェニルホスフェート、からなる群、およびこれらの組み合わせから選択される、請求項1に記載の原料。
- 前記組成物は、実質的に少なくとも1つの可塑剤と少なくとも1つの共重合体からなる請求項1に記載の原料。
- 前記組成物は、100℃以上のガラス転移温度を示す、請求項1に記載の原料。
- 前記カルボン酸は、メタクリル酸を含む、請求項1に記載の原料。
- 前記メタクリル酸アルキルは、メタクリル酸メチルを含む、請求項1に記載の原料。
- 前記カルボン酸は、前記共重合体のためのモノマーの総重量に基づいて、前記共重合のためのモノマーの15.0重量%から60.0重量%を構成する、請求項1に記載の原料。
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US10/898,814 | 2004-07-26 | ||
US10/898,814 US7754807B2 (en) | 1999-04-20 | 2004-07-26 | Soluble material and process for three-dimensional modeling |
PCT/US2005/025507 WO2006020279A2 (en) | 2004-07-26 | 2005-07-15 | Soluble material and process for three-dimensional modeling |
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JP2008507619A JP2008507619A (ja) | 2008-03-13 |
JP2008507619A5 JP2008507619A5 (ja) | 2008-09-04 |
JP5039549B2 true JP5039549B2 (ja) | 2012-10-03 |
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US (2) | US7754807B2 (ja) |
EP (1) | EP1773560A2 (ja) |
JP (1) | JP5039549B2 (ja) |
CN (1) | CN101027170A (ja) |
WO (1) | WO2006020279A2 (ja) |
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US11141901B2 (en) | 2015-03-31 | 2021-10-12 | Kyoraku Co., Ltd. | Molded resin strand, method for modeling three-dimensional object, and method for manufacturing molded resin strand |
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US7780897B2 (en) * | 2005-04-22 | 2010-08-24 | Board Of Regents, The University Of Texas System | Hydrogel constructs using stereolithography |
FR2893018B1 (fr) * | 2005-11-09 | 2008-03-14 | Commissariat Energie Atomique | Procede de formation de supports presentant des motifs, tels que des masques de lithographie. |
US7896209B2 (en) * | 2008-04-30 | 2011-03-01 | Stratasys, Inc. | Filament drive mechanism for use in extrusion-based digital manufacturing systems |
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US8155775B2 (en) * | 2008-10-02 | 2012-04-10 | Stratasys, Inc. | Support structure packaging |
US8246888B2 (en) * | 2008-10-17 | 2012-08-21 | Stratasys, Inc. | Support material for digital manufacturing systems |
CN102369243B (zh) | 2009-03-19 | 2014-11-05 | 界面解决方案Ip有限责任公司 | 生物基聚合物组合物 |
JP2011005667A (ja) * | 2009-06-23 | 2011-01-13 | Altech Co Ltd | サポート材除去装置 |
JP2011005668A (ja) * | 2009-06-23 | 2011-01-13 | Altech Co Ltd | サポート材除去装置 |
JP2011005666A (ja) * | 2009-06-23 | 2011-01-13 | Altech Co Ltd | 循環式サポート材除去装置 |
EP2445701B1 (en) * | 2009-06-23 | 2017-02-01 | Stratasys, Inc. | Consumable materials having customized characteristics |
US8236227B2 (en) * | 2009-09-30 | 2012-08-07 | Stratasys, Inc. | Method for building three-dimensional models in extrusion-based digital manufacturing systems using tracked filaments |
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2004
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2005
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Cited By (3)
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US11141901B2 (en) | 2015-03-31 | 2021-10-12 | Kyoraku Co., Ltd. | Molded resin strand, method for modeling three-dimensional object, and method for manufacturing molded resin strand |
US10988603B2 (en) | 2015-09-29 | 2021-04-27 | Kyoraku Co., Ltd. | Molded resin strand |
US11332627B2 (en) | 2017-01-31 | 2022-05-17 | Kyoraku Co., Ltd. | Filament resin molded article |
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WO2006020279A3 (en) | 2007-04-05 |
US20100270707A1 (en) | 2010-10-28 |
EP1773560A2 (en) | 2007-04-18 |
US7754807B2 (en) | 2010-07-13 |
US8227540B2 (en) | 2012-07-24 |
WO2006020279A2 (en) | 2006-02-23 |
JP2008507619A (ja) | 2008-03-13 |
US20050004282A1 (en) | 2005-01-06 |
CN101027170A (zh) | 2007-08-29 |
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