JP2012233153A5 - - Google Patents
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半導体発光装置（ＬＥＤ）の封止材などに使用されているヒドロシリル化反応硬化型のポリシロキサン組成物（以下、ヒドロシリル系ポリシロキサン組成物ともいう。）は、ＬＥＤパッケージなどに対する接着性を高める技術が求められている。 A hydrosilylation reaction curable polysiloxane composition (hereinafter also referred to as a hydrosilyl polysiloxane composition) used for a sealing material of a semiconductor light emitting device (LED) is a technology for improving adhesion to an LED package or the like. Is required.
基板や金属配線と封止材との接着性を高めるためには、接着促進剤であるエポキシ基含有ポリシロキサンのエポキシ基含有量を多くする必要がある。しかしながら、このような接着促進剤を多く用いた場合、輝度が低下するおそれがある。 In order to improve the adhesion between the substrate or the metal wiring and the sealing material, it is necessary to increase the epoxy group content of the epoxy group-containing polysiloxane which is an adhesion promoter. However, when many such adhesion promoters are used, there is a risk that the luminance will decrease.
前記硬化性組成物においては、前記密着性基が、エポキシ基を有する基であることが好ましい。
前記硬化性組成物においては、前記ポリシロキサン（Ａ）が、下記化学式（２）：
In the curable composition, the adhesive group is preferably a group having an epoxy group.
In the curable composition, the polysiloxane (A) is the following chemical formula (2):
また、他の発明は、下記化学式（２）： Further, another aspect of the present invention, the following chemical formula (2):
ポリシロキサン（Ａ）としては、下記化学式（１）： The polysiloxane (A), the following chemical formula (1):
ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉの合計に対するａの割合は、前記合計を１００％とした場合、好ましくは０％以上６０％以下であり、より好ましくは、５％以上４０％以下である。ｂの割合は、好ましくは０％以上５０％以下であり、より好ましくは、０％以上２０％以下である。ｃの割合は、好ましくは０％以上３０％以下であり、より好ましくは、０％以上２０％以下である。ｄの割合は、好ましくは０％以上１０％以下であり、より好ましくは、０％以上５％以下である。ｅの割合は、好ましくは０％以上５０％以下であり、より好ましくは、０％以上３０％以下である。ｆの割合は、０％以上９０％以下であり、好ましくは２０％以上９０％以下であり、より好ましくは、４０％以上８０％以下である。ｇの割合は、好ましくは０％以上１０％以下であり、より好ましくは、０％以上５％以下である。ｈの割合は、好ましくは０％以上５０％以下であり、より好ましくは、０％以上３０％以下である。ｉの割合は、好ましくは０％以上１０％以下であり、より好ましくは、０％以上５％以下である。ただし、ａ＋ｃの割合は０％より大きく、ｄ＋ｇの割合は０％より大きい。 The ratio of a to the total of a, b, c, d, e, f, g, h and i is preferably 0% or more and 60% or less, more preferably 5%, when the total is 100%. % To 40%. The ratio of b is preferably 0% or more and 50% or less, and more preferably 0% or more and 20% or less. The ratio of c is preferably 0% or more and 30% or less, and more preferably 0% or more and 20% or less. The ratio of d is preferably 0% or more and 10% or less, and more preferably 0% or more and 5% or less. The ratio of e is preferably 0% or more and 50% or less, and more preferably 0% or more and 30% or less. The ratio of f is 0% or more and 90% or less, preferably 20% or more and 90% or less, and more preferably 40% or more and 80% or less. The ratio of g is preferably 0% or more and 10% or less, and more preferably 0% or more and 5% or less. The ratio of h is preferably 0% or more and 50% or less, and more preferably 0% or more and 30% or less. The ratio of i is preferably 0% or more and 10% or less, and more preferably 0% or more and 5% or less. However, the ratio of a + c is larger than 0%, and the ratio of d + g is larger than 0%.
前記化学式（１）で示されるポリシロキサンの中でも、下記化学式（２）で示されるポリシロキサンが、基板や金属配線などに対する接着性と輝度とを高度に両立しうる硬化物を形成することから好ましい。 Among the polysiloxane represented by Formula (1), preferably from the polysiloxane represented by the following chemical formula (2), to form a cured product capable of highly achieving both adhesion and luminance with respect to such a substrate and a metal wire .
アルケニル基を有する基としては、上述のアルケニル基を有する基と同じ基が例示される。密着性基を有する基としては、上述の密着性基と同じ基を有する基が例示される。エポキシ基を有する基としては、上述のエポキシ基を有する基と同じ基が例示される。１価の炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基等のアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；クロロメチル基、３−クロロプロピル基、３,３,３−トリフルオロプロピル基，ノナフルオロブチルエチル基等の置換アルキル基が例示される。
Examples of the group having an alkenyl group include the same groups as the above-described groups having an alkenyl group. Examples of the group having an adhesive group include groups having the same group as the above-mentioned adhesive group. As group which has an epoxy group, the same group as the group which has the above-mentioned epoxy group is illustrated. Examples of monovalent hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups; aryl groups such as phenyl, tolyl, xylyl, and naphthyl groups; aralkyl groups such as benzyl groups and phenethyl groups; chloromethyl group, 3-chloropropyl group, 3,3,3-triflate Luo Ropuropiru group, a substituted alkyl group such as nonafluorobutyl ethyl groups.
ヒドロシリル化反応用触媒（Ｃ）の具体例としては、白金系触媒、ロジウム系触媒、パラジウム系触媒を挙げることができる。これらの中で、本組成物の硬化促進の観点から白金系触媒が好ましい。白金系触媒としては、たとえば、白金−アルケニルシロキサン錯体等が挙げられる。アルケニルシロキサンとしては、たとえば、１,３−ジビニル−１,１,３,３−テトラメチルジシロキサン、１,３,５,７−テトラメチル−１,３,５,７−テトラビニルシクロテトラシロキサン等が挙げられる。特に、錯体の安定性の観点から、１,３−ジビニル−１,１,３,３−テトラメチルジシロキサンが好ましい。 Specific examples of the hydrosilylation catalyst (C) include a platinum-based catalyst, a rhodium-based catalyst, and a palladium-based catalyst. Among these, a platinum-based catalyst is preferable from the viewpoint of promoting the curing of the present composition. Examples of the platinum-based catalyst include a platinum-alkenylsiloxane complex. Examples of the alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane. Etc. In particular, from the viewpoint of stability of the complex, 1,3-divinyl-1,1,3,3-tetra- disiloxane is preferable.
（１）ポリシロキサンの合成
（１−１）ポリシロキサンの合成
[合成例１] ポリシロキサン（ＡＲ１）の合成
攪拌機、還流冷却管、投入口、温度計付き四口フラスコに１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン８２ｇ、フェニルトリメトキシシラン５２５ｇ、水１４３ｇ、トリフルオロメタンスルホン酸０．４ｇおよびトルエン５００ｇを投入して混合し、１時間加熱還流した。冷却後、下層を分離除去し、上層であるトルエン溶液層を水洗した。水洗したトルエン溶液層に水酸化カリウム０．４ｇを加え、水分離管から水を除去しながら還流した。水の除去完了後、固形分濃度が７５質量％となるまで濃縮し、さらに５時間還流した。冷却後、酢酸０．６ｇを投入して中和した後、ろ過して得られたトルエン溶液を水洗した。その後、減圧濃縮してポリシロキサン（ＡＲ１）を得た。ゲルパーミエーションクロマトグラフィーでポリシロキサン（ＡＲ１）のポリスチレン換算重量平均分子量を測定したところ、２０００であった。ポリシロキサン（ＡＲ１）の化学式は（ＶｉＭｅ2ＳｉＯ1/2）25（ＰｈＳｉＯ3/2）75（Ｖｉはビニル基、Ｍｅはメチル基、Ｐｈはフェニル基を示す。添え字はｍｏｌ％を示す）であった。
[合成例２] ポリシロキサン（Ａ１）の合成
攪拌機、還流冷却管、投入口、温度計付き四口フラスコに１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン８２ｇ、水１４３ｇ、フェニルトリメトキシシラン５２１ｇ、トリフルオロメタンスルホン酸０．４ｇおよびトルエン５００ｇを投入して混合し、１時間加熱還流した。冷却後、下層を分離除去し、上層であるトルエン溶液層を水洗した。水洗したトルエン溶液層に３−グリシドキシプロピルメチルジメトキシシラン４ｇと水酸化カリウム０．５ｇとを加え１時間加熱還流した。続いて、メタノールを留去し、過剰の水を共沸脱水で除いた。続いて４時間加熱還流した。反応後のトルエン溶液は冷却後、酢酸０．６ｇで中和し水洗した。水除去後、トルエンを減圧下に留去濃縮してアルケニル基２５モル％及びエポキシ基０．５モル％を有する（ポリシロキサン中に含まれる全Ｓｉ原子の数を１００モル％とする）ポリシロキサン（Ａ１）を得た。ゲルパーミエーションクロマトグラフィーでポリシロキサン（Ａ１）のポリスチレン換算重量平均分子量を測定したところ、２０００であった。ポリシロキサン（Ａ１）の化学式は（ＶｉＭｅ2ＳｉＯ1/2）25（ＰｈＳｉＯ3/2）74.5（ＥｐＭｅＳｉＯ2/2）0.5（Ｖｉはビニル基、Ｍｅはメチル基、Ｐｈはフェニル基、Ｅｐはグリシドキシプロピル基を示す。添え字はｍｏｌ％を示す）であった。ポリシロキサン（Ａ１）中に含まれる全Ｓｉ原子の数を１００モル％とするとき、アルケニル基の含有割合は２５ｍｏｌ％、エポキシ基の含有割合は０．５ｍｏｌ％、アリール基の含有割合は７４．５ｍｏｌ％であった。
(1) Synthesis of polysiloxane (1-1) Synthesis of polysiloxane
[Synthesis Example 1] Synthesis of polysiloxane (AR1) Stirrer, reflux condenser, charging port, 4-neck flask with thermometer, 82 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, phenyltri 525 g of methoxysilane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were added and mixed, and the mixture was heated to reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was washed with water. To the toluene solution layer washed with water, 0.4 g of potassium hydroxide was added and refluxed while removing water from the water separation tube. After the removal of water was completed, the solution was concentrated until the solid concentration became 75% by mass, and further refluxed for 5 hours. After cooling, 0.6 g of acetic acid was added to neutralize, and the toluene solution obtained by filtration was washed with water. Then, it concentrated under reduced pressure and obtained polysiloxane (AR1). It was 2000 when the polystyrene conversion weight average molecular weight of polysiloxane (AR1) was measured by the gel permeation chromatography. The chemical formula of polysiloxane (AR1) is (ViMe 2 SiO 1/2 ) 25 (PhSiO 3/2 ) 75 (Vi represents a vinyl group, Me represents a methyl group, Ph represents a phenyl group, and the subscript represents mol%) Met.
[Synthesis Example 2] Synthesis of polysiloxane (A1) Stirrer, reflux condenser, charging port, 4-neck flask with thermometer, 82 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 143 g of water Then, 521 g of phenyltrimethoxysilane, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were added and mixed, followed by heating under reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was washed with water. To the toluene solution layer washed with water, 4 g of 3-glycidoxypropylmethyldimethoxysilane and 0.5 g of potassium hydroxide were added and heated to reflux for 1 hour. Subsequently, methanol was distilled off and excess water was removed by azeotropic dehydration. Subsequently, the mixture was heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After removing water, toluene is distilled off and concentrated under reduced pressure to have 25 mol% of alkenyl groups and 0.5 mol% of epoxy groups (the number of all Si atoms contained in the polysiloxane is 100 mol%). (A1) was obtained. It was 2000 when the polystyrene conversion weight average molecular weight of polysiloxane (A1) was measured by the gel permeation chromatography. The chemical formula of polysiloxane (A1) is (ViMe 2 SiO 1/2 ) 25 (PhSiO 3/2 ) 74.5 (EpMeSiO 2/2 ) 0.5 (Vi is a vinyl group, Me is a methyl group, Ph is a phenyl group, Ep is a glycerin) It represents a sidoxypropyl group, and the subscript indicates mol%). When the number of all Si atoms contained in the polysiloxane (A1) is 100 mol%, the alkenyl group content is 25 mol%, the epoxy group content is 0.5 mol%, and the aryl group content is 74.%. It was 5 mol%.
[合成例３] ポリシロキサン（Ａ２）の合成
攪拌機、還流冷却管、投入口、温度計付き四口フラスコに１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン８２ｇ、フェニルトリメトキシシラン５１８ｇ、水１４３ｇ、トリフルオロメタンスルホン酸０．４ｇおよびトルエン５００ｇを投入して混合し、１時間加熱還流した。冷却後、下層を分離除去し、上層であるトルエン溶液層を水洗した。水洗したトルエン溶液層に３−グリシドキシプロピルメチルジメトキシシラン８ｇと水酸化カリウム０．５ｇとを加え１時間加熱還流した。続いて、メタノールを留去し、過剰の水を共沸脱水で除いた。続いて４時間加熱還流した。反応後のトルエン溶液は冷却後、酢酸０．６ｇで中和し水洗した。水除去後、トルエンを減圧下に留去濃縮してアルケニル基２５モル％及びエポキシ基１モル％を有する（ポリシロキサン中に含まれる全Ｓｉ原子の数を１００モル％とする）ポリシロキサン（Ａ２）を得た。ゲルパーミエーションクロマトグラフィーでポリシロキサン（Ａ２）のポリスチレン換算重量平均分子量を測定したところ、２０００であった。ポリシロキサン（Ａ２）の化学式は（ＶｉＭｅ2ＳｉＯ1/2）25（ＰｈＳｉＯ3/2）74（ＥｐＭｅＳｉＯ2/2）1（Ｖｉはビニル基、Ｍｅはメチル基、Ｐｈはフェニル基、Ｅｐはグリシドキシプロピル基を示す。添え字はｍｏｌ％を示す）であった。ポリシロキサン（Ａ２）中に含まれる全Ｓｉ原子の数を１００モル％とするとき、アルケニル基の含有割合は２５ｍｏｌ％、エポキシ基の含有割合は１ｍｏｌ％、アリール基の含有割合は７４ｍｏｌ％であった。
[Synthesis Example 3] Synthesis of polysiloxane (A2) Stirrer, reflux condenser, charging port, 4-neck flask with thermometer, 82 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, phenyltri 518 g of methoxysilane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were added and mixed, and the mixture was heated to reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was washed with water. To the toluene solution layer washed with water, 8 g of 3-glycidoxypropylmethyldimethoxysilane and 0.5 g of potassium hydroxide were added and heated under reflux for 1 hour. Subsequently, methanol was distilled off and excess water was removed by azeotropic dehydration. Subsequently, the mixture was heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After removing water, toluene was distilled off and concentrated under reduced pressure to have 25 mol% of alkenyl groups and 1 mol% of epoxy groups (the number of all Si atoms contained in the polysiloxane was 100 mol%) (A2 ) It was 2000 when the polystyrene conversion weight average molecular weight of polysiloxane (A2) was measured by the gel permeation chromatography. The chemical formula of polysiloxane (A2) is (ViMe 2 SiO 1/2 ) 25 (PhSiO 3/2 ) 74 (EpMeSiO 2/2 ) 1 (Vi is a vinyl group, Me is a methyl group, Ph is a phenyl group, and Ep is a glycerin. It represents a sidoxypropyl group, and the subscript indicates mol%). When the total number of Si atoms contained in the polysiloxane (A2) is 100 mol%, the alkenyl group content is 25 mol%, the epoxy group content is 1 mol%, and the aryl group content is 74 mol%. It was.
[合成例４] ポリシロキサン（Ａ３）の合成
攪拌機、還流冷却管、投入口、温度計付き四口フラスコに１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン８２ｇ、フェニルトリメトキシシラン５１１ｇ、水１４３ｇ、トリフルオロメタンスルホン酸０．４ｇおよびトルエン５００ｇを投入して混合し、１時間加熱還流した。冷却後、下層を分離除去し、上層であるトルエン溶液層を水洗した。水洗したトルエン溶液層に３−グリシドキシプロピルメチルジメトキシシラン１６ｇと水酸化カリウム０．５ｇとを加え１時間加熱還流した。続いて、メタノールを留去し、過剰の水を共沸脱水で除いた。続いて４時間加熱還流した。反応後のトルエン溶液は冷却後、酢酸０．６ｇで中和し水洗した。水除去後、トルエンを減圧下に留去濃縮して、アルケニル基２５モル％及びエポキシ基２モル％を有する（ポリシロキサン中に含まれる全Ｓｉ原子の数を１００モル％とする）ポリシロキサン（Ａ３）を得た。ゲルパーミエーションクロマトグラフィーでポリシロキサン（Ａ３）のポリスチレン換算重量平均分子量を測定したところ、２０００であった。ポリシロキサン（Ａ３）の化学式は（ＶｉＭｅ2ＳｉＯ1/2）25（ＰｈＳｉＯ3/2）73（ＥｐＭｅＳｉＯ2/2）2（Ｖｉはビニル基、Ｍｅはメチル基、Ｐｈはフェニル基、Ｅｐはグリシドキシプロピル基を示す。添え字はｍｏｌ％を示す）であった。ポリシロキサン（Ａ３）中に含まれる全Ｓｉ原子の数を１００モル％とするとき、アルケニル基の含有割合は２５ｍｏｌ％、エポキシ基の含有割合は２ｍｏｌ％、アリール基の含有割合は７３ｍｏｌ％であった。
[Synthesis Example 4] Synthesis of polysiloxane (A3) Stirrer, reflux condenser, charging port, 4-neck flask with thermometer, 82 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, phenyltri 511 g of methoxysilane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were added and mixed, and the mixture was heated to reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was washed with water. The washed toluene solution layer 3 a glycidoxy and methyl dimethoxy silane 16g and water potassium oxide 0.5g was heated under reflux for 1 hour was added. Subsequently, methanol was distilled off and excess water was removed by azeotropic dehydration. Subsequently, the mixture was heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After water removal, toluene was distilled off and concentrated under reduced pressure to obtain 25% by mole of alkenyl groups and 2% by mole of epoxy groups (with the total number of Si atoms contained in the polysiloxane being 100% by mole) ( A3) was obtained. It was 2000 when the polystyrene conversion weight average molecular weight of polysiloxane (A3) was measured by the gel permeation chromatography. The chemical formula of polysiloxane (A3) is (ViMe 2 SiO 1/2 ) 25 (PhSiO 3/2 ) 73 (EpMeSiO 2/2 ) 2 (Vi is a vinyl group, Me is a methyl group, Ph is a phenyl group, Ep is a glycerin) It represents a sidoxypropyl group, and the subscript indicates mol%). When the total number of Si atoms contained in the polysiloxane (A3) is 100 mol%, the alkenyl group content is 25 mol%, the epoxy group content is 2 mol%, and the aryl group content is 73 mol%. It was.
[合成例５] ポリシロキサン（Ａ４）の合成
攪拌機、還流冷却管、投入口、温度計付き四口フラスコに１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン４９ｇ、フェニルトリメトキシシラン４４２ｇ、ジメチルジメトキシシラン８５ｇ、水１４３ｇ、トリフルオロメタンスルホン酸０．４ｇおよびトルエン５００ｇを投入して混合し、１時間加熱還流した。冷却後、下層を分離除去し、上層であるトルエン溶液層を水洗した。水洗したトルエン溶液層に３−グリシドキシプロピルメチルジメトキシシラン８ｇと水酸化カリウム０．５ｇとを加え１時間加熱還流した。続いて、メタノールを留去し、過剰の水を共沸脱水で除いた。続いて４時間加熱還流した。反応後のトルエン溶液は冷却後、酢酸０．６ｇで中和し水洗した。水除去後、トルエンを減圧下に留去濃縮して、アルケニル基１５モル％及びエポキシ基１モル％を有する（ポリシロキサン中に含まれる全Ｓｉ原子の数を１００モル％とする）ポリシロキサン（Ａ４）を得た。ゲルパーミエーションクロマトグラフィーでポリシロキサン（Ａ４）のポリスチレン換算重量平均分子量を測定したところ、１８００であった。ポリシロキサン（Ａ４）の化学式は（ＶｉＭｅ2ＳｉＯ1/2）15（ＰｈＳｉＯ3/2）64（Ｍｅ2ＳｉＯ2/2）20（ＥｐＭｅＳｉＯ2/2）1（Ｖｉはビニル基、Ｍｅはメチル基、Ｐｈはフェニル基、Ｅｐはグリシドキシプロピル基を示す。添え字はｍｏｌ％を示す）であった。ポリシロキサン（Ａ４）中に含まれる全Ｓｉ原子の数を１００モル％とするとき、アルケニル基の含有割合は１５ｍｏｌ％、エポキシ基の含有割合は１ｍｏｌ％、アリール基の含有割合は６４ｍｏｌ％であった。
[Synthesis Example 5] Synthesis of polysiloxane (A4) In a four-necked flask equipped with a stirrer, a reflux condenser, an inlet, and a thermometer, 49 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, phenyltri 442 g of methoxysilane, 85 g of dimethyldimethoxysilane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were added and mixed, followed by heating under reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was washed with water. To the toluene solution layer washed with water, 8 g of 3-glycidoxypropylmethyldimethoxysilane and 0.5 g of potassium hydroxide were added and heated under reflux for 1 hour. Subsequently, methanol was distilled off and excess water was removed by azeotropic dehydration. Subsequently, the mixture was heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After removal of water, toluene is distilled off and concentrated under reduced pressure to obtain a polysiloxane having 15 mol% of alkenyl groups and 1 mol% of epoxy groups (with the total number of Si atoms contained in the polysiloxane being 100 mol%). A4) was obtained. It was 1800 when the polystyrene conversion weight average molecular weight of polysiloxane (A4) was measured by the gel permeation chromatography. The chemical formula of polysiloxane (A4) is (ViMe 2 SiO 1/2 ) 15 (PhSiO 3/2 ) 64 (Me 2 SiO 2/2 ) 20 (EpMeSiO 2/2 ) 1 (Vi is a vinyl group, Me is a methyl group Ph represents a phenyl group, Ep represents a glycidoxypropyl group, and the subscript represents mol%). When the total number of Si atoms contained in the polysiloxane (A4) is 100 mol%, the alkenyl group content is 15 mol%, the epoxy group content is 1 mol%, and the aryl group content is 64 mol%. It was.
[合成例６] ポリシロキサン（Ａ５）の合成
攪拌機、還流冷却管、投入口、温度計付き四口フラスコに１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン８２ｇ、フェニルトリメトキシシラン５２５ｇ、水１４３ｇ、トリフルオロメタンスルホン酸０．４ｇおよびトルエン５００ｇを投入して混合し、１時間加熱還流した。冷却後、下層を分離除去し、上層であるトルエン溶液層を水洗した。水洗したトルエン溶液層に３−グリシドキシプロピルメチルジメトキシシラン３１４ｇと水１３０ｇと水酸化カリウム０．５ｇとを加え１時間加熱還流した。続いて、メタノールを留去し、過剰の水を共沸脱水で除いた。続いて４時間加熱還流した。反応後のトルエン溶液は冷却後、酢酸０．６ｇで中和し水洗した。水除去後、トルエンを減圧下に留去濃縮して、アルケニル基２５モル％及びエポキシ基４０モル％を有する（ポリシロキサン中に含まれる全Ｓｉ原子の数を１００モル％とする）ポリシロキサン（Ａ５）を得た。ゲルパーミエーションクロマトグラフィーでポリシロキサン（Ａ５）のポリスチレン換算重量平均分子量を測定したところ、１６００であった。ポリシロキサン（Ａ５）の化学式は（ＶｉＭｅ2ＳｉＯ1/2）25（ＰｈＳｉＯ3/2） 35 （ＥｐＭｅＳｉＯ2/2）40（Ｖｉはビニル基、Ｍｅはメチル基、Ｐｈはフェニル基、Ｅｐはグリシドキシプロピル基を示す。添え字はｍｏｌ％を示す）であった。ポリシロキサン（Ａ５）中に含まれる全Ｓｉ原子の数を１００モル％とするとき、アルケニル基の含有割合は２５ｍｏｌ％、エポキシ基の含有割合は４０ｍｏｌ％、アリール基の含有割合は３５ｍｏｌ％であった。
[Synthesis Example 6] Synthesis of polysiloxane (A5) Stirrer, reflux condenser, charging port, 4-neck flask with thermometer, 82 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, phenyltri 525 g of methoxysilane, 143 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were added and mixed, and the mixture was heated to reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was washed with water. To the toluene solution layer washed with water, 314 g of 3-glycidoxypropylmethyldimethoxysilane, 130 g of water and 0.5 g of potassium hydroxide were added and heated under reflux for 1 hour. Subsequently, methanol was distilled off and excess water was removed by azeotropic dehydration. Subsequently, the mixture was heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After water removal, toluene was distilled off and concentrated under reduced pressure to obtain 25% by mole of alkenyl groups and 40% by mole of epoxy groups (with the total number of Si atoms contained in the polysiloxane being 100% by mole) ( A5) was obtained. It was 1600 when the polystyrene conversion weight average molecular weight of polysiloxane (A5) was measured by the gel permeation chromatography. The chemical formula of polysiloxane (A5) is (ViMe 2 SiO 1/2 ) 25 (PhSiO 3/2 ) 35 (EpMeSiO 2/2 ) 40 (Vi is a vinyl group, Me is a methyl group, Ph is a phenyl group, and Ep is a glycerin. It represents a sidoxypropyl group, and the subscript indicates mol%). When the total number of Si atoms contained in the polysiloxane (A5) is 100 mol%, the alkenyl group content is 25 mol%, the epoxy group content is 40 mol%, and the aryl group content is 35 mol%. there were.
[合成例７] ポリシロキサン（Ａ６）の合成
攪拌機、還流冷却管、投入口、温度計付き四口フラスコに１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン３３ｇ、フェニルトリメトキシシラン４４２ｇ、ジメチルジメトキシシラン８５ｇ、ジフェニルジメトキシシラン４３ｇ、水１５５ｇ、トリフルオロメタンスルホン酸０．４ｇおよびトルエン５００ｇを投入して混合し、１時間加熱還流した。冷却後、下層を分離除去し、上層であるトルエン溶液層を水洗した。水洗したトルエン溶液層に３−グリシドキシプロピルメチルジメトキシシラン８ｇと水酸化カリウム０．５ｇとを加え１時間加熱還流した。続いて、メタノールを留去し、過剰の水を共沸脱水で除いた。続いて４時間加熱還流した。反応後のトルエン溶液は冷却後、酢酸０．６ｇで中和し水洗した。水除去後、トルエンを減圧下に留去濃縮して、アルケニル基１０モル％及びエポキシ基１モル％を有する（ポリシロキサン中に含まれる全Ｓｉ原子の数を１００モル％とする）ポリシロキサン（Ａ６）を得た。ゲルパーミエーションクロマトグラフィーでポリシロキサン（Ａ６）のポリスチレン換算重量平均分子量を測定したところ、１８００であった。ポリシロキサン（Ａ６）の化学式は（ＶｉＭｅ2ＳｉＯ1/2）10（ＰｈＳｉＯ3/2）64（Ｐｈ2ＳｉＯ2/2）5（Ｍｅ2ＳｉＯ2/2）20（ＥｐＭｅＳｉＯ2/2）1（Ｖｉはビニル基、Ｍｅはメチル基、Ｐｈはフェニル基、Ｅｐはグリシドキシプロピル基を示す。添え字はｍｏｌ％を示す）であった。ポリシロキサン（Ａ６）中に含まれる全Ｓｉ原子の数を１００モル％とするとき、アルケニル基の含有割合は１０ｍｏｌ％、エポキシ基の含有割合は１ｍｏｌ％、アリール基の含有割合は７４ｍｏｌ％であった。
[Synthesis Example 7] Synthesis of polysiloxane (A6) Stirrer, reflux condenser, charging port, 4-neck flask with thermometer, 33 g of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, phenyltri 442 g of methoxysilane, 85 g of dimethyldimethoxysilane, 43 g of diphenyldimethoxysilane, 155 g of water, 0.4 g of trifluoromethanesulfonic acid and 500 g of toluene were mixed and heated to reflux for 1 hour. After cooling, the lower layer was separated and removed, and the upper toluene solution layer was washed with water. To the toluene solution layer washed with water, 8 g of 3-glycidoxypropylmethyldimethoxysilane and 0.5 g of potassium hydroxide were added and heated under reflux for 1 hour. Subsequently, methanol was distilled off and excess water was removed by azeotropic dehydration. Subsequently, the mixture was heated to reflux for 4 hours. The toluene solution after the reaction was cooled, neutralized with 0.6 g of acetic acid and washed with water. After water removal, toluene was distilled off and concentrated under reduced pressure to have a polysiloxane having an alkenyl group of 10 mol% and an epoxy group of 1 mol% (the total number of Si atoms contained in the polysiloxane was 100 mol%). A6) was obtained. It was 1800 when the polystyrene conversion weight average molecular weight of polysiloxane (A6) was measured by the gel permeation chromatography. The chemical formula of polysiloxane (A6) is (ViMe 2 SiO 1/2 ) 10 (PhSiO 3/2 ) 64 (Ph 2 SiO 2/2 ) 5 (Me 2 SiO 2/2 ) 20 (EpMeSiO 2/2 ) 1 ( Vi represents a vinyl group, Me represents a methyl group, Ph represents a phenyl group, Ep represents a glycidoxypropyl group, and the subscript represents mol%). When the total number of Si atoms contained in the polysiloxane (A6) is 100 mol%, the alkenyl group content is 10 mol%, the epoxy group content is 1 mol%, and the aryl group content is 74 mol%. It was.
［合成例８］ ポリシロキサン（Ｂ１）の合成
攪拌機、還流冷却管、投入口、温度計付き四口フラスコにフェニルトリメトキシシラン１９５ｇとトリフルオロメタンスルホン酸０．２ｇを投入して混合し、攪拌しつつ水１３ｇを１５分間で滴下し、滴下終了後、１時間加熱還流した。室温まで冷却した後、１，１，３，３−テトラメチルジシロキサン１１９ｇを加え、攪拌しつつ、酢酸８８ｇを滴下した。滴下終了後、混合液を攪拌しつつ５０℃に昇温し、３時間反応させた。室温まで冷却した後、トルエンと水を加え、良く混合して静置し、水層を分離除去した。上層であるトルエン溶液層を水洗した後、減圧濃縮して、メチルフェニルハイドロジェンポリシロキサン（Ｂ１）を得た。ポリシロキサン（Ｂ１）の化学式は（ＨＭｅ2ＳｉＯ1/2）60（ＰｈＳｉＯ3/2）40（Ｍｅはメチル基、Ｐｈはフェニル基を示す。添え字はｍｏｌ％を示す）であった。
[Synthesis Example 8] Synthesis of polysiloxane (B1) 195 g of phenyltrimethoxysilane and 0.2 g of trifluoromethanesulfonic acid were added to a stirrer, a reflux condenser, a charging port, and a four-necked flask with a thermometer, mixed, and stirred. While adding 13 g of water dropwise over 15 minutes, the mixture was heated to reflux for 1 hour after the completion of the dropping. After cooling to room temperature, 119 g of 1,1,3,3-tetramethyldisiloxane was added, and 88 g of acetic acid was added dropwise with stirring. After completion of the dropwise addition, the mixture was heated to 50 ° C. with stirring and reacted for 3 hours. After cooling to room temperature, toluene and water were added, mixed well and allowed to stand, and the aqueous layer was separated and removed. The upper toluene solution layer was washed with water and then concentrated under reduced pressure to obtain methylphenylhydrogenpolysiloxane (B1). The chemical formula of the polysiloxane (B1) was (HMe 2 SiO 1/2 ) 60 (PhSiO 3/2 ) 40 (Me represents a methyl group, Ph represents a phenyl group, and the subscript represents mol%).
［合成例９］ ポリシロキサン（Ｂ２）の合成
攪拌機、還流冷却管、投入口、温度計付き四口フラスコにジフェニルジメトキシシラン２２０ｇとトリフルオロメタンスルホン酸０．６ｇを投入して混合し、１，１，３，３−テトラメチルジシロキサン１４７ｇを加え、攪拌しつつ酢酸１０８ｇを３０分間かけて滴下した。滴下終了後、混合液を攪拌しつつ５０℃に昇温して３時間反応させた。室温まで冷却した後、トルエンと水を加え、良く混合して静置し、水層を分離除去した。上層であるトルエン溶液層を３回水洗した後、減圧濃縮して、ジフェニルハイドロジェンポリシロキサン（Ｂ２）を得た。ポリシロキサン（Ｂ２）の化学式は（ＨＭｅ2ＳｉＯ1/2）50（Ｐｈ2ＳｉＯ2/2）50（Ｍｅはメチル基、Ｐｈはフェニル基を示す。添え字はｍｏｌ％を示す）であった。
（１−２）重量平均分子量
得られたポリシロキサンの重量平均分子量（Ｍｗ）は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により下記条件で測定し、ポリスチレン換算値として求めた。
[Synthesis Example 9] Synthesis of polysiloxane (B2) 220 g of diphenyldimethoxysilane and 0.6 g of trifluoromethanesulfonic acid were added to and mixed with a stirrer, a reflux condenser, a charging port, and a four-necked flask with a thermometer. , 3,3-tetramethyldisiloxane 147 g was added, and 108 g of acetic acid was added dropwise over 30 minutes while stirring. After completion of dropping, the mixture was stirred and heated to 50 ° C. and reacted for 3 hours. After cooling to room temperature, toluene and water were added, mixed well and allowed to stand, and the aqueous layer was separated and removed. The upper toluene solution layer was washed with water three times and then concentrated under reduced pressure to obtain diphenylhydrogenpolysiloxane (B2). The chemical formula of polysiloxane (B2) was (HMe 2 SiO 1/2 ) 50 (Ph 2 SiO 2/2 ) 50 (Me represents a methyl group, Ph represents a phenyl group, and the subscript represents mol%). .
(1-2) Weight average molecular weight The weight average molecular weight (Mw) of the obtained polysiloxane was measured by gel permeation chromatography (GPC) under the following conditions and determined as a polystyrene equivalent value.
本発明の硬化性組成物は、その硬化物が透明でありながら、高温雰囲気下に置かれても光透過率の低下が小さく、高い接着性を有するので、光学用半導体素子および光半導体部材の封止材、接着剤、ポッティング剤、保護コーティング剤、アンダーフィル剤等として有用である。本発明の硬化物は、高温に曝されても光透過率の低下が小さいので、高温条件下の製造工程においても光透過率の低下が小さく、長期信頼性に優れるという特徴がある。本発明の硬化物は、特に高輝度の発光素子などの光学用半導体装置に用いられたとき、全放射束が高くなるので、高輝度の光源の近傍に用いられる光学部材として有用である。 In the curable composition of the present invention, the cured product is transparent, and even when placed in a high-temperature atmosphere, the decrease in light transmittance is small and it has high adhesiveness. sealing materials, adhesives, potting agents, protective coating agents, useful as an underfill agent. The cured product of the present invention is characterized in that the decrease in light transmittance is small even when exposed to high temperatures, so that the decrease in light transmittance is small even in the production process under high temperature conditions, and the long-term reliability is excellent. The cured product of the present invention is useful as an optical member used in the vicinity of a high-intensity light source because the total radiant flux increases when used in an optical semiconductor device such as a high-intensity light emitting element.
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| JP4862032B2 (en) * | 2008-12-05 | 2012-01-25 | 信越化学工業株式会社 | Addition-curable silicone composition that provides a cured product having a high refractive index, and an optical element sealing material comprising the composition |
| JP4913858B2 (en) * | 2009-04-14 | 2012-04-11 | 日東電工株式会社 | Composition for thermosetting silicone resin |
| JP2011057755A (en) * | 2009-09-07 | 2011-03-24 | Shin-Etsu Chemical Co Ltd | Silicone composition and cured product thereof |
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2012
- 2012-02-20 JP JP2012034100A patent/JP5505436B2/en active Active
- 2012-04-20 TW TW101114054A patent/TWI499644B/en active
- 2012-04-20 TW TW104108949A patent/TW201525073A/en unknown
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2014
- 2014-01-27 JP JP2014012162A patent/JP5696798B2/en active Active
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