JP2004277739A - 選択的レーザー焼結のための焼結粉末、その製造方法、成形体の製造方法および該成形体 - Google Patents
選択的レーザー焼結のための焼結粉末、その製造方法、成形体の製造方法および該成形体 Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- B29C64/141—Processes of additive manufacturing using only solid materials
- B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
-
- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such 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
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
- B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
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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
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Abstract
【解決手段】選択的レーザー焼結のための焼結粉末が少なくとも1種のポリアミドおよび少なくとも1種のポリ(N−メチルメタクリルイミド)(PMMI)、ポリメチルメタクリレート(PMMA)および/またはPMMI−PMMAコポリマーを含有する。
【効果】選択的レーザー焼結により製造される部材のより良好な寸法安定性および表面特性が可能になる。
【選択図】なし
Description
DE3510691、例1により製造した、加水分解重合により製造し、相対溶液粘度ηrel1.61(酸性のm−クレゾール中)およびCOOH 72ミリモル/kgまたはNH2 68ミリモル/kgの末端基含有率を有する制御されていないPA12 40kgを、2−ブタノンにより変性され、かつ含水率1%を有するエタノール350l中のIRGANOX (R) 1098 0.3kgと共に0.8m3の攪拌容器(直径=90cm、高さ=170cm)中で5時間以内に145℃にし、かつ撹拌下(パドル形撹拌機、直径=42cm、回転数=91rpm)にこの温度で1時間放置した。引き続きジャケット温度を120℃に低下させ、かつこの回転数において45K/hの冷却速度で内部温度を120℃にした。この時点から同じ冷却速度でジャケット温度を内部温度よりも2K〜3K低く維持した。内部温度を同じ冷却速度で117℃にし、かつ次いで60分間、一定に維持した。その後、40K/hの冷却速度で内部温度を111℃にした。この温度で沈澱が開始され、これは熱の発生により認識することができる。25分後に内部温度が低下し、これは沈澱の終了を示していた。懸濁液を75℃に冷却した後、該懸濁液をパドル形乾燥器に移した。撹拌装置によりエタノールをここから70℃/400ミリバールで留去し、かつ残留物を引き続き、20ミリバール/85℃で3時間、後乾燥させた。
<40μm:16質量%
<50μm:44質量%
<63μm:85質量%
<80μm:92質量%
<100μm:100質量%
BET: 6.9m2/g、
かさ密度: 429g/l
レーザー回折:d(10%):42μm、d(50%):69μm、d(90%):91μm。
加水分解による重合によって製造された、制御されたPA 12、Degussa社のVestamid L1600タイプを40kg、二軸スクリュー混合装置(Bersttorf ZE25)中、225℃でIRGANOX (R) 245 0.3kgおよびPMMI(Pleximid8813、Roehm社)0.8kgと共に押し出し、かつストランドとして造粒した。該顆粒を引き続き低温(−40℃)において衝撃ミル中で0〜120μmの粒径分布に粉砕した。引き続きAerosil 200 40g(0.1部)を室温および500回転/分で混合した。
DE2906647、例1により製造し、56μmの平均粒径d50(レーザー回折)およびDIN53466により459g/lのかさ密度を有するポリアミド12粉末1900g(95部)に、ドライブレンド法でPleximid 8813 100g(5部)を、ヘンシェルミキサーFML10/KM23を使用して50℃で700回転/分において3分間混合した。引き続きAerosil 200 2g(0.1部)を室温および500回転/分で3分間混合した。
例3からの粉末をレーザー焼結装置により上記のビーム補正の測定のための試験体に構成し、かつISO3167による多目的試験体に構成した。後者の部材においてEN ISO 527による引張試験によって機械的な値を測定した(第1表)。製造はそのつど、EOS社のレーザー焼結装置EOSINT P360を用いて行った。
Claims (24)
- 選択的レーザー焼結のための焼結粉末において、該粉末が少なくとも1種のポリアミドおよび少なくとも1種のポリ(N−メチルメタクリルイミド)(PMMI)、ポリメチルメタクリレート(PMMA)および/またはPMMI−PMMAコポリマーを含有することを特徴とする、選択的レーザー焼結のための焼結粉末。
- カルボンアミド基あたり少なくとも8個の炭素原子を有するポリアミドを含有する、請求項1記載の焼結粉末。
- 制御されていないポリアミドを含有する、請求項1または2記載の焼結粉末。
- ポリアミド612、ポリアミド11またはポリアミド12または前記のポリアミドをベースとするコポリアミドを含有する、請求項1から3までのいずれか1項記載の焼結粉末。
- 粉末が、粉末中に存在するポリマーに対してPMMI、PMMAおよび/またはPMMI−PMMAコポリマーを0.01〜30質量%含有する、請求項1から4までのいずれか1項記載の焼結粉末。
- 粉末が、粉末中に存在するポリマーの合計に対してPMMI、PMMAおよび/またはPMMI−PMMAコポリマーを0.5〜15質量%含有する、請求項5記載の焼結粉末。
- 粉末がPMMI、PMMAまたはPMMI−PMMAコポリマー粒子およびポリアミド粒子の混合物を含有する、請求項1から6までのいずれか1項記載の焼結粉末。
- 粉末がポリアミド粒子中に配合されたPMMI、PMMAおよび/またはPMMI−PMMAコポリマーを含有する、請求項1から6までのいずれか1項記載の焼結粉末。
- さらに助剤および/または充填剤および/または顔料を含有する、請求項1から8までのいずれか1項記載の焼結粉末。
- 助剤として流動化助剤を含有する、請求項9記載の焼結粉末。
- 充填剤としてガラス粒子を含有する、請求項9または10記載の焼結粉末。
- 充填剤としてアルミニウム粒子を含有する、請求項9または10記載の焼結粉末。
- 請求項1から12までのいずれか1項記載の焼結粉末の製造方法において、少なくとも1種のポリアミドをPMMI、PMMAおよび/またはPMMI−PMMAコポリマーと混合することを特徴とする、請求項1から12までのいずれか1項記載の焼結粉末の製造方法。
- 再沈澱または粉砕により得られたポリアミド粉末を有機溶剤中に溶解するか、または懸濁させるか、または塊状でPMMI、PMMAまたはPMMI−PMMAコポリマーと混合する、請求項13記載の方法。
- PMMI、PMMAおよび/またはPMMI−PMMAコポリマーをポリアミドの溶融物中に配合し、かつ得られた混合物を粉砕によりレーザー焼結粉末に加工する、請求項13記載の方法。
- 請求項1から12までのいずれか1項記載の焼結粉末を選択的にレーザー焼結することにより成形体を製造する方法。
- 少なくともPMMI、PMMAまたはPMMI−PMMAコポリマーおよび少なくとも1種のポリアミドを含有することを特徴とする、レーザー焼結により製造された成形体。
- カルボンアミド基あたり少なくとも8個の炭素原子を有するポリアミドを含有する、請求項17記載の成形体。
- ポリアミド612、ポリアミド11および/またはポリアミド12を含有する、請求項17または18記載の成形体。
- 存在するポリマーの合計に対してPMMIまたはPMMAまたはPMMI−PMMAコポリマーを0.01〜30質量%含有する、請求項17から19までのいずれか1項記載の成形体。
- 存在するポリマーの合計に対してPMMIまたはPMMAまたはPMMI−PMMAコポリマーを0.5〜15質量%含有する、請求項19記載の成形体。
- 充填剤および/または顔料を含有する、請求項17から21までのいずれか1項記載の成形体。
- 充填剤の1種類がガラス粒子である、請求項22記載の成形体。
- 充填剤の1種類がアルミニウム粒子である、請求項22記載の成形体。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10311437A DE10311437A1 (de) | 2003-03-15 | 2003-03-15 | Laser-Sinter-Pulver mit PMMI, PMMA und/oder PMMI-PMMA-Copolymeren, Verfahren zu dessen Herstellung und Formkörper, hergestellt aus diesem Laser-Sinterpulver |
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JP2004277739A true JP2004277739A (ja) | 2004-10-07 |
JP4587277B2 JP4587277B2 (ja) | 2010-11-24 |
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EP (1) | EP1460108B1 (ja) |
JP (1) | JP4587277B2 (ja) |
KR (1) | KR20040081714A (ja) |
CN (1) | CN100591722C (ja) |
AU (1) | AU2004201050A1 (ja) |
BR (1) | BRPI0400260A (ja) |
DE (1) | DE10311437A1 (ja) |
ES (1) | ES2396709T3 (ja) |
TW (1) | TW200510469A (ja) |
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JP2020517494A (ja) * | 2017-04-24 | 2020-06-18 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトCovestro Deutschland Ag | 混合熱可塑性構造材料を使用した付加製造法 |
JP2021529694A (ja) * | 2018-10-04 | 2021-11-04 | アルケマ フランス | 3d印刷された半結晶性及びアモルファスのポリマー物品 |
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JP2018001606A (ja) * | 2016-07-01 | 2018-01-11 | コニカミノルタ株式会社 | 粉末材料、粉末材料の製造方法、立体造形物の製造方法および立体造形装置 |
JP2020517494A (ja) * | 2017-04-24 | 2020-06-18 | コベストロ、ドイチュラント、アクチエンゲゼルシャフトCovestro Deutschland Ag | 混合熱可塑性構造材料を使用した付加製造法 |
JP2021529694A (ja) * | 2018-10-04 | 2021-11-04 | アルケマ フランス | 3d印刷された半結晶性及びアモルファスのポリマー物品 |
JP7223126B2 (ja) | 2018-10-04 | 2023-02-15 | アルケマ フランス | 3d印刷された半結晶性及びアモルファスのポリマー物品 |
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ES2396709T3 (es) | 2013-02-25 |
US20040180980A1 (en) | 2004-09-16 |
EP1460108A1 (de) | 2004-09-22 |
CN1534063A (zh) | 2004-10-06 |
BRPI0400260A (pt) | 2004-12-28 |
EP1460108B1 (de) | 2012-10-03 |
CN100591722C (zh) | 2010-02-24 |
TW200510469A (en) | 2005-03-16 |
KR20040081714A (ko) | 2004-09-22 |
DE10311437A1 (de) | 2004-09-23 |
JP4587277B2 (ja) | 2010-11-24 |
AU2004201050A1 (en) | 2004-09-30 |
US7135525B2 (en) | 2006-11-14 |
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