CN106433552A - 用于光固化液体硅橡胶的铂催化剂和led封装胶组合物 - Google Patents
用于光固化液体硅橡胶的铂催化剂和led封装胶组合物 Download PDFInfo
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Abstract
本发明公开了一种用于光固化液体硅橡胶的铂催化剂和LED封装胶组合物。该铂催化剂的化学式为[(R3)(R4)(R5)Pt(R1C(O)CHC(O)R2)]2；其中，R1和R2不同，R1、R2为Me，‑OEt，Ph，‑CF3，呋喃，叔丁基，异丙基，噻吩、卤代苯基、二氟甲基中的一种基团；R3、R4、R5均为烷基。LED封装胶组合物中含有1～1000ppm的上述的铂催化剂。本发明的提供的催化剂与常规固化光源光谱匹配，有效提高了光源利用率；其最强吸收峰与苯基硅油吸收峰完美分离，有效解决了催化剂与高折射率LED封装胶最强吸收范围重叠的问题；采用本发明提供的液体硅橡胶组合物可实现较好的光固化效果。
Description
技术领域
本发明涉及有机硅领域，具体涉及一种用于光固化液体硅橡胶的铂催化剂和LED封装胶组合物。
背景技术
硅橡胶因其独特的性能，广泛用于电子电器元件、建筑、汽车、电子、食品、医疗等领域，特别是加成型液体硅橡胶在LED封装领域广泛应用。硅橡胶催化剂是制备加成型硅橡胶材料的重要组份，用于硅组份交联固化，形成硅橡胶，用于加成型液体硅橡胶的催化剂主要是铂的配合物，通过加热催化剂引发液体硅橡胶硫化生成硅橡胶，工业上硫化过程包括预硫化(60℃左右)和硫化(100～180℃)两个过程，硫化时间需要约几个小时，时间过长硫化太慢，降低生产效率。
光固化和电子束固化技术被归纳为具有“5E”特点的工业技术，所述“5E”是指Efficienct高效、Enabling适应性广、Economical经济、Energy saving节能、Enviromentalfriendly环境友好。光固化技术的优点如下：1、固化速率快，一般在几秒到几十秒之间，最快的可在0.05～0.1s的时间内固化，产品可适用于多种基材，如纸张，木材，塑料，金属，皮革，石材，玻璃，陶瓷等，特别是对一些热敏感材质如纸张、塑料或电子元器件等尤其适用；2、生产效率高、能耗低，光固化设备投资相对较低，容易实现流水线生产，常温快速固化，其能耗只有热固化配方产品的1/10～1/5。采用光固化技术来实现加成型硅橡胶硫化具有明显的进步意义。
高功率LED封装胶中采用含有苯基的硅油或硅树脂，这些含有苯基的硅油或硅树脂在紫外区有很强的吸收(苯基硅树脂的吸收范围<350nm，强吸收峰250～300nm，具体如图1所示)，这个吸收区域与很多光活性的铂(Pt)配合物催化剂的吸收峰重叠(吸收范围200～300nm，强吸收峰在深紫外区域<280nm，)，阻碍了Pt配合物对光的吸收，因此，这类Pt配合物催化剂在高功率LED封装胶应用中活性不佳，固化时间变长，不适用高功率LED封装胶应用。文献Journal of Photochemistry and Photobiology A:Chemistry 97(1996)163-170，报道了几例具有较长吸收波长的铂配合物(如含苯的吸收波长为335nm，含-CF3的吸收波长为325nm)，但是这些配合物的吸收光谱与常见的固化光源高压汞灯产生的光谱不匹配，光源的利用效率较低；现有的高压汞灯在335nm处的光强<10％，365nm为100％，具体如表1所示；另外，这些配合物在液体硅橡胶中的溶解性也比较低，难以配置成高浓度的溶液，不便于实际应用。
表1高压汞灯主要谱线相对强度
| 波长/nm | 相对强度 | 波长/nm | 相对强度 |
| 222.4 | 14.0 | 296.7 | 16.6 |
| 232.0 | 8.0 | 302.2～302.8 | 23.9 |
| 236.0 | 6.0 | 312.6～313.2 | 49.9 |
| 238.0 | 8.6 | 334.1 | 9.3 |
| 240.0 | 7.3 | 365.0～366.3 | 100.0 |
| 248.2 | 8.6 | 404.5～407.8 | 42.2 |
| 253.7 | 16.6 | 435.8 | 77.5 |
| 257.1 | 6.0 | 546.0 | 93.0 |
| 265.2～265.5 | 15.3 | 577.0～579.0 | 76.5 |
| 270.0 | 4.0 | 1014.0 | 40.6 |
| 275.3 | 2.7 | 1128.7 | 12.6 |
| 280.4 | 9.3 | 1357.3 | 15.3 |
| 289.4 | 6.0 |
为解决光固化硅橡胶实际应用中对光敏催化剂的强烈需求，应该开发具有UV高活性，具有较长吸收的、与固化光源发射光谱匹配，具有良好溶解性的铂配合物催化剂。
发明内容
[要解决的技术问题]
本发明的目的是解决上述现有技术问题，提供一种用于光固化液体硅橡胶的铂催化剂和LED封装胶组合物。
[技术方案]
为了达到上述的技术效果，本发明采取以下技术方案：
一种用于光固化液体硅橡胶的铂催化剂，它的化学式为[(R3)(R4)(R5)Pt(R1C(O)CHC(O)R2)]2；其中，R1和R2不同，R1、R2为Me，-OEt，Ph，-CF3，呋喃，叔丁基，异丙基，噻吩、卤代苯基、二氟甲基中的一种基团；R3、R4、R5均为烷基；
该铂催化剂的分子结构式如下：
本发明更进一步的技术方案，所述R1、R2为异丙基、呋喃、叔丁基、噻吩、卤代苯基、二氟甲基中的一种基团。
本发明更进一步的优选实施方案，所述烷基为甲基、乙基、丙基、异丙基、丁基、叔丁基或戊基。
一种LED封装胶组合物，该组合物中含有1～1000ppm的上述的铂催化剂。
本发明更进一步的优选实施方案，组合物中含有5～100ppm上述的铂催化剂。
本发明更进一步的技术方案，所述的LED封装胶组合物，它是由A组分和B组分制备而成，所述A组分包括苯基乙烯基硅树脂、MDQ树脂、权利要求1所述的铂催化剂；所述B组分包括高苯基含氢硅油或高苯基含氢硅树脂、增粘剂。
本发明更进一步的技术方案，所述的LED封装胶组合物，它是由按质量份计的A组分和B组分制成；所述A组分包括苯基乙烯基硅树脂、MDQ树脂、权利要求1所述的铂催化剂；所述B组分包括高苯基含氢硅油或高苯基含氢硅树脂、增粘剂。
本发明更进一步的技术方案，该LED封装胶组合物是由按质量份计的A组分和B组分制成；所述A组分包括15～80份的苯基乙烯基硅树脂、0～5份的MDQ树脂和浓度为3000ppm的权利要求1所述的铂催化剂制备的溶液；所述B组分包括20～35份高苯基含氢硅油或高苯基含氢硅树脂、0～3份增粘剂。
本发明更进一步的技术方案，该LED封装胶是单组份组合物，它是由以下原料制备而成：苯基乙烯基硅树脂、MDQ、权利要求1所述铂催化剂、高苯基含氢硅油或高苯基含氢硅树脂和增粘剂。
本发明更进一步的技术方案，该LED封装胶是由以下质量份的原料制备而成：15～80份的苯基乙烯基硅树脂、0～5份的MDQ树脂、20～35份高苯基含氢硅油或高苯基含氢硅树脂、0～3份增粘剂和浓度为3000ppm的权利要求1所述的铂催化剂制备的溶液。
本发明用于光固化液体硅橡胶的铂催化剂其吸收峰包括350～375nm，且本发明的铂催化剂具有良好的溶解性，能配制浓度大于500ppm的铂催化剂溶液。
本发明更进一步的技术方案，所述铂催化剂制备的溶液中使用的溶剂为乙烯基双封头、乙烯基硅油。
下面将详细地说明本发明。
所述浓度为3000ppm的权利要求1所述的铂催化剂制备的溶液是指将铂催化剂配制成浓度为3000ppm的铂催化剂溶液后，根据所述LED封装胶组合物中铂催化剂最终的浓度配制使用适量质量份的铂催化剂溶液；保证铂催化剂在组合物中的终浓度为1～1000ppm；优选5～100ppm。本发明的铂催化剂具有较长的吸收峰，其吸收范围在200～400nm，特别是在250～260nm、355～370nm有较强的吸收，355～370nm处的强吸收与常见的365nm紫外固化灯(高压汞灯)发射光谱匹配，且避开了含苯基硅树脂或含苯基硅油在250～300nm处的强吸收，解决了LED封装胶中相关组份的吸收峰与催化剂吸收峰重叠的问题，且催化剂的吸收光谱与高压汞灯产生的光谱匹配，使固化光源充分利用。并且本发明的铂催化剂具有良好的溶解性，可配制铂含量大于500ppm的硅氧烷溶液。
本发明的铂催化剂中R1和R2为不同的基团，并且当R1、R2为异丙基、呋喃、叔丁基、噻吩、卤代苯基、二氟甲基中的一种基团时，该铂催化剂的溶解性较好，且该铂催化剂均在355～370nm有较强的吸收。
当本发明的LED封装胶组合物是由A组分和B组分制备而成时，A组分与B组分配制好后，分开保存；在进行封装胶固化时，将A组分和B组分混合。当LED封装胶组合物是单组份组合物时，需现配现用。
采用本发明的铂催化剂，可以用光固化技术实现液体硅橡胶固化，解决了采用加热引发催化剂硫化生成硅橡胶，硫化时间过长，硫化太慢，降低生产效率等问题。
[有益效果]
本发明与现有技术相比，具有以下的有益效果：
本发明的提供的铂催化剂具有较长的吸收峰，解决了LED封装胶中相关组份的吸收峰与催化剂吸收峰重叠的问题，催化剂配合物的吸收光谱与高压汞灯产生的光谱匹配，并且提供的催化剂具有良好的溶解性，可配置浓度大于500ppm的硅氧烷溶液，采用本发明提供的液体硅橡胶组合物可实现较好的光固化效果。
附图说明
图1为苯基硅树脂吸收图谱示意图；
图2为本发明实施例1制备得到的铂催化剂吸收图谱示意图。
具体实施方式
下面结合本发明的实施例对本发明作进一步的阐述和说明。
实施例1：
一种用于光固化液体硅橡胶的铂催化剂(Cat 2)，其分子结构式如下：
该铂催化剂的制备方法如下：
①(TTA)Na的制备：取等摩尔2-噻吩甲酰三氟丙酮与NaOH，加入到适量的乙醇中，室温搅拌超过2小时，蒸干溶剂得浅黄色粉末(TTA)Na；
②铂催化剂Cat 2的制备：取100mg[Pt(CH3)3]2SO4，与100mg(TTA)Na放于烧瓶中，加入20ml丙酮，加热回流至少5小时后，过滤得浅黄色液体，然后蒸干溶剂，用热的正己烷萃取后蒸干溶剂得90mg铂催化剂，所得铂催化剂在250～260nm、355～370nm处均有吸收，并且355～370nm的吸收更强，其吸收图谱见图2。图中，苯基硅树脂的吸收峰与该铂催化剂的最强吸收范围完全分离，因此将该铂催化剂应用于光固化技术中，可以有效避免催化剂与原料吸收峰的重叠，提高反应效率。
实施例2
利用实施例1的铂催化剂制备得到光固化硅橡胶组合物：
①铂催化剂溶液的配制：取71.2mg铂催化剂于玻璃管中，先加入少量二氯甲烷，然后加入乙烯基双封头至10g，得铂催化剂含量为3000ppm的铂催化剂溶液，所得溶液为澄清透明，略有米黄色。该步骤使用的少量二氯甲烷是为了增大铂催化剂的溶解度，提升该铂催化剂在乙烯基双封头溶解量。
②光固化硅橡胶组合物1的配制：取A、B双组分混合，A组分：苯基摩尔含量为50％的苯基乙烯基硅树脂50份，苯基摩尔含量为40％、乙烯基摩尔含量1％的透明液体状MDQ树脂4份，0.14～2.7份浓度为3000ppm铂催化剂溶液，最终使铂催化剂在组合物中的含量在5～100ppm；B组分：苯基摩尔含量为35％、折射率大于1.50、粘度小于1Pa·s的高苯基含氢硅油25份，增粘剂3份，增粘剂选用乙烯基三甲氧基硅烷偶联剂V06，混合后充分搅拌均匀，脱泡得无色、澄清透明光固化胶料。
③光固化硅橡胶组合物2的配制：苯基摩尔含量为50％的苯基乙烯基硅树脂50份，苯基摩尔含量为40％、乙烯基摩尔含量1％的透明液体状MDQ树脂4份，0.14～2.7份浓度为3000ppm铂催化剂溶液，使铂催化剂在混合料中的含量在5～100ppm，苯基摩尔含量为35％、折射率大于1.50、粘度小于1Pa·s的高苯基含氢硅油25份，增粘剂3份，增粘剂选用乙烯基三甲氧基硅烷偶联剂V06，混合，然后充分搅拌均匀，脱泡得无色、澄清透明光固化胶料
光固化效果测试：
取铂催化剂含量为100ppm的光固化硅橡胶组合物1涂覆与载玻片上，使厚度<5mm，然后将载玻片放于三用紫外分析下(WFH-203，上海驰唐电子有限公司)，打开365nm光源，胶料<30min发生固化，得无色透明片状薄膜。
取铂催化剂含量为30ppm的光固化硅橡胶组合物1涂覆与载玻片上，使厚度<5mm，然后将载玻片放于手持式UV固化装置内(YH-GGJ1KW，河北保定益弘机电设备有限公司)，UV固化装置波长365nm，胶料<30min发生固化，得无色透明片状薄膜。
取铂催化剂含量为100ppm的光固化硅橡胶组合物2涂覆与载玻片上，使厚度<15mm，然后将载玻片放于手持式UV固化装置内(YH-GGJ1KW，河北保定益弘机电设备有限公司)，使光源从翻口塞正上面照射，UV固化装置波长365nm，胶料<30min发生固化，将固化后的胶料从翻口塞中拿出得无色透明圆柱块状固体。
取铂催化剂含量为5ppm的光固化硅橡胶组合物2涂覆与载玻片上，使厚度<5mm，然后将载玻片放于三用紫外分析下(WFH-203，上海驰唐电子有限公司)，打开365nm光源，胶料<3h发生固化，得无色透明片状薄膜。
综上所述，本发明的铂催化剂吸收范围250～260nm、355～370nm，并且吸收范围为355～370nm的吸收峰值相对较高，避开了含苯基硅树脂或硅油在250～300nm的吸收，能充分365nm紫外固化装置的发射光谱，从而能进行较快的光固化效果，利用采用本发明的催化剂含量为5～100ppm在365nm紫外固化装置照射，使高折射的含苯基硅树脂或含苯基硅油LED液体封装胶组合物在30min内发生固化，固化深度不小于15mm。
尽管这里参照本发明的解释性实施例对本发明进行了描述，上述实施例仅为本发明较佳的实施方式，本发明的实施方式并不受上述实施例的限制，应该理解，本领域技术人员可以设计出很多其他的修改和实施方式，这些修改和实施方式将落在本申请公开的原则范围和精神之内。
Claims (10)
1.一种用于光固化液体硅橡胶的铂催化剂，其特征在于它的化学式为[(R3)(R4)(R5)Pt(R1C(O)CHC(O)R2)]2；其中，R1和R2不同，R1、R2为Me、-OEt、Ph、-CF3、呋喃、叔丁基、异丙基、噻吩、卤代苯基、二氟甲基中的一种基团；R3、R4、R5均为烷基；
该铂催化剂的分子结构式如下：
2.根据权利要求1所述的用于光固化液体硅橡胶的铂催化剂，其特征在于所述R1、R2为异丙基、呋喃、叔丁基、噻吩、卤代苯基、二氟甲基中的一种基团。
3.根据权利要求1所述的用于光固化液体硅橡胶的铂催化剂，其特征在于所述烷基为甲基、乙基、丙基、异丙基、丁基、叔丁基或戊基。
4.一种LED封装胶组合物，其特征在于该组合物中含有1～1000ppm的权利要求1所述的铂催化剂。
5.根据权利要求4所述的LED封装胶组合物，其特征在于该组合物中含有5～100ppm权利要求1所述的铂催化剂。
6.根据权利要求4或5所述的LED封装胶组合物，其特征在于它是由A组分和B组分制备而成，所述A组分包括苯基乙烯基硅树脂、MDQ树脂、权利要求1所述的铂催化剂；所述B组分包括高苯基含氢硅油或高苯基含氢硅树脂、增粘剂。
7.根据权利要求6所述的LED封装胶组合物，其特征在于它是由按质量份计的A组分和B组分制成；所述A组分包括15～80份的苯基乙烯基硅树脂、0～5份的MDQ树脂和0.14～2.7份浓度为3000ppm的权利要求1所述的铂催化剂制备的溶液；所述B组分包括20～35份高苯基含氢硅油或高苯基含氢硅树脂、0～3份增粘剂。
8.根据权利要求5所述的LED封装胶组合物，其特征在于该LED封装胶是单组份组合物，它是由以下原料制备而成：苯基乙烯基硅树脂、MDQ、权利要求1所述铂催化剂、高苯基含氢硅油或高苯基含氢硅树脂和增粘剂。
9.根据权利要求8所述的LED封装胶组合物，其特征在于该LED封装胶是由以下质量份的原料制备而成：15～80份的苯基乙烯基硅树脂、0～5份的MDQ树脂、20～35份高苯基含氢硅油或高苯基含氢硅树脂、0～3份增粘剂和0.14～2.7份浓度为3000ppm的权利要求1所述的铂催化剂制备的溶液。
10.根据权利要求7或9所述的LED封装胶组合物，其特征在于所述铂催化剂制备的溶液中使用的溶剂为乙烯基双封头、乙烯基硅油。
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