TWI798343B - 可固化聚矽氧組成物及其經固化產物 - Google Patents
可固化聚矽氧組成物及其經固化產物 Download PDFInfo
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- TWI798343B TWI798343B TW108103083A TW108103083A TWI798343B TW I798343 B TWI798343 B TW I798343B TW 108103083 A TW108103083 A TW 108103083A TW 108103083 A TW108103083 A TW 108103083A TW I798343 B TWI798343 B TW I798343B
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- silicon
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- ZEUIOZPPYUDCRR-YLALLHFRSA-N 1-archaetidyl-1D-myo-inositol 3-phosphate Chemical compound CC(C)CCC[C@@H](C)CCC[C@@H](C)CCC[C@@H](C)CCOC[C@H](OCC[C@H](C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)COP(O)(=O)O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](OP(O)(O)=O)[C@H]1O ZEUIOZPPYUDCRR-YLALLHFRSA-N 0.000 claims description 3
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages
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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
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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Abstract
本發明係關於一種可固化聚矽氧組成物,其包含不含鎘量子點,該不含鎘量子點之量係該組成物之約0.01至約10質量%,其中該組成物可藉由矽氫化反應固化並且在所有矽原子鍵結之有機基團中具有至少約10 mol%的芳基。可固化聚矽氧組成物展現出量子點之優異可分散性,並且固化以形成展現出優異顏色轉換效率的經固化產物。
Description
本發明係關於包含量子點之可固化聚矽氧組成物、及其經固化產物。
發光二極體(light-emitting diode, LED)在照明材料中是重要的,諸如汽車燈、交通信號燈、一般照明、液晶顯示器(liquid crystal display, LCD)背光及顯示螢幕。目前,LED裝置一般係由無機固態複合半導體製成,諸如AIGaAs(紅色)、AIGalnP(橙色-黃色-綠色)、及AIGalnN(綠色-藍色)。然而,使用可用固態複合半導體之混合物,不能產生發出白光的固態LED。因此,目前的一種顏色混合以產生所需顏色(包括白色)之方法是使用磷光體組合,該等磷光體放置在固態LED的頂部,藉此由該等磷光體吸收來自LED之光,然後以不同頻率重新發射。亦可藉由將藍色LED與黃色磷光體組合來製造白色LED;然而,當使用此方法時,由於缺乏LED和磷光體的調節能力,色彩控制及現色性可能很差。
在利用由尺寸大約為2至50 nm之顆粒組成的複合半導體之性質方面,已獲得實質上的關注,該等顆粒常稱為量子點(quantum dot, QD)。早期基於量子點之發光裝置已藉由以下來製造:將膠態產生的量子點嵌入光學清透的LED封裝介質(一般而言為聚矽氧或丙烯酸酯)中,接著將其放置在固態LED之頂部上(參見專利文件1及2)。量子點之使用相較於更習知磷光體之使用可能具有某些顯著優點,諸如調節發射波長的能力、強吸收性質、及低散射。
由前述論述將瞭解的是,許多至今已被廣泛研究的量子點併入了鎘離子。然而,有許多環境問題與使用鎘及其他重金屬(諸如基於汞及鉛的材料)相關聯,因此需要開發不含鎘量子點。具體而言,所欲的是產生不含鎘量子點,該等不含鎘量子點展現出與目前基於鎘之量子點類似的單分散性及大小可調節光致發光光譜。
矽氫化可固化聚矽氧組成物形成具有優異特性(諸如耐候性及耐熱性)的經固化產物,且其等藉由加熱特別快速地固化,而不會在固化時產生副產物。此類組成物係用作為電氣/電子裝置之黏著劑、密封劑、或塗佈劑。
藉由摻合不含鎘量子點來使用可固化聚矽氧組成物,以轉換來自LED之發射波長。然而,由於量子點的可分散性差,量子點會聚集,因此造成LED顏色轉換效率變得不均勻的問題。先前技術文件 專利文件
專利文件1:中國專利申請公開案第104119679 A號
專利文件2:韓國專利申請公開案第10-2017-0085058 A1號
技術問題
本發明之目的是提供一種可固化聚矽氧組成物,該可固化聚矽氧組成物展現出量子點之優異可分散性,並且固化以形成展現出優異顏色轉換效率的經固化產物。本發明之另一目的是提供一種經固化產物,該經固化產物展現出量子點之優異可分散性及優異顏色轉換效率。問題之解決方案
本發明之可固化聚矽氧組成物包含不含鎘量子點,該不含鎘量子點之量係該組成物之約0.01至約10質量%,其中該組成物可藉由矽氫化反應固化並且在所有矽原子鍵結之有機基團中具有至少約10 mol%的芳基。
該量子點可包含選自由下列所組成之群組的材料:ZnS、ZnSe、ZnTe、InP、InAs、InSb、AIP、AIS、AIAs、AlSb、GaN、GaP、GaAs、GaSb、PbS、PbSe、Si、Ge、及其組合。在進一步實施例中,該量子點可選自奈米粒子,該等奈米粒子包含此等材料中之一者之核、及此等材料中之另一者之一或多個殼。替代地或此外,該量子點可包含此等材料中之一者之核及一完全不同材料之殼、或一完全不同材料之核及包含此等材料中之至少一者之至少一個殼。
在各種實施例中,該可固化聚矽氧組成物包含:
(A) 一分子中具有至少兩個矽原子鍵結之烯基及至少一個矽原子鍵結之芳基的有機聚矽氧烷;
(B) 一分子具有至少兩個矽原子鍵結之氫原子的有機聚矽氧烷,其量使得此組分中所含之矽原子鍵結之氫原子的含量相對於1莫耳的組分(A)中所含之烯基係約0.1至約10莫耳;
(C) 該不含鎘量子點,其量係該組成物之約0.01至約10質量%;及
(D) 矽氫化反應催化劑,其量加速該組成物之固化。
在某些實施例中,該可固化聚矽氧組成物進一步包含(E)矽氫化反應抑制劑,以每100質量份的組分(A)及(B)之總量計,(E)之量係約0.01至約3質量份。
該可固化聚矽氧組成物可係用於電氣/電子裝置之黏著劑、密封劑、或塗佈劑。
本發明之經固化產物係藉由固化上述可固化聚矽氧組成物而產生。發明效果
本發明之可固化聚矽氧組成物展現出量子點之優異可分散性,並且固化以形成展現出優異顏色轉換效率的經固化產物。此外,本發明之經固化產物展現出量子點之優異可分散性並且展現出優異顏色轉換效率。
用語「包含(comprising/ comprise)」在本文中係以其最廣泛意義來使用,以表示並涵蓋「包括(including/ include)」、「基本上由...所組成(consist(ing) essentially of)」、及「由...所組成(consist(ing) of)」。使用「例如(for example/ e.g.)」、「諸如(such as)」、及「包括(including)」來列示說明性實例不會只限於所列示之實例。因此,「例如」或「諸如」意指「例如,但不限於(for example, but not limited to)」或「諸如,但不限於(such as, but not limited to)」,且涵蓋類似或等效實例。本文中所使用之用語「約(about)」用來合理涵蓋或描述由儀器分析所測得之數值上的微小變化,或者由於樣本處理所致之數值上的微小變化。此等微小變化可在數值之±0至25、±0至10、±0至5、或±0至2.5%的量級內。此外,用語「約」當與值之範圍相關聯時,即適用於範圍之兩個數值。再者,即使未明示陳述,用語「約」仍可適用於數值。
大體上,本文中所使用之連字號「-」或破折號「–」在範圍中表示「至」或「到」;「>」表示「高於」或「大於」;「≥」表示「至少」或「大於或等於」;「<」表示「低於」或「小於」;而「≤」表示「至多」或「小於或等於」。在個別基礎上,前述各專利申請案、專利、及/或專利申請公開案係明確以引用方式全文併入本文之一或多個非限制性實施例中。
應當理解的是,所附申請專利範圍並不限於實施方式中所述之明確特定化合物、組成物、或方法,該等化合物、組成物、或方法可以在落入所附申請專利範圍之範疇內的特定實施例之間變化。關於本說明書中賴以描述各種實施例之特定特徵或態樣的馬庫西(Markush)群組,應瞭解到不同、特殊及/或非預期的結果可能自各別馬庫西群組的各成員獲得並且獨立於所有其他馬庫西成員。可個別或組合地憑藉馬庫西群組的各成員,並對落於隨附申請專利範圍之範疇中的具體實施例提供充分支持。
亦應理解的是,描述本發明之各種實施例所依賴的任何範圍與次範圍皆獨立且共同落入隨附申請專利範圍之範疇中,並且將其理解為描述且預想到包括整體及/或其中部分值的所有範圍,即使此些值在本文中並未明白寫出。所屬技術領域中具有通常知識者可輕易認可的是,所列舉的範圍和子範圍充分描述並使本發明的各種實施例得以實行,並且這樣的範圍和子範圍可被進一步描述為相關的二等分、三等分、四等分、五等分等等。以下僅作為一個實例,「0.1至0.9」的範圍可進一步分述為下三分之一(即0.1至0.3)、中三分之一(即0.4至0.6)以及上三分之一(即0.7至0.9),其個別且共同落入隨附申請專利範圍之範疇中,並且可被個別及/或共同地憑藉,而且會對落於隨附申請專利範圍之範疇中的具體實施例提供充分支持。此外,關於界定或修飾一範圍的詞語,例如「至少」、「大於」、「小於」、「不超過」與類似者,應理解為此類詞語包括次範圍及/或上限或下限。以下作為另一個實例,一「至少10」的範圍自然包括至少10至35的子範圍、至少10至25的子範圍、25至35的子範圍等等,並且可個別及/或共同地憑藉各子範圍,而且會對落於隨附申請專利範圍之範疇中的具體實施例提供充分支持。最後,可憑藉落入所揭示範圍的個別數字,並且對落於隨附申請專利範圍之範疇中的具體實施例提供充分支持。舉例而言,「1至9」的範圍包括各種個別整數如3、以及包括小數點(或分數)的個別數字如4.1,其可被憑藉,並且對落於隨附申請專利範圍之範疇中的具體實施例提供充分支持。
<可固化聚矽氧組成物>
首先,將詳細描述本發明之可固化聚矽氧組成物。在各種實施例中,可固化聚矽氧組成物包含不含鎘量子點,該不含鎘量子點之量係該組成物之約0.01至約10質量%。
不含鎘量子點沒有限制。在各種實施例中,量子點包括至少一種半導體材料,例如ZnS、ZnSe、InP、GaN等。某些半導體材料可能具有相對低的量子效率,這歸因於在奈米粒子表面處之缺陷及懸鍵發生的非輻射性電子-電洞復合。為了至少部分地解決此等問題,奈米粒子核可至少部分地塗佈有一或多層(在本文亦稱為「殼」)不同於核之材料,例如不同於「核」之材料的半導體材料。該或各殼中所包括之材料可併入來自元素週期表第2至16族中任一或多者之離子。當奈米粒子具有二或更多個殼時,各殼可由不同材料形成。在一例示性核/殼材料中,核係由以上指明之材料中之一者形成,且殼包括具有較大能帶隙能量且晶格尺寸與核材料類似的半導體材料。例示性殼材料包括(但不限於)ZnS、ZnO、MgS、MgSe、MgTe、及GaN。例示性多殼奈米粒子係InP/ZnS/ZnO及Zn-Cu-In-S。在核內與遠離表面狀態的電荷載體之限制提供具更大穩定性和更高量子產率之奈米粒子。
雖然所揭示方法不限於任何特定奈米粒子材料,但所揭示方法的優點是該等方法可用於將不含鎘量子點(亦即,包含不含鎘之材料的奈米粒子)之表面改質。已發現,特別難以將不含鎘量子點之表面改質。當使用先前技術方法(諸如先前技術的配位基交換方法)以將此類不含鎘量子點之表面改質時,不含鎘量子點容易降解。例如,已觀察到嘗試將不含鎘奈米粒子之表面改質時,會造成此類奈米粒子之發光量子產率(quantum yield, QY)顯著降低。另一方面,所揭示方法提供具有高QY的經表面改質之不含鎘奈米粒子。例如,所揭示方法已導致不含鎘奈米粒子可分散於水中,且其所具有的QY大於約20%,可選地大於約25%,可選地大於約30%,可選地大於約35%,且可選地大於約40%。不含鎘奈米粒子的實例包括包含半導體材料(例如ZnS、ZnSe、ZnTe、InP、InAs、InSb、AIP、AIS、AIAs、AlSb、GaN、GaP、GaAs、GaSb、PbS、PbSe、Si、Ge)之奈米粒子,且特別是包含此等材料中之一者之核、及此等材料中之另一者之一或多個殼的奈米粒子。
合適的不含鎘量子點係市售可得,諸如由PlasmaChem GmbH生產的PL-QD-CF-Kit10、PL-QD-CF-Kit25、及PL-QD-CF-Kit100;由Ocean NanoTech Company生產的Streptavidine Cd-free Quantum Dots;及由Nanoco Technologies Ltd生產的CFQD(R)
量子點。
在各種實施例中,不含鎘量子點之量係組成物之約0.01至約10質量%、可選地約0.01至約5質量%、或可選地約0.05至約5質量%的量。據認為,當量子點之含量不小於上述範圍之下限時,所得經固化產物具有優異顏色轉換效率,且另一方面,當量子點之含量不大於上述範圍之上限時,所得可固化聚矽氧組成物具有良好的可操作性。
在各種實施例中,可固化聚矽氧組成物可藉由矽氫化反應固化並且在所有矽原子鍵結之有機基團中具有至少約10 mol%的芳基。
在某些實施例中,此可固化聚矽氧組成物可包含:
(A) 一分子中具有至少兩個矽原子鍵結之烯基及至少一個矽原子鍵結之芳基的有機聚矽氧烷;
(B) 一分子具有至少兩個矽原子鍵結之氫原子的有機聚矽氧烷,其量使得此組分中所含之矽原子鍵結之氫原子的含量相對於1莫耳的組分(A)中所含之烯基係約0.1至約10莫耳;
(C) 該不含鎘量子點,其量係該組成物之約0.01至約10質量%;及
(D) 矽氫化反應催化劑,其量加速該組成物之固化。
組分(A)係一分子中具有至少兩個矽原子鍵結之烯基及至少一個矽原子鍵結之芳基的有機聚矽氧烷。組分(A)之分子結構的實例包括直鏈、部分分支的直鏈、支鏈、環狀、及樹枝狀結構。在某些實施例中,組分(A)之分子結構係選自直鏈、部分分支的直鏈、及樹枝狀結構。
烯基之實例包括具有2至12個碳之烯基,諸如乙烯基、烯丙基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一烯基、及十二烯基。組分(A)中烯基之鍵結位置沒有特別限制,且其實例包括(多個)分子末端及/或分子之(多個)側鏈。
在組分(A)中,除烯基之外的矽原子鍵結之有機基團沒有限制,且可例示如下:具有1至12個碳之烷基、具有6至20個碳之芳基、具有7至20個碳之芳烷基、及其中在此等基團中一些或所有鍵結的氫原子經鹵素原子(諸如氯原子及溴原子)取代的基團。矽原子鍵結之有機基團之實例包括烷基,諸如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、及十二烷基;芳基,諸如苯基、甲苯基、二甲苯基、萘基、蒽基、菲基、及芘基;芳烷基,諸如苄基、苯乙基、萘基乙基、萘基丙基、蒽基乙基、菲基乙基、及芘基乙基;及鹵化基團,諸如3-氯丙基、及3,3,3-三氟丙基。在某些實施例中,在一分子中,矽原子鍵結之有機基團中之至少一者係芳基。在進一步實施例中,在一分子中,矽原子鍵結之有機基團中之至少一者係苯基。在此等實施例中,芳基之含量係組成物中所有矽原子鍵結之有機基團之至少約10 mol%。
組分(B)係一分子中具有至少兩個矽原子鍵結之氫原子的有機聚矽氧烷。組分(B)之分子結構的實例包括直鏈、部分分支的直鏈、支鏈、環狀、及樹枝狀結構。在某些實施例中,組分(B)之分子結構係選自直鏈、部分分支的直鏈、及樹枝狀結構。組分(B)中矽原子鍵結之氫原子之鍵結位置沒有特別限制,且其實例包括(多個)分子末端及/或分子之(多個)側鏈。此外,組分(B)中鍵結至矽原子的基團(排除氫原子)之實例包括烷基,諸如甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、及十二烷基;芳烷基,諸如苄基、苯乙基、萘基乙基、萘基丙基、蒽基乙基、菲基乙基、及芘基乙基;鹵化烷基,諸如氯甲基、3-氯丙基、及3,3,3-三氟丙基;環氧丙基氧基烷基(glycidoxyalkyl),諸如3-環氧丙基氧基丙基及4-環氧丙基氧基丁基;及環氧環己基烷基,諸如2-(3,4-環氧環己基)乙基及3-(3,4-環氧環己基)丙基。
組分(B)之實例包括1,1,3,3-四甲基二矽氧烷、1,3,5,7-四甲基環四矽氧烷、參(二甲基氫矽氧基)甲基矽烷、參(二甲基氫矽氧基)苯基矽烷、1-(3-環氧丙基氧基丙基)-1,3,5,7-四甲基環四矽氧烷、1,5-二(3-環氧丙基氧基丙基)-1,3,5,7-四甲基環四矽氧烷、1-(3-環氧丙基氧基丙基)-5-三甲氧基矽基乙基-1,3,5,7-四甲基環四矽氧烷、在兩個分子末端以三甲基矽氧基封端之甲基氫聚矽氧烷、在兩個分子末端以三甲基矽氧基封端之二甲基矽氧烷-甲基氫矽氧烷共聚物、在兩個分子末端以二甲基氫矽氧基封端之二甲基聚矽氧烷、在兩個分子末端以二甲基氫矽氧基封端之二苯基聚矽氧烷、在兩個分子末端以二甲基氫矽氧基封端之二甲基矽氧烷-甲基氫矽氧烷共聚物、在兩個分子末端以三甲基矽氧基封端之甲基氫矽氧烷-二苯基矽氧烷共聚物、在兩個分子末端以三甲基矽氧基封端之甲基氫矽氧烷-二苯基矽氧烷-二甲基矽氧烷共聚物、三甲氧基矽烷之水解縮合物、由(CH3
)2
HSiO1/2
單元及SiO4/2
單元組成之共聚物、由(CH3
)2
HSiO1/2
單元、SiO4/2
單元、及(C6
H5
)SiO3/2
單元組成之共聚物、及此等中至少兩種類型的混合物。
在各種實施例中,本發明組成物中組分(B)之含量係使得有以下情形之量:每1莫耳的組分(A)中所含之總烯基中,組分(B)中所含之矽原子鍵結之氫原子係在約0.1至約10莫耳的範圍中,且可選地在約0.5至約5莫耳的範圍中。據認為,當組分(B)之含量不小於上述範圍之下限時,所得組成物會充分固化,且另一方面,當該含量不大於上述範圍之上限時,所得經固化產物之耐熱性增強,且使用此組成物產生的光學半導體裝置之可靠性因而增強。
組分(C)係如上所述的不含鎘量子點。在各種實施例中,組分(C)之含量係在組成物之約0.01至約10質量%的範圍中。
組分(D)係用來加速本發明組成物之固化的矽氫化反應催化劑。組分(D)之實例包括基於鉑的催化劑、基於銠的催化劑、及基於鈀的催化劑。在某些實施例中,組分(D)係基於鉑的催化劑。基於鉑的催化劑之實例包括基於鉑的化合物,諸如鉑細粉、鉑黑、擔載鉑之二氧化矽細粉、擔載鉑之活性碳、氯鉑酸、氯鉑酸之醇溶液、鉑的烯烴錯合物、及鉑的烯基矽氧烷錯合物。
本發明組成物中組分(D)之含量係加速固化本發明組成物之量。在各種實施例中,本發明組成物中組分(D)之含量係使得有以下情形之量:此催化劑中金屬原子之量係在約0.01至約1,000質量ppm的範圍中。據認為,當組分(D)之含量不小於上述範圍之下限時,所得組成物會充分固化,且另一方面,當組分(D)之含量不大於上述範圍之上限時,所得經固化產物耐變色。
本發明組成物可含有(E)矽氫化反應抑制劑,以延長環境溫度下的可用時間並增強儲存穩定性。組分(E)之實例包括炔醇,諸如1-乙炔基環己-1-醇、2-甲基-3-丁炔-2-醇、3,5-二甲基-1-己炔-3-醇、及2-苯基-3-丁炔-2-醇;烯炔化合物,諸如3-甲基-3-戊烯-1-炔及3,5-二甲基-3-己烯-1-炔;甲基烯基矽氧烷寡聚物,諸如1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷及1,3,5,7-四甲基-1,3,5,7-四己烯基環四矽氧烷;炔氧基矽烷,諸如二甲基雙(3-甲基-1-丁炔-3-氧基)矽烷及甲基乙烯基雙(3-甲基-1-丁炔-3-氧基)矽烷;及基於三烯丙基三聚異氰酸酯的化合物。
組分(E)的含量沒有特別限制。在各種實施例中,以每100質量份的組分(A)至(C)之總量計,該含量係在約0.01至約3質量份的範圍中,或可選地在約0.01至約1質量份的範圍中。據認為,當組分(E)之含量不小於上述範圍之下限時,確保本發明組成物之合適可用壽命,且另一方面,當該含量不大於上述範圍之上限時,確保本發明組成物之合適可加工性。
在各種實施例中,本發明組成物可含有磷光體,以轉換來自光學半導體元件之發射波長。磷光體的實例包括廣泛用於發光二極體(LED)的物質,諸如黃色、紅色、綠色、及藍色發光磷光體,諸如基於氧化物的磷光體、基於氧氮化物的磷光體、基於氮化物的磷光體、基於硫化物的磷光體、及基於氧硫化物的磷光體。基於氧化物之磷光體的實例包括含有鈰離子之釔、鋁、及石榴石類型的YAG綠色至黃色發光磷光體;含有鈰離子之鋱、鋁、及石榴石類型的TAG黃色發光磷光體;及含有鈰或銪離子之矽酸鹽綠色至黃色發光磷光體。基於氧氮化物之磷光體的實例包括含有銪離子之矽、鋁、氧、及氮類型的SiAlON紅色至綠色發光磷光體。基於氮化物之磷光體的實例包括含有銪離子之鈣、鍶、鋁、矽、及氮類型的CASN紅色發光磷光體。基於硫化物之磷光體的實例包括含有銅離子或鋁離子之ZnS綠色發光磷光體。基於氧硫化物之磷光體的實例包括含有銪離子之Y2
O2
S紅色發光磷光體。可將二或更多種類型的此等磷光體組合以供使用。
磷光體的平均粒徑沒有特別限制。在各種實施例中,平均粒徑係在約1至約50 µm的範圍中,或可選地在約5至約20 µm的範圍中。據認為,當磷光體的平均粒徑不小於上述範圍之下限時,混合時的黏度增加受到抑制,且另一方面,當平均粒徑不大於上述範圍之上限時,達到優異的透光率。
在各種實施例中,磷光體之含量相對於組成物之總量係在約0.1至約70質量%的範圍中,可選地在約1至約70質量%的範圍中,或可選地在約5至約70質量%的範圍中。
現在將詳細描述本發明的經固化產物。本發明之經固化產物係藉由固化上述可固化聚矽氧組成物而形成。經固化產物的形狀沒有特別限制,且實例包括片狀及膜狀。此外,此經固化產物可為密封或塗佈光學半導體元件或類似者之形式。實施例
以下實例說明可固化聚矽氧組成物及經固化產物,該等實例旨在說明而非限制本發明。在式中,Me、Vi、及Ph分別代表甲基、乙烯基、及苯基。此外,如下測量可固化聚矽氧組成物及其經固化產物的特性,並將結果顯示於表1中。
<量子點(QD)之可分散性>
目視觀察所獲得之可固化聚矽氧組成物中量子點之分散狀況,並評估其結果如下。
○:量子點均勻分散
Δ:量子點部分聚集
×:量子點大多聚集
<相對顏色轉換效率>
顏色轉換效率係定義為相對光致發光量子產率(photoluminescence quantum yield, PLQY),其中PLQY係定義為:
基本測量方法幾乎同於商品化的Hamamatsu C11347-11 Quantaurus-QY Absolute PL量子產率光譜儀(排除激發光源)。針對此測試,QD係由藍光源(而非UV燈)激發。
當將比較例1的顏色轉換效率設定為100%時,相對顏色轉換效率係相對值。
<實施實例1至3及比較例1至2>
將下列組分混合於表1所示之組成物(質量份)中以製備可固化聚矽氧組成物。應注意的是,表1中的「SiH/Vi」值係指相對於1莫耳的對應於組分(A)之組分中所含之烯基,對應於組分(B)之組分中所含之矽原子鍵結之氫原子的莫耳數。此外,組分(D)之含量係以相對於可固化聚矽氧組成物含量的鉑金屬含量(質量ppm)表示,且組分(E)之含量係以相對於可固化聚矽氧組成物含量的含量(質量ppm)表示。
使用以下組分作為組分(A)。
組分(A-1):由下式所代表之二甲基聚矽氧烷:
ViMe2
SiO(Me2
SiO)160
SiMe2
Vi
組分(A-2):由下式所代表之二甲基聚矽氧烷:
ViPh2
SiO(Me2
SiO)12
SiPh2
Vi
組分(A-3):由下式所代表之二甲基矽氧烷-二苯基矽氧烷共聚物:
ViMe2
SiO(Me2
SiO)200
(Ph2
SiO)50
SiMe2
Vi
組分(A-4):由下式所代表之甲基苯基聚矽氧烷:
ViMe2
SiO(MePhSiO)25
SiMe2
Vi
使用以下組分作為組分(B)。
組分(B-1):由下式所代表之有機三矽氧烷:
HMe2
SiOPh2
SiOSiMe2
H
組分(B-2):由以下平均單元式所代表之有機聚矽氧烷:
(HMe2
SiO1/2
)0.6
(PhSiO3/2
)0.4
組份(B-3):由下式所代表之甲基氫聚矽氧烷:
Me3
SiO(MeHSiO)50
SiMe3
使用以下組分作為組分(C)。
組分(C-1):不含鎘之疏水性Zn-Cu-In-S/ZnS量子點(由PlasmaChem生產的PL-QD-CF-Kit100)
使用下列組分作為組分(D)。
組分(D-1):於1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷中之鉑-1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物溶液(溶液含有0.12質量%的鉑)
從表1中的結果清楚看出,發現在實施實例1至3中製備的可固化聚矽氧組成物之經固化產物展現出優異顏色轉換效率,這是因為相較於在比較例1至2中製備的可固化聚矽氧組成物之經固化產物,量子點具有卓越的可分散性。產業利用性
本發明之可固化聚矽氧組成物展現出不含鎘量子點之優異可分散性,並且固化以形成展現出優異顏色轉換效率的經固化產物。因此,本發明之可固化聚矽氧組成物適合作為光學半導體裝置(諸如發光二極體(LED))中之光學半導體元件的密封劑、保護性塗佈劑、及類似者。
本文中已用說明性之方式描述本發明,並且應理解的是所使用之用語皆意欲為說明詞語之性質而非限制。鑑於上述教示,本發明之許多修改和變化皆係可能的。在隨附申請專利範圍之範疇內,本發明可用不同於所具體描述者之其他方式實施。在本文中已明確預想到獨立及附屬(單一及多重附屬兩者)請求項之所有組合的標的。
無
無
Claims (7)
- 一種可固化聚矽氧組成物,其包含不含鎘量子點,該不含鎘量子點之量係該組成物之0.01至10質量%,其中該組成物可藉由矽氫化反應固化並且在所有矽原子鍵結之有機基團中具有至少10mol%的芳基,其中該量子點包含選自由以下者所組成之群組的材料:ZnS、ZnSe、ZnTe、InP、InAs、InSb、AIP、AIS、AIAs、AlSb、GaN、GaP、GaAs、GaSb、PbS、PbSe、Si、Ge、及其組合。
- 如請求項1之可固化聚矽氧組成物,其中該量子點包含該等材料中之至少一者之核、及該等材料中之至少一種另一者之一或多個殼。
- 如請求項1或2之可固化聚矽氧組成物,其包含:(A)一分子中具有至少兩個矽原子鍵結之烯基及至少一個矽原子鍵結之芳基的有機聚矽氧烷;(B)一分子中具有至少兩個矽原子鍵結之氫原子的有機聚矽氧烷,其量使得此組分中所含之該等矽原子鍵結之氫原子的含量相對於1莫耳的組分(A)中所含之該等烯基係0.1至10莫耳;(C)該不含鎘量子點,其量係該組成物之0.01至10質量%;及(D)矽氫化反應催化劑,其量加速該組成物之固化。
- 如請求項3之可固化聚矽氧組成物,其進一步包含(E)矽氫化反應抑制劑。
- 如請求項4之可固化聚矽氧組成物,其中以每100質量份的組分(A)及(B)之總量計,組分(E)係以0.01至3質量份的量存在。
- 如請求項1或2之可固化聚矽氧組成物,其中該組成物係用於電氣/電子裝置之黏著劑、密封劑、或塗佈劑。
- 一種經固化產物,其係藉由固化如請求項1至5中任一項之可固 化聚矽氧組成物產生。
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