JP6727290B2 - 熱硬化性シリコーン組成物を用いて3dプリンティングする方法 - Google Patents
熱硬化性シリコーン組成物を用いて3dプリンティングする方法 Download PDFInfo
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- JP6727290B2 JP6727290B2 JP2018509615A JP2018509615A JP6727290B2 JP 6727290 B2 JP6727290 B2 JP 6727290B2 JP 2018509615 A JP2018509615 A JP 2018509615A JP 2018509615 A JP2018509615 A JP 2018509615A JP 6727290 B2 JP6727290 B2 JP 6727290B2
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- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- AFCAKJKUYFLYFK-UHFFFAOYSA-N tetrabutyltin Chemical compound CCCC[Sn](CCCC)(CCCC)CCCC AFCAKJKUYFLYFK-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- SYRHIZPPCHMRIT-UHFFFAOYSA-N tin(4+) Chemical class [Sn+4] SYRHIZPPCHMRIT-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical compound [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C64/10—Processes of additive manufacturing
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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
- B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- 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
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- 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
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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
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/205—Means for applying layers
- B29C64/209—Heads; Nozzles
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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
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
- B29C64/295—Heating elements
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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
- B33Y10/00—Processes of additive manufacturing
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- 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
- 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
- B33Y80/00—Products made by additive manufacturing
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G77/04—Polysiloxanes
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- C08L83/04—Polysiloxanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Description
本方法は、I)第1の熱硬化性シリコーン組成物を3Dプリンターによってプリンティングすることで、層を形成する工程を含む。以下に詳述するとおり、各種の3Dプリンター及び/又は3Dプリンティングの方法論(すなわち、「3Dプリンティングプロセス」)を用いることができる。更に以下に記載のとおり、各種の熱硬化性シリコーン組成物を、本発明の方法に用いることができる。
第1及び第2の熱硬化性シリコーン組成物は、互いに同一のものでも異なっていてもよく、工程III)及びIV)を繰り返す際、独立して選択される熱硬化性シリコーン組成物を用いてもよい。簡略化のため、第1及び第2の熱硬化性シリコーン組成物を、工程III)及びIV)を繰り返す際に任意選択的に用いられる任意の他の熱硬化性シリコーン組成物と共に、以下まとめて単に「熱硬化性シリコーン組成物」、「熱硬化性シリコーン組成物の各々」、又は「熱硬化性シリコーン組成物のうちの少なくとも1つ」と呼ぶ。このような用語又は表現の言及により、本方法で用いられる熱硬化性シリコーン組成物のいずれかに言及することができ、まとめて言及されてはいるものの、熱硬化性シリコーン組成物の各々は、独立して選択されるものでよい。
(R1R2 2SiO1/2)w(R2 2SiO2/2)x(R2SiO3/2)y(SiO4/2)z (I)
(式中、各R1は独立して選択されるヒドロカルビル基であり、置換でも非置換であってもよく、各R2は、独立してR1及びアルケニル基から選択されるが、ただし、R2のうち少なくとも2個はアルケニル基であり、w、x、y、及びzは、w+x+y+z=1となるモル分率である。)を有する。当該技術分野において理解されるとおり、直鎖オルガノポリシロキサンでは、下付き文字y及びzは一般に0であるのに対し、樹脂では、下付き文字y及び/又はzは0より大きい。w、x、y、及びzに関し、様々な代替実施形態について以下に記載する。これらの実施形態において、下付き文字wは、0〜0.9999、あるいは0〜0.999、あるいは0〜0.99、あるいは0〜0.9、あるいは0.9〜0.999、あるいは0.9〜0.999、あるいは0.8〜0.99、あるいは0.6〜0.99の値であってよい。下付き文字xは、典型的には0〜0.9、あるいは0〜0.45、あるいは0〜0.25の値である。下付き文字yは、典型的には0〜0.99、あるいは0.25〜0.8、あるいは0.5〜0.8の値である。下付き文字zは、典型的には0〜0.99、あるいは0〜0.85、あるいは0.85〜0.95、あるいは0.6〜0.85、あるいは0.4〜0.65、あるいは0.2〜0.5、あるいは0.1〜0.45、あるいは0〜0.25、あるいは0〜0.15の値である。
(R1R3 2SiO1/2)w’(R3 2SiO2/2)x’(R3SiO3/2)y’(SiO4/2)z’ (II)
(式中、各R1は上に定義されており、各R3は、独立してR1、及びヒドロキシル基、加水分解性基、又はそれらの組み合わせから選択されるが、ただし、R3のうちの少なくとも2個はヒドロキシル基、加水分解性基、又はそれらの組み合わせであり、w’、x’、y’、及びz’は、w’+x’+y’+z’=1となるモル分率である。)を有する。当該技術分野において理解されるとおり、直鎖オルガノポリシロキサンでは、下付き文字y’及びz’は一般に0であるのに対し、樹脂では、下付き文字y’及び/又はz’は0より大きい。w’、x’、y’、及びz’に関し、様々な代替実施形態について以下に記載する。これらの実施形態において、下付き文字w’は、0〜0.9999、あるいは0〜0.999、あるいは0〜0.99、あるいは0〜0.9、あるいは0.9〜0.999、あるいは0.9〜0.999、あるいは0.8〜0.99、あるいは0.6〜0.99の値であってよい。下付き文字x’は、典型的には0〜0.9、あるいは0〜0.45、あるいは0〜0.25の値である。下付き文字y’は、典型的には0〜0.99、あるいは0.25〜0.8、あるいは0.5〜0.8の値である。下付き文字z’は、典型的には0〜0.99、あるいは0〜0.85、あるいは0.85〜0.95、あるいは0.6〜0.85、あるいは0.4〜0.65、あるいは0.2〜0.5、あるいは0.1〜0.45、あるいは0〜0.25、あるいは0〜0.15の値である。
(R1R4 2SiO1/2)w”(R4 2SiO2/2)x”(R4SiO3/2)y”(SiO4/2)z” (III)
(式中、各R1は上に定義されており、各R4は、独立してR1及び不飽和基から選択されるが、ただし、R4のうちの少なくとも2個は不飽和基であり、w”、x”、y”、及びz”は、w”+x”+y”+z”=1となるモル分率である。)を有する。当該技術分野において理解されるとおり、直鎖オルガノポリシロキサンでは、下付き文字y”及びz”は一般に0であるのに対し、樹脂では、下付き文字y”及び/又はz”は0より大きい。w”、x”、y”、及びz”に関し、様々な代替実施形態について以下に記載する。これらの実施形態において、下付き文字w”は、0〜0.9999、あるいは0〜0.999、あるいは0〜0.99、あるいは0〜0.9、あるいは0.9〜0.999、あるいは0.9〜0.999、あるいは0.8〜0.99、あるいは0.6〜0.99の値であってよい。下付き文字x”は、典型的には0〜0.9、あるいは0〜0.45、あるいは0〜0.25の値である。下付き文字y”は、典型的には0〜0.99、あるいは0.25〜0.8、あるいは0.5〜0.8の値である。下付き文字z”は、典型的には0〜0.99、あるいは0〜0.85、あるいは0.85〜0.95、あるいは0.6〜0.85、あるいは0.4〜0.65、あるいは0.2〜0.5、あるいは0.1〜0.45、あるいは0〜0.25、あるいは0〜0.15の値である。
Vi4Si、PhSiVi3、MeSiVi3、PhMeSiVi2、Ph2SiVi2、及びPhSi(CH2CH=CH2)3
(式中、Meはメチル、Phはフェニル、Viはビニルである。)を有するシランが挙げられるが、これらに限定されない。
PhSi(OSiMe2Vi)3、Si(OSiMe2Vi)4、MeSi(OSiMe2Vi)3、及びPh2Si(OSiMe2Vi)2
(式中、Meはメチル、Viはビニル、Phはフェニルである。)を有するシロキサンが挙げられるが、これらに限定されない。
(R1R5 2SiO1/2)w”’(R5 2SiO2/2)x”’(R5SiO3/2)y”’(SiO4/2)z”’ (IV)
(式中、各R1は上に定義されており、各R5は、独立してR1及びエポキシ置換された基から選択されるが、ただし、R5のうちの少なくとも2個はエポキシ置換された基であり、w”’、x”’、y”’、及びz”’は、w”’+x”’+y”’+z”’=1となるモル分率である。)を有する。当該技術分野において理解されるとおり、直鎖オルガノポリシロキサンでは、下付き文字y”’及びz”’は一般に0であるのに対し、樹脂では、下付き文字y”’及び/又はz”’は0より大きい。w”’、x”’、y”’、及びz”’に関し、様々な代替実施形態について以下に記載する。これらの実施形態において、下付き文字w”’は、0〜0.9999、あるいは0〜0.999、あるいは0〜0.99、あるいは0〜0.9、あるいは0.9〜0.999、あるいは0.9〜0.999、あるいは0.8〜0.99、あるいは0.6〜0.99の値であってよい。下付き文字x”’は、典型的には0〜0.9、あるいは0〜0.45、あるいは0〜0.25の値である。下付き文字y”’は、典型的には0〜0.99、あるいは0.25〜0.8、あるいは0.5〜0.8の値である。下付き文字z”’は、典型的には0〜0.99、あるいは0〜0.85、あるいは0.85〜0.95、あるいは0.6〜0.85、あるいは0.4〜0.65、あるいは0.2〜0.5、あるいは0.1〜0.45、あるいは0〜0.25、あるいは0〜0.15の値である。
在庫品の熱硬化性シリコーン組成物に修正を加える。具体的には、在庫品の熱硬化性シリコーン組成物は、Dow Corning Corporation(Midland,MI)から市販のSylgard(登録商標)184である。Sylgard(登録商標)184は、一般的には2部の組成物(ヒドロシリル化硬化性)であり、Sylgard(登録商標)184に添付の製品データシートに記載のとおり、その部の混合比は、10対1(塩基対硬化剤)である。しかし、Sylgard(登録商標)184に修正を加え、部の比が1対1(塩基対硬化剤)のものを準備する。更に、触媒をPt4触媒とし、阻害剤を1−エチニル−1−シクロヘキサノールとする。触媒、阻害剤、及び硬化剤の濃度に修正を加えて、所望の硬化時間を得た。具体的には、修正を加えた熱硬化性シリコーン組成物の総重量に各々基づいて、触媒の存在量を0.25〜2重量%、阻害剤の存在量を0.5〜2.5重量%、及び硬化剤の存在量を2.5〜10重量%、とする。
Claims (13)
- 3次元(3D)物品を形成する方法であって、
I)第1の熱硬化性シリコーン組成物を3Dプリンターによってプリンティングすることで、層を形成する工程であって、前記プリンティング前に前記第1の熱硬化性シリコーン組成物が加熱されていない、工程と、
II)前記層を加熱することで、少なくとも部分的に硬化された層を形成する工程、
III)第2の熱硬化性シリコーン組成物を前記少なくとも部分的に硬化された層上に前記3Dプリンターによってプリンティングすることで、後続の層を形成する工程であって、前記プリンティング前に前記第2の熱硬化性シリコーン組成物が加熱されていない、工程と、
IV)前記後続の層を加熱することで、少なくとも部分的に硬化された後続の層を形成する工程、並びに
V)任意選択的に、任意の追加の層のために独立して選択される熱硬化性シリコーン組成物を用い、工程III)及びIV)を繰り返すことで、前記3D物品を形成する工程、を含み、
前記第1及び第2の熱硬化性シリコーン組成物を、互いに同一のもの、又は異なるものとし、前記第1及び第2の熱硬化性シリコーン組成物を、放射線によっては硬化せず、
前記第1及び第2の熱硬化性シリコーン組成物が、独立して、縮合硬化性シリコーン組成物、ヒドロシリル化硬化性シリコーン組成物、フリーラジカル硬化性シリコーン組成物、及び二元硬化シリコーン組成物から選択される、3次元(3D)物品を形成する方法。 - 工程II)及びIV)が、独立して、(i)上に前記層をプリンティングする基材を介し、伝導加熱すること、(ii)前記特定の熱硬化性シリコーン組成物を、前記3Dプリンター又はその構成要素を介し加熱すること、(iii)赤外線加熱すること、(iv)電磁加熱すること、(v)伝熱流体による加熱用浴、(vi)前記特定の熱硬化性シリコーン組成物の発熱反応から加熱すること、(vii)磁気加熱すること、及び(viii)それらの組み合わせ、から選択される、請求項1に記載の方法。
- 前記第1及び第2の熱硬化性シリコーン組成物を同一のものとする、請求項1又は2に記載の方法。
- 前記第1及び/又は第2の熱硬化性シリコーン組成物に含まれるヒドロシリル化硬化性シリコーン組成物が、(A)1分子当たり平均して少なくとも2個のケイ素結合アルケニル基又はケイ素結合水素原子を有するオルガノポリシロキサン、(B)前記オルガノポリシロキサン(A)中の前記ケイ素結合アルケニル基又はケイ素結合水素原子と反応することができる、1分子当たり平均して少なくとも2個のケイ素結合水素原子又はケイ素結合アルケニル基を有する有機ケイ素化合物、及び(C)ヒドロシリル化触媒を含む、請求項1に記載の方法。
- 前記第1及び/又は第2の熱硬化性シリコーン組成物に含まれる縮合硬化性シリコーン組成物が、(A’)1分子当たり平均して少なくとも2個のケイ素結合ヒドロキシル基又は加水分解性基を有するオルガノポリシロキサン、任意選択的に(B’)1分子当たり平均して少なくとも2個のケイ素結合水素原子、ヒドロキシル基、又は加水分解性基を有する有機ケイ素化合物、及び(C’)縮合触媒を含み、並びに任意選択的に、前記縮合硬化性シリコーン組成物を複数部の組成物とし、構成成分(A’)を第1の部の中のものとし、構成成分(B’)を、前記第1の部とは別個の第2の部の中のものとし、構成成分(C’)を、前記第2の部の中のもの、及び/又は前記第1及び第2の部とは別個の第3の部の中のものとする、請求項1に記載の方法。
- 前記第1及び/又は第2の熱硬化性シリコーン組成物に含まれるフリーラジカル硬化性シリコーン組成物が、(A”)平均して少なくとも2個のケイ素結合不飽和基を有するオルガノポリシロキサン、及び(C”)有機パーオキサイドを含む、請求項1に記載の方法。
- 前記第1及び第2の熱硬化性シリコーン組成物を、互いに異なるものとする、請求項1に記載の方法。
- 前記第1及び/又は第2の熱硬化性シリコーン組成物を、第1の部及び前記第1の部とは別個の第2の部を少なくとも含む複数部の熱硬化性シリコーン組成物とし、任意選択的に、前記複数部の熱硬化性シリコーン組成物の前記別個の部を、プリンティングの前に二元吐出プリンティングノズル中で混合する、請求項1〜7のいずれか一項に記載の方法。
- 前記3Dプリンターが、熱融解フィラメント製造プリンター、選択的レーザー焼結プリンター、選択的レーザー溶融プリンター、ステレオリソグラフィプリンター、粉末層(バインダージェット)プリンター、マテリアルジェットプリンター、直接金属レーザー焼結プリンター、電子線溶融プリンター、積層対象物製造積層プリンター、指向性エネルギー積層プリンター、レーザー粉末形成プリンター、ポリジェットプリンター、インクジェッティングプリンター、マテリアルジェッティングプリンター、及びシリンジ押出成形プリンターから選択される、請求項1〜8のいずれか一項に記載の方法。
- 工程II)で形成された前記少なくとも部分的に硬化された層が、周囲条件への暴露に際し、その形状を維持する、請求項1〜9のいずれか一項に記載の方法。
- 工程II)及びIV)での加熱を、周囲温度より高く300℃以下から独立して選択される温度にて行う、請求項1〜10のいずれか一項に記載の方法。
- 前記第1及び/又は第2の熱硬化性組成物を、剪断減粘性とする、請求項1〜11のいずれか一項に記載の方法。
- 第1の熱硬化性シリコーン組成物の硬化物を含む、少なくとも部分的に硬化された層と、
前記少なくとも部分的に硬化された層の上に形成され、且つ、第2の熱硬化性シリコーン組成物の硬化物を含む、少なくとも部分的に硬化された後続の層と、
任意選択的に、独立して選択される熱硬化性シリコーン組成物の硬化物を含む任意の追加の層と、
を含む3D物品であって、
前記第1及び第2の熱硬化性シリコーン組成物が、互いに同一、又は異なり、
前記第1及び第2の熱硬化性シリコーン組成物の硬化物は、放射線硬化物ではなく、
前記第1及び第2の熱硬化性シリコーン組成物が、独立して、縮合硬化性シリコーン組成物、ヒドロシリル化硬化性シリコーン組成物、フリーラジカル硬化性シリコーン組成物、及び二元硬化シリコーン組成物から選択され、
前記第1及び第2の熱硬化性シリコーン組成物が、剪断減粘性であり、
前記第1及び第2の熱硬化性シリコーン組成物が、25℃で1〜1,000,000センチストークスの粘度を有する、3D物品。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20230173130A (ko) | 2021-04-23 | 2023-12-26 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 광조형용 자외선 경화성 실리콘 조성물, 그 경화물 및 경화물의 제조 방법 |
Families Citing this family (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG11201607898XA (en) | 2014-03-25 | 2016-10-28 | Biobots Inc | Methods, devices, and systems for the fabrication of materials and tissues utilizing electromagnetic radiation |
CN108136662B (zh) * | 2015-09-03 | 2021-08-06 | 美国陶氏有机硅公司 | 使用可热固化有机硅组合物的3d印刷方法 |
CN108137925B (zh) | 2015-09-10 | 2022-02-25 | 美国陶氏有机硅公司 | 使用热塑性有机硅组合物的3d印刷方法 |
KR102145530B1 (ko) * | 2015-09-14 | 2020-08-19 | 타이거 코팅스 게엠베하 운트 코. 카게 | 열경화성의 중합체성 파우더 조성물의 용도 |
GB201603107D0 (en) | 2016-02-23 | 2016-04-06 | Dow Corning | Low temperature cure silicone elastomer |
JP6656045B2 (ja) * | 2016-03-29 | 2020-03-04 | 信越化学工業株式会社 | 担持白金触媒を含有する樹脂組成物、及びそれを用いた熱硬化性オルガノポリシロキサン組成物ならびにその硬化方法 |
KR102252348B1 (ko) * | 2016-05-16 | 2021-05-14 | 한국전자기술연구원 | 3d 프린팅에 사용되는 폴리디메틸실록산 기반의 광경화형 고분자 및 제조 방법 |
US10363732B2 (en) * | 2016-08-22 | 2019-07-30 | Honeywell Federal Maufacturing & Technologies, LLC | Systems and methods for generating slice files from native CAD geometries |
EP3321074A1 (en) | 2016-11-11 | 2018-05-16 | Dow Corning Corporation | A device for formfree printing a three-dimensional object in layers |
US10576683B2 (en) * | 2017-01-16 | 2020-03-03 | The Boeing Company | Multi-part filaments for additive manufacturing and related systems and methods |
CN110997325B (zh) * | 2017-03-30 | 2022-08-23 | 美国陶氏有机硅公司 | 形成多孔三维(3d)制品的方法 |
WO2018183803A1 (en) * | 2017-03-30 | 2018-10-04 | Dow Silicones Corporation | Method of preparing porous silicone article and use of the silicone article |
WO2018206995A1 (en) | 2017-05-10 | 2018-11-15 | Elkem Silicones France Sas | Method for manufacturing a silicone elastomer article using a 3d printer |
EP3694907A4 (en) * | 2017-09-26 | 2021-08-18 | Saint-Gobain Performance Plastics Corporation | PHOTOSETTING COMPOSITIONS AND 3D PRINTING PROCESSES USING THEM |
US10689491B2 (en) * | 2017-09-29 | 2020-06-23 | Lawrence Livermore National Security, Llc | Silicone formulations for 3D printing |
KR20200042930A (ko) | 2017-09-29 | 2020-04-24 | 와커 헤미 아게 | 하나보다 많은 종류의 실리콘 재료로 제조된 3d 인쇄 성형 부품 |
WO2019077555A1 (en) * | 2017-10-20 | 2019-04-25 | Auckland Uniservices Limited | 3D PRINTING METHODS AND APPARATUS |
JP6615849B2 (ja) * | 2017-11-22 | 2019-12-04 | マクセルホールディングス株式会社 | モデル材用組成物 |
US20200290266A1 (en) * | 2017-11-28 | 2020-09-17 | Arevo, Inc. | Materials, Methods and Systems for Printing Three-Dimensional Objects by Direct Energy Deposition |
EP3732020B1 (en) * | 2017-12-26 | 2023-05-17 | Braskem America, Inc. | Method of additive manufacturing using high performance polyolefins |
CN112262034B (zh) * | 2018-06-08 | 2022-08-16 | 埃肯有机硅(上海)有限公司 | 可固化有机硅组合物 |
TW202010806A (zh) * | 2018-09-03 | 2020-03-16 | 美商陶氏有機矽公司 | 低黏度組成物及使用該組成物之3d列印方法 |
US11104075B2 (en) | 2018-11-01 | 2021-08-31 | Stratasys, Inc. | System for window separation in an additive manufacturing process |
US10723069B2 (en) | 2018-11-01 | 2020-07-28 | Origin Laboratories, Inc. | Method for build separation from a curing interface in an additive manufacturing process |
NL2021916B1 (en) | 2018-11-01 | 2020-05-14 | Univ Delft Tech | Acoustic Liner |
WO2020194448A1 (ja) * | 2019-03-25 | 2020-10-01 | 株式会社ニコン | 造形システム |
CN113840880A (zh) * | 2019-05-22 | 2021-12-24 | 汉高股份有限及两合公司 | 用于清洁和后处理3d打印光固化有机硅的方法 |
US11460356B2 (en) | 2019-06-07 | 2022-10-04 | The University Of Kansas | Functional soft materials and methods of making and using thereof |
WO2021003108A1 (en) * | 2019-07-01 | 2021-01-07 | Elkem Silicones USA Corp. | Two-part curable liquid silicone rubber composition |
TW202134045A (zh) * | 2019-10-25 | 2021-09-16 | 德商漢高智慧財產控股公司 | 可三維圖案化之熱介面 |
WO2021202811A1 (en) | 2020-03-31 | 2021-10-07 | Greene, Tweed Technologies, Inc. | Method for forming layered thermoset silicone and thermoplastic articles using additive manufacturing, articles formed therefrom and apparatus for use therein |
WO2022081271A1 (en) | 2020-10-13 | 2022-04-21 | Cabot Corporation | Conductive photo-curable compositions for additive manufacturing |
DE102021106369A1 (de) | 2021-03-16 | 2022-09-22 | Universität Rostock | Pulverbett-3D-Druckverfahren zur Herstellung elastischer Formkörper aus Siliconen und für das Verfahren geeignetes Siliconharz-haltiges Pulver |
US11964425B2 (en) | 2021-05-12 | 2024-04-23 | Elkem Silicones USA Corp. | Method for producing a three-dimensional printed article |
US20220380549A1 (en) | 2021-05-12 | 2022-12-01 | Elkem Silicones USA Corp. | Method for producing a three-dimensional printed article |
CN114770932A (zh) * | 2022-03-30 | 2022-07-22 | 共享智能装备有限公司 | 用于3d打印产品的高效固化方法 |
EP4344873A1 (en) | 2022-09-27 | 2024-04-03 | Elkem Silicones France SAS | Post-treatment of a 3d-printed elastomer silicone article |
Family Cites Families (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4783289A (en) * | 1986-04-01 | 1988-11-08 | Toray Silicone Co., Ltd. | Process for molding silicone rubber compositions |
US4780260A (en) * | 1986-09-24 | 1988-10-25 | Toray Silicone Company, Ltd. | Method for producing silicone rubber moldings having a hard exterior layer |
US4766176A (en) | 1987-07-20 | 1988-08-23 | Dow Corning Corporation | Storage stable heat curable organosiloxane compositions containing microencapsulated platinum-containing catalysts |
JPH0214244A (ja) * | 1988-06-30 | 1990-01-18 | Toray Dow Corning Silicone Co Ltd | 加熱硬化性オルガノポリシロキサン組成物 |
US5387380A (en) | 1989-12-08 | 1995-02-07 | Massachusetts Institute Of Technology | Three-dimensional printing techniques |
US5204055A (en) | 1989-12-08 | 1993-04-20 | Massachusetts Institute Of Technology | Three-dimensional printing techniques |
US5679727A (en) | 1996-03-28 | 1997-10-21 | Dow Corning Corporation | Curable organosiloxane composition with improved hysteresis characteristics |
US20050014005A1 (en) | 2003-07-18 | 2005-01-20 | Laura Kramer | Ink-jettable reactive polymer systems for free-form fabrication of solid three-dimensional objects |
US7482404B2 (en) | 2004-02-17 | 2009-01-27 | The Goodyear Tire & Rubber Company | Liquid polymer |
EP1926602B1 (en) | 2005-09-21 | 2014-06-18 | Dow Corning Corporation | Ambient lithographic method using organoborane amine complexes |
JP2007106070A (ja) | 2005-10-17 | 2007-04-26 | Kokusai Kiban Zairyo Kenkyusho:Kk | 3次元積層造形方法とその装置 |
GB0607438D0 (en) * | 2006-04-13 | 2006-05-24 | Dow Corning | Water containing silicone rubber device, process to make the device and uses for it |
DE102008043316A1 (de) | 2008-10-30 | 2010-05-06 | Wacker Chemie Ag | Verfahren zur Herstellung von Siliconformkörpern aus durch Licht vernetzbaren Siliconmischungen |
US8637585B2 (en) | 2008-12-01 | 2014-01-28 | Basf Se | Silsesquioxane photoinitiators |
MX2011008279A (es) | 2009-02-17 | 2011-11-04 | Dow Corning | Sello de gel de silicona y metodo para su preparacion y uso. |
JP4913858B2 (ja) * | 2009-04-14 | 2012-04-11 | 日東電工株式会社 | 熱硬化性シリコーン樹脂用組成物 |
US20120133079A1 (en) | 2009-06-05 | 2012-05-31 | David Sykes | Silicone rubber compositions |
US8814002B2 (en) * | 2011-09-07 | 2014-08-26 | Zen Design Solutions Limited | Delivery system |
KR102041096B1 (ko) * | 2012-07-30 | 2019-11-07 | 다우 실리콘즈 코포레이션 | 열 전도성 축합 반응 경화성 폴리오가노실록산 조성물 및 조성물의 제조 방법 및 사용 방법 |
US9312416B2 (en) * | 2012-11-12 | 2016-04-12 | Dow Corning Corporation | Method of forming an electronic article |
WO2014108364A1 (en) * | 2013-01-10 | 2014-07-17 | Luxexcel Holding B.V. | Method of printing an optical element |
US20150084222A1 (en) * | 2013-09-24 | 2015-03-26 | Fenner, U.S., Inc. | Filament for fused deposit modeling |
EP3068821B1 (en) | 2013-11-11 | 2018-10-03 | Dow Silicones Corporation | Uv-curable silicone composition, cured products thereof, and methods of using the same |
EP3071939B1 (en) | 2013-11-18 | 2019-07-31 | President and Fellows of Harvard College | Printed stretchable strain sensor |
JP2015109337A (ja) | 2013-12-04 | 2015-06-11 | 日東電工株式会社 | 光半導体装置用熱硬化性樹脂組成物およびそれを用いて得られる光半導体装置用リードフレーム、ならびに光半導体装置 |
WO2015107333A1 (en) * | 2014-01-14 | 2015-07-23 | King's College London | 3d printing of facial prostheses |
CN106804110B (zh) | 2014-09-17 | 2020-11-27 | 美国陶氏有机硅公司 | 使用可光固化的有机硅组合物的3d印刷方法 |
DE102014222685A1 (de) * | 2014-11-06 | 2016-05-12 | Wacker Chemie Ag | Verfahren zur Herstellung von Siliconelastomerteilen |
EP3297808A1 (en) * | 2015-05-22 | 2018-03-28 | LUXeXcel Holding B.V. | Method for printing a three-dimensional structure and a system for printing a three-dimensional structure |
CN108136662B (zh) * | 2015-09-03 | 2021-08-06 | 美国陶氏有机硅公司 | 使用可热固化有机硅组合物的3d印刷方法 |
CN105238064B (zh) | 2015-09-29 | 2019-04-09 | 广东标美硅氟新材料有限公司 | 一种有机硅材料及其制备方法和其应用于3d打印的方法 |
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KR20230173130A (ko) | 2021-04-23 | 2023-12-26 | 신에쓰 가가꾸 고교 가부시끼가이샤 | 광조형용 자외선 경화성 실리콘 조성물, 그 경화물 및 경화물의 제조 방법 |
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KR102143330B1 (ko) | 2020-08-12 |
CN108136662B (zh) | 2021-08-06 |
CN108136662A (zh) | 2018-06-08 |
EP3344441B1 (en) | 2024-10-16 |
EP3344441A1 (en) | 2018-07-11 |
WO2017040874A1 (en) | 2017-03-09 |
JP2020073357A (ja) | 2020-05-14 |
US11192354B2 (en) | 2021-12-07 |
KR20180073560A (ko) | 2018-07-02 |
JP2018528882A (ja) | 2018-10-04 |
US20180186076A1 (en) | 2018-07-05 |
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