TWI801654B - Addition hardening polysiloxane composition and semiconductor device - Google Patents

Addition hardening polysiloxane composition and semiconductor device Download PDF

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TWI801654B
TWI801654B TW108130545A TW108130545A TWI801654B TW I801654 B TWI801654 B TW I801654B TW 108130545 A TW108130545 A TW 108130545A TW 108130545 A TW108130545 A TW 108130545A TW I801654 B TWI801654 B TW I801654B
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小材利之
木村真司
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日商信越化學工業股份有限公司
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Abstract

本發明之課題在於提供一種賦予硬化快速、高透光率、且高溫耐久性優異之硬化物之加成硬化型聚矽氧組成物，及使用此之半導體裝置。 其解決手段為一種加成硬化型聚矽氧組成物，其特徵為含有： (A)下述平均單位式(1)所示之有機聚矽氧烷，

Figure 108130545-A0101-11-0001-1
(B)下述平均單位式(2)所示之有機聚矽氧烷，
Figure 108130545-A0101-11-0001-2
(C)下述平均組成式(3)所示之1分子中至少具有2個Si-H鍵之有機氫聚矽氧烷，
Figure 108130545-A0101-11-0001-3
及， (D)矽氫化反應觸媒。An object of the present invention is to provide an addition-curable polysiloxane composition that provides a cured product that cures rapidly, has high light transmittance, and is excellent in high-temperature durability, and a semiconductor device using the composition. The solution is an addition-hardening polysiloxane composition characterized by containing: (A) an organopolysiloxane represented by the following average unit formula (1),
Figure 108130545-A0101-11-0001-1
(B) organopolysiloxane represented by the following average unit formula (2),
Figure 108130545-A0101-11-0001-2
(C) An organohydrogenpolysiloxane having at least two Si-H bonds in one molecule represented by the following average composition formula (3),
Figure 108130545-A0101-11-0001-3
And, (D) Hydrosilation reaction catalyst.

Description

加成硬化型聚矽氧組成物及半導體裝置Addition hardening polysiloxane composition and semiconductor device

本發明係關於加成硬化型聚矽氧組成物，及藉由該組成物之硬化物被覆半導體元件之半導體裝置。The present invention relates to an addition-hardening polysiloxane composition and a semiconductor device in which a semiconductor element is coated with a cured product of the composition.

因矽氫化反應而硬化之加成硬化型聚矽氧組成物係使用作為光耦合器、發光二極體、固體攝影元件等之光學用半導體裝置中之半導體元件之保護塗覆劑。此種半導體元件之保護塗覆劑會有由於從半導體元件產生之熱或光而硬度或透明性產生變化的情況。為了抑制該變化，過往係以將Q單位(SiO2 )導入於分子內(專利文獻1~4)，以及將軟鏈段導入於組成中來進行對應(專利文獻5)。然而，此種對應方法仍無法對應永久性材料之硬度變化。又，周邊元件由於係使用對容易受熱之樹脂，在以20~80℃等低溫度使其硬化時，一般由於係增加硬化觸媒之量來進行對應，故具有不經濟的缺點。 [先前技術文獻] [專利文獻]Addition-curable polysiloxane compositions hardened by hydrosilylation reactions are used as protective coating agents for semiconductor devices in optical semiconductor devices such as optical couplers, light-emitting diodes, and solid-state imaging devices. Such a protective coating agent for a semiconductor element may change in hardness or transparency due to heat or light generated from the semiconductor element. In order to suppress this change, conventionally, Q units (SiO 2 ) were introduced into the molecule (Patent Documents 1 to 4) and soft segments were introduced into the composition (Patent Document 5). However, this corresponding method is still unable to respond to changes in the hardness of permanent materials. In addition, since the peripheral components are made of resin that is easy to be heated, when it is cured at a low temperature such as 20-80°C, it is generally necessary to increase the amount of hardening catalyst to deal with it, so it has a disadvantage of being uneconomical. [Prior Art Document] [Patent Document]

[專利文獻1]日本特開平7-252419號公報 [專利文獻2]日本特開2011-252175號公報 [專利文獻3]日本特開2013-067683號公報 [專利文獻4]日本特開2009-052038號公報 [專利文獻5]日本特開2007-63538號公報[Patent Document 1] Japanese Patent Application Laid-Open No. 7-252419 [Patent Document 2] Japanese Unexamined Patent Publication No. 2011-252175 [Patent Document 3] Japanese Unexamined Patent Publication No. 2013-067683 [Patent Document 4] Japanese Unexamined Patent Publication No. 2009-052038 [Patent Document 5] Japanese Unexamined Patent Publication No. 2007-63538

[發明所欲解決之課題][Problem to be Solved by the Invention]

本發明係有鑑於上述情況所完成者，其目的在於提供一種賦予硬化快速、高透光率，且高溫耐久性優異之硬化物之加成硬化型聚矽氧組成物、及使用此之半導體裝置。 [用以解決課題之手段]The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an addition-curable polysiloxane composition that provides a cured product that cures quickly, has high light transmittance, and is excellent in high-temperature durability, and a semiconductor device using the same . [Means to solve the problem]

為了解決上述課題，本發明提供一種加成硬化型聚矽氧組成物，其特徵為包含： (A)下述平均單位式(1)所示之有機聚矽氧烷，

Figure 02_image001
(式中，R1 可為相同或相異之取代或未取代之脂肪族一價烴基，全部R1 之中0.1~50%為烯基。X1 為氫原子或烷基。a1、b1、c1為滿足0.1≦a1≦1、0≦b1≦0.75、0≦c1≦0.1，且a1+b1+c1=1之數。) (B)下述平均單位式(2)所示之有機聚矽氧烷：相對於(A)成分100質量份為0~5,000質量份，
Figure 02_image003
(式中，R2 可為相同或相異之取代或未取代之脂肪族一價烴基，全部R2 之中0.01~25莫耳%為烯基。a2、b2為滿足0.33≦a2≦0.999、0.001≦b2≦0.67，且a2+b2=1之正數。) (C)下述平均組成式(3)所示之1分子中至少具有2個Si-H鍵之有機氫聚矽氧烷：相對於(A)成分與(B)成分之合計100質量份為1~200質量份，
Figure 02_image005
(式中，R3 為脂肪族不飽和烴基以外之可為相同或相異之取代或未取代之一價烴基。d、e為滿足0.7≦d≦2.1、0.01≦e≦1.0，且0.8≦d+e≦2.7之正數。)， 及， (D)矽氫化反應觸媒：相對於組成物全體並以金屬原子之質量換算成為0.01~500ppm之量。In order to solve the above problems, the present invention provides an addition-curable polysiloxane composition characterized by comprising: (A) an organopolysiloxane represented by the following average unit formula (1),
Figure 02_image001
(In the formula, R1 can be the same or different substituted or unsubstituted aliphatic monovalent hydrocarbon groups, and 0.1~50% of all R1s are alkenyl groups. X1 is a hydrogen atom or an alkyl group. a1, b1, c1 is a number satisfying 0.1≦a1≦1, 0≦b1≦0.75, 0≦c1≦0.1, and a1+b1+c1=1.) (B) Organic polysilicon represented by the following average unit formula (2) Oxane: 0 to 5,000 parts by mass relative to 100 parts by mass of component (A),
Figure 02_image003
(In the formula, R2 can be the same or different substituted or unsubstituted aliphatic monovalent hydrocarbon groups, and 0.01~25 mole% of all R2 are alkenyl groups. a2 and b2 satisfy 0.33≦a2≦0.999, 0.001≦b2≦0.67, and a2+b2=1 positive number.) (C) Organohydrogenpolysiloxane having at least 2 Si-H bonds in one molecule represented by the following average composition formula (3): relative 1 to 200 parts by mass for a total of 100 parts by mass of component (A) and component (B),
Figure 02_image005
(In the formula, R3 is a substituted or unsubstituted monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group, which may be the same or different. d and e satisfy 0.7≦d≦2.1, 0.01≦e≦1.0, and 0.8≦ A positive number of d+e≦2.7.), and, (D) Hydrosilylation reaction catalyst: an amount of 0.01 to 500 ppm in terms of the mass of metal atoms relative to the entire composition.

由此種本發明之加成硬化型聚矽氧組成物所構成之硬化物由於硬化快速、高透光率、且高溫耐久性優異，故有用作為光反射材料，例如，發光裝置用，尤其係有用作為發光二極體用之密封材料。The cured product composed of the addition-curable polysiloxane composition of the present invention is useful as a light-reflecting material, for example, for light-emitting devices, especially for Useful as a sealing material for light-emitting diodes.

又，前述(A)成分中，前述平均單位式(1)中之R1 係以包含碳數1~3烷基者為佳。Also, in the aforementioned (A) component, R in the aforementioned average unit formula (1) is preferably one that includes an alkyl group having 1 to 3 carbon atoms.

若為此種者，可取得耐熱性及硬化性更加優異之硬化物。In such a case, a cured product having more excellent heat resistance and curability can be obtained.

又，前述(A)成分中，以前述平均單位式(1)中之R1 當中，甲基之含有率為80莫耳%以上，剩餘係乙烯基為佳。Also, in the above-mentioned component (A), among R1 in the above-mentioned average unit formula (1), the content of methyl group is 80 mol% or more, and the remainder is preferably vinyl group.

若為此種者，可取得耐熱性及硬化性更加優異之硬化物。In such a case, a cured product having more excellent heat resistance and curability can be obtained.

又，相對於(A)成分與(B)成分之合計100質量份，以更含有(E)含有環氧基之有機矽烷化合物，及，有機聚矽氧烷之任一者或該兩者0.01~3質量份為佳。Also, with respect to the total of 100 parts by mass of the components (A) and (B), further contain (E) an epoxy group-containing organosilane compound, and either one or both of the organopolysiloxane by 0.01 ~3 parts by mass is better.

藉由如此般作成包含(E)成分者，可使接著性提升。Adhesiveness can be improved by making it contain (E)component in this way.

並且，本發明提供一種半導體裝置，其特徵為藉由如上述之加成硬化型聚矽氧組成物之硬化物被覆半導體元件者。Furthermore, the present invention provides a semiconductor device characterized in that a semiconductor element is coated with a cured product of the above-mentioned addition-curable polysiloxane composition.

若為此種半導體裝置，由於係由如上述般硬化快速、高透光率，且高溫耐久性優異之硬化物所構成，故會成為信賴性優異之半導體裝置。 [發明之效果]Such a semiconductor device can be a highly reliable semiconductor device because it is composed of a cured product that hardens quickly, has high light transmittance, and is excellent in high-temperature durability as described above. [Effect of Invention]

由本發明之加成硬化型聚矽氧組成物所構成之硬化物，由於硬化快速、高透光率、且高溫耐久性優異，故有用作為光反射材料，例如，發光裝置用，尤其係發光二極體用之密封材料。The cured product composed of the addition-curable polysiloxane composition of the present invention is useful as a light-reflecting material, for example, for light-emitting devices, especially for light-emitting diodes, due to its rapid curing, high light transmittance, and excellent high-temperature durability. Sealing material for polar bodies.

本發明者等對於上述課題經過重複精心研討之結果，發現含有具有特定構造之有機聚矽氧烷之加成硬化型聚矽氧組成物會賦予硬化性、透明性、耐熱性皆優之硬化物，進而完成本發明。As a result of repeated studies on the above-mentioned problems, the inventors of the present invention have found that an addition-curable polysiloxane composition containing an organopolysiloxane having a specific structure can provide a cured product having excellent curability, transparency, and heat resistance. , and then complete the present invention.

即，本發明為一種加成硬化型聚矽氧組成物，其特徵為含有： (A)下述平均單位式(1)所示之有機聚矽氧烷，

Figure 02_image007
(式中，R1 可為相同或相異之取代或未取代之脂肪族一價烴基，全部R1 之中0.1~50%為烯基。X1 為氫原子或烷基。a1、b1、c1為滿足0.1≦a1≦1、0≦b1≦0.75、0≦c1≦0.1，且a1+b1+c1=1之數。) (B)下述平均單位式(2)所示之有機聚矽氧烷：相對於(A)成分100質量份為0~5,000質量份，
Figure 02_image009
(式中，R2 可為相同或相異之取代或未取代之脂肪族一價烴基，全部R2 之中0.01~25莫耳%為烯基。a2、b2為滿足0.33≦a2≦0.999、0.001≦b2≦0.67，且a2+b2=1之正數。) (C)下述平均組成式(3)所示之1分子中至少具有2個Si-H鍵之有機氫聚矽氧烷：相對於(A)成分與(B)成分之合計100質量份為1~200質量份，
Figure 02_image011
(式中，R3 為脂肪族不飽和烴基以外之可為相同或相異之取代或未取代之一價烴基。d、e為滿足0.7≦d≦2.1、0.01≦e≦1.0，且0.8≦d+e≦2.7之正數。)， 及， (D)矽氫化反應觸媒：相對於組成物全體並以金屬原子之質量換算成為0.01~500ppm之量。That is, the present invention is an addition-curable polysiloxane composition characterized by containing: (A) an organopolysiloxane represented by the following average unit formula (1),
Figure 02_image007
(In the formula, R1 can be the same or different substituted or unsubstituted aliphatic monovalent hydrocarbon groups, and 0.1~50% of all R1s are alkenyl groups. X1 is a hydrogen atom or an alkyl group. a1, b1, c1 is a number satisfying 0.1≦a1≦1, 0≦b1≦0.75, 0≦c1≦0.1, and a1+b1+c1=1.) (B) Organic polysilicon represented by the following average unit formula (2) Oxane: 0 to 5,000 parts by mass relative to 100 parts by mass of component (A),
Figure 02_image009
(In the formula, R2 can be the same or different substituted or unsubstituted aliphatic monovalent hydrocarbon groups, and 0.01~25 mole% of all R2 are alkenyl groups. a2 and b2 satisfy 0.33≦a2≦0.999, 0.001≦b2≦0.67, and a2+b2=1 positive number.) (C) Organohydrogenpolysiloxane having at least 2 Si-H bonds in one molecule represented by the following average composition formula (3): relative 1 to 200 parts by mass for a total of 100 parts by mass of component (A) and component (B),
Figure 02_image011
(In the formula, R3 is a substituted or unsubstituted monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group, which may be the same or different. d and e satisfy 0.7≦d≦2.1, 0.01≦e≦1.0, and 0.8≦ A positive number of d+e≦2.7.), and, (D) Hydrosilylation reaction catalyst: an amount of 0.01 to 500 ppm in terms of the mass of metal atoms relative to the entire composition.

以下，詳細說明關於本發明，但本發明並非係受到該等所限定者。尚且，本說明書中，黏度係藉由旋轉黏度計進行測量之値。Hereinafter, the present invention will be described in detail, but the present invention is not limited thereto. Also, in this specification, the viscosity is a value measured by a rotational viscometer.

＜加成硬化型聚矽氧組成物＞ 本發明之加成硬化型聚矽氧組成物含有下述之(A)~(D)成分而成。以下，詳細說明關於各成分。＜Addition hardening polysiloxane composition＞ The addition-curable polysiloxane composition of the present invention contains the following components (A)~(D). Hereinafter, each component will be described in detail.

[(A)成分] (A)成分為下述平均單位式(1)所示之有機聚矽氧烷。

Figure 02_image013
(式中，R1 可為相同或相異之取代或未取代之脂肪族一價烴基，全部R1 之中0.1~50%為烯基。X1 為氫原子或烷基。a1、b1、c1為滿足0.1≦a1≦1、0≦b1≦0.75、0≦c1≦0.1，且a1+b1+c1=1之數。)[Component (A)] Component (A) is an organopolysiloxane represented by the following average unit formula (1).
Figure 02_image013
(In the formula, R1 can be the same or different substituted or unsubstituted aliphatic monovalent hydrocarbon groups, and 0.1~50% of all R1s are alkenyl groups. X1 is a hydrogen atom or an alkyl group. a1, b1, c1 is a number satisfying 0.1≦a1≦1, 0≦b1≦0.75, 0≦c1≦0.1, and a1+b1+c1=1.)

作為R1 中之烯基，較佳例示如乙烯基、烯丙基、丁烯基、戊烯基、己烯基，以乙烯基為特佳。R1 之中，烯基之含有率為0.1~50莫耳%，較佳為0.1~30莫耳%，特佳為0.3~20莫耳%。若未滿0.1莫耳%，組成物之硬化性變得不充足，若超過50莫耳%時則硬化物變脆。The alkenyl in R 1 is preferably exemplified by vinyl, allyl, butenyl, pentenyl, and hexenyl, and vinyl is particularly preferred. In R 1 , the alkenyl group content is 0.1-50 mol%, preferably 0.1-30 mol%, particularly preferably 0.3-20 mol%. If it is less than 0.1 mol %, the curability of the composition will be insufficient, and if it exceeds 50 mol %, the cured product will become brittle.

又，作為R1 中之烯基以外之鍵結於矽原子之有機基，可例示如甲基、乙基、丙基、丁基、戊基、己基、庚基等之烷基；氯甲基、3-氯丙基、3,3,3-三氟丙基等之鹵素化烷基取代或未取代之脂肪族一價烴基，其中在耐熱性之面上以甲基為最佳。R1 之中，作為該等之烯基以外之鍵結於矽原子之有機基之含有率，若為20莫耳%以上，由於能賦予安定之耐熱性而為佳，較佳為40莫耳%以上。Also, as an organic group bonded to a silicon atom other than an alkenyl group in R, examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc.; chloromethyl , 3-chloropropyl, 3,3,3-trifluoropropyl and other halogenated alkyl-substituted or unsubstituted aliphatic monovalent hydrocarbon groups, among which methyl is the best in terms of heat resistance. In R 1 , as the content rate of the organic group bonded to the silicon atom other than the alkenyl group, if it is 20 mole % or more, since it can impart stable heat resistance, it is preferable, and it is more preferably 40 mole. %above.

(A)成分中，上述平均單位式(1)中之R1 為包含碳數1~3之烷基者時，由於可取得耐熱性及硬化性優異之硬化物，故為特佳。In the component (A), when R 1 in the above-mentioned average unit formula (1) is an alkyl group having 1 to 3 carbon atoms, it is particularly preferable because a cured product having excellent heat resistance and curability can be obtained.

又，(A)成分中，在上述平均單位式(1)中之R1 之中，甲基之含有率為80莫耳%以上，剩餘為乙烯基時，由於可取得耐熱性及硬化性優異之硬化物，故為特佳。In addition, in the component (A), among R1 in the above-mentioned average unit formula (1), the content of the methyl group is 80 mol% or more, and when the remainder is a vinyl group, it is excellent in heat resistance and curability. The hardened product, so it is especially good.

X1 為氫原子或烷基，作為該烷基，可舉出如與作為R1 所例示者為相同之基，尤其係以甲基或乙基為佳。X 1 is a hydrogen atom or an alkyl group, and examples of the alkyl group include the same groups as exemplified for R 1 , particularly preferably a methyl group or an ethyl group.

a1為0.1~1，b1為0~0.75，c1為0~0.1，a1+b1+c1為1。a1、b1及c1在上述範圍外時，取得之硬化物之硬度及／或強度會變得不充足。a1 is 0.1~1, b1 is 0~0.75, c1 is 0~0.1, and a1+b1+c1 is 1. When a1, b1, and c1 are outside the above-mentioned ranges, the hardness and/or strength of the cured product obtained will become insufficient.

a1較佳為0.15~0.9，特佳為0.2~0.8，b1較佳為0~0.5，特佳為0~0.4，c1較佳為0~0.05。Preferably a1 is 0.15-0.9, particularly preferably 0.2-0.8, b1 is preferably 0-0.5, particularly preferably 0-0.4, and c1 is preferably 0-0.05.

(A)成分之分子量並無限定，以藉由使用THF溶劑之凝膠滲透層析(GPC)測量而得之以標準聚苯乙烯換算之重量平均分子量(Mw)在500~20,000為佳，較佳為700~15,000，特佳為1,000~10,000。(A) The molecular weight of the component is not limited, and the weight average molecular weight (Mw) obtained by standard polystyrene conversion measured by gel permeation chromatography (GPC) using THF solvent is preferably 500~20,000. The best is 700~15,000, and the best is 1,000~10,000.

[(B)成分] (B)成分為下述平均單位式(2)所示之有機聚矽氧烷。

Figure 02_image015
(式中，R2 可為相同或相異之取代或未取代之脂肪族一價烴基，全部R2 之中0.01~25莫耳%為烯基。a2、b2為滿足0.33≦a2≦0.999、0.001≦b2≦0.67，且a2+b2=1之正數。)[(B) Component] (B) Component is an organopolysiloxane represented by the following average unit formula (2).
Figure 02_image015
(In the formula, R2 can be the same or different substituted or unsubstituted aliphatic monovalent hydrocarbon groups, and 0.01~25 mole% of all R2 are alkenyl groups. a2 and b2 satisfy 0.33≦a2≦0.999, 0.001≦b2≦0.67, and a2+b2=1 positive number.)

R2 可舉出如與(A)成分中之R1 相同者，作為R2 中之烯基，較佳可例示如乙烯基、烯丙基、丁烯基、戊烯基、己烯基，以乙烯基為特佳。R2 之中，烯基之含有率為0.01~25莫耳%，較佳為0.1~20莫耳%，特佳為0.3~20莫耳%。若未滿0.01莫耳%，組成物之硬化性變得不充足，超過25莫耳%時，硬化物變脆。R 2 can be exemplified as the same as R 1 in the (A) component, as alkenyl in R 2 , preferably vinyl, allyl, butenyl, pentenyl, hexenyl can be exemplified, Vinyl is especially preferred. In R 2 , the alkenyl group content is 0.01-25 mol%, preferably 0.1-20 mol%, particularly preferably 0.3-20 mol%. If it is less than 0.01 mol%, the curability of the composition becomes insufficient, and if it exceeds 25 mol%, the cured product becomes brittle.

又，作為R2 中之烯基以外之鍵結於矽原子之有機基，可例示如甲基、乙基、丙基、丁基、戊基、己基、庚基等之烷基；經氯甲基、3-氯丙基、3,3,3-三氟丙基等之鹵化烷基取代或未取代之脂肪族一價烴基，其中在耐熱性之面上，以甲基為最佳。R2 之中，作為該等脂肪族一價烴基之含有率，若在20莫耳%以上，由於可賦予安定耐熱性而為佳，較佳為40莫耳%以上。Also, as an organic group bonded to a silicon atom other than an alkenyl group in R , examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc.; Halogenated alkyl, 3-chloropropyl, 3,3,3-trifluoropropyl and other aliphatic monovalent hydrocarbon groups substituted or unsubstituted, among which methyl is the best in terms of heat resistance. In R 2 , the content of the aliphatic monovalent hydrocarbon group is preferably at least 20 mol%, since stability and heat resistance can be imparted, and is preferably at least 40 mol%.

a2為0.33~0.999，較佳為0.90~0.998，更佳為0.956~0.997。b2為0.001~0.67，較佳為0.002~0.10，更佳為0.003~0.044。a2及b2在上述範圍外時，取得之硬化物之硬度及／或強度會變得不充足。a2 is 0.33-0.999, preferably 0.90-0.998, more preferably 0.956-0.997. b2 is 0.001-0.67, preferably 0.002-0.10, more preferably 0.003-0.044. When a2 and b2 are outside the above-mentioned ranges, the hardness and/or strength of the obtained hardened product will become insufficient.

上述(B)成分之配合量相對於(A)成分100質量份為0~5,000質量份，較佳為10~3000質量份，更佳為20~1,000質量份。配合量超過5,000質量份時，無法取得充足硬度及／或強度。The compounding quantity of the said (B) component is 0-5,000 mass parts with respect to 100 mass parts of (A) components, Preferably it is 10-3000 mass parts, More preferably, it is 20-1,000 mass parts. When the compounding quantity exceeds 5,000 mass parts, sufficient hardness and/or intensity|strength cannot be acquired.

[(C)成分] (C)成分為下述平均組成式(3)所示之有機氫聚矽氧烷。

Figure 02_image017
(式中，R3 為脂肪族不飽和烴基以外之可為相同或相異之取代或未取代之一價烴基。d、e為滿足0.7≦d≦2.1、0.01≦e≦1.0，且0.8≦d+e≦2.7之正數。)[Component (C)] Component (C) is an organohydrogenpolysiloxane represented by the following average composition formula (3).
Figure 02_image017
(In the formula, R3 is a substituted or unsubstituted monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group, which may be the same or different. d and e satisfy 0.7≦d≦2.1, 0.01≦e≦1.0, and 0.8≦ A positive number of d+e≦2.7.)

(C)成分在25℃下之黏度係以0.5~1,000mPa・s為佳，以1~500mPa・s為較佳。The viscosity of component (C) at 25°C is preferably 0.5~1,000mPa·s, more preferably 1~500mPa·s.

R3 所示之一價烴基之碳原子數係以1~20為佳，較佳為1~10，作為此種烴基，可舉出如甲基、乙基、丙基、異丙基、丁基、tert-丁基、己基等之烷基、環己基等之環烷基等之飽和烴基、苯基、甲苯基等之芳基、苄基、苯基乙基等之芳烷基、3,3,3-三氟丙基等之鹵素取代烴基、氰基取代烴基等，以甲基為佳。The number of carbon atoms of the monovalent hydrocarbon group represented by R3 is preferably 1 to 20, preferably 1 to 10. Examples of such hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, etc. tert-butyl, alkyl such as hexyl, saturated hydrocarbon such as cyclohexyl, such as cyclohexyl, aryl such as phenyl, tolyl, aralkyl such as benzyl, phenylethyl, etc., 3, A halogen-substituted hydrocarbon group such as 3,3-trifluoropropyl, a cyano-substituted hydrocarbon group, etc., is preferably methyl.

從與(A)成分之相溶性及硬化物之物性等之觀點，以鍵結於矽原子之全部R3 與H(氫原子)之中20莫耳%以上為甲基者為佳，以50莫耳%以上為甲基者為較佳。From the viewpoint of the compatibility with component (A) and the physical properties of the hardened product, among all the R 3 and H (hydrogen atoms) bonded to the silicon atom, 20 mol% or more are methyl groups, and 50 More than mol% is methyl.

(C)成分為1分子中至少具有2個，較佳3個以上之Si-H鍵(即，鍵結於矽原子之氫原子)，在25℃下之黏度係以0.5~1,000mPa・s為佳，以1~500mPa・s為較佳。(C) Component has at least 2, preferably 3 or more Si-H bonds (that is, hydrogen atoms bonded to silicon atoms) in one molecule, and the viscosity at 25°C is 0.5~1,000mPa·s Preferably, 1~500mPa·s is the best.

作為(C)成分之矽氧烷鏈之構造，並非係受到特別限定者，以直鏈狀或環狀之有機氫聚矽氧烷為佳。The structure of the siloxane chain as the component (C) is not particularly limited, and linear or cyclic organohydrogenpolysiloxane is preferable.

d、e為滿足0.7≦d≦2.1、0.01≦e≦1.0，且0.8≦d+e≦2.7之正數，d、e上述範圍外時，取得之硬化物之硬度及／或強度會變得不充足。d and e are positive numbers satisfying 0.7≦d≦2.1, 0.01≦e≦1.0, and 0.8≦d+e≦2.7. If d and e are outside the above range, the hardness and/or strength of the hardened product obtained will become insufficient adequate.

d較佳為滿足1.0≦d≦1.8，e較佳為滿足0.02≦e≦1.0，更佳為滿足0.10≦e≦1.0，d+e較佳為滿足1.01≦d+e≦2.4，更佳為滿足1.6≦d+e≦2.2之正數。d preferably satisfies 1.0≦d≦1.8, e preferably satisfies 0.02≦e≦1.0, more preferably satisfies 0.10≦e≦1.0, d+e preferably satisfies 1.01≦d+e≦2.4, more preferably Satisfy the positive number of 1.6≦d+e≦2.2.

(C)成分之配合量相對於(A)成分100質量份為1~200質量份，較佳為5~80質量份，配合量若未滿1質量份，則硬化性變得不充足，超過200質量份時則無法取得充分之硬度及／或強度。The compounding quantity of (C) component is 1-200 mass parts with respect to 100 mass parts of (A) component, Preferably it is 5-80 mass parts. At 200 parts by mass, sufficient hardness and/or strength cannot be obtained.

(C)成分當中，以(C)成分中之矽原子鍵結氫原子(即，SiH基)對(A)成分及(B)成分中之烯基合計的莫耳比成為0.5~5莫耳／莫耳，尤其係成為1~3莫耳／莫耳之量來配合為較佳。Among the components (C), the molar ratio of the silicon atom in the component (C) bonded to the hydrogen atom (that is, SiH group) to the total alkenyl group in the component (A) and the component (B) is 0.5~5 mol / Mole, especially the amount of 1~3 Mole/Mole is better.

[(D)成分] (D)成分之矽氫化反應觸媒係促進(A)成分及(B)成分中之烯基，與(C)成分中之矽原子鍵結氫原子的矽氫化反應用之觸媒。作為此種(D)成分，可例示如鉑系觸媒、銠系觸媒、鈀系觸媒，由於鉑系觸媒能顯著地促進本組成物之硬化，故以鉑系觸媒為佳。作為該鉑系觸媒，可例示如鉑微粉末、氯化鉑酸、氯化鉑酸之醇溶液、鉑-烯基矽氧烷錯合物、鉑-烯烴錯合物、鉑-羰基錯合物，尤其係以鉑-烯基矽氧烷錯合物為佳。作為烯基矽氧烷，可例示如1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷、1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷、該等烯基矽氧烷之甲基之一部分被乙基、苯基等之基所取代之烯基矽氧烷、該等烯基矽氧烷之乙烯基被烯丙基、己烯基等之基所取代之烯基矽氧烷。尤其，由於該鉑-烯基矽氧烷錯合物之安定性良好，故以1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷為佳。[(D) ingredient] (D) The hydrosilylation reaction catalyst of the component is a catalyst for promoting the hydrosilylation reaction of the alkenyl group in the (A) component and (B) component, and the hydrogen atom bonded to the silicon atom in the (C) component. Such (D) component includes, for example, platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. Platinum-based catalysts are preferred because they can remarkably accelerate the hardening of the present composition. Examples of the platinum catalyst include fine platinum powder, chloroplatinic acid, alcohol solution of chloroplatinic acid, platinum-alkenyl siloxane complex, platinum-olefin complex, platinum-carbonyl complex Compounds, especially platinum-alkenyl siloxane complexes are preferred. Examples of alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3, 5,7-Tetravinylcyclotetrasiloxane, alkenylsiloxanes in which part of the methyl group of these alkenylsiloxanes is replaced by ethyl, phenyl, etc. groups, these alkenylsiloxanes Alkenyl siloxane in which the vinyl group is substituted by allyl, hexenyl, etc. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because the platinum-alkenylsiloxane complex has good stability.

又，為了提升該鉑-烯基矽氧烷錯合物之安定性，以對該錯合物添加1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷、1,3-二烯丙基-1,1,3,3-四甲基二矽氧烷、1,3-二乙烯基-1,3-二甲基-1,3-二苯基二矽氧烷、1,3-二乙烯基-1,1,3,3-四苯基二矽氧烷、1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷等之烯基矽氧烷或二甲基矽氧烷寡聚物等之有機矽氧烷寡聚物為佳，尤其係以添加烯基矽氧烷為佳。Also, in order to improve the stability of the platinum-alkenylsiloxane complex, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-diphenyldisiloxane Oxane, 1,3-divinyl-1,1,3,3-tetraphenyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinyl Alkenyl siloxanes such as cyclotetrasiloxane or organosiloxane oligomers such as dimethyl siloxane oligomers are preferable, and it is especially preferable to add alkenyl siloxanes.

(D)成分之含量只要係會促進本組成物之硬化(矽氫化反應)即可，具體而言，相對於本組成物，以本成分中之金屬原子以質量單位計成為0.01~500ppm範圍內之量為佳，更以成為0.05~100ppm之範圍內之量為佳，尤其係以成為0.01~50ppm範圍內之量為佳。(D)成分之含量在上述範圍外時，不僅無法取得充分硬化性，且會引起著色等之問題，以及並不經濟。(D) The content of the component is sufficient as long as it promotes the hardening (hydrosilylation reaction) of the composition. Specifically, the metal atoms in the composition are in the range of 0.01 to 500 ppm by mass. The amount is preferable, more preferably in the range of 0.05 to 100 ppm, especially preferably in the range of 0.01 to 50 ppm. When the content of the component (D) is out of the above-mentioned range, not only sufficient curability cannot be obtained, but also problems such as coloring may be caused, and it is not economical.

[(E)成分] 本發明之加成硬化型聚矽氧組成物亦可更包含：含有環氧基之有機矽烷化合物或有機聚矽氧烷作為(E)成分。(E)成分為提升對於鍍銀、鋁、聚酞醯胺、氧化鋁陶瓷、聚伸環已基二亞甲基對苯二甲酸酯之接著性用之接著助劑，作為環氧基，具體地例示時，可舉出如3-環氧丙氧基丙基、4-環氧丙氧基丁基等之環氧丙氧基烷基；2-(3,4-環氧基環己基)乙基、3-(3,4-環氧基環己基)丙基等之環氧基環己基烷基；4-環氧乙烷基丁基、8-環氧乙烷基辛基等之環氧乙烷基烷基等之含環氧基之一價有機基。在以下例示該等含有一價有機基之有機聚矽氧烷及、有機矽烷化合物。

Figure 02_image019
[Component (E)] The addition-curable polysiloxane composition of the present invention may further include: an epoxy group-containing organosilane compound or organopolysiloxane as component (E). (E) The component is an adhesive aid for improving the adhesion of silver plating, aluminum, polyphthalamide, alumina ceramics, and polycyclohexyl dimethylene terephthalate, as an epoxy group, When specifically exemplified, glycidoxyalkyl groups such as 3-glycidoxypropyl, 4-glycidoxybutyl, etc.; 2-(3,4-epoxycyclohexyl) ) ethyl, 3-(3,4-epoxycyclohexyl) propyl, etc. epoxycyclohexylalkyl; 4-oxiranylbutyl, 8-oxiranyloctyl, etc. A valent organic group containing an epoxy group such as an oxiranyl alkyl group. These monovalent organic group-containing organopolysiloxane and organosilane compounds are exemplified below.
Figure 02_image019

相對於(A)成分及(B)成分之合計100質量份，(E)成分之含量係以0.01~3質量份為佳，較佳為0.03~2質量份，更佳為0.1~1質量份。若在此種範圍內，可不對耐熱性造成影響而取得良好接著性。The content of component (E) is preferably 0.01 to 3 parts by mass, more preferably 0.03 to 2 parts by mass, more preferably 0.1 to 1 part by mass, based on 100 parts by mass of the total of components (A) and (B) . If it exists in such a range, favorable adhesiveness can be acquired without affecting heat resistance.

[任意成分] 本組成物中，作為其他任意成分，亦可含有乙炔基環己醇、2-甲基-3-丁炔-2-醇、3,5-二甲基-1-己炔-3-醇、2-苯基-3-丁炔-2-醇等之炔醇；3-甲基-3-戊烯-1-炔、3,5-二甲基-3己烯-1-炔等之烯炔化合物；1,3,5,7-四甲基-1,3,5,7-四乙烯基環四矽氧烷、1,3,5,7-四甲基-1,3,5,7-四己烯基環四矽氧烷、苯並***等之反應抑制劑。此反應抑制劑之含量並無限定，相對於(A)成分與(B)成分之合計100質量份，以在0.0001~5質量份之範圍內為佳。[optional ingredient] In this composition, as other optional components, ethynylcyclohexanol, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, Alkyne alcohols such as 2-phenyl-3-butyn-2-ol; alkenes such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne Alkyne compounds; 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5, Reaction inhibitor of 7-tetrahexenylcyclotetrasiloxane, benzotriazole, etc. The content of this reaction inhibitor is not limited, but it is preferably in the range of 0.0001 to 5 parts by mass with respect to 100 parts by mass of the total of (A) component and (B) component.

又，本組成物亦可含有提升該接著性用之接著賦予劑。作為該接著賦予劑，以一分子中至少具有1個，較佳為2個以上鍵結於矽原子之烷氧基的有機矽化合物為佳。作為該烷氧基，可例示如甲氧基、乙氧基、丙氧基、丁氧基、甲氧基乙氧基，尤其係以甲氧基為佳。又，作為此有機矽化合物之鍵結於矽原子之烷氧基以外之基，可舉出如作為R1 等所例示之前述烷基、前述烯基、前述芳基、前述芳烷基、前述鹵化烷基等之取代或未取代之一價烴基；3-甲基丙烯醯氧基丙基等之含丙烯醯基之一價有機基；氫原子。具體地可例示如含(甲基)丙烯醯基之矽烷耦合劑等之矽烷耦合劑或其部分水解縮合物(矽烷耦合劑之寡聚物)等。In addition, this composition may contain an adhesive imparting agent for improving the adhesiveness. As the adhesive imparting agent, an organosilicon compound having at least one, preferably two or more, alkoxy groups bonded to a silicon atom in one molecule is preferable. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and methoxyethoxy, and methoxy is particularly preferred. In addition, examples of the group other than the alkoxy group bonded to the silicon atom of the organosilicon compound include the aforementioned alkyl group, the aforementioned alkenyl group, the aforementioned aryl group, the aforementioned aralkyl group, the aforementioned A substituted or unsubstituted valent hydrocarbon group such as a halogenated alkyl group; a valent organic group containing an acryl group such as a 3-methacryloxypropyl group; a hydrogen atom. Specifically, silane coupling agents such as (meth)acryloyl group-containing silane coupling agents or their partial hydrolyzed condensates (oligomers of silane coupling agents) and the like can be exemplified.

更具體地可例示如，3-甲基丙烯醯氧基丙基三甲氧基矽烷等之矽烷化合物；一分子中分別至少具有各1個鍵結於矽原子之烯基或鍵結於矽原子之氫原子、及鍵結於矽原子之烷氧基的矽氧烷化合物、至少具有1個鍵結於矽原子之烷氧基的矽烷化合物，或矽氧烷化合物與一分子中分別至少具有各1個鍵結於矽原子之羥基與鍵結於矽原子之烯基之矽氧烷化合物的混合物、甲基聚矽酸酯、乙基聚矽酸酯、含環氧基之乙基聚矽酸酯。More specifically, for example, silane compounds such as 3-methacryloxypropyltrimethoxysilane; one molecule has at least one alkenyl group bonded to a silicon atom or an alkenyl group bonded to a silicon atom. A siloxane compound having a hydrogen atom and an alkoxy group bonded to a silicon atom, a silane compound having at least one alkoxy group bonded to a silicon atom, or a siloxane compound and a siloxane compound having at least 1 of each A mixture of siloxane compounds with a hydroxyl group bonded to a silicon atom and an alkenyl group bonded to a silicon atom, methyl polysilicate, ethyl polysilicate, epoxy-containing ethyl polysilicate .

該接著賦予劑係以低黏度液狀為佳，其黏度並無限定，以25℃下在1~500mPa・s之範圍內為佳。The adhesive imparting agent is preferably in the form of a low-viscosity liquid, and its viscosity is not limited, but it is preferably in the range of 1 to 500 mPa·s at 25°C.

又，上述組成物中，該接著賦予劑之含量並無限定，相對於(A)成分100質量份，以0.01~10質量份為佳。In addition, in the above-mentioned composition, the content of the adhesive imparting agent is not limited, but it is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A).

又，本組成物中，作為其他任意之成分，亦可含有二氧化矽、玻璃、氧化鋁、氧化鋅等之無機質填充劑；聚甲基丙烯酸酯樹脂等之有機樹脂微粉末；耐熱劑、染料、顏料、難燃性賦予劑、溶劑等。In addition, this composition may also contain inorganic fillers such as silicon dioxide, glass, aluminum oxide, and zinc oxide; organic resin fine powder such as polymethacrylate resin; heat-resistant agents, dyes, etc., as other optional components. , pigments, flame retardancy imparting agents, solvents, etc.

又，本組成物係以硬化後形成JIS規定之硬度使用硬度計A(Durometer A)為10以上，尤其係30~90之硬化物者為佳。In addition, this composition is preferably a hardened product with a hardness of 10 or more, especially 30 to 90, with a hardness specified by JIS after hardening.

又，本組成物為了賦予具有被組成物之硬化物所被覆之半導體元件之半導體裝置充分之信賴性，故以硬化而得之硬化物之可見光(589nm)中之折射率(25℃)在1.4以上，硬化物之透光率(25℃)在80%以上為佳。In addition, in order to impart sufficient reliability to a semiconductor device having a semiconductor element covered with a cured product of the composition, the cured product obtained by curing has a refractive index (25°C) of 1.4 in visible light (589 nm). Above, the light transmittance (25°C) of the cured product is better than 80%.

尚且，該折射率係可藉由例如阿貝式折射率計進行測量。此時，藉由改變阿貝式折射率計中之光源波長，而可測量任意波長之折射率。又，此透光率係例如可藉由利用分光光度計測量光徑長2.0mm之硬化物來求得。Also, the refractive index can be measured by, for example, an Abbe type refractometer. At this time, the refractive index of any wavelength can be measured by changing the wavelength of the light source in the Abbe refractometer. In addition, this light transmittance can be obtained by measuring, for example, a cured product with an optical path length of 2.0 mm using a spectrophotometer.

又，使本組成物硬化而得之硬化物在200nm~250nm波長中之紫外線透過率(25℃)係以10%以下為佳。此係為了在藉由本組成物之硬化物覆蓋半導體元件而成之半導體裝置在受到200nm~250nm短波長之紫外線時，防止構成該半導體裝置之材料劣化。該紫外線透過率係例如可藉由利用分光光度計測量光徑長2.0mm之硬化物來求得。In addition, the UV transmittance (25°C) of the cured product obtained by curing the composition is preferably 10% or less at a wavelength of 200nm to 250nm. This is to prevent the deterioration of the material constituting the semiconductor device when the semiconductor device formed by covering the semiconductor element with the cured product of this composition is exposed to short-wavelength ultraviolet rays of 200nm to 250nm. The ultraviolet transmittance can be obtained, for example, by measuring a cured product with an optical path length of 2.0 mm using a spectrophotometer.

本組成物係會在室溫或藉由加熱而使硬化進行，但為了迅速硬化，以進行加熱為佳。作為此加熱溫度，以50~200℃之範圍內為佳。This composition can be hardened at room temperature or by heating, but heating is preferred for rapid hardening. As this heating temperature, it is preferable to be in the range of 50-200 degreeC.

使本組成物硬化而得之硬化物可取得彈性體狀，例如膠狀，或柔軟橡膠狀乃至於具有彈性之樹脂狀。此種本組成物係能使用作為電氣・電子用之接著劑、封裝劑(potting agent)、保護塗覆劑、底部填充劑，尤其係由於透光率為高，故適宜作為光學用途之半導體元件之接著劑、封裝劑、保護塗覆劑、底部填充劑。The hardened product obtained by hardening the composition can be in the form of an elastomer, such as a gel, or a soft rubber or even a resin with elasticity. This kind of composition can be used as adhesives, potting agents, protective coatings, and underfills for electrical and electronic applications, and is especially suitable for semiconductor components for optical applications because of its high light transmittance. Adhesives, encapsulants, protective coatings, and underfills.

本發明更提供一種半導體裝置，其係使用此種本發明之加成硬化型聚矽氧組成物。The present invention further provides a semiconductor device using the addition-hardening polysiloxane composition of the present invention.

以下，參照圖式說明關於本發明之半導體裝置，但本發明並非係受限於該等者。Hereinafter, a semiconductor device related to the present invention will be described with reference to the drawings, but the present invention is not limited thereto.

圖1為展示本發明之半導體裝置之一例(此情況為LED(發光二極體))的示意剖面圖。FIG. 1 is a schematic cross-sectional view showing an example of a semiconductor device of the present invention (LED (light emitting diode) in this case).

本發明之半導體裝置1係為在已形成鍍銀基板2之封裝3上，半導體晶片4已被晶片接合，該半導體晶片4係藉由接合線5而被引線接合。In the semiconductor device 1 of the present invention, a semiconductor chip 4 is chip-bonded on a package 3 on which a silver-plated substrate 2 has been formed, and the semiconductor chip 4 is wire-bonded by a bonding wire 5 .

且，藉由上述本發明之加成硬化型聚矽氧組成物之硬化物6而被覆半導體晶片4。And, the semiconductor wafer 4 is covered with the cured product 6 of the addition-curable polysiloxane composition of the present invention.

半導體晶片4之被覆係藉由塗布上述本發明之加成硬化型聚矽氧組成物6並藉由加熱而使加成硬化型聚矽氧組成物6硬化來實施。又，當然亦可藉由公知之硬化方法在其他公知之硬化條件下使其硬化。The semiconductor wafer 4 is coated by applying the above-mentioned addition-curable polysiloxane composition 6 of the present invention and curing the addition-curable polysiloxane composition 6 by heating. Also, of course, it can also be cured by a known curing method under other known curing conditions.

尚且，於此情況，從作成不易受到外部應力之影響，又極力抑制灰塵等之附著的觀點，加成硬化型聚矽氧組成物6係以藉由硬化而形成JIS規定之硬度使用硬度計A測量為30以上之硬化物者為佳。Also, in this case, from the standpoint of making it less susceptible to external stress and suppressing the adhesion of dust as much as possible, the addition-curable polysiloxane composition 6 is hardened to a hardness specified by JIS using a durometer A It is better to measure more than 30 hardened objects.

本發明之加成硬化型聚矽氧組成物由於會形成高透光率、對基材之密著性高，且耐龜裂性優異，耐熱後之硬度變化為小之硬化物，故使用此種本發明之組成物之本發明之半導體裝置成為信賴性優異者，特別適宜作為二極體、LED等。 [實施例]The addition-curable polysiloxane composition of the present invention can form a cured product with high light transmittance, high adhesion to the substrate, excellent crack resistance, and small change in hardness after heat resistance, so it is used The semiconductor device of the present invention having such a composition of the present invention is excellent in reliability, and is particularly suitable as a diode, LED, and the like. [Example]

以下，展示實施例與比較例來具體地說明本發明，但本發明並非係受到下述實施例等所限制者。Hereinafter, although an Example and a comparative example are shown and this invention is concretely demonstrated, this invention is not limited by the following Examples etc.

尚且，實施例中之黏度係使用旋轉黏度計所測量之在25℃之値，重量平均分子量係藉由使用THF溶劑之凝膠滲透層析(GPC)進行測量而得之以標準聚苯乙烯換算之値。又，加成硬化型聚矽氧組成物、及其硬化物之特性係如以下操作進行評價，並將結果展示於表1。Furthermore, the viscosity in the examples is the value at 25°C measured using a rotational viscometer, and the weight average molecular weight is measured by gel permeation chromatography (GPC) using THF solvent and converted to standard polystyrene The value. Also, the properties of the addition-curable polysiloxane composition and its cured product were evaluated as follows, and the results are shown in Table 1.

[硬化性] 使用阿爾法科技公司製流變儀MDR2000，在120℃下進行測量加成硬化型聚矽氧組成物30分鐘，與結束時相比較，將抵達10%力矩之時間設為T10，將抵達90%力矩之時間設為T90，並評價材料抵達硬化狀態之速度。T10與T90之間之差越小，則達成硬化之時間越快，即顯示硬化性良好。[hardening] Use the rheometer MDR2000 made by Alpha Technology Co., Ltd. to measure the addition hardening polysiloxane composition at 120°C for 30 minutes. Compared with the end time, set the time to reach 10% torque as T10, and reach 90% torque The time is set as T90, and the speed at which the material reaches the hardened state is evaluated. The smaller the difference between T10 and T90, the faster the time to harden, which means good hardenability.

[硬度] 藉由使用熱風循環式烤箱以150℃加熱加成硬化型聚矽氧組成物3小時而製作出硬化物。使用硬度計A硬度計測量此硬化物之硬度。[hardness] The cured product was produced by heating the addition-curable polysiloxane composition at 150° C. for 3 hours using a hot-air circulation oven. The hardness of this hardened product was measured using a durometer A durometer.

[透光率] 測量藉由使用150℃之熱風循環式烤箱加熱加成硬化型聚矽氧組成物3小時使其硬化所製作之硬化物(光徑長2.0mm)在25℃下400nm波長之透光率。[Transmittance] The light transmittance at 400nm wavelength at 25°C of the cured product (optical path length 2.0mm) produced by heating the addition-curable polysiloxane composition in a hot air circulation oven at 150°C for 3 hours to harden was measured.

[耐龜裂性] 將如圖1所示地製作並以150℃×4小時之加熱硬化之封裝放入將{-40℃(30分鐘)、100℃(30分鐘)}作為1循環之熱衝撃試驗機中，以光學顯微鏡觀察經過100循環後之封裝，在硬化物上發現龜裂時評為×，未發現龜裂時評為○，有無龜裂並不明顯時評為△。[crack resistance] Put the package made as shown in Figure 1 and heat hardened at 150°C x 4 hours into a thermal shock tester that uses {-40°C (30 minutes), 100°C (30 minutes)} as a cycle, and The package after 100 cycles was observed with an optical microscope. When cracks were found on the cured product, it was rated as ×, when no cracks were found, it was rated as ○, and when the presence or absence of cracks was not obvious, it was rated as △.

[耐熱性(透明性)] 將上述測量透光率所使用之硬化物更在180℃之熱風循環式烤箱中加熱500小時後，測量25℃下之400nm波長之透光率，並換算成將加熱前之透光率設為100之値來進行評價。[heat resistance (transparency)] After heating the cured product used in the above measurement of light transmittance in a hot air circulation oven at 180°C for 500 hours, measure the light transmittance at 400nm wavelength at 25°C, and convert the light transmittance before heating to A value of 100 is used for evaluation.

[耐熱性(硬度)] [heat resistance (hardness)]

將上述測量硬度所使用之硬化物更在180℃之熱風循環式烤箱中加熱500小時後，使用硬度計A硬度計測量此硬化物之硬度，並換算成將加熱前之硬度設為100之值來進行評價。測量值到達測量極限以上時，當作極限以上。 After heating the hardened object used for the above hardness measurement in a hot air circulation oven at 180°C for 500 hours, measure the hardness of the hardened object with a hardness meter A hardness meter, and convert it into a value with the hardness before heating as 100 to evaluate. When the measured value exceeds the measurement limit, it is deemed to be above the limit.

[實施例1] [Example 1]

混合作為(A)成分之下述平均單位式(I)所示之分枝鏈狀有機聚矽氧烷{性狀=固體狀(25℃)、鍵結於矽原子之全有機基中鍵結於矽原子之乙烯基之含有率=4.0莫耳%、鍵結於矽原子之全有機基中鍵結於矽原子之甲基含有率=96莫耳%、標準聚苯乙烯換算之重量平均分子量=13,000}50質量份，作為(B)成分之分子鏈末端二甲基乙烯基矽氧基封鏈二甲基聚矽氧烷(鍵結於矽原子之乙烯基之含有率=0.6莫耳%)50質量份，作為(C)成分之下述式(II)所示之有機氫聚矽氧烷(黏度5,000mPa‧s)4.5質量份，作為(D)成分之鉑之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物：相對於組成物全體並以鉑金屬之質量換算為20ppm之量，作為反應抑制劑之乙炔基環己醇0.1質量份，作為接著賦予劑之下述構造式(III)所示之化合物0.5質量份，而調製出黏度3,500mPa‧s之加成硬化型聚矽氧組成物。 Mix the branched chain organopolysiloxane represented by the following average unit formula (I) as the component (A) {property = solid (25°C), bonded to the silicon atom in the whole organic group Vinyl group content of silicon atoms = 4.0 mole %, methyl group content of silicon atoms bonded to silicon atoms in all organic groups bonded to silicon atoms = 96 mole %, weight average molecular weight in terms of standard polystyrene = 13,000}50 parts by mass, molecular chain terminal dimethylvinylsiloxy-blocked chain dimethyl polysiloxane as component (B) (content rate of vinyl groups bonded to silicon atoms = 0.6 mol%) 50 parts by mass, organohydrogenpolysiloxane (viscosity 5,000mPa‧s) represented by the following formula (II) as component (C) 4.5 parts by mass, platinum 1,3-diethylene as component (D) Radixyl-1,1,3,3-tetramethyldisiloxane complex: 0.1 mass of ethynylcyclohexanol as a reaction inhibitor in an amount of 20 ppm based on the mass of platinum metal relative to the entire composition parts, and 0.5 parts by mass of a compound represented by the following structural formula (III) as an adhesive imparting agent to prepare an addition-curable polysiloxane composition with a viscosity of 3,500 mPa‧s.

(CH3SiO3/2)0.7((CH3)3SiO1/2)0.236((CH2=C H)(CH3)2SiO1/2)0.064 (I) (CH 3 SiO 3/2 ) 0.7 ((CH 3 ) 3 SiO 1/2 ) 0.236 ((CH 2 =CH)(CH 3 ) 2 SiO 1/2 ) 0.064 (I)

(CH3)3SiO((H)(CH3)SiO)10Si(CH3)3 (II) (CH 3 ) 3 SiO((H)(CH 3 )SiO) 10 Si(CH 3 ) 3 (II)

Figure 108130545-A0305-02-0022-1
Figure 108130545-A0305-02-0022-1

[實施例2] [Example 2]

混合作為(A)成分之下述平均單位式(IV)所示之分枝鏈狀有機聚矽氧烷{性狀=固體狀(25℃)、鍵結於矽原子之全有機基中鍵結於矽原子之乙烯基含有率=4.0莫耳%、鍵結於矽原子之全有機基中鍵結於矽原子之甲基含有率=96莫耳%、重量平均分子量=15,000}50質量份，作為(B)成分之分子鏈末端二甲基乙烯基矽氧基封鏈二甲基聚矽氧烷(黏度5,000mPa‧s、鍵結於矽原子之乙烯基含有率=0.6莫耳%)50質量份，作為(C)成分之上述式(II)所示之有機氫聚矽氧烷5.0質量份，作為(D)成分之鉑之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物：相對於組成物全體並以鉑金屬之質量換算為20ppm之量，作為反應抑制劑之乙炔基環己醇0.1質量份，作為接著賦予劑之下述構造式(V)所示之化合物1.0質量份，而調製出黏度3,500mPa‧s之加成硬化型聚矽氧組成物。 Mix the branched chain organopolysiloxane represented by the following average unit formula (IV) as the component (A) {property = solid (25°C), bonded to the silicon atom in the whole organic group Vinyl group content of silicon atoms = 4.0 mol %, methyl content rate of silicon atoms bonded to silicon atoms in all organic groups bonded to silicon atoms = 96 mol %, weight average molecular weight = 15,000} 50 parts by mass, as (B) Molecular chain terminal dimethylvinylsiloxy-blocked chain dimethyl polysiloxane (viscosity 5,000mPa‧s, content of vinyl groups bonded to silicon atoms = 0.6 mol%) 50 mass Parts, 5.0 parts by mass of organohydrogenpolysiloxane represented by the above formula (II) as component (C), 1,3-divinyl-1,1,3,3-platinum as component (D) Tetramethyldisiloxane complex: an amount of 20 ppm based on the mass of platinum metal relative to the entire composition, 0.1 parts by mass of ethynylcyclohexanol as a reaction inhibitor, and the following structure as an adhesive agent 1.0 parts by mass of the compound represented by formula (V) was used to prepare an addition-hardening polysiloxane composition with a viscosity of 3,500 mPa‧s.

(CH3SiO3/2)0.65((CH3)3SiO1/2)0.286((CH2= CH)(CH3)2SiO1/2)0.064 (IV) (CH 3 SiO 3/2 ) 0.65 ((CH 3 ) 3 SiO 1/2 ) 0.286 ((CH 2 = CH)(CH 3 ) 2 SiO 1/2 ) 0.064 (IV)

Figure 02_image027
Figure 02_image027

[比較例1] 混合下述平均單位式(VI)所示之分枝鏈狀之有機聚矽氧烷{性狀=固體狀(25℃)、鍵結於矽原子之全有機基中鍵結於矽原子之乙烯基含有率=7.4莫耳%、鍵結於矽原子之全有機基中鍵結於矽原子之甲基含有率=92.6莫耳%、重量平均分子量=3,600}50質量份，分子鏈末端二甲基乙烯基矽氧基封鏈二甲基聚矽氧烷(黏度5,000mPa・s、鍵結於矽原子之乙烯基含有率=0.6莫耳%)50質量份，上述式(II)所示之有機氫聚矽氧烷4.0質量份，鉑之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物：相對於組成物全體並以鉑金屬之質量換算為20ppm之量，作為反應抑制劑之乙炔基環己醇0.1質量份，作為接著賦予劑之上述構造式(V)所示之化合物2.0質量份，而調製出黏度6,500mPa・s之加成硬化型聚矽氧組成物。

Figure 02_image029
[Comparative Example 1] A branched chain organopolysiloxane represented by the following average unit formula (VI) was mixed {properties = solid (25°C), bonded to silicon atoms in all organic groups Vinyl content of silicon atoms = 7.4 mol%, content of methyl groups bonded to silicon atoms in all organic groups bonded to silicon atoms = 92.6 mol%, weight average molecular weight = 3,600} 50 parts by mass, molecule 50 parts by mass of chain-end dimethylvinylsiloxy-blocked chain dimethyl polysiloxane (viscosity 5,000 mPa·s, vinyl group content rate bonded to silicon atoms = 0.6 mol%), the above formula (II ) 4.0 parts by mass of organohydrogenpolysiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum: The mass conversion of platinum metal is 20ppm, 0.1 mass part of ethynyl cyclohexanol as a reaction inhibitor, and 2.0 mass parts of the compound represented by the above structural formula (V) as a bonding agent to prepare a viscosity of 6,500mPa・s addition hardening polysiloxane composition.
Figure 02_image029

[比較例2] 混合下述平均單位式(VII)所示之分枝鏈狀之有機聚矽氧烷{性狀=固體狀(25℃)、鍵結於矽原子之全有機基中鍵結於矽原子之乙烯基含有率=6.3莫耳%、鍵結於矽原子之全有機基中鍵結於矽原子之甲基含有率=93.8莫耳%、重量平均分子量=5,600}50質量份，分子鏈末端二甲基乙烯基矽氧基封鏈二甲基聚矽氧烷(黏度5,000mPa・s、鍵結於矽原子之乙烯基含有率=0.6莫耳%)50質量份，上述式(II)所示之有機氫聚矽氧烷4.0質量份，鉑之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物：相對於組成物全體並以鉑金屬之質量換算為20ppm之量，作為反應抑制劑之乙炔基環己醇0.1質量份，作為接著賦予劑之上述構造式(V)所示之化合物2.0質量份，而調製出黏度6,500mPa・s之加成硬化型聚矽氧組成物。

Figure 02_image031
[Comparative Example 2] A branched chain organopolysiloxane represented by the following average unit formula (VII) was mixed {property = solid (25°C), bonded to silicon atoms in all organic groups Vinyl content of silicon atoms = 6.3 mol%, content of methyl groups bonded to silicon atoms in all organic groups bonded to silicon atoms = 93.8 mol%, weight average molecular weight = 5,600} 50 parts by mass, molecule 50 parts by mass of chain-end dimethylvinylsiloxy-blocked chain dimethyl polysiloxane (viscosity 5,000 mPa·s, vinyl group content rate bonded to silicon atoms = 0.6 mol%), the above formula (II ) 4.0 parts by mass of organohydrogenpolysiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum: The mass conversion of platinum metal is 20ppm, 0.1 mass part of ethynyl cyclohexanol as a reaction inhibitor, and 2.0 mass parts of the compound represented by the above structural formula (V) as an adhesive agent to prepare a viscosity of 6,500mPa・s addition hardening polysiloxane composition.
Figure 02_image031

[比較例3] 混合下述平均單位式(VIII)所示之分枝鏈狀之有機聚矽氧烷{性狀=固體狀(25℃)、鍵結於矽原子之全有機基中鍵結於矽原子之乙烯基含有率=20莫耳%、鍵結於矽原子之全有機基中鍵結於矽原子之苯基含有率=60莫耳%、重量平均分子量=1,600}45質量份，分子鏈兩末端二甲基乙烯基矽氧基封鏈甲基苯基聚矽氧烷(黏度3,500mPa・s、鍵結於矽原子之乙烯基含有率=0.20莫耳%、鍵結於矽原子之全有機基中鍵結於矽原子之苯基含有率=49莫耳%)55質量份，下述式(IX)所示之分子鏈兩末端二甲基氫矽氧基封鏈甲基苯基聚矽氧烷24質量份，鉑之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷錯合物：相對於組成物全體並以鉑金屬之質量換算為2.5ppm之量，作為反應抑制劑之乙炔基環己醇0.1質量份、作為接著賦予劑之上述構造式(V)所示之化合物2.0質量份，而調製出黏度1,700mPa・s之加成硬化型聚矽氧組成物。

Figure 02_image033
[Comparative Example 3] A branched chain organopolysiloxane represented by the following average unit formula (VIII) was mixed {property = solid (25°C), bonded to silicon atoms in all organic groups Vinyl content of silicon atoms = 20 mol%, content of phenyl groups bonded to silicon atoms in all organic groups bonded to silicon atoms = 60 mol%, weight average molecular weight = 1,600} 45 parts by mass, molecule Dimethylvinylsiloxy-blocked chain methylphenylpolysiloxane at both ends of the chain (viscosity 3,500mPa·s, content of vinyl groups bonded to silicon atoms = 0.20 mole %, vinyl groups bonded to silicon atoms The content of phenyl groups bonded to silicon atoms in the total organic group = 49 mole %) 55 parts by mass, the two ends of the molecular chain shown in the following formula (IX) dimethyl hydrogen siloxy blocked chain methyl phenyl 24 parts by mass of polysiloxane, platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex: relative to the entire composition and in terms of mass of platinum metal The amount of 2.5ppm, 0.1 mass part of ethynylcyclohexanol as a reaction inhibitor, 2.0 mass parts of the compound represented by the above structural formula (V) as an adhesive imparting agent, and prepared addition hardening with a viscosity of 1,700mPa·s type polysiloxane composition.
Figure 02_image033

[比較例4] 除了在實施例1中，將上述平均單位式(I)所示之分枝鏈狀有機聚矽氧烷取代成下述平均單位式(X)所示之分枝鏈狀之有機聚矽氧烷{性狀=固體狀(25℃)、鍵結於矽原子之全有機基中見結於矽原子之乙烯基含有率=16.7莫耳%、鍵結於矽原子之全有機基中鍵結於矽原子之苯基含有率=3.3莫耳%、重量平均分子量2,100}以外，其他係與實施例1同樣地操作而調製出黏度2,300mPa・s之加成硬化型聚矽氧組成物。

Figure 02_image035
[Comparative Example 4] Except in Example 1, the branched chain organopolysiloxane represented by the above average unit formula (I) was replaced with the branched chain organopolysiloxane represented by the following average unit formula (X) Organopolysiloxane {properties = solid (25°C), among all organic groups bonded to silicon atoms, content of vinyl groups bonded to silicon atoms = 16.7 mol%, all organic groups bonded to silicon atoms Except for the content of phenyl groups bonded to silicon atoms = 3.3 mol%, and the weight average molecular weight of 2,100}, the addition-hardening polysiloxane composition with a viscosity of 2,300mPa·s was prepared in the same manner as in Example 1. thing.
Figure 02_image035

Figure 02_image037
Figure 02_image037

如表1所示，實施例1及2之硬化物之硬度皆為充足，硬化物之硬化性、透光率及耐熱性皆為良好，且也並未在硬化物上發現龜裂產生。並且，也未產生觸媒毒所造成之剝離，且密著性為高者。As shown in Table 1, the hardness of the cured products in Examples 1 and 2 is sufficient, and the cured products have good curability, light transmittance and heat resistance, and no cracks are found on the cured products. In addition, no peeling due to catalyst poison occurred, and the adhesiveness was high.

另一方面，在比較例1、3、4中，硬度雖為充足者，但有發現龜裂產生，具有SiO2 單位之比較例1之硬化性為較差者。又，具有SiO單位之比較例2也並無龜裂產生，但耐熱性為較差者。又，包含具有苯基之有機聚矽氧烷之比較例3、4也係耐熱性較差者。並且，已產生觸媒毒所造成之剝離。On the other hand, in Comparative Examples 1, 3, and 4, although the hardness was sufficient, cracks were observed, and Comparative Example 1 having SiO 2 units had poor hardenability. Also, in Comparative Example 2 having SiO units, no cracks occurred, but the heat resistance was inferior. In addition, Comparative Examples 3 and 4 containing organopolysiloxanes having a phenyl group were also inferior in heat resistance. Also, peeling caused by catalyst poison has occurred.

根據以上，可證明根據本發明之加成硬化型聚矽氧組成物，由於會形成高透光率，對基材之密著性為高，且耐熱性・耐龜裂性皆優之硬化物，故適宜為各種光學用途等者。Based on the above, it can be proved that the addition-curable polysiloxane composition according to the present invention forms a cured product with high light transmittance, high adhesion to the substrate, and excellent heat resistance and crack resistance. , so it is suitable for various optical applications.

上述實施例中，使用本發明之加成硬化型聚矽氧組成物作為半導體元件之封裝劑，但本發明之加成硬化型聚矽氧組成物由於特別係高透光率，故其他也能適宜使用作為光學用途之半導體元件之接著劑、保護塗覆劑、底部填充劑等，又，亦能使用作為電氣・電子用之接著劑、封裝劑、保護塗覆劑、底部填充劑等。In the above-mentioned embodiments, the addition-curable polysiloxane composition of the present invention is used as an encapsulant for semiconductor elements, but the addition-curable polysiloxane composition of the present invention is particularly high in light transmittance, so others can also be used. Suitable for use as adhesives, protective coatings, underfills, etc. for semiconductor elements for optical applications, and also as adhesives, encapsulants, protective coatings, underfills, etc. for electrical and electronic applications.

尚且，本發明並非係受到上述實施形態所限定者。上述實施形態僅為例示，具有與本發明之申請專利範圍記載之技術思想為實質相同之構成，且具有相同作用效果者，無論何種型態皆係包含在本發明之技術範圍內。In addition, the present invention is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and those having substantially the same configuration as the technical idea described in the claims of the present invention, and having the same function and effect, are included in the technical scope of the present invention regardless of the type.

1:半導體裝置 2:鍍銀基板 3:封裝 4:半導體晶片 5:接合線 6:加成硬化型聚矽氧組成物(之硬化物)1: Semiconductor device 2: Silver plated substrate 3: Encapsulation 4: Semiconductor wafer 5: Bonding wire 6: Addition hardening polysiloxane composition (hardened product)

[圖1]展示本發明之半導體裝置之一例的示意剖面圖。[ Fig. 1 ] A schematic cross-sectional view showing an example of a semiconductor device of the present invention.

1:半導體裝置 1: Semiconductor device

2:鍍銀基板 2: Silver plated substrate

3:封裝 3: Encapsulation

4:半導體晶片 4: Semiconductor wafer

5:接合線 5: Bonding wire

6:加成硬化型聚矽氧組成物(之硬化物) 6: Addition hardening polysiloxane composition (hardened product)

Claims (3)

一種加成硬化型聚矽氧組成物，其特徵為含有：(A)下述平均單位式(1)所示之有機聚矽氧烷，(R1SiO3/2)a1(R1 3SiO1/2)b1(X1O1/2)c1…(1)式中，R1為經取代或未取代之脂肪族一價烴基且可為相同或相異，全部R1之中0.1~20%為烯基，且甲基之含有率為80莫耳%以上，X1為氫原子或烷基，a1、b1、c1為滿足0.1≦a1≦1、0≦b1≦0.75、0≦c1≦0.1，且a1+b1+c1=1之數；(B)下述平均單位式(2)所示之有機聚矽氧烷：相對於(A)成分100質量份為10~5,000質量份，(R2 2SiO)a2(R2 3SiO1/2)b2…(2)式中，R2為經取代或未取代之脂肪族一價烴基且可為相同或相異，全部R2之中0.01~25莫耳%為烯基，a2、b2為滿足0.33≦a2≦0.999、0.001≦b2≦0.67，且a2+b2=1之正數；(C)下述平均組成式(3)所示之1分子中至少具有2個Si-H鍵之有機氫聚矽氧烷：相對於(A)成分與(B)成分之合計100質量份為1~200質量份，R3 dHeSiO[(4-d-e)/2]…(3)式中，R3為脂肪族不飽和烴基以外之經取代或未取代之一價烴基且可為相同或相異，d、e為滿足0.7≦d≦2.1、 0.01≦e≦1.0，且0.8≦d+e≦2.7之正數；及，(D)矽氫化反應觸媒：相對於組成物全體並以金屬原子之質量換算成為0.01~500ppm之量。 An addition-hardening polysiloxane composition characterized by containing: (A) an organopolysiloxane represented by the following average unit formula (1), (R 1 SiO 3/2 ) a1 (R 1 3 SiO 1/2 ) b1 (X 1 O 1/2 ) c1 ...(1) In the formula, R 1 is a substituted or unsubstituted aliphatic monovalent hydrocarbon group and can be the same or different, and 0.1 ~ 20% is alkenyl, and the content of methyl group is more than 80 mole%, X1 is a hydrogen atom or an alkyl group, and a1, b1, c1 satisfy 0.1≦a1≦1, 0≦b1≦0.75, 0≦c1 ≦0.1, and the number of a1+b1+c1=1; (B) organopolysiloxane represented by the following average unit formula (2): 10 to 5,000 parts by mass relative to 100 parts by mass of component (A), (R 2 2 SiO) a2 (R 2 3 SiO 1/2 ) b2 ... (2) In the formula, R 2 is a substituted or unsubstituted aliphatic monovalent hydrocarbon group and can be the same or different, all R 2 0.01~25 mole% of them are alkenyl groups, a2 and b2 are positive numbers satisfying 0.33≦a2≦0.999, 0.001≦b2≦0.67, and a2+b2=1; (C) the following average composition formula (3) Organohydrogenpolysiloxane having at least two Si-H bonds in one molecule: 1 to 200 parts by mass relative to 100 parts by mass of the total of components (A) and (B), R 3 d H e SiO [ (4-de)/2] ... (3) In the formula, R 3 is a substituted or unsubstituted monovalent hydrocarbon group other than an aliphatic unsaturated hydrocarbon group and can be the same or different, and d and e satisfy 0.7≦d ≦2.1, 0.01≦e≦1.0, and a positive number of 0.8≦d+e≦2.7; and, (D) Hydrosilation reaction catalyst: an amount of 0.01-500 ppm in terms of the mass of metal atoms relative to the entire composition. 如請求項1之加成硬化型聚矽氧組成物，其中相對於(A)成分與(B)成分之合計100質量份，更含有(E)含有環氧基之有機矽烷化合物，及，有機聚矽氧烷之任一者或該兩者0.01~3質量份。 The addition-curable polysiloxane composition according to claim 1, which further contains (E) an epoxy group-containing organosilane compound relative to 100 parts by mass of the total of (A) component and (B) component, and organic 0.01 to 3 parts by mass of either polysiloxane or both. 一種半導體裝置，其特徵為藉由如請求項1或2之加成硬化型聚矽氧組成物之硬化物被覆半導體元件者。 A semiconductor device characterized in that a semiconductor element is coated with a hardened product of the addition-curable polysiloxane composition as claimed in claim 1 or 2.
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TW201734135A (en) * 2015-11-13 2017-10-01 信越化學工業股份有限公司 Addition-curable silicone resin composition, method for producing said composition, and optical semiconductor device
JP2018076415A (en) * 2016-11-08 2018-05-17 信越化学工業株式会社 Thermosetting silicone composition, die bonding material, and optical semiconductor device

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