JP2019514730A - 軟質相ドメインを有する硬質相からなるビーズポリマー - Google Patents
軟質相ドメインを有する硬質相からなるビーズポリマー Download PDFInfo
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- JP2019514730A JP2019514730A JP2018555247A JP2018555247A JP2019514730A JP 2019514730 A JP2019514730 A JP 2019514730A JP 2018555247 A JP2018555247 A JP 2018555247A JP 2018555247 A JP2018555247 A JP 2018555247A JP 2019514730 A JP2019514730 A JP 2019514730A
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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
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/34—Process control of powder characteristics, e.g. density, oxidation or flowability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B28—WORKING CEMENT, CLAY, OR STONE
- B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
- B28B1/00—Producing shaped prefabricated articles from the material
- B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
-
- 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
- B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
-
- 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
- B33Y10/00—Processes of additive manufacturing
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
Description
バインダージェッティングは、付加製造プロセスであり、本方法をうまく説明する用語である3Dインクジェット粉体印刷としても知られている。この方法において、液状バインダーは、例えば市販のインクジェットプリントヘッドにより、粉末層に施与され、それにより、この粉末層の一部を意図的に互いに結合させる。液状バインダーの施与と交互に新たな粉末層を施与することで、最終的に、3次元の製品が成形される。この方法において、インクジェットプリントヘッドは殊に、粉末床の上を選択的に移動し、液状バインダー材料を、固化させたい箇所に正確に印刷する。固化の例は、インク中の液状ビニル系モノマーと粉末に含有されている過酸化物との反応である。この反応は、触媒、例えばアミン系触媒により、室温で行われるほど大幅に促進される。このプロセスは、成形品が完成するまで層ごとに繰り返される。印刷プロセスの終了後、成形体は粉末床から取り出され、適宜、後処理に送られる。
本発明の根底にある課題は、バインダージェッティング法を、製品を時間をかけて後処理する必要なく、プラスチック粒子を印刷することができることで、加速させることであった。
驚くべきことに、これらの課題は、バインダージェッティング法により粉末床から3次元の物体を製造する新規な方法によって解決された。本方法では、以下の方法工程を複数回繰り返すことで3次元の物体が形成される:a)粉末床の表面に新たな粉末層を施与する方法工程、およびb)バインダーを選択的に施与し、引き続き、または同時に、このバインダーを粉末床中で硬化させる方法工程。本発明によると、その際、粉末床は少なくとも1種の粒子を有し、この粒子は、10〜500μmの直径および少なくとも2つの異なる相を有することを特徴とする。本発明によると、第一相は、ガラス転移温度が40℃未満であり、第二相は、ガラス転移温度が70℃超である。本発明によると、ガラス転移温度は、DSC(示差走査熱量測定)により測定される。
Claims (9)
- バインダージェッティング法により粉末床から、以下の方法工程:
a)前記粉末床の表面に新たな粉末層を施与し、かつ
b)バインダーを選択的に施与し、引き続き、または同時に、前記バインダーを前記粉末床中で硬化させ、ここで前記粉末床は、少なくとも1種の粒子を有する、
を複数回繰り返すことで、3次元の物体を製造する方法において、
前記粒子は、10〜500μmの直径および少なくとも2つの異なる相を有し、ここで、第一相は、DSCにより測定して、40℃未満のガラス転移温度を有し、第二相は、DSCにより測定して、70℃超のガラス転移温度を有することを特徴とする、前記方法。 - 前記粒子が、前記バインダーの硬化に適した開始剤または前記硬化を促進する触媒もしくは促進剤を少なくとも1種含有するポリマー粒子であることを特徴とする、請求項1記載の方法。
- 前記ポリマー粒子は、平均直径が30〜110μmのPMMA懸濁ポリマーであることを特徴とする、請求項1または2記載の方法。
- 前記ポリマー粒子の前記第一相は、少なくとも60質量%が、アクリレートから製造された30℃未満のガラス転移温度を有する相であることを特徴とする、請求項1から3までのいずれか1項記載の方法。
- 前記ポリマー粒子の前記第二相は、少なくとも60質量%が、MMAから製造された80℃超のガラス転移温度を有する相であることを特徴とする、請求項1から4までのいずれか1項記載の方法。
- 前記2相ポリマー粒子を、前記のそれぞれの相を生じさせる双方のモノマー混合物を逐次添加しながらの懸濁重合により製造したことを特徴とする、請求項1から5までのいずれか1項記載の方法。
- まず前記第二相を重合により製造して、それから、前記第一相を製造するための前記モノマー混合物をこの懸濁液に添加することを特徴とする、請求項6記載の方法。
- 双方のモノマー相が少なくとも1種の開始剤を含有することを特徴とし、前記第一相を製造するための第二のモノマー混合物中の1つまたは複数の開始剤が、より高い分解温度を有することを特徴とする、請求項6または7記載の方法。
- 前記第一相と前記第二相との比が、1:9〜1:1.5の間にあることを特徴とする、請求項1から8までのいずれか1項記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16166134.3 | 2016-04-20 | ||
EP16166134.3A EP3235867A1 (de) | 2016-04-20 | 2016-04-20 | Perlpolymerisat aus hartphase mit domänen einer weichphase |
PCT/EP2017/058796 WO2017182364A1 (de) | 2016-04-20 | 2017-04-12 | Perlpolymerisat aus hartphase mit domänen einer weichphase |
Publications (2)
Publication Number | Publication Date |
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JP2019514730A true JP2019514730A (ja) | 2019-06-06 |
JP6887441B2 JP6887441B2 (ja) | 2021-06-16 |
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Application Number | Title | Priority Date | Filing Date |
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JP2018555247A Active JP6887441B2 (ja) | 2016-04-20 | 2017-04-12 | 軟質相ドメインを有する硬質相からなるビーズポリマー |
Country Status (20)
Country | Link |
---|---|
US (1) | US10793731B2 (ja) |
EP (2) | EP3235867A1 (ja) |
JP (1) | JP6887441B2 (ja) |
KR (1) | KR102366882B1 (ja) |
CN (1) | CN109071909B (ja) |
AU (1) | AU2017253536B2 (ja) |
BR (1) | BR112018071479B1 (ja) |
CA (1) | CA3021423A1 (ja) |
DK (1) | DK3445821T3 (ja) |
ES (1) | ES2905683T3 (ja) |
HR (1) | HRP20220324T1 (ja) |
HU (1) | HUE057957T2 (ja) |
IL (1) | IL262272B (ja) |
MX (1) | MX2018012466A (ja) |
PL (1) | PL3445821T3 (ja) |
PT (1) | PT3445821T (ja) |
SG (1) | SG11201809193RA (ja) |
SI (1) | SI3445821T1 (ja) |
TW (1) | TWI709477B (ja) |
WO (1) | WO2017182364A1 (ja) |
Cited By (1)
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KR20210120370A (ko) * | 2020-03-26 | 2021-10-07 | 최성환 | 주물사 소재를 이용한 냉각코어의 3d 프린팅 방법 |
Families Citing this family (9)
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EP3231588A1 (de) | 2016-04-12 | 2017-10-18 | Evonik Röhm GmbH | Sprühgetrocknetes weichphasenemulsionspolymerisat für das auffüllen der zwickel in perlpolymerisatschichten im binder jetting verfahren |
KR102340960B1 (ko) | 2016-09-28 | 2021-12-17 | 에보닉 오퍼레이션스 게엠베하 | 바인더 젯팅 방법을 사용하는 3d 프린팅에서의 다공성 비드 중합체의 용도 및 제조 |
CN108220643B (zh) * | 2018-01-29 | 2019-06-28 | 华中科技大学 | 一种钨颗粒增强非晶基复合材料的制备方法 |
US20200298466A1 (en) * | 2019-03-22 | 2020-09-24 | Lawrence Livermore National Security, Llc | Additive manufacture of hierarchically porous materials with high resolution |
US11766080B2 (en) | 2020-06-26 | 2023-09-26 | Mark Lamoncha | Face shield for attachment to goggles or eyeglasses |
US11865261B2 (en) | 2020-07-14 | 2024-01-09 | Mark Lamoncha | Respirator mask |
EP4108362A1 (en) | 2021-06-22 | 2022-12-28 | Evonik Operations GmbH | Material system for 3d printing |
EP4108692A1 (en) | 2021-06-22 | 2022-12-28 | Evonik Operations GmbH | Material system for 3d printing |
EP4108361A1 (en) | 2021-06-22 | 2022-12-28 | Evonik Operations GmbH | Material system for 3d printing |
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2016
- 2016-04-20 EP EP16166134.3A patent/EP3235867A1/de not_active Withdrawn
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2017
- 2017-04-12 PT PT177162641T patent/PT3445821T/pt unknown
- 2017-04-12 MX MX2018012466A patent/MX2018012466A/es unknown
- 2017-04-12 PL PL17716264T patent/PL3445821T3/pl unknown
- 2017-04-12 US US16/094,879 patent/US10793731B2/en active Active
- 2017-04-12 KR KR1020187030162A patent/KR102366882B1/ko active IP Right Grant
- 2017-04-12 SI SI201731060T patent/SI3445821T1/sl unknown
- 2017-04-12 WO PCT/EP2017/058796 patent/WO2017182364A1/de active Application Filing
- 2017-04-12 ES ES17716264T patent/ES2905683T3/es active Active
- 2017-04-12 HR HRP20220324TT patent/HRP20220324T1/hr unknown
- 2017-04-12 BR BR112018071479-8A patent/BR112018071479B1/pt active IP Right Grant
- 2017-04-12 AU AU2017253536A patent/AU2017253536B2/en active Active
- 2017-04-12 EP EP17716264.1A patent/EP3445821B1/de active Active
- 2017-04-12 CA CA3021423A patent/CA3021423A1/en active Pending
- 2017-04-12 DK DK17716264.1T patent/DK3445821T3/da active
- 2017-04-12 CN CN201780024549.6A patent/CN109071909B/zh active Active
- 2017-04-12 JP JP2018555247A patent/JP6887441B2/ja active Active
- 2017-04-12 SG SG11201809193RA patent/SG11201809193RA/en unknown
- 2017-04-12 HU HUE17716264A patent/HUE057957T2/hu unknown
- 2017-04-17 TW TW106112802A patent/TWI709477B/zh active
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2018
- 2018-10-10 IL IL262272A patent/IL262272B/en unknown
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KR20210120370A (ko) * | 2020-03-26 | 2021-10-07 | 최성환 | 주물사 소재를 이용한 냉각코어의 3d 프린팅 방법 |
KR102383639B1 (ko) | 2020-03-26 | 2022-04-06 | 최성환 | 주물사 소재를 이용한 냉각코어의 3d 프린팅 방법 |
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AU2017253536A1 (en) | 2018-12-06 |
DK3445821T3 (da) | 2022-03-14 |
CA3021423A1 (en) | 2017-10-26 |
SI3445821T1 (sl) | 2022-03-31 |
EP3445821A1 (de) | 2019-02-27 |
HRP20220324T1 (hr) | 2022-05-13 |
TW201806731A (zh) | 2018-03-01 |
HUE057957T2 (hu) | 2022-06-28 |
KR102366882B1 (ko) | 2022-02-23 |
PL3445821T3 (pl) | 2022-03-28 |
PT3445821T (pt) | 2022-02-01 |
MX2018012466A (es) | 2019-02-21 |
IL262272B (en) | 2022-04-01 |
JP6887441B2 (ja) | 2021-06-16 |
CN109071909A (zh) | 2018-12-21 |
ES2905683T3 (es) | 2022-04-11 |
WO2017182364A1 (de) | 2017-10-26 |
AU2017253536B2 (en) | 2020-12-03 |
EP3235867A1 (de) | 2017-10-25 |
US20190127598A1 (en) | 2019-05-02 |
BR112018071479A2 (pt) | 2019-02-19 |
KR20180136951A (ko) | 2018-12-26 |
TWI709477B (zh) | 2020-11-11 |
CN109071909B (zh) | 2022-10-18 |
SG11201809193RA (en) | 2018-11-29 |
IL262272A (en) | 2018-11-29 |
BR112018071479B1 (pt) | 2023-01-24 |
EP3445821B1 (de) | 2021-12-22 |
US10793731B2 (en) | 2020-10-06 |
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