TWI831201B - 一種三維印刷品之製造方法 - Google Patents
一種三維印刷品之製造方法 Download PDFInfo
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- TWI831201B TWI831201B TW111117920A TW111117920A TWI831201B TW I831201 B TWI831201 B TW I831201B TW 111117920 A TW111117920 A TW 111117920A TW 111117920 A TW111117920 A TW 111117920A TW I831201 B TWI831201 B TW I831201B
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WKWOFMSUGVVZIV-UHFFFAOYSA-N n-bis(ethenyl)silyl-n-trimethylsilylmethanamine Chemical compound C[Si](C)(C)N(C)[SiH](C=C)C=C WKWOFMSUGVVZIV-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000671 polyethylene glycol diacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
本發明係關於一種用光可固化聚矽氧組合物製造三維(3D)印刷品之方法,該組合物包括含有特定(甲基)丙烯酸酯基團作為端基的聚矽氧。
Description
本發明係關於一種使用包含(甲基)丙烯酸酯聚矽氧聚合物之光可固化組合物製造三維(3D)印刷品之方法。
3D印刷技術(亦稱作積層製造(AM)、快速原型設計或分層製造)涵蓋多種不同技術且用於產生幾乎任何形狀或幾何形狀之三維物件而無需模具或機械加工。當今,由於可能的商業應用眾多,積層製造正經歷極強勁發展勢頭,且具有重要的增長潛力。為了使其使用增加,必須擴大可與積層製造設備一起使用之材料範圍。
一類重要的可固化聚矽氧組合物藉由熱固性交聯固化,其在3D印刷機上之使用複雜且幾乎不與積層製造方法相容。實際上,在逐層3D印刷製程中,各層必須保持其形狀。隨著產品高度增加,下層不能保持其形狀及流動,導致所建構結構變形或塌陷。因此,獲得不當形狀之聚矽氧部件。
已制定若干解決方案以規避此可印刷性問題。例如,在WO2018/206689中,聚矽氧3D印刷物件係經由3D-液體沈積模型化製程獲得,其中可固化聚矽氧組合物具有足夠流變特性,可避免印刷物件在完全固化之前在室溫下塌陷或變形。此類方法之主要缺點為缺少製程精確度(>100微米/層)且需要對成品物件進行後處理以確保固化製程完全完成。
基於光聚合之3D印刷技術現在愈來愈受到關注。其自液體材料開始,以局部沈積且固化該材料,或自液體桶中選擇性固化該材料。此類技術之實例為UV-立體微影(SLA)、UV-數位光處理(DLP)、連續液體界面生產(CLIP)、UV擠出及噴墨沈積。
UV-立體微影(SLA)揭示於例如WO2015197495中。例如,UV-立體微影(SLA)使用雷射光束,其通常藉由掃描器系統在X-Y (水平)平面上移動。藉由來自生成之資料源之資訊導引之電動機驅動鏡面將激雷射光束發送至表面上。
UV-數位光處理(DLP)揭示於例如WO2016181149及US20140131908中。在UV-數位光處理(DLP)中,將3D模型發送至印刷機,且將一桶液態聚合物在安全光條件下曝露於來自DLP投影儀之光。DLP投影儀將3D模型之影像顯示至液態聚合物上。DLP投影儀可安裝在窗口下,該窗口可由透明彈性膜製成,其中來自DLP投影儀之UV光透過該膜。
連續液體界面生產(CLIP,最初為連續液體相間印刷)揭示於例如WO2014126837及WO2016140891中,其例如使用光聚合來產生具有多種形狀之光滑側面固體物件。
擠出3D印刷製程揭示於例如WO2015107333、WO2016109819及WO2016134972中。例如,在此製程中,經由噴嘴擠出材料以印刷物件之一個截面,其可對各層重複。能量源可直接連接至噴嘴上,使其緊隨擠出後立即固化,或可與噴嘴分離以延遲固化。一旦各層完成,噴嘴或建構平台通常在X-Y (水平)平面中移動,隨後在Z軸(垂直)平面中移動。UV固化可在沈積後立即進行,或板在UV光下移動以在沈積與UV固化之間產生延遲。可使用支撐材料以避免在空氣中擠出長絲材料。可使用一些後加工處理來提高印刷表面之品質。
噴墨沈積揭示於例如WO201740874、WO2016071241、WO2016134972、WO2016188930、WO2016044547及WO2014108364中,其例如使用材料噴射印刷機,該印刷機具有在印刷區域周圍移動之印刷頭,該印刷頭例如藉由UV聚合噴射特定液態可固化組合物。噴墨噴嘴形成液滴之能力以及其體積及速度均受材料之表面張力影響。
由於3D光聚合係基於使用在曝露於特定波長之光源時可固化/光聚合的呈液態之單體/寡聚物,光可固化聚矽氧組合物由於其固化材料之許多優點,諸如可撓性、生物相容性、對電氣及電子組件之隔熱特性及良好耐化學性、耐溫性及耐候性而備受關注。
當今用於3D印刷之光可固化液態聚矽氧組合物主要為與光活化催化劑偶合之聚加成可固化聚矽氧組合物。此技術之問題為反應之催化作用並非瞬時的,且在使用例如3D噴墨印刷時,固化產物常常需要後固化。
另一新方法描述於US2020071525中,其中描述用於製造立體印刷3D印刷聚矽氧結構之光可固化聚(矽氧烷)組合物,其包含:
(a)具有第一端基有機官能基及第二端基有機官能基之第一可聚合聚(矽氧烷),各端基包含丙烯酸酯基團或甲基丙烯醯氧基丙基,
(b)包含重複單元之第二可聚合聚(矽氧烷),該等重複單元中之至少一些具有側鏈可聚合基團,
(c)光引發劑,其較佳為(2,4,6-三甲基苯甲醯基)苯基亞膦酸乙酯(TPO-L),及
(d)敏化劑,其較佳為異丙基9-氧硫𠮿(ITX)。
特定而言,含有甲基丙烯醯氧基丙基端基之較佳組分(a)具有下式:
其具有約10 kDa至約60 kDa之較佳分子量。其描述為適用於建構微型裝置,且3D印刷結構較佳具有約0.5至1 MPa之低楊氏模數(Young's modulus)及約140%之斷裂伸長率。藉由將光引發劑濃度含量升高至約0.8% (組合物總重量之重量%),獲得最大約160%之斷裂伸長率。然而,在此含量下,光引發劑在固化後引發黃色材料,其在許多應用中不合乎需要。此外,所有實例包括使用異丙基9-氧硫(ITX)作為敏化劑。
因此,仍需要自聚矽氧光聚合物組合物中獲得3D物件,該等組合物使固化產物具有更高斷裂伸長率,特定而言遠高於以上參考文獻中所述之140%,適於經受3D-UV印刷技術,諸如UV-立體微影(SLA)、UV-數位光處理(DLP)、連續液體界面生產(CLIP)、UV擠出及噴墨沈積。此外,亦需要改良抗張強度及其他物理特性,從而打開其在各種領域,諸如保健、電子、航太、運輸、建築、工業備件、密封及用密封墊黏結中之應用。
本發明之一個目標為提供一種用光可固化聚矽氧組合物製造三維印刷品之方法,該組合物產生具有更高斷裂伸長率特性,特定而言遠高於先前技術中所述之140%,且具有改良之抗張強度及其他物理特性的固化產物,從而打開光可固化聚矽氧組合物在3D印刷中的應用,用於各種領域,諸如保健、電子、航太、運輸、建築、工業備件、密封及用密封墊黏結。
本發明之另一目標為提供一種用光可固化聚矽氧組合物製造三維印刷品之方法,該組合物不一定需要使用諸如異丙基9-氧硫(ITX)之敏化劑。
本發明之另一目標為提供根據本發明之方法形成之三維(3D)印刷品。
此等目標以及其他係藉由本發明來達成,本發明係關於一種三維印刷品之製造方法,其包含
1) 提供光可固化組合物
X,其包含:
(a) 100重量份之至少一種有機聚矽氧烷聚合物
CE,其具有下式(1):
M*D
xM* (1)
其中:
• M*為:R
1(R)
2SiO
1/2;
• D為(R)
2SiO
2/2;
• x ≥ 60,較佳60≤x≤500,且最佳90≤x≤400,
• R為選自由甲基、乙基、丙基、三氟丙基及苯基組成之群之烷基,且R最佳為甲基,
• R
1為通式-C
nH
2nO-CH
2CHR
2(CH
2)
m-OCOCH=CHR
3之部分,其中n為3或4且m為0或1,且m較佳為1,R
2為H、OH或-C
zH
2z-CH
2OH,z為0、1、2或3且R
3為H或-CH
3;
(b) 0至20重量份、較佳1至20重量份、且甚至更佳1至10重量份之至少一種有機聚矽氧烷聚合物
XL,其具有以下式(2):
M D
v(D
ACR)
wM (2)
其中
• M為:R
2(R)
2SiO
1/2;(R)
3SiO
1/2或R
4(R)
2SiO
1/2• D為(R)
2SiO
2/2;
• D
ACR為(R
2)(R)SiO
2/2;
• y為0至500,較佳10至500,且最佳50至400,
• w為0至50,較佳1至25,且最佳3至20,且當w=0時,y為1至500且M表示:R
2(R)
2SiO
1 / 2或R
4(R)
2SiO
1 / 2;
• R為選自由甲基、乙基、丙基、三氟丙基及苯基組成之群之烷基,且R最佳為甲基,
• R
2為以下通式之部分:
o -C
nH
2nO-CH
2CHR
2(CH
2)
m-OCOCH=CHR
3,其中n為3或4且m為0或1,R
2為H、OH或-C
zH
2z-CH
2OH,z為0、1、2或3且R
3為H或-CH
3;或
o -C
nH
2nO-COCH=CHR
3,其中n為3或4且R
3為H或-CH
3;
• R
4為式(3)之部分:
(c) 0.01至10重量份、較佳0.01至3重量份之至少一種光引發劑
PI,
(d)至少15重量份、較佳20至100重量份、且甚至更佳20至50重量份之至少一種無機填充劑
F,
(e) 0至10重量份之至少一種敏化劑
PS,
(f) 0至10000重量份之至少一種光可固化有機(甲基)丙烯酸酯-單體/寡聚物
M,及
(g) 0至10重量份之至少一種添加劑
I,
2) 將該光可固化組合物
X曝露於光化輻射以在板或支撐物上形成固化橫截面,及
3)在先前固化之截面上用新層重複步驟1)及2),以建立三維印刷品。
值得讚揚地,為了達成此等目標,本申請人完全驚人地且出乎意料地證明,相對於根據先前技術之標準丙烯酸酯化封端聚矽氧((甲基)丙烯醯氧丙基端基),藉由使用特定丙烯酸酯化封端聚矽氧(根據本發明之3-丙烯醯氧基-2-羥基丙氧基丙基端基)與該光可固化組合物
X中之至少15重量份(對於100重量份丙烯酸酯化封端聚矽氧)無機填充劑組合,有可能經由3D-UV印刷獲得固化材料,其具有遠高於先前技術中所述之140%的更高斷裂伸長率、良好抗張強度及其他物理特性的一些改良,從而開啟光可固化聚矽氧組合物在3D印刷中的應用,其用於各種領域,諸如保健、電子、航太、運輸、建築、工業備件、密封及用密封墊黏結及其類似者。結果係在不使用諸如異丙基9-氧硫等敏化劑之情況下獲得的,其使得3D印刷方法更靈活,可使用更廣泛的3D-UV印刷機。
在較佳實施例中,根據本發明之有機聚矽氧烷聚合物
CE具有4000 g/mol至40000 g/mol、較佳5700 g/mol至30000 g/mol、且甚至更佳5700 g/mol至24000 g/mol之平均分子量。
在另一較佳實施例中,選擇組分及組分之量以使得組合物
X在25℃下之動態黏度低於50 Pa.s且較佳在25℃下之動態黏度低於20 Pa.s。在此情況下,組合物
X可藉由普通SLA印刷機或DLP印刷機,諸如ASIGA MAX進行處理。
術語「動態黏度」意欲意謂伴隨材料中流動速率梯度之存在的剪應力。本報告中參考之所有黏度均對應於動態黏度之量值,該量值係在25℃下或根據標準ASTM D445以本身已知之方式量測的。黏度通常使用布氏黏度計(Brookfield viscometer)來量測。
在較佳實施例中,該有機聚矽氧烷聚合物
CE包含具有羥基之甲基(丙烯酸酯)部分作為端基且具有一般平均式:
M*Dx M*
其中
• M*為:R
1(R)
2SiO
1/2;
• D為(R)
2SiO
2/2;
• x ≥ 60,較佳60≤x≤500,且最佳90≤x≤400,
• R為選自由甲基、乙基、丙基、三氟丙基及苯基組成之群之烷基,且R最佳為甲基,
• R
1為通式-C
nH
2nO-CH
2CHR
2(CH
2)
m-OCOCH=CHR
3之部分,其中n為3或4且m為0或1,R
2為OH或-C
zH
2z-CH
2OH,z為1、2或3且R
3為H或-CH
3。
在另一較佳實施例中,有機聚矽氧烷聚合物
CE(具有3-丙烯醯氧基2-羥基丙氧基丙基端基之聚二甲基矽氧烷)具有以下式(4):
其中n ≥ 60,且較佳60≤n≤500,且最佳80≤n≤400。
在較佳實施例中,有機聚矽氧烷聚合物
XL係選自由聚合物(5)至(8)組成之群:
其中a為1至20,且較佳a為1至10,b為1至500,且較佳b為10至500。
其中n為10至400,較佳n為50至200,且甚至更佳n為50至150。
其中n為1至500,且較佳n為1至200。
其中a為2至50,且較佳a為2至20;b為0至500,且較佳b為10至400。
光引發劑之適合實例包括醯基磷氧化物或醯基膦氧化物。溶劑可與諸如異丙醇(IPA)等光引發劑組合使用以使其溶解於聚矽氧組合物中。
根據本發明之適合光引發劑為Norrish I型之彼等,其在用UV光能量照射時分解產生自由基。較佳光引發劑為膦氧化物之衍生物,諸如:
(9)二苯基(2,4,6-三甲基苯甲醯基)膦氧化物(TPO)
(10) (2,4,6-三甲基苯甲醯基)苯基亞膦酸乙酯(TPO-L)
(11):苯基雙(2,4,6-三甲基苯甲醯基)膦氧化物(BAPO)
CPO-1及CPO-2可根據
Molecules2020, 25(7), 1671,
New Phosphine Oxides as High PerformanceNear
UV Type I Photoinitiators of Radical Polymerization中所述之方案製備。
其他合適之光引發劑為諸如US2016/0168177 A1中所述之液態雙醯基膦氧化物或諸如US2008/0004464中所述之醯基膦。
最佳光引發劑為(2,4,6-三甲基苯甲醯基)苯基亞膦酸乙酯(10) (TPO-L)。
合適之無機填充劑
F可選自由以下組成之群:增強無機填充劑
F1、導熱無機填充劑
F2、導電無機填充劑
F3及其混合物。
在一些實施例中,增強無機填充劑
F1係選自二氧化矽及/或氧化鋁,較佳選自二氧化矽。作為可使用之二氧化矽,設想特徵如下之填充劑:細粒尺寸通常小於或等於0.1 μm且比表面積與重量之比高,通常在大約50平方公尺/公克至大於300平方公尺/公克範圍內。此類型之二氧化矽為市售產品且在製造聚矽氧組合物之技術中熟知。此等二氧化矽可為膠體二氧化矽、熱解製備之二氧化矽(稱為燃燒二氧化矽或煙霧狀二氧化矽)或藉由濕法製備之二氧化矽(沈澱二氧化矽)或此等二氧化矽之混合物。出於本發明之目的,用於製備能夠形成無機填充劑之二氧化矽之化學性質及方法並不重要,其限制條件為二氧化矽對印刷產品具有增強作用。當然亦可使用各種二氧化矽的切割物。此等二氧化矽粉末具有通常接近或等於0.1 μm之平均粒度及大於50 m
2/g、較佳50至400 m
2/g、尤其150至350 m
2/g之BET比表面積5。此等二氧化矽視情況藉助於選自滿足至少兩個標準之分子組之至少一種相容劑預處理:
a) 在氫鍵區域中與二氧化矽自身及與周圍的聚矽氧油具有高相互作用;及
b)自身或其降解產物易於藉由在氣體流中於真空下加熱而自最終混合物中移除,且低分子量化合物係較佳的。
此等二氧化矽亦可藉由添加未處理之二氧化矽及至少一種性質類似於可用於預處理且如上所定義之相容劑來原位處理。
相容劑係根據處理方法(預處理或原位)選擇且可例如選自包含以下之群:氯矽烷;聚有機環矽氧烷,諸如八甲基環矽氧烷(D4);矽氮烷,較佳二矽氮烷或其混合物,六甲基二矽氮烷(HMDZ)為較佳矽氮烷且可能與二乙烯基四甲基二矽氮烷相關;每分子具有一或多個連接至矽之羥基的聚有機矽氧烷;胺,諸如具有低分子量之氨或烷基胺,諸如二乙胺;烷氧基矽烷,諸如甲基醯氧基丙基三甲氧基矽烷;具有低分子量之有機酸,諸如甲酸或乙酸,或丙烯酸及其混合物。在原位處理之情況下,相容劑較佳在水存在下使用。就此而言之更多細節,可參考例如專利FR-B-2 764 894。
可使用先前技術之相容方法,藉由矽氮烷提供早期處理(例如FR-A-2 320 324)或延遲處理(例如EP-A-462 032),應記住根據所使用之二氧化矽,其使用一般將不可能在機械特性,特定而言藉由在根據本發明之兩個場合處理獲得之延展性方面獲得最佳結果。
在較佳實施例中,無機填充劑
F係選自由以下組成之群:膠態二氧化矽、煙霧狀二氧化矽、沈澱二氧化矽或其混合物。
作為增強無機填充劑
F1之實例,可使用氧化鋁且特定言之有利地採用以已知方式摻雜或未摻雜之高度分散性氧化鋁。當然亦可能使用各種氧化鋁之切割物。較佳地,所用增強填充劑為單獨採用或與氧化鋁混合之燃燒二氧化矽。
可根據本發明設想使用補充填充劑,諸如導熱無機填充劑
F2及/或導電無機填充劑
F3。兩者皆可藉由表面積改質劑進行表面處理,該改質劑用於控制填充劑形狀之形態及/或填充填充劑之內部空隙/孔隙。表面積改質劑之引入降低了填充劑之總表面積。
合適之導熱無機填充劑
F2包括氮化硼、氮化鋁、銅、銀、鋁、鎂、黃銅、金、鎳、氧化鋁、氧化鋅、氧化鎂、氧化鐵、氧化銀、氧化銅、塗有金屬之有機粒子、鍍銀之鎳、鍍銀之銅、鍍銀之鋁、鍍銀之玻璃、銀片、銀粉、碳黑、石墨、金剛石、碳奈米管、二氧化矽及其混合物。較佳地,導熱無機填充劑
F2為氮化硼。
合適之導電無機填充劑
F3包括金屬或其他組分。特定而言,其可包括例如填充劑,諸如碳黑、石墨;金屬組分,諸如鋁、銅、黃銅、青銅、鎳或鐵;導電無機顏料,諸如氧化錫、氧化鐵及二氧化鈦;無機鹽;及其組合。特別適用的為石墨,且尤其為合成石墨。其亦可包括合成石墨、天然石墨及其組合。一特定實施例亦可包括銀粒子、鍍銀核心粒子及碳奈米管。
若存在,敏化劑
PS係在1 ppm至至多10重量份範圍內。最佳用量係在組合物
X之全部含量的10至100 ppm範圍內。
敏化劑意謂吸收光能量且藉由轉移此能量至受體分子而充當供體之分子。
合適之敏化劑
PS 之實例包括由以下組成之群:二苯甲酮及其衍生物、9-氧硫及其衍生物、蒽醌及其衍生物、甲酸苯甲酯、樟腦醌、二苯基乙二酮、菲醌、香豆素及豆素酮(cetocoumarine)及其混合物。
二苯甲酮衍生物意謂經取代之二苯甲酮及二苯甲酮之聚合形式。術語「9-氧硫𠮿衍生物」係指經取代之9-氧硫𠮿及蒽醌衍生物、經取代之蒽醌,尤其係指蒽醌磺酸及經丙烯醯胺基取代之蒽醌。
作為合適之敏化劑
PS的特定實例,可尤其提及以下產品:異丙基9-氧硫;二苯甲酮;樟腦醌;9-𠮿酮;蒽醌;1,4-二羥基蒽醌;2-甲基蒽醌;2,2'-雙(3-羥基-1,4-萘醌);2,6-二羥基蒽醌;1-羥基環己基-苯基酮;1,5-二羥基蒽醌;1,3-二苯基-1,3-丙烷-二酮;5,7-二羥基黃酮;過氧化二苯甲醯基;2-苯甲醯苯甲酸;2-羥基-2-甲基苯丙酮;2-苯基苯乙酮;蒽酮;4,4'-二甲氧基安息香;菲醌;2-乙基蒽醌;2-甲基蒽醌;2-乙基蒽醌;1,8-二羥基蒽醌;過氧化二苯甲醯;2,2-二甲氧基-2-苯基苯乙酮;安息香;2-羥基-2-甲基苯丙酮;苯甲醛;4-(2-羥基乙氧基)苯基-(2-羥基-2-甲基丙基)酮;苯甲醯基-丙酮;(2,4,6-三甲基苯甲醯基)苯基亞膦酸乙酯及其混合物。
作為敏化劑
PS之商業產品的實例,可提及以下產品:Esacure
®TZT、Speedcure
®MBP、Omnipol
®BP及9-氧硫衍生物、Irgacure
®907、Omnipol
®TX及Genopol
®TX-1產品。
其他實例包括WO2018/234643中所述之氧蔥酮或經取代之9-氧硫類型的化合物及以下化合物(14)至(30):
作為根據本發明適用之二苯甲酮的另一實例,可提及化合物(31):
此化合物對應於產品Ebecryl P36 (CAS:85340-63-2)。
當光可固化有機(甲基)丙烯酸酯-單體/寡聚物
M存在時,添加如上文所述之敏化劑可能係有用的。
合適之光可固化有機(甲基)丙烯酸酯-單體/寡聚物
M之實例包括但不限於以下:聚乙二醇二丙烯酸酯(PEGDA)、1,6-雙(金屬氯氧基-2-乙毒硼胺基)-2,4,4-三甲基二十烷(1,6-bis-(metalocriloxi-2-etoxicarbolamino)-2,4,4-trimethylexane,UDMA)、三二乙醇二甲基丙烯酸酯(TEGDMA)、雙酚A-甲基丙烯酸縮水甘油酯或2,2-雙-4-2-(氫氧化-3-間肼基丙酸-1-氧基)丙烷(2,2-bis-4-2-(hydroxi-3-metacriloxiprop-1-oxi)propane,Bis-GMA)、三羥甲基丙烷三丙烯酸酯(TTA)及雙酚A乙氧基化二丙烯酸酯(Bis-EDA)。
本發明可固化聚矽氧組合物可視情況包含至少一種添加劑
I,只要其不干擾固化機制或對目標特性無不利影響。該添加劑之選擇取決於使用該等組合物之應用及所需特性。其可包括單獨使用或作為混合物使用之各種類型的添加劑,諸如顏料、消光劑(delustrant;matting agent)、熱及/或光穩定劑、抗靜電劑、阻燃劑、抗細菌劑、抗真菌劑及觸變劑。
在較佳實施例中,選擇組分及組分(a)至(g)之量以使得組合物X在25℃下之動態黏度低於50 Pa.S且較佳在25℃下之動態黏度低於20 Pa.S,以允許容易使用標準UV-3D印刷機。
在較佳實施例中,經由3D印刷機使用選自由以下組成之群的技術提供光可固化組合物
X:UV-立體微影(SLA)、UV-數位光處理(DLP)、連續液體界面生產(CLIP)、噴墨沈積及UV擠出。此等技術及相關3D印刷設備已為熟習此項技術者所熟知。
為建構物件,使用3D數位檔案,例如經由CAD軟體(諸如SolidWorks、Sculpt或SelfCAD)。此等檔案(通常STL檔案)係藉由切片機處理,其將模型切割為薄層以進行印刷。隨後將指令發送至3D印刷機。
本發明之其他優點及特性將在閱讀以下以說明方式給出且絕非限制性的實例時呈現。
實例 I ) 實例中使用之原材料:1)具有雙(3-丙烯醯氧基2-羥基丙氧基丙基)端基
之聚二甲基矽氧烷
CE:
聚二甲基矽氧烷聚合物
CE - 1(比較):n = 6;25℃下之黏度170 mPa.s。
聚二甲基矽氧烷聚合物
CE - 2(比較) n = 45,25℃下之黏度200 mPa.s
聚二甲基矽氧烷聚合物
CE - 3(本發明) n為250至280;25℃下之黏度1200 mPa.s
2)具有雙(丙烯醯氧基)端基之聚二甲基矽氧烷
CE(比較):
聚二甲基矽氧烷聚合物
CE - 4(比較) n = 130,黏度430 mPa.s
3) 在鏈中具有(丙烯醯氧基-2-羥基丙氧基丙基)基團之聚二甲基矽氧烷
XL:
聚二甲基矽氧烷聚合物
XL - 1;a為3至4且b為約220。
聚二甲基矽氧烷聚合物
XL - 2;a為7至8且b為約80。
4) 聚合物
XL - 3:n = 95:
5) 在鏈中具有(3-丙烯醯氧基2-羥基丙氧基丙基)端基之聚二甲基矽氧烷
XL - 4(其中a為2至3且b140至170)
6) 無機填充劑
F1 :由Wacker以商品名HDK
®H2000出售之熱解二氧化矽表面處理(三甲基矽烷氧基)。
7) 光引發劑
PI : TPO-L:2,4,6-三甲基苯甲醯基二-苯基亞膦酸酯。
BAPO:苯基雙(2,4,6-三甲基苯甲醯基)膦氧化物。
TPO:2,4,6-三甲基苯甲醯基二苯膦氧化物。
8) 溶劑:IPA = 異丙醇。
9) 添加劑:Kri-Color反式顏料(顏料)
II ) 物理特性 黏度 :樣品黏度係在25℃下根據ASTM D445或ISO3104量測。
硬度 :固化樣品之硬度係在25℃下根據ASTM D2240或ISO868量測。
抗張強度及斷裂伸長率 :基於可固化聚矽氧組合物之固化樣品的抗張強度及斷裂伸長率係在25℃下根據ASTM D412或ISO37量測。
撕裂強度 :固化樣品之撕裂強度係在25℃下根據ASTM D624或ISO34-1量測。
III ) 調配物 ( 固化及用 3D 印刷機 Asiga 進行 3D - 印刷 )調配物係根據表1、2、3或4製備。
隨後將其手動混合或用高速混合器混合。隨後將所得混合物倒入容量為1公升且印刷板為XYZ:119×67×75 mm之Asiga 3D印刷機的桶中。隨後設計H2試樣(長度40mm+/-0,5,厚度2mm+/-0,2)之「.stl」檔案. 2 mm厚度試樣係用「.stl」檔案及27層的構建程序製備。各層具有75微米之厚度。在30秒內照射第一層以達成與平台之良好黏著力,且在385 nm及5.8 mW/cm
2下在20秒內照射隨後各層。3D印刷後,試樣可在180秒內在UV盒/正面/反面以405 nm進行後固化。
在下表中給出物理特性。
表1:調配物及物理特性(重量%)。
表2:調配物及物理特性(重量%)。
實例 | 1 - 比較 | 2 - 比較 | 3- 本發明 | |
聚合物 CE-1 | 75,00% | 0,00% | 0,00% | |
聚合物 CE-2 | 0,00% | 75,00% | 0,00% | |
聚合物 CE-3 | 0,00% | 0,00% | 75,00% | |
聚二甲基矽氧烷聚合物 XL-1 | 4,00% | 4,00% | 4,00% | |
無機填充劑 F1 | 30,00% | 30,00% | 30,00% | |
光引發劑 TPO-L | 1,00% | 1,00% | 1,00% | |
機械特性 | ||||
抗張 (psi) | 太脆而無法測試 | 太脆而無法測試 | 366 | |
抗張 (MPa) | 2.52 | |||
伸長率 (%) | 182 | |||
撕裂 (lb/inch) | 26 | |||
撕裂 (N/mm) | 4.55 | |||
硬度 ( 肖氏 A ) | 90 | 72 | 28,2 |
實例 | 4- 比較 | 5- 本發明 | 6- 本發明 | 7- 本發明 | 8- 本發明 |
聚合物 CE-3 | 100,00% | 100,00% | 100,00% | 100,00% | 100,00% |
聚二甲基矽氧烷聚合物 XL-1 | 5,09% | 5,33% | 5,04% | 5,11% | 5,11% |
無機填充劑 F1 | 11,83% | 26,67% | 45,80% | 51,26% | 57,66% |
顏料 | 0,24% | 0,00% | 0,00% | 1,58% | 0,00% |
光引發劑 TPO-L | 0,24% | 0,27% | 0,31% | 0,32% | 0,33% |
抗張 (psi) | 278 | 306 | 384 | 458 | 588 |
抗張 (MPa) | 1.92 | 2.11 | 2.65 | 3.16 | 4.05 |
伸長率 (%) | 108 | 214 | 196 | 200 | 252 |
撕裂 (lb/in) | 11 | 15,1 | 59 | 67 | 90 |
撕裂 (N/mm) | 1.93 | 2.64 | 10.33 | 11.73 | 15.76 |
硬度 ( 肖氏 A) | 27 | 28,5 | 25,9 | 32,9 | 34,5 |
實例4 (比較)與實例5至8 (根據本發明)之比較顯示,藉由使用特定丙烯酸酯化封端聚矽氧(根據本發明之丙烯醯氧基丙氧基丙基端基與至少15重量份(對於100重量份丙烯酸酯化封端聚矽氧)無機填充劑之組合,有可能經由3D-UV影印獲得具有遠高於先前技術中所述之140%的更高斷裂伸長率特性且在存在上述填充劑時具有極好抗張強度及撕裂特性。
表3:在5 mW/cm
2下之調配物及物理特性(重量%)
實例 | 9 | 10 | 11 |
聚合物 CE-3 | 100,00% | 0 | 0 |
聚二甲基矽氧烷聚合物 CE-4(比較) | 0 | 100,00% | 0 |
具有(甲基丙烯醯氧基丙基)端基之聚二甲基矽氧烷 XL-3 | 0 | 0 | 100,00% |
光引發劑 TPO-L | 0,40% | 0,40% | 0,40% |
伸長率 (%) | 108 | 70 | 50 |
實例9與10之間的比較顯示,與先前技術中所用之具有丙烯醯氧基丙基端基之標準聚二甲基矽氧烷
CE - 4相比,在本發明中所用之具有(丙烯醯氧基丙氧基丙基)端基之聚二甲基矽氧烷
CE在斷裂伸長率特性(+30%)方面已顯示出優良特性(即使不具有無機填充劑)。
表4:調配物及物理特性(重量%)。
實例 | 10- 本發明 | 11- 本發明 | 12- 本發明 |
聚合物 CE-3 | 75% | 75% | 75% |
在鏈中具有(丙烯醯氧基羥基丙氧基丙基)基團之聚二甲基矽氧烷 XL-1 | 4% | 0 | 0 |
在鏈中具有(丙烯醯氧基羥基丙氧基丙基)基團之聚二甲基矽氧烷 XL-2 | 0 | 4% | 0 |
在鏈中具有(丙烯醯氧基羥基丙氧基丙基)端基之聚二甲基矽氧烷 XL-4 | 0 | 0 | 4% |
無機填充劑 F1 | 20% | 20% | 20% |
光引發劑 TPO-L | 1% | 1% | 1% |
抗張 (psi) | 306 | 340 | 305 |
抗張 (MPa) | 2.11 | 2.34 | 2.10 |
伸長率 (%) | 214 | 150 | 150 |
撕裂 (lb/in) | 15,1 | 10,19 | 13,95 |
撕裂 (N/mm) | 2.64 | 1.78 | 2.44 |
硬度 ( 肖氏 A) | 28,5 | 26,8 | 32 |
在表4中,使用多種具有丙烯酸酯基團之聚二甲基矽氧烷(交聯劑),有可能獲得極佳斷裂伸長率特性。
Claims (8)
- 一種三維印刷品之製造方法,其包含1)提供光可固化組合物X,其包含:(a)100重量份之至少一種有機聚矽氧烷聚合物CE,其具有以下式(1):M*Dx M* (1)其中:M*為:R1(R)2SiO1/2;D為(R)2SiO2/2;x60,R為選自由甲基、乙基、丙基、三氟丙基及苯基組成之群之烷基,R1為通式-CnH2nO-CH2CHR2(CH2)m-OCOCH=CHR3之部分,其中n為3或4且m為0或1,R2為H、OH或-CzH2z-CH2OH,z為1、2或3且R3為H或-CH3;(b)0至20重量份之至少一種有機聚矽氧烷聚合物XL,其具有以下式(2):M Dv(DACR)w M (2)其中M為:R2(R)2SiO1/2;(R)3SiO1/2或R4(R)2SiO1/2 D為(R)2SiO2/2;DACR為(R2)(R)SiO2/2;y為0至500, w為0至50,且當w=0時,y為1至500且M表示:R2(R)2SiO1/2或R4(R)2SiO1/2;R為選自由甲基、乙基、丙基、三氟丙基及苯基組成之群之烷基,R2為以下通式之部分:-CnH2nO-CH2CHR2(CH2)m-OCOCH=CHR3,其中n為3或4且m為0或1,R2為H、OH或-CzH2z-CH2OH,z為1、2或3且R3為H或-CH3;或-CnH2nO-COCH=CHR3,其中n為3或4且R3為H或-CH3;R4為式(3)之部分:
- 如請求項1之方法,其中該有機聚矽氧烷聚合物CE具有4000g/mol至 40000g/mol之平均分子量。
- 如請求項1之方法,其中該無機填充劑F係選自由以下組成之群:膠態二氧化矽、煙霧狀二氧化矽、沈澱二氧化矽或其混合物。
- 如請求項1之方法,其中選擇該等組分及該等組分之量,以使得該組合物X在25℃下之動態黏度低於50Pa.s。
- 如請求項1之方法,其中該光可固化組合物X係經由3D印刷機使用選自由以下組成之群的技術提供:UV-立體微影(SLA)、UV-數位光處理(DLP)、連續液體界面生產(CLIP)、噴墨沈積及UV擠出。
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