CN102453327A - 具有高折射率的聚硅氧树脂组合物 - Google Patents

具有高折射率的聚硅氧树脂组合物 Download PDF

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CN102453327A
CN102453327A CN2010105255206A CN201010525520A CN102453327A CN 102453327 A CN102453327 A CN 102453327A CN 2010105255206 A CN2010105255206 A CN 2010105255206A CN 201010525520 A CN201010525520 A CN 201010525520A CN 102453327 A CN102453327 A CN 102453327A
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silane
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田珮
李旭修
张佩君
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3M Innovative Properties Co
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Priority to PCT/US2011/056312 priority patent/WO2012058023A1/en
Priority to US13/877,681 priority patent/US20130210982A1/en
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Abstract

本发明系关于一种聚硅氧树脂组合物,其包含具有至少一端氢基的聚硅氧树脂、具有至少一C1-6烷氧基的金属烷氧化物及具有至少一乙烯基及至少一C1-6烷氧基或羟基的端基的硅烷,该组合物经固化后具有大于1.4的折射率。本发明亦关于利用此组合物所封装的光电装置。

Description

具有高折射率的聚硅氧树脂组合物
技术领域
本发明系关于一种聚硅氧树脂组合物,以及藉由该组合物的固化产物所封装的光电装置。
背景技术
由于聚硅氧树脂具有较佳的光学性质,如热稳定性、耐候性、耐旋旋光性及可挠性,以及相较于环氧树脂材料的高可靠性的优点,因此常用于光电装置中。然而,聚硅氧树脂的折射率约为1.4,当其作为诸如发光二极管(LED)的光电装置的封装材料时,将导致低萃取效率(extraction efficiency),并进而减少LED的亮度。
先前技艺中已有利用有机合成技术制作高折射率材料的相关揭示。例如,JP63077872揭示增加主结构中溴及碘原子的比率以增加材料的折射率,此方法所提升的折射率有限,且在日益重视的环保观念下,此种含卤素材料的使用将逐渐受到限制。
中国台湾专利公开第200609299号系提供一种作为LED封装材料的聚硅氧树脂组合物,其藉由增加芳基的含量以获得具有高折射率的聚硅氧树脂组合物。然而,此方式将使得组合物的稳定性降低,且在高温的环境下易产生黄化。
本案发明人发现,本发明的聚硅氧树脂组合物具有高折射率,同时可保有聚硅氧树脂的优点。
发明内容
本发明的一目的系提供一种聚硅氧树脂组合物,其包含:
(a)聚硅氧树脂,其具有至少一端氢基;
(b)金属烷氧化物,其具有至少一C1-6烷氧基;及
(c)硅烷,其具有至少一乙烯基及至少一C1-6烷氧基或羟基的端基。
本发明另一目的系提供一种封装光电装置的方法,其包含:
(a)提供一光电装置;及
(b)以前述的聚硅氧树脂组合物封装该光电装置。
本发明另一目的系提供一种发光半导体装置。
本发明另一目的系提供一种调整聚硅氧树脂折射率的方法。
附图说明
图1显示具有由本发明组合物所制备的固化聚硅氧树脂的LED装置的横截面。
图2为金属烷氧化物与乙烯基硅烷的反应产物的红外线光谱。
具体实施方式
本发明系一种聚硅氧树脂组合物,其包含:
(a)聚硅氧树脂,其具有至少一端氢基;
(b)金属烷氧化物,其具有至少一C1-6烷氧基;及
(c)硅烷,其具有至少一乙烯基及至少一C1-6烷氧基或羟基的端基。
为使本发明的特征和优点能更明显易懂,下文特举本发明的较佳实施方式,并配合所附图式详细说明如下:
聚硅氧树脂
本发明组合物的组份(a)为具有至少一端氢基的聚硅氧树脂,其包含如下所示结构的化合物:
(HR1SiO)x-(R2R3SiO)y
其中R1、R2及R3可为相同或不同的C1-6烷基,较佳为C1-4烷基;x及y为聚合数,x至少为1。
聚硅氧树脂可根据所需性质(如耐热性、耐用性及机械强度)而加以选择,其可为单一聚硅氧或包含两种或两种以上不同黏度、结构、平均分子量、硅氧单元及序列的聚二硅氧的组合。
聚硅氧树脂的分子量并无特别限制,较佳的重量平均分子量可自500至200,000的范围,更佳为自700至60,000的范围。本发明组合物中,聚硅氧树脂的含量,以整体组合物总重量计,系约20重量%至约60重量%,较佳约30重量%至约40重量%。
金属烷氧化物
本发明组合物的组份(b)为如下所示结构的金属烷氧化物:
Rm-M(OR′)n
其中R及R′可为相同或不同的C1-6烷基,较佳为C1-4烷基;M为具有空轨域的金属或半导体材料,较佳为钛(Ti)、锆(Zr)、铝(Al)、铌(Nb)、铟(In)、铈(Ce)、铪(Hf)、钽(Ta)、硅(Si)或锗(Ge),更佳为钛、锆及铝;m为0至3的整数,n为1至4的整数,且1≤m+n≤4。
较佳的金属烷氧化物包括Zr(OBu)4、Ti(OBu)4或其混合物。
本发明组合物中,金属烷氧化物的含量,以整体组合物总重量计,系约30重量%至约70重量%,较佳约50重量%至约60重量%。
硅烷
本发明组合物的组份(c)为具有至少一乙烯基及至少一C1-6烷氧基或羟基的端基的硅烷,适用于本发明组合物的硅烷可包含但不限于乙烯三甲氧硅烷、乙烯三乙氧硅烷、乙烯叁(2-甲氧基乙氧基)硅烷、乙烯甲基二甲氧硅烷、乙烯甲基二乙氧硅烷、乙烯苯基二甲氧硅烷或其混合物。
本发明组合物中,硅烷的含量,以整体组合物总重量计,系约1重量%至约10重量%。
封装光电装置
本发明组合物可用于封装光电装置,诸如发光半导体装置,该发光半导体装置可为LED,光电装置所用的封装技术为此项技术中所熟知者。举例而言,在将光电装置封装于未经固化的聚硅氧树脂组合物中后,通常在模具中进行组合物的固化。可将此等组合物藉由加热在一或多个阶段中固化。举例而言,固化可在室温至200℃范围内的温度下进行。
图1显示具有由本发明组合物所制备的固化聚硅氧树脂的LED装置1的横截面。该LED装置1包含一LED芯片11,该LED芯片11可直接电性连接引线架12的阳极或阴极,并由导线13连接于该引线架12的另一阴极或阳极。该LED芯片11可为含有任何能发出所需光线的半导体层的p-n接面的LED芯片。举例而言,该LED芯片11可含有任何所需III-V族化合物半导体层,例如砷化镓、砷化镓、铝氮化镓、氮化铟镓及磷化镓,或II-IV族化合物半导体层,例如硒化锌、碲化镉及硫硒化锌,或IV-IV族化合物半导体层,例如碳化硅。该LED芯片11系由本发明聚硅氧树脂组合物制得的封装物14所封装。
本发明将经由下列实施例进一步加以详细描述,唯该叙述仅系用以例示说明本发明,而非对本发明范围作任何限制,任何熟悉此项技艺的人士可轻易达成的修饰及改变均包括于本案说明书揭示内容及所附申请专利范围所载的范围内。
实施例
聚硅氧树脂组合物的合成
实施例1
取14克乙烯基三甲氧基硅烷、5克二苯基二甲氧基硅烷、30克甲苯、10克乙醇及数滴醋酸加入三颈烧瓶中混合,并于室温下搅拌30分钟,接着加入12.5克Zr(OBu)4,于80℃下逆馏3小时。待逆馏后,取上层溶液加入旋转蒸发器(Büchi),于70℃下将溶剂移除。之后得到19克微黄但极为澄清的溶液,并进行红外线光谱(IR)分析鉴定,结果如图2所示。
实施例2
Figure BSA00000332632500031
取10克Ti(OBu)4、30克甲苯、4.5克乙醇、数滴醋酸及5克三甲氧基硅烷于室温下搅拌30分钟,接着与15克三甲基甲氧基硅烷一起加入三颈烧瓶中混合,并于80℃下逆馏3小时。待逆馏后,取上层溶液加入旋转蒸发器(Büchi),于70℃下将溶剂移除。之后得到16克微黄但极为澄清的溶液。
实施例3
取0.6克实例2所得溶液、1.55克X-101(聚硅氧树脂,仁菖有限公司)及2%铂于室温下搅拌30分钟。
比较例1
取1366A及1366B(聚硅氧树脂,仁菖有限公司)各0.5克,于室温下搅拌30分钟。
聚硅氧树脂组合物的折射率测试
分别取一定量的实例3及比较例1所得溶液,以甲苯稀释为原溶液的50重量%,之后分别取数滴经稀释溶液滴加于芯片上,置于转速设定为500RPM的旋转涂布机中运转30秒,再于150℃下烘烤30分钟。最后使用棱镜耦合仪(Prism coupler,MetriconModel 2010)于632.8nm下量测经烘烤材料的折射率。所得结果列于表1。
表一
在不脱离本发明的范畴及原理的情况下,本发明的各种修改及更改对熟习此项技术者将变得显而易见,且应了解本发明并不会不当地限于上文所阐明的说明性实施例。所有公开案及专利案以引用的方式并入本文中,如同每一个别公开案或专利案系经具体及个别指示而已引用方式并入本文中一般。

Claims (23)

1.一种聚硅氧树脂组合物,其包含
(a)聚硅氧树脂,其具有至少一端氢基;
(b)金属烷氧化物,其具有至少一C1-6烷氧基;及
(c)硅烷,其具有至少一乙烯基及至少一C1-6烷氧基或羟基的端基。
2.根据权利要求1所述的组合物,其包含约20重量%至约60重量%的聚硅氧树脂。
3.根据权利要求2所述的组合物,其包含约30重量%至约40重量%的聚硅氧树脂。
4.根据权利要求1所述的组合物,其包含约30重量%至约70重量%的金属烷氧化物。
5.根据权利要求4所述的组合物,其包含约50重量%至约60重量%的金属烷氧化物。
6.根据权利要求1所述的组合物,其包含约1重量%至约10重量%的硅烷。
7.根据权利要求6所述的组合物,其包含约2重量%至约6重量%的硅烷。
8.根据权利要求1所述的组合物,其中该组合物经固化后具有大于1.4的折射率。
9.根据权利要求1所述的组合物,其中该金属烷氧化物的结构如下式:
Rm-M(OR′)n
其中M为具有空轨域的金属或半导体材料;
R及R′可独立为相同或不同的C1-6烷基;
m为0至3的整数;
n为1至4的整数;及
1≤m+n≤4。
10.根据权利要求9所述的组合物,其中M系选自由钛、锆、铝、铌、铟、铈、铪、钽、硅及锗所组成的群。
11.根据权利要求10所述的组合物,其中M系选自由钛、锆及铝所组成的群。
12.根据权利要求9所述的组合物,其中R及R′可独立为相同或不同的C1-4烷基。
13.根据权利要求9所述的组合物,其中m为0及n为4。
14.根据权利要求1所述的组合物,其中该金属烷氧化物为Zr(OBu)4或Ti(OBu)4
15.根据权利要求1所述的组合物,其中该硅烷系选自由乙烯三甲氧硅烷、乙烯三乙氧硅烷、乙烯叁(2-甲氧基乙氧基)硅烷、乙烯甲基二甲氧硅烷、乙烯甲基二乙氧硅烷、乙烯苯基二甲氧硅烷及其混合物所组成的群。
16.根据权利要求15所述的组合物,其中该硅烷为乙烯三甲氧硅烷。
17.一种封装光电装置的方法,其包含
(a)提供一光电装置;及
(b)以根据权利要求1所述的聚硅氧树脂组合物封装该光电装置。
18.根据权利要求17所述的方法,其进一步包含固化该聚硅氧树脂组合物。
19.根据权利要求17所述的方法,其中该光电装置为发光半导体装置。
20.根据权利要求19所述的方法,其中该发光半导体装置为发光二极管(LED)。
21.一种发光半导体装置,其包含以根据权利要求1所述的组合物的固化产物所封装的组件。
22.一种调整聚硅氧树脂折射率的方法,其包含添加具有至少一C1-6烷氧基的金属烷氧化物及具有至少一乙烯基及至少一C1-6烷氧基或羟基的端基的硅烷于具有至少一端氢硫基的聚硅氧树脂。
23.根据权利要求22所述的方法,其中该折射率大于1.4。
CN2010105255206A 2010-10-27 2010-10-27 具有高折射率的聚硅氧树脂组合物 Pending CN102453327A (zh)

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CN106589951A (zh) * 2016-11-30 2017-04-26 庞倩桃 聚硅氧树脂组合物

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TWI751997B (zh) * 2015-12-22 2022-01-11 日商琳得科股份有限公司 硬化性組合物、硬化性組合物的製造方法、硬化物、硬化性組合物的使用方法以及光裝置

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JPS6377872A (ja) 1986-09-18 1988-04-08 Nippon Shokubai Kagaku Kogyo Co Ltd 新規臭素化チオフエン誘導体
US6512037B1 (en) * 2001-06-06 2003-01-28 Dow Corning Corporation Silicone composition and cured silicone product
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CN103881651A (zh) * 2013-10-18 2014-06-25 广州众恒光电科技有限公司 一种高折射led封装硅胶的制备方法
CN106589951A (zh) * 2016-11-30 2017-04-26 庞倩桃 聚硅氧树脂组合物

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