JP7388865B2 - Addition-curing silicone composition, cured product thereof, and semiconductor device - Google Patents

Addition-curing silicone composition, cured product thereof, and semiconductor device Download PDF

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JP7388865B2
JP7388865B2 JP2019185533A JP2019185533A JP7388865B2 JP 7388865 B2 JP7388865 B2 JP 7388865B2 JP 2019185533 A JP2019185533 A JP 2019185533A JP 2019185533 A JP2019185533 A JP 2019185533A JP 7388865 B2 JP7388865 B2 JP 7388865B2
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大輔 平野
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Description

本発明は、付加硬化型シリコーン組成物、その硬化物、及び該硬化物を用いた半導体装置に関する。 The present invention relates to an addition-curable silicone composition, a cured product thereof, and a semiconductor device using the cured product.

付加硬化型シリコーン組成物は、付加反応性炭素－炭素二重結合を含有するオルガノポリシロキサンおよびケイ素に結合した水素原子を有する有機ケイ素化合物を含み、ヒドロシリル化反応によって硬化して硬化物を与える。このようにして得られる硬化物は、耐熱性、耐寒性、電気絶縁性に優れ、また、透明であるため、発光ダイオード（ＬＥＤ）の封止材などの各種光学用途に用いられている（特許文献１、特許文献２）。 The addition-curable silicone composition contains an organopolysiloxane containing an addition-reactive carbon-carbon double bond and an organosilicon compound having a silicon-bonded hydrogen atom, and is cured by a hydrosilylation reaction to give a cured product. The cured product obtained in this way has excellent heat resistance, cold resistance, electrical insulation properties, and is transparent, so it is used for various optical applications such as a sealing material for light emitting diodes (LEDs) (patented Literature 1, Patent Literature 2).

しかしながら、一般的にシリコーンからなる光学素子封止材はガスバリア性が低く、外部からの腐食性ガスの侵入により銀電極が変色する結果、ＬＥＤの輝度が低下してしまう場合がある。 However, optical element sealing materials made of silicone generally have low gas barrier properties, and as a result of the silver electrodes becoming discolored due to the intrusion of corrosive gases from the outside, the brightness of the LED may decrease.

そこで、多環式炭化水素骨格を含有する付加硬化型シリコーン組成物を用いた光学素子封止材が提案されている（特許文献３、４）。このような組成物から得られる封止材は高いガスバリア性を有するため、外部からの腐食性ガスの侵入を防ぎ、銀電極の変色を抑えることが可能である。また、該組成物からなる硬化物は非常に優れた靱性を有しており、これによって熱衝撃等の外的影響によるクラック等を抑制できる。しかしながら、これらの多環式炭化水素骨格を含有する付加硬化型シリコーン組成物は熱により変色しやすいという欠点があるため、特にハイパワーのＬＥＤには使用できないといった問題が存在している。 Therefore, an optical element sealing material using an addition-curing silicone composition containing a polycyclic hydrocarbon skeleton has been proposed (Patent Documents 3 and 4). Since the sealing material obtained from such a composition has high gas barrier properties, it is possible to prevent corrosive gases from entering from the outside and suppress discoloration of the silver electrode. In addition, the cured product made of the composition has extremely excellent toughness, which can suppress cracks caused by external influences such as thermal shock. However, addition-curing silicone compositions containing these polycyclic hydrocarbon skeletons have the disadvantage of being easily discolored by heat, and therefore cannot be used particularly in high-power LEDs.

特開２００４－１８６１６８号公報Japanese Patent Application Publication No. 2004-186168 特開２００４－１４３３６１号公報Japanese Patent Application Publication No. 2004-143361 特開２００８－０６９２１０号公報JP2008-069210A 特開２０１２－０４６６０４号公報Japanese Patent Application Publication No. 2012-046604

本発明は、上記問題を解決するためになされたものであり、透明性、耐熱変色性、靱性に優れた硬化物を与える付加硬化型シリコーン組成物を提供することを目的とする。 The present invention was made to solve the above problems, and an object of the present invention is to provide an addition-curable silicone composition that provides a cured product with excellent transparency, heat discoloration resistance, and toughness.

上記課題を達成するために、本発明では、下記（Ａ）、（Ｂ）及び（Ｃ）を含む付加硬化型シリコーン組成物を提供する。
（Ａ）下記式（１）で表される有機ケイ素化合物と、下記式（２）で表される直鎖状シロキサン及び下記式（３）で表される三次元網状シロキサンとの付加反応物であって、１分子中にＳｉＨ基を２個以上有する付加反応物、

Figure 0007388865000001
（式中、Ｒ１は置換または非置換の炭素原子数１～１２の２価炭化水素基である。）
Figure 0007388865000002
 （式中、Ｒ２、Ｒ４は独立に置換または非置換の炭素原子数１～１２の１価炭化水素基であり、Ｒ３は独立に単結合または非置換の炭素数１～４の２価炭化水素基である。ａは１～３の整数であり、ｂは０～１００の整数である。）
（Ｒ５ ３ＳｉＯ１／２）ｃ（Ｒ５ ２ＳｉＯ２／２）ｄ（ＳｉＯ４／２）ｅ（ＸＯ１／２）ｆ （３）
（式中、Ｒ５は独立に置換または非置換の炭素原子数１～１２の１価炭化水素基であり、但し、Ｒ５の全数のうち０．１～４０％はアルケニル基であり、かつ、１０～９９．９％はアリール基である。Ｘは水素原子またはアルキル基であり、ｃは０．１～０．５の数であり、ｄは０．１～０．６の数であり、ｅは０．２～０．８の数であり、ｆは０～０．２の数であり、ｃ＋ｄ＋ｅ＋ｆ＝１である。）
（Ｂ）アルケニル基を１分子中に２個以上有する化合物、
（Ｃ）ヒドロシリル化反応触媒 In order to achieve the above object, the present invention provides an addition-curable silicone composition containing the following (A), (B), and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1), a linear siloxane represented by the following formula (2), and a three-dimensional network siloxane represented by the following formula (3). and an addition reaction product having two or more SiH groups in one molecule,
Figure 0007388865000001
 (In the formula, R 1 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)
Figure 0007388865000002
 (In the formula, R 2 and R 4 are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 3 is independently a single bond or unsubstituted 2 to 4 carbon atoms. It is a valence hydrocarbon group. a is an integer of 1 to 3, and b is an integer of 0 to 100.)
(R 5 3 SiO 1/2 ) c (R 5 2 SiO 2/2 ) d (SiO 4/2 ) e (XO 1/2 ) f (3)
(In the formula, R 5 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, provided that 0.1 to 40% of the total number of R 5 is an alkenyl group, and , 10 to 99.9% are aryl groups. X is a hydrogen atom or an alkyl group, c is a number from 0.1 to 0.5, and d is a number from 0.1 to 0.6. , e is a number from 0.2 to 0.8, f is a number from 0 to 0.2, and c+d+e+f=1.)
(B) a compound having two or more alkenyl groups in one molecule,
(C) Hydrosilylation reaction catalyst

本発明の付加硬化型シリコーン組成物であれば、透明性、耐熱変色性、靱性に優れた硬化物を与える付加硬化型シリコーン組成物を提供できる。 The addition-curable silicone composition of the present invention can provide an addition-curable silicone composition that provides a cured product with excellent transparency, heat discoloration resistance, and toughness.

本発明の付加硬化型シリコーン組成物は、上記Ｒ１がフェニレン基であり、Ｒ２、Ｒ４が独立にメチル基またはフェニル基であり、Ｒ３が単結合であることが好ましい。 In the addition-curable silicone composition of the present invention, it is preferable that R 1 is a phenylene group, R 2 and R 4 are independently a methyl group or a phenyl group, and R 3 is a single bond.

本発明の付加硬化型シリコーン組成物は、さらに前記直鎖状シロキサンが、下記式（４）で表される直鎖状シロキサンを含むことが好ましい。
［（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２］２［（Ｃ６Ｈ５）２ＳｉＯ２／２］ｂ （４）
（式中、ｂは前記のとおりである。） In the addition-curable silicone composition of the present invention, it is preferable that the linear siloxane further includes a linear siloxane represented by the following formula (4).
[(CH 2 =CH) (C 6 H 5 ) (CH 3 ) SiO 1/2 ] 2 [(C 6 H 5 ) 2 SiO 2/2 ] b (4)
(In the formula, b is as described above.)

また、前記三次元網状シロキサンが、下記式（５）で表される三次元網状シロキサンを含むことが好ましい。
［（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２］ｃ［（Ｃ６Ｈ５）２ＳｉＯ２／２］ｄ［ＳｉＯ４／２］ｅ （５）
（式中、ｃ、ｄ、ｅは前記のとおりであり、ｃ＋ｄ＋ｅ＝１である。） Further, it is preferable that the three-dimensional network siloxane includes a three-dimensional network siloxane represented by the following formula (5).
[( CH2 =CH)( C6H5 ) ( CH3 )SiO1/ 2 ] c [( C6H5 ) 2SiO2 / 2 ] d [SiO4 /2 ] e (5)
(In the formula, c, d, and e are as described above, and c+d+e=1.)

さらに、本発明の付加硬化型シリコーン組成物は、前記（Ｂ）が下記式（６）で表されるシロキサンを含むことが好ましい。

Figure 0007388865000003
（式中、Ｒ６は独立にメチル基又はフェニル基であり、Ｒ７は独立に置換または非置換の炭素原子数１～１２の１価炭化水素基であり、ｇは０～５０の整数であり、ｈは０～１００の整数である。ただし、ｇが０のときＲ６はフェニル基であり、かつ、ｈは１～１００の整数である。括弧が付されたシロキサン単位の配列は任意であってよい。） Furthermore, in the addition-curable silicone composition of the present invention, it is preferable that the above (B) contains a siloxane represented by the following formula (6).
Figure 0007388865000003
 (In the formula, R 6 is independently a methyl group or phenyl group, R 7 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and g is an integer of 0 to 50. , h is an integer from 0 to 100. However, when g is 0, R 6 is a phenyl group, and h is an integer from 1 to 100. The arrangement of the siloxane units in parentheses is arbitrary. )

また、前記（Ｂ）が下記式（７）で表されるシロキサンを含むことが好ましい。
［（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２］２［（Ｃ６Ｈ５）２ＳｉＯ２／２］ｉ （７）
（式中、ｉは１～５０の整数である。） Moreover, it is preferable that the said (B) contains the siloxane represented by following formula (7).
[ ( CH2 =CH) ( C6H5)( CH3 )SiO1 / 2 ] 2 [ (C6H5) 2SiO2/2 ] i ( 7 )
(In the formula, i is an integer from 1 to 50.)

前記（Ｂ）は前記式（３）で表される三次元網状シロキサンを含んでもよい。 The above (B) may include a three-dimensional network siloxane represented by the above formula (3).

さらに、前記（Ｂ）が、下記式（５）で表される三次元網状シロキサンを含むことが好ましい。
［（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２］ｃ［（Ｃ６Ｈ５）２ＳｉＯ２／２］ｄ［ＳｉＯ４／２］ｅ （５）
（式中、ｃ、ｄ、ｅは前記のとおりであり、ｃ＋ｄ＋ｅ＝１である。） Furthermore, it is preferable that the above (B) contains a three-dimensional network siloxane represented by the following formula (5).
[( CH2 =CH)( C6H5 ) ( CH3 )SiO1/ 2 ] c [( C6H5 ) 2SiO2 / 2 ] d [SiO4 /2 ] e (5)
(In the formula, c, d, and e are as described above, and c+d+e=1.)

本発明において、前記Ｒ１や、前記直鎖状シロキサン、前記三次元網状シロキサン、（Ｂ）成分等が上記のようなものであると、より確実に本発明の効果を発揮できる。 In the present invention, when R1 , the linear siloxane, the three-dimensional network siloxane, component (B), etc. are as described above, the effects of the present invention can be more reliably exerted.

また本発明は、前記付加硬化型シリコーン組成物を硬化してなる硬化物を提供する。 The present invention also provides a cured product obtained by curing the addition-curing silicone composition.

本発明の硬化物であれば、透明性、耐熱変色性、靱性に優れる。 The cured product of the present invention has excellent transparency, heat discoloration resistance, and toughness.

本発明の硬化物は、１８０℃で１，０００時間静置後、厚さ２ｍｍにおける波長４００ｎｍの光透過率（２５℃）が６０％以上であることが好ましい。 The cured product of the present invention preferably has a light transmittance (at 25° C.) at a wavelength of 400 nm at a thickness of 2 mm of 60% or more after standing at 180° C. for 1,000 hours.

このような光透過率を有する硬化物であれば、発光ダイオード素子の保護、封止もしくは接着、波長変更もしくは調整またはレンズ等の用途に好適に使用できるほか、レンズ材料、光学デバイスもしくは光学部品用封止材、ディスプレイ材料等の各種の光学部品用材料、電子デバイスもしくは電子部品用絶縁材料、更にはコーティング材料としても有用な材料となる。 A cured product with such light transmittance can be suitably used for protection, sealing or adhesion of light emitting diode elements, wavelength change or adjustment, lenses, etc., as well as lens materials, optical devices, or optical parts. It is a material useful as a material for various optical parts such as a sealing material and a display material, an insulating material for electronic devices or electronic parts, and even as a coating material.

さらに本発明は、前記硬化物により半導体素子が被覆されたものである半導体装置を提供する。 Furthermore, the present invention provides a semiconductor device in which a semiconductor element is covered with the cured product.

使用する本発明の付加硬化型シリコーン組成物が透明性、耐熱変色性、靱性に優れた硬化物を形成するため、この付加硬化型シリコーン組成物を用いた本発明の半導体装置は、信頼性に優れたものとなる。 Since the addition-curing silicone composition of the present invention used forms a cured product with excellent transparency, heat discoloration resistance, and toughness, the semiconductor device of the present invention using this addition-curing silicone composition has high reliability. It will be excellent.

本発明の付加硬化型シリコーン組成物は、透明性、耐熱変色性、靱性に優れた硬化物を与えることができる。従って、発光ダイオード素子の保護、封止もしくは接着、波長変更もしくは調整またはレンズ等の用途に好適に使用できる。このため、本発明の付加硬化型シリコーン組成物から得られる硬化物は、発光ダイオード素子の保護、封止もしくは接着、波長変更もしくは調整またはレンズ等の用途に好適に使用できる。また、レンズ材料、光学デバイスもしくは光学部品用封止材、ディスプレイ材料等の各種の光学部品用材料、電子デバイスもしくは電子部品用絶縁材料、更にはコーティング材料としても有用である。さらに、このような硬化物を用いた本発明の半導体装置は、信頼性に優れたものとなる。 The addition-curable silicone composition of the present invention can provide a cured product with excellent transparency, heat discoloration resistance, and toughness. Therefore, it can be suitably used for purposes such as protecting, sealing or adhering light emitting diode elements, changing or adjusting wavelength, or as lenses. Therefore, the cured product obtained from the addition-curable silicone composition of the present invention can be suitably used for purposes such as protecting, sealing, or adhering light-emitting diode elements, changing or adjusting wavelength, or making lenses. It is also useful as a lens material, a sealing material for optical devices or optical components, a material for various optical components such as a display material, an insulating material for electronic devices or electronic components, and a coating material. Furthermore, the semiconductor device of the present invention using such a cured product has excellent reliability.

本発明の付加硬化型シリコーン組成物の硬化物を用いた光半導体装置の一例を示す概略断面図である。FIG. 1 is a schematic cross-sectional view showing an example of an optical semiconductor device using a cured product of the addition-curable silicone composition of the present invention.

上述のように、透明性、耐熱変色性、靱性に優れた硬化物を与える付加硬化型シリコーン組成物の開発が求められていた。 As mentioned above, there has been a need to develop an addition-curable silicone composition that provides a cured product with excellent transparency, heat discoloration resistance, and toughness.

本発明者は、上記課題について鋭意検討を重ねた結果、特定の成分を含む付加硬化型シリコーン組成物であれば、上記課題を解決できることを見出し、本発明を完成させた。 As a result of extensive studies on the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using an addition-curing silicone composition containing a specific component, and have completed the present invention.

即ち、本発明は、下記（Ａ）、（Ｂ）及び（Ｃ）を含む付加硬化型シリコーン組成物である。
（Ａ）下記式（１）で表される有機ケイ素化合物と、下記式（２）で表される直鎖状シロキサン及び下記式（３）で表される三次元網状シロキサンとの付加反応物であって、１分子中にＳｉＨ基を２個以上有する付加反応物、

Figure 0007388865000004
（式中、Ｒ１は置換または非置換の炭素原子数１～１２の２価炭化水素基である。）
Figure 0007388865000005
 （式中、Ｒ２、Ｒ４は独立に置換または非置換の炭素原子数１～１２の１価炭化水素基であり、Ｒ３は独立に単結合または非置換の炭素数１～４の２価炭化水素基である。ａは１～３の整数であり、ｂは０～１００の整数である。）
（Ｒ５ ３ＳｉＯ１／２）ｃ（Ｒ５ ２ＳｉＯ２／２）ｄ（ＳｉＯ４／２）ｅ（ＸＯ１／２）ｆ （３）
（式中、Ｒ５は独立に置換または非置換の炭素原子数１～１２の１価炭化水素基であり、但し、Ｒ５の全数のうち０．１～４０％はアルケニル基であり、かつ、１０～９９．９％はアリール基である。Ｘは水素原子またはアルキル基であり、ｃは０．１～０．５の数であり、ｄは０．１～０．６の数であり、ｅは０．２～０．８の数であり、ｆは０～０．２の数であり、ｃ＋ｄ＋ｅ＋ｆ＝１である。）
（Ｂ）アルケニル基を１分子中に２個以上有する化合物、
（Ｃ）ヒドロシリル化反応触媒 That is, the present invention is an addition-curable silicone composition containing the following (A), (B), and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1), a linear siloxane represented by the following formula (2), and a three-dimensional network siloxane represented by the following formula (3). and an addition reaction product having two or more SiH groups in one molecule,
Figure 0007388865000004
 (In the formula, R 1 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)
Figure 0007388865000005
 (In the formula, R 2 and R 4 are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 3 is independently a single bond or unsubstituted 2 to 4 carbon atoms. It is a valence hydrocarbon group. a is an integer of 1 to 3, and b is an integer of 0 to 100.)
(R 5 3 SiO 1/2 ) c (R 5 2 SiO 2/2 ) d (SiO 4/2 ) e (XO 1/2 ) f (3)
(In the formula, R 5 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, provided that 0.1 to 40% of the total number of R 5 is an alkenyl group, and , 10 to 99.9% are aryl groups. X is a hydrogen atom or an alkyl group, c is a number from 0.1 to 0.5, and d is a number from 0.1 to 0.6. , e is a number from 0.2 to 0.8, f is a number from 0 to 0.2, and c+d+e+f=1.)
(B) a compound having two or more alkenyl groups in one molecule,
(C) Hydrosilylation reaction catalyst

以下、本発明について詳細に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be explained in detail, but the present invention is not limited thereto.

［付加硬化型シリコーン組成物］
［（Ａ）成分］
本発明の付加硬化型シリコーン組成物における（Ａ）成分は、下記式（１）で表される有機ケイ素化合物と、下記式（２）で表される直鎖状シロキサン及び下記式（３）で表される三次元網状シロキサンとの付加反応物であって、１分子中にＳｉＨ基を２個以上有する付加反応物である。

Figure 0007388865000006
（式中、Ｒ１は置換または非置換の炭素原子数１～１２の２価炭化水素基である。）
Figure 0007388865000007
 （式中、Ｒ２、Ｒ４は独立に置換または非置換の炭素原子数１～１２の１価炭化水素基であり、Ｒ３は独立に単結合または非置換の炭素数１～４の２価炭化水素基である。ａは１～３の整数であり、ｂは０～１００の整数である。）
（Ｒ５ ３ＳｉＯ１／２）ｃ（Ｒ５ ２ＳｉＯ２／２）ｄ（ＳｉＯ４／２）ｅ（ＸＯ１／２）ｆ （３）
（式中、Ｒ５は独立に置換または非置換の炭素原子数１～１２の１価炭化水素基であり、但し、Ｒ５の全数のうち０．１～４０％はアルケニル基であり、かつ、１０～９９．９％はアリール基である。Ｘは水素原子またはアルキル基であり、ｃは０．１～０．５の数であり、ｄは０．１～０．６の数であり、ｅは０．２～０．８の数であり、ｆは０～０．２の数であり、ｃ＋ｄ＋ｅ＋ｆ＝１である。） [Addition-curing silicone composition]
[(A) Component]
Component (A) in the addition-curable silicone composition of the present invention includes an organosilicon compound represented by the following formula (1), a linear siloxane represented by the following formula (2), and a linear siloxane represented by the following formula (3). It is an addition reaction product with the three-dimensional network siloxane shown above, and is an addition reaction product having two or more SiH groups in one molecule.
Figure 0007388865000006
 (In the formula, R 1 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)
Figure 0007388865000007
 (In the formula, R 2 and R 4 are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 3 is independently a single bond or unsubstituted 2 to 4 carbon atoms. It is a valence hydrocarbon group. a is an integer of 1 to 3, and b is an integer of 0 to 100.)
(R 5 3 SiO 1/2 ) c (R 5 2 SiO 2/2 ) d (SiO 4/2 ) e (XO 1/2 ) f (3)
(In the formula, R 5 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, provided that 0.1 to 40% of the total number of R 5 is an alkenyl group, and , 10 to 99.9% are aryl groups. X is a hydrogen atom or an alkyl group, c is a number from 0.1 to 0.5, and d is a number from 0.1 to 0.6. , e is a number from 0.2 to 0.8, f is a number from 0 to 0.2, and c+d+e+f=1.)

上記式（１）において、Ｒ１で表される炭素原子数１～１２の２価炭化水素基としては、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ペンチレン基、ｎ－ヘキシレン基、シクロヘキシレン基、ｎ－オクチレン基等のアルキレン基、フェニレン基、ナフチレン基等のアリーレン基等や、これらの基の水素原子の一部又は全部がフッ素、臭素、塩素等のハロゲン原子等で置換されたものが挙げられ、Ｒ１としては、フェニレン基が特に好ましい。 In the above formula (1), the divalent hydrocarbon group having 1 to 12 carbon atoms represented by R 1 includes a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-pentylene group, and an n-pentylene group. - Alkylene groups such as hexylene group, cyclohexylene group, n-octylene group, arylene groups such as phenylene group, naphthylene group, etc., and some or all of the hydrogen atoms of these groups are halogen atoms such as fluorine, bromine, chlorine, etc. Examples include those substituted with, etc., and R 1 is particularly preferably a phenylene group.

上記式（１）で表される有機ケイ素化合物の好適な具体例を下記に示すが、これらに限定されるものではない。また、上記式（１）で表される有機ケイ素化合物は１種単独でも２種以上を組み合わせても使用することができる。

Figure 0007388865000008
Preferred specific examples of the organosilicon compound represented by the above formula (1) are shown below, but the invention is not limited thereto. Further, the organosilicon compounds represented by the above formula (1) can be used alone or in combination of two or more.
Figure 0007388865000008

上記式（２）において、Ｒ２およびＲ４で表される炭素原子数１～１２の１価炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、オクチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、ビニル基、アリル基、プロペニル基等のアルケニル基、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、フェニルエチル基、フェニルプロピル基等のアラルキル基等や、これらの基の水素原子の一部又は全部がフッ素、臭素、塩素等のハロゲン原子等で置換されたものが挙げられ、メチル又はフェニル基が好ましい。 In the above formula (2), monovalent hydrocarbon groups having 1 to 12 carbon atoms represented by R 2 and R 4 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert - Alkyl groups such as butyl group, pentyl group, neopentyl group, hexyl group, octyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group, propenyl group, phenyl group, tolyl group, xylyl group, Aryl groups such as naphthyl groups, aralkyl groups such as benzyl groups, phenylethyl groups, phenylpropyl groups, etc., and some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, etc. Methyl or phenyl groups are preferred.

Ｒ３で表される非置換の炭素原子数１～４の２価炭化水素基としては、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基等のアルキレン基が挙げられる。Ｒ３が単結合である場合は、ケイ素原子にビニル基が直接結合している有機ケイ素化合物を表す。Ｒ３としては単結合が特に好ましい。 Examples of the unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms represented by R 3 include alkylene groups such as methylene group, ethylene group, n-propylene group, and n-butylene group. When R 3 is a single bond, it represents an organosilicon compound in which a vinyl group is directly bonded to a silicon atom. A single bond is particularly preferred as R3 .

ａは１～３の整数であり、１であることが好ましい。ｂは０～１００の整数であり、０～１０が好ましく、０がより好ましい。ｂが１００を超えると、硬化物の硬度が不充分なものとなる場合がある。 a is an integer from 1 to 3, preferably 1. b is an integer from 0 to 100, preferably 0 to 10, and more preferably 0. If b exceeds 100, the hardness of the cured product may be insufficient.

上記式（２）で表される直鎖状シロキサンの具体例を下記に示すが、これらに限定されるものではない。また、上記式（２）で表される直鎖状シロキサンは１種単独でも２種以上を組み合わせても使用することができる。

Figure 0007388865000009
Specific examples of the linear siloxane represented by the above formula (2) are shown below, but the invention is not limited thereto. Moreover, the linear siloxane represented by the above formula (2) can be used alone or in combination of two or more types.
Figure 0007388865000009

このような直鎖状シロキサンの中でも、下記式（４）で表されるものが好ましい。
［（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２］２［（Ｃ６Ｈ５）２ＳｉＯ２／２］ｂ （４）
（式中、ｂは前記のとおりである。） Among such linear siloxanes, those represented by the following formula (4) are preferred.
[(CH 2 =CH) (C 6 H 5 ) (CH 3 ) SiO 1/2 ] 2 [(C 6 H 5 ) 2 SiO 2/2 ] b (4)
(In the formula, b is as described above.)

上記式（３）において、Ｒ５は独立に置換もしくは非置換の炭素原子数１～１２の１価炭化水素基であり、但し、Ｒ５の全数のうち０．１～４０％はアルケニル基であり、好ましくは０．１～２０％、さらに好ましくは０．１～１０％である。アルケニル基が４０％を超えると、硬化物が脆くなり靭性に劣るものとなる場合がある。
かつ、Ｒ５の全数のうち１０～９９．９％はアリール基であり、好ましくは３０～９９．９％、さらに好ましくは５０～９９．９％である。アリール基が１０％未満であると、他の成分との相溶性が劣る場合がある。 In the above formula (3), R 5 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, provided that 0.1 to 40% of the total number of R 5 is an alkenyl group. The content is preferably 0.1 to 20%, more preferably 0.1 to 10%. If the alkenyl group content exceeds 40%, the cured product may become brittle and have poor toughness.
In addition, 10 to 99.9% of the total number of R 5 is an aryl group, preferably 30 to 99.9%, more preferably 50 to 99.9%. If the aryl group content is less than 10%, the compatibility with other components may be poor.

Ｒ５のうち、アルケニル基およびアリール基以外の非置換または置換の１価炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基等の炭素原子数１～６のアルキル基；クロロメチル基、３，３，３－トリフルオロプロピル基等の炭素原子数１～４のハロアルキル基が挙げられる。中でも、炭素原子数１～６のアルキル基が好ましく、特に好ましくはメチル基である。 Among R5 , examples of unsubstituted or substituted monovalent hydrocarbon groups other than alkenyl groups and aryl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, Examples include alkyl groups having 1 to 6 carbon atoms such as t-butyl group; haloalkyl groups having 1 to 4 carbon atoms such as chloromethyl group and 3,3,3-trifluoropropyl group. Among these, an alkyl group having 1 to 6 carbon atoms is preferred, and a methyl group is particularly preferred.

ｃは０．１～０．５、ｄは０．１～０．６、ｅは０．２～０．８、ｆは０～０．２の数であり、ｃ＋ｄ＋ｅ＋ｆ＝１．０である。好ましくはｃは０．１～０．４、ｄは０．１～０．５、ｅは０．３～０．８、ｆは０～０．１の数であり、さらに好ましくは、ｃは０．１５～０．４、ｄは０．２～０．５、ｅは０．３～０．６５の数であり、ｆは０である。ｃが０．１未満であると（Ａ）成分の架橋剤としての機能が不足し、ｃが０．５を超えると、硬化物が脆くなり靭性に劣るものとなる場合がある。ｄが０．１未満であると硬化物が靭性に劣るものとなる場合があり、ｄが０．６を超えると硬化物の硬度が不充分なものとなる場合がある。ｅが０．２未満であると硬化物の硬度が不充分なものとなる場合があり、ｅが０．８を超えると硬化物が脆くなり靭性に劣るものとなる場合がある。ｆが０．２を超えると組成物の保存安定性が悪化したり、組成物中の他の成分との相溶性が低下することにより透明性が損なわれる場合がある。 c is a number from 0.1 to 0.5, d is a number from 0.1 to 0.6, e is a number from 0.2 to 0.8, f is a number from 0 to 0.2, and c+d+e+f=1.0. Preferably, c is a number from 0.1 to 0.4, d is from 0.1 to 0.5, e is from 0.3 to 0.8, and f is a number from 0 to 0.1. More preferably, c is a number from 0 to 0.1. 0.15 to 0.4, d is a number from 0.2 to 0.5, e is a number from 0.3 to 0.65, and f is 0. When c is less than 0.1, the function of component (A) as a crosslinking agent is insufficient, and when c exceeds 0.5, the cured product may become brittle and have poor toughness. When d is less than 0.1, the cured product may have poor toughness, and when d exceeds 0.6, the hardness of the cured product may be insufficient. When e is less than 0.2, the hardness of the cured product may be insufficient, and when e exceeds 0.8, the cured product may become brittle and have poor toughness. When f exceeds 0.2, the storage stability of the composition may deteriorate, and the transparency may be impaired due to a decrease in compatibility with other components in the composition.

上記式（３）で表される三次元網状シロキサンは、例えばジクロロジフェニルシランやジアルコキシジフェニルシラン等の二官能性シランとテトラクロロシランやテトラアルコキシシラン等を加水分解・縮合させた後、または加水分解・縮合と同時に、アルケニル基を含有するシロキサン単位で末端を封鎖することにより得ることができる。 The three-dimensional network siloxane represented by the above formula (3) can be produced by hydrolyzing and condensing a bifunctional silane such as dichlorodiphenylsilane or dialkoxydiphenylsilane with tetrachlorosilane or tetraalkoxysilane, or by hydrolyzing - Can be obtained by capping the terminal with a siloxane unit containing an alkenyl group simultaneously with condensation.

上記式（３）で表される三次元網状シロキサンの具体例を下記に示すが、これらに限定されるものではない。また、上記式（３）で表される化合物は１種単独でも２種以上を組み合わせても使用することができる。
［（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２］０．２５［（Ｃ６Ｈ５）２ＳｉＯ２／２］０．３［ＳｉＯ４／２］０．４５
［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］０．２５［（Ｃ６Ｈ５）２ＳｉＯ２／２］０．３［ＳｉＯ４／２］０．４５ Specific examples of the three-dimensional network siloxane represented by the above formula (3) are shown below, but the invention is not limited thereto. Furthermore, the compounds represented by the above formula (3) can be used alone or in combination of two or more.
[( CH2 =CH)( C6H5 )( CH3 )SiO1/ 2 ] 0.25 [ (C6H5 ) 2SiO2 /2 ] 0.3 [SiO4 /2 ] 0.45
[(CH 2 =CH) (CH 3 ) 2 SiO 1/2 ] 0.25 [(C 6 H 5 ) 2 SiO 2/2 ] 0.3 [SiO 4/2 ] 0.45

このような三次元網状シロキサンの中でも、下記式（５）で表されるものが好ましい。
［（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２］ｃ［（Ｃ６Ｈ５）２ＳｉＯ２／２］ｄ［ＳｉＯ４／２］ｅ （５）
（式中、ｃ、ｄ、ｅは前記のとおりであり、ｃ＋ｄ＋ｅ＝１である。） Among such three-dimensional network siloxanes, those represented by the following formula (5) are preferred.
[( CH2 =CH)( C6H5 ) ( CH3 )SiO1/ 2 ] c [( C6H5 ) 2SiO2 / 2 ] d [SiO4 /2 ] e (5)
(In the formula, c, d, and e are as described above, and c+d+e=1.)

［（Ａ）成分の調製］
本発明の付加硬化型シリコーン組成物における（Ａ）成分は、上記式（２）で表される直鎖状シロキサン及び上記式（３）で表される三次元網状シロキサン中に含まれるアルケニル基１モルに対して、上記式（１）で表される化合物を、過剰量、好ましくは１モルを越え１０モル以下、より好ましくは１．５モルを越え５モル以下混合して両者の存在下でヒドロシリル化反応を行う事により得ることができる。 [Preparation of component (A)]
Component (A) in the addition-curable silicone composition of the present invention is an alkenyl group 1 contained in the linear siloxane represented by the above formula (2) and the three-dimensional network siloxane represented by the above formula (3). In the presence of both, an excess amount of the compound represented by formula (1) is mixed with respect to the mole, preferably more than 1 mole and less than 10 moles, more preferably more than 1.5 moles and less than 5 moles. It can be obtained by performing a hydrosilylation reaction.

（Ａ）成分中に、上記式（２）で表される直鎖状シロキサン及び上記式（３）で表される三次元網状シロキサンに由来する未反応のアルケニル基が存在していてもよいが、全てのアルケニル基がヒドロシリル化反応していることが好ましい。 In component (A), unreacted alkenyl groups derived from the linear siloxane represented by the above formula (2) and the three-dimensional network siloxane represented by the above formula (3) may be present. , it is preferred that all alkenyl groups undergo a hydrosilylation reaction.

前記ヒドロシリル化反応に用いる触媒としては、公知のものを使用することができる。例えば、白金金属を担持したカーボン粉末、白金黒、塩化第２白金、塩化白金酸、塩化白金酸と一価アルコールとの反応生成物、塩化白金酸とオレフィン類との錯体、白金ビスアセトアセテート等の白金系触媒；パラジウム系触媒、ロジウム系触媒等の白金族金属系触媒が挙げられる。また、付加反応条件、精製条件、溶媒の使用等については特に限定されず、公知の方法を用いればよい。 As the catalyst used in the hydrosilylation reaction, known catalysts can be used. For example, carbon powder supporting platinum metal, platinum black, platinum chloride, chloroplatinic acid, reaction products of chloroplatinic acid and monohydric alcohol, complexes of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. Platinum-based catalysts include platinum group metal catalysts such as palladium-based catalysts and rhodium-based catalysts. Further, addition reaction conditions, purification conditions, use of solvent, etc. are not particularly limited, and known methods may be used.

本発明の付加硬化型シリコーン組成物における（Ａ）成分は、１種の化合物からなるものでも、２種以上の化合物の組み合わせ（混合物）からなるものでもよい。 Component (A) in the addition-curable silicone composition of the present invention may consist of one type of compound or a combination (mixture) of two or more types of compounds.

（Ａ）成分を構成する化合物１分子中にＳｉＨ基を２個以上有することは適切な測定手段を選択することにより確認できる。（Ａ）成分を構成する化合物が２種以上である場合には、適切な測定手段の組み合わせ（例えば、１Ｈ－ＮＭＲとＧＰＣなど）を選択することにより化合物ごとに１分子中にＳｉＨ基を２個以上有することを確認できる。 The presence of two or more SiH groups in one molecule of the compound constituting component (A) can be confirmed by selecting an appropriate measuring means. (A) When there are two or more types of compounds constituting the component, SiH groups can be added to one molecule for each compound by selecting an appropriate combination of measurement methods (for example, 1 H-NMR and GPC, etc.). It can be confirmed that there are two or more.

［（Ｂ）成分］
本発明の付加硬化型シリコーン組成物における（Ｂ）成分は、アルケニル基を１分子中に２個以上有する化合物である。 [(B) Component]
Component (B) in the addition-curable silicone composition of the present invention is a compound having two or more alkenyl groups in one molecule.

アルケニル基としては、ビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基等の直鎖状アルケニル基、ノルボルネニル基、シクロヘキセニル基等の環状アルケニル基が挙げられ、ビニル基、アリル基が好ましい。 Examples of the alkenyl group include linear alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, and octenyl group, and cyclic alkenyl groups such as norbornenyl group and cyclohexenyl group. , vinyl group, and allyl group are preferred.

（Ｂ）成分の具体例としては、特に限定されないが、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・ジフェニルシロキサン共重合体等が挙げられる。 Specific examples of component (B) include, but are not limited to, dimethylsiloxane/methylvinylsiloxane copolymer with trimethylsiloxy groups endblocked at both molecular chain ends, dimethylsiloxane/diphenylsiloxane/methylvinylsiloxane endblocked with trimethylsiloxy groups at both molecular chain ends. Copolymers, dimethylsiloxane/diphenylsiloxane copolymers with dimethylvinylsiloxy groups endblocked at both molecular chain ends, and the like.

また、シロキサン以外のものとしては下記式で表される化合物等が挙げられるが、これらに限定されるものではない。

Figure 0007388865000010
In addition, compounds other than siloxane include, but are not limited to, compounds represented by the following formulas.
Figure 0007388865000010

（Ｂ）成分は、下記式（６）で表される直鎖状のオルガノポリシロキサンを含むことが好ましい。

Figure 0007388865000011
（式中、Ｒ６は独立にメチル基又はフェニル基であり、Ｒ７は独立に置換または非置換の炭素原子数１～１２の１価炭化水素基であり、ｇは０～５０の整数であり、ｈは０～１００の整数である。ただし、ｇが０のときＲ６はフェニル基であり、かつ、ｈは１～１００の整数である。括弧が付されたシロキサン単位の配列は任意であってよい。） It is preferable that component (B) contains a linear organopolysiloxane represented by the following formula (6).
Figure 0007388865000011
 (In the formula, R 6 is independently a methyl group or phenyl group, R 7 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and g is an integer of 0 to 50. , h is an integer from 0 to 100. However, when g is 0, R 6 is a phenyl group, and h is an integer from 1 to 100. The arrangement of the siloxane units in parentheses is arbitrary. )

Ｒ７で表される炭素原子数１～１２の１価炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、オクチル基等のアルキル基、シクロヘキシル基等のシクロアルキル基、ビニル基、アリル基、プロペニル基等のアルケニル基、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、フェニルエチル基、フェニルプロピル基等のアラルキル基等や、これらの基の水素原子の一部又は全部がフッ素、臭素、塩素等のハロゲン原子等で置換されたものが挙げられ、中でも、炭素原子数１～６のアルキル基、フェニル基、ビニル基が好ましく、特にメチル基が好ましい。 The monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R 7 includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, Alkyl groups such as hexyl groups and octyl groups, cycloalkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl groups, allyl groups, and propenyl groups, aryl groups such as phenyl groups, tolyl groups, xylyl groups, and naphthyl groups, benzyl groups, Examples include aralkyl groups such as phenylethyl groups and phenylpropyl groups, and those in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, etc. Among them, the number of carbon atoms 1 to 6 alkyl groups, phenyl groups, and vinyl groups are preferred, and methyl groups are particularly preferred.

上記式（６）において、ｇは０～５０の整数とすることができ、１～１０であることが好ましく、１～７であることがより好ましく、１～４であることが更に好ましい。ｈは０～１００の整数とすることができ、０～５０であることが好ましく、０～１０であることがより好ましく、０～４であることが更に好ましい。 In the above formula (6), g can be an integer of 0 to 50, preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 4. h can be an integer from 0 to 100, preferably from 0 to 50, more preferably from 0 to 10, even more preferably from 0 to 4.

式（６）で表されるオルガノポリシロキサンは、例えば、ジクロロジフェニルシランやジアルコキシジフェニルシラン等の二官能性シランを加水分解・縮合させた後、または加水分解・縮合と同時に、アルケニル基を含有するシロキサン単位で末端を封鎖することにより得られる。 The organopolysiloxane represented by formula (6) contains an alkenyl group, for example, after or simultaneously with hydrolysis and condensation of a bifunctional silane such as dichlorodiphenylsilane or dialkoxydiphenylsilane. It can be obtained by capping the ends with siloxane units.

式（６）で表されるオルガノポリシロキサンは、下記式（７）としても表すことができる。
［（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２］２［（Ｃ６Ｈ５）２ＳｉＯ２／２］ｉ （７）
（式中、ｉは１～５０の整数である。） The organopolysiloxane represented by the formula (6) can also be represented by the following formula (7).
[ ( CH2 =CH) ( C6H5)( CH3 )SiO1 / 2 ] 2 [ (C6H5) 2SiO2/2 ] i ( 7 )
(In the formula, i is an integer from 1 to 50.)

式（６）、（７）で表されるオルガノポリシロキサンの好適な具体例を下記に示すが、これらに限定されるものではない。
［（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２］２［（Ｃ６Ｈ５）２ＳｉＯ２／２］３
［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］２［（Ｃ６Ｈ５）２ＳｉＯ２／２］３ Preferred specific examples of the organopolysiloxanes represented by formulas (6) and (7) are shown below, but the invention is not limited thereto.
[(CH 2 =CH) (C 6 H 5 ) (CH 3 ) SiO 1/2 ] 2 [(C 6 H 5 ) 2 SiO 2/2 ] 3
[(CH 2 =CH) (CH 3 ) 2 SiO 1/2 ] 2 [(C 6 H 5 ) 2 SiO 2/2 ] 3

また、（Ｂ）成分は下記式（３）で表される三次元網状オルガノポリシロキサンを含有してもよい。
（Ｒ５ ３ＳｉＯ１／２）ｃ（Ｒ５ ２ＳｉＯ２／２）ｄ（ＳｉＯ４／２）ｅ（ＸＯ１／２）ｆ （３）
（式中、Ｒ５、Ｘ、ｃ、ｄ、ｅ、およびｆは上記のとおりであり、ｃ＋ｄ＋ｅ＋ｆ＝１である。） Moreover, the component (B) may contain a three-dimensional network organopolysiloxane represented by the following formula (3).
(R 5 3 SiO 1/2 ) c (R 5 2 SiO 2/2 ) d (SiO 4/2 ) e (XO 1/2 ) f (3)
(In the formula, R 5 , X, c, d, e, and f are as described above, and c+d+e+f=1.)

三次元網状シロキサンとしては、上記（Ａ）成分において例示されたものと同様のものが挙げられ、下記式（５）で表されるものが好ましい。
［（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２］ｃ［（Ｃ６Ｈ５）２ＳｉＯ２／２］ｄ［ＳｉＯ４／２］ｅ （５）
（式中、ｃ、ｄ、ｅは上記のとおりであり、ｃ＋ｄ＋ｅ＝１である。） Examples of the three-dimensional network siloxane include those exemplified for component (A) above, and those represented by the following formula (5) are preferred.
[( CH2 =CH)( C6H5 ) ( CH3 )SiO1/ 2 ] c [( C6H5 ) 2SiO2 / 2 ] d [SiO4 /2 ] e (5)
(In the formula, c, d, and e are as described above, and c+d+e=1.)

三次元網状シロキサンの具体例を下記に示すが、これらに限定されるものではない。
［（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２］０．２５［（Ｃ６Ｈ５）２ＳｉＯ２／２］０．３［ＳｉＯ４／２］０．４５
［（ＣＨ２＝ＣＨ）（ＣＨ３）２ＳｉＯ１／２］０．２５［（Ｃ６Ｈ５）２ＳｉＯ２／２］０．３［ＳｉＯ４／２］０．４５ Specific examples of the three-dimensional network siloxane are shown below, but the invention is not limited thereto.
[( CH2 =CH)( C6H5 )( CH3 )SiO1/ 2 ] 0.25 [ (C6H5 ) 2SiO2 /2 ] 0.3 [SiO4 /2 ] 0.45
[(CH 2 =CH) (CH 3 ) 2 SiO 1/2 ] 0.25 [(C 6 H 5 ) 2 SiO 2/2 ] 0.3 [SiO 4/2 ] 0.45

（Ｂ）成分は、１種単独でも２種以上を組み合わせても使用することができる。 Component (B) can be used alone or in combination of two or more.

（Ｂ）成分の配合量は、組成物中のアルケニル基に対するＳｉＨ基のモル比（ＳｉＨ基／アルケニル基）が０．５以上５以下となる量が好ましく、より好ましくは０．８以上２以下となる量である。前記モル比（ＳｉＨ基／脂肪族不飽和基）が０．５以上５以下であれば、本発明の組成物を十分に硬化させることができる。 The blending amount of component (B) is preferably such that the molar ratio of SiH groups to alkenyl groups in the composition (SiH groups/alkenyl groups) is 0.5 or more and 5 or less, more preferably 0.8 or more and 2 or less. This is the amount. When the molar ratio (SiH group/aliphatic unsaturated group) is 0.5 or more and 5 or less, the composition of the present invention can be sufficiently cured.

［（Ｃ）成分］
本発明の（Ｃ）成分であるヒドロシリル化反応触媒は、上記（Ａ）成分の調製に用いられるものと同様のものが使用できる。 [(C) Component]
The hydrosilylation reaction catalyst which is component (C) of the present invention can be the same as that used in the preparation of component (A) above.

本発明の付加硬化型シリコーン組成物への（Ｃ）成分の配合量は、触媒としての有効量であればよく、特に制限されないが、組成物全体の質量に対して、白金族金属原子として、好ましくは１～５００ｐｐｍ、より好ましくは１～１００ｐｐｍ、さらに好ましくは２～１２ｐｐｍとなる量を配合することが好ましい。前記範囲内の配合量とすることで、硬化反応に要する時間が適度のものとなり、硬化物の着色を抑制できる。 The amount of component (C) to be blended in the addition-curing silicone composition of the present invention is not particularly limited as long as it is an effective amount as a catalyst, but as platinum group metal atoms based on the mass of the entire composition, It is preferred that the amount is preferably 1 to 500 ppm, more preferably 1 to 100 ppm, and still more preferably 2 to 12 ppm. By setting the blending amount within the above range, the time required for the curing reaction becomes appropriate, and coloring of the cured product can be suppressed.

［その他の成分］
本発明の付加硬化型シリコーン組成物には、上記（Ａ）～（Ｃ）成分に加え、必要に応じて酸化防止剤、無機充填剤、接着性向上剤等の成分を配合してもよい。 [Other ingredients]
In addition to the above-mentioned components (A) to (C), the addition-curable silicone composition of the present invention may contain components such as an antioxidant, an inorganic filler, and an adhesion improver, if necessary.

［酸化防止剤］
本発明の付加硬化型シリコーン組成物の硬化物中には、上記（Ｂ）成分中の付加反応性炭素－炭素二重結合が未反応のまま残存している場合があり、それが大気中の酸素により酸化されることで硬化物が着色する原因となり得る。そこで、必要に応じ、本発明の付加硬化型シリコーン組成物に酸化防止剤を配合することにより、このような着色を未然に防止することができる。 [Antioxidant]
In the cured product of the addition-curable silicone composition of the present invention, the addition-reactive carbon-carbon double bond in the component (B) may remain unreacted, and this Oxidation by oxygen may cause coloring of the cured product. Therefore, such coloring can be prevented by adding an antioxidant to the addition-curing silicone composition of the present invention, if necessary.

酸化防止剤としては、公知のものを使用することができ、例えば、２，６－ジ－ｔ－ブチル－４－メチルフェノール、２，５－ジ－ｔ－アミルヒドロキノン、２，５－ジ－ｔ－ブチルヒドロキノン、４，４‘－ブチリデンビス（３－メチル－６－ｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔ－ブチルフェノール）、２，２‘－メチレンビス（４－エチル－６－ｔ－ブチルフェノール）等が挙げられる。これらは、１種単独でも２種以上を組み合わせても使用することができる。 As the antioxidant, known antioxidants can be used, such as 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, and 2,5-di-t-amylhydroquinone. t-Butylhydroquinone, 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4- ethyl-6-t-butylphenol) and the like. These can be used alone or in combination of two or more.

なお、この酸化防止剤を使用する場合、その配合量は特に制限されないが、上記（Ａ）成分と（Ｂ）成分との合計質量に対して、通常、１～１０，０００ｐｐｍ、特に１０～１，０００ｐｐｍ程度配合することが好ましい。前記範囲内の配合量とすることによって、酸化防止能力が十分発揮され、着色、白濁、酸化劣化等の発生がなく光学的特性に優れた硬化物が得られる。 When using this antioxidant, its amount is not particularly limited, but it is usually 1 to 10,000 ppm, especially 10 to 1 ppm, based on the total mass of components (A) and (B). ,000 ppm is preferable. By incorporating the amount within the above range, the antioxidant ability is fully exhibited, and a cured product with excellent optical properties without coloration, cloudiness, oxidative deterioration, etc. can be obtained.

［無機充填剤］
本発明の付加硬化型シリコーン組成物の粘度や、本発明の付加硬化型シリコーン組成物から得られる硬化物の硬度等を調整したり、強度を向上させたり、蛍光体の分散を良くするために、ナノシリカや、溶融シリカ、結晶性シリカ、酸化チタン、ナノアルミナ、アルミナ等の無機充填剤を添加しても良い。 [Inorganic filler]
To adjust the viscosity of the addition-curable silicone composition of the present invention, the hardness of the cured product obtained from the addition-curable silicone composition of the present invention, improve the strength, and improve the dispersion of the phosphor. , nanosilica, fused silica, crystalline silica, titanium oxide, nanoalumina, alumina, and other inorganic fillers may be added.

［接着性向上剤］
本発明の付加硬化型シリコーン組成物には、接着性向上剤を配合してもよい。接着性向上剤としては、シランカップリング剤やそのオリゴマー、シランカップリング剤と同様の反応性基を有するポリシロキサン等が例示される。 [Adhesion improver]
The addition-curable silicone composition of the present invention may contain an adhesion improver. Examples of the adhesion improver include a silane coupling agent, an oligomer thereof, and a polysiloxane having the same reactive group as the silane coupling agent.

接着性向上剤は、本発明の付加硬化型シリコーン組成物及びその硬化物の基材に対する接着性を向上させるために組成物に配合される任意成分である。ここで、基材とは、金、銀、銅、ニッケルなどの金属材料、酸化アルミニウム、窒化アルミニウム、酸化チタンなどのセラミック材料、シリコーン樹脂、エポキシ樹脂などの高分子材料を指す。接着性向上剤は、１種単独でも２種以上を組み合わせても使用することができる。 The adhesion improver is an optional component that is added to the composition in order to improve the adhesion of the addition-curable silicone composition of the present invention and its cured product to a substrate. Here, the base material refers to metal materials such as gold, silver, copper, and nickel, ceramic materials such as aluminum oxide, aluminum nitride, and titanium oxide, and polymer materials such as silicone resin and epoxy resin. The adhesion improvers can be used alone or in combination of two or more.

接着性向上剤を使用する場合の配合量は、上記（Ａ）成分と（Ｂ）の合計１００質量部に対し、好ましくは１～３０質量部であり、より好ましくは、１～１０質量部である。このような配合量であると、本発明の熱硬化性シリコーン組成物及びその硬化物は、基材に対する接着性が効果的に向上し、また、着色が起こりにくい。 When using an adhesion improver, the blending amount is preferably 1 to 30 parts by mass, more preferably 1 to 10 parts by mass, based on the total of 100 parts by mass of components (A) and (B). be. With such a blending amount, the thermosetting silicone composition of the present invention and its cured product effectively improve the adhesion to the substrate, and are less likely to be colored.

接着性向上剤の好適な具体例としては、下記式で表されるものが挙げられるが、これらに限定されるものではない。

Figure 0007388865000012
Preferred specific examples of the adhesion improver include those represented by the following formulas, but are not limited thereto.
Figure 0007388865000012

［その他］
また、ポットライフを確保するために、１－エチニルシクロヘキサノール、３，５－ジメチル－１－ヘキシン－３－オール等の付加反応制御剤を配合することができる。 [others]
Further, in order to ensure pot life, addition reaction control agents such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyn-3-ol can be added.

更に、太陽光線、蛍光灯等の光エネルギーによる光劣化に抵抗性を付与するため光安定剤を用いることも可能である。この光安定剤としては、光酸化劣化で生成するラジカルを補足するヒンダードアミン系安定剤が適しており、酸化防止剤と併用することで、酸化防止効果はより向上する。光安定剤の具体例としては、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート、４－ベンゾイル－２，２，６，６－テトラメチルピペリジン等が挙げられる。 Furthermore, it is also possible to use a light stabilizer to impart resistance to photodeterioration caused by light energy such as sunlight and fluorescent lamps. As this light stabilizer, a hindered amine stabilizer that captures radicals generated by photooxidative deterioration is suitable, and when used in combination with an antioxidant, the antioxidant effect is further improved. Specific examples of the light stabilizer include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, and the like.

また、本発明組成物を封止材料として用いる場合には、基材との接着性を向上させるためにシランカップリング剤を配合してもよいし、クラック防止のため可塑剤を添加してもよい。 Furthermore, when the composition of the present invention is used as a sealing material, a silane coupling agent may be added to improve adhesion to the base material, or a plasticizer may be added to prevent cracking. good.

［硬化物］
本発明の付加硬化型シリコーン組成物を硬化して本発明の硬化物とする。前記硬化物は、硬度、靭性が高く、短波長領域の光透過性、透明性、耐熱変色性に優れる。なお、本発明の付加硬化型シリコーン組成物の硬化条件については、特に制限されないが、６０～１８０℃、５～１８０分の条件とすることが好ましい。 [Cured product]
The addition-curable silicone composition of the present invention is cured to obtain the cured product of the present invention. The cured product has high hardness and toughness, and is excellent in light transmittance in a short wavelength region, transparency, and heat discoloration resistance. Note that the curing conditions for the addition-curable silicone composition of the present invention are not particularly limited, but preferably conditions are 60 to 180°C and 5 to 180 minutes.

本発明の付加硬化型シリコーン組成物から得られる硬化物は、厚さ２ｍｍにおける波長４００ｎｍの初期の光透過率（２５℃）が８０％以上であることが好ましい。 The cured product obtained from the addition-curable silicone composition of the present invention preferably has an initial light transmittance (25° C.) at a wavelength of 400 nm at a thickness of 2 mm of 80% or more.

さらに、本発明の硬化物は、１８０℃で１，０００時間静置後、厚さ２ｍｍにおける波長４００ｎｍの光透過率（２５℃）は６０％以上であることが好ましい。本発明は、このような耐熱変色性を有することができる。 Further, the cured product of the present invention preferably has a light transmittance (at 25° C.) at a wavelength of 400 nm at a thickness of 2 mm of 60% or more after being allowed to stand at 180° C. for 1,000 hours. The present invention can have such heat discoloration resistance.

このような光学特性を有する本発明の硬化物であれば、発光ダイオード素子の保護、封止もしくは接着、波長変更もしくは調整またはレンズ等の用途に好適に使用できるほか、レンズ材料、光学デバイスもしくは光学部品用封止材、ディスプレイ材料等の各種の光学部品用材料、電子デバイスもしくは電子部品用絶縁材料、更にはコーティング材料としても有用な材料となる。 The cured product of the present invention having such optical properties can be suitably used for protection, sealing or adhesion of light emitting diode elements, wavelength change or adjustment, lenses, etc., as well as lens materials, optical devices or optical The material is useful as a sealing material for components, a material for various optical components such as a display material, an insulating material for electronic devices or electronic components, and even a coating material.

［半導体装置］
本発明では更に、上記の付加硬化型シリコーン組成物から得られる硬化物により半導体素子が被覆された半導体装置を提供する。 [Semiconductor device]
The present invention further provides a semiconductor device in which a semiconductor element is coated with a cured product obtained from the above addition-curable silicone composition.

以下、図１を参照して、本発明の付加硬化型シリコーン組成物の硬化物を用いた半導体装置（以下、「本発明の半導体装置」ともいう）について説明するが、本発明はこれらに限定されるものではない。 Hereinafter, with reference to FIG. 1, a semiconductor device using a cured product of the addition-curable silicone composition of the present invention (hereinafter also referred to as "semiconductor device of the present invention") will be described, but the present invention is limited thereto. It is not something that will be done.

図１は、本発明の半導体装置の一例を示す概略断面図である。本発明の半導体装置１は、銀メッキ基板２が形成されたパッケージ３上に、半導体チップ４がダイボンドされており、この半導体チップ４は、ボンディングワイヤ５によりワイヤボンディングされている。そして、上述した本発明の付加硬化型シリコーン組成物の硬化物６により、半導体チップ４が被覆されている。半導体チップ４の被覆は、上述した本発明の付加硬化型シリコーン組成物（硬化性組成物）を塗布し、加熱により付加硬化型シリコーン組成物を硬化させることにより行われる。なお、その他公知の硬化条件下で公知の硬化方法により硬化させても良い。 FIG. 1 is a schematic cross-sectional view showing an example of a semiconductor device of the present invention. In the semiconductor device 1 of the present invention, a semiconductor chip 4 is die-bonded onto a package 3 on which a silver-plated substrate 2 is formed, and this semiconductor chip 4 is wire-bonded with a bonding wire 5. The semiconductor chip 4 is coated with the cured product 6 of the addition-curable silicone composition of the present invention described above. The semiconductor chip 4 is coated by applying the above-mentioned addition-curing silicone composition (curable composition) of the present invention and curing the addition-curing silicone composition by heating. In addition, it may be cured by a known curing method under other known curing conditions.

この場合、外部応力の影響を受け難くし、又ゴミ等の付着を極力抑えるという観点から、上記付加硬化型シリコーン組成物は、硬化により、ＪＩＳやＡＳＴＭ Ｄ ２２４０に規定の硬さがデュロメータＤで３０以上の硬化物を形成するものであることが好ましい。 In this case, from the viewpoint of making it less susceptible to external stress and minimizing the adhesion of dust, etc., the above-mentioned addition-curing silicone composition has a hardness of durometer D specified by JIS or ASTM D 2240 by curing. It is preferable that it forms a cured product of 30 or more.

本発明の付加硬化型シリコーン組成物は、透明性、耐熱変色性、靱性に優れた硬化物を形成するため、この付加硬化型シリコーン組成物を用いた本発明の半導体装置は、信頼性に優れたものとなる。 Since the addition-curing silicone composition of the present invention forms a cured product with excellent transparency, heat discoloration resistance, and toughness, the semiconductor device of the present invention using this addition-curing silicone composition has excellent reliability. It becomes something.

以下、実施例及び比較例を用いて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples, but the present invention is not limited thereto.

また、実施例において、１Ｈ－ＮＭＲ測定はブルカー・バイオスピン社製ＡＶＡＮＣＥ ＩＩＩを使用した。ＧＰＣ（ゲルパーミエーションクロマトグラフィー）測定は、東ソー（株）製ＨＬＣ－８３２０ＧＰＣを用い、移動相としてテトラヒドロフラン（ＴＨＦ）を使用し、ポリスチレン換算の重量平均分子量（Ｍｗ）を求めた。 Furthermore, in the examples, AVANCE III manufactured by Bruker Biospin was used for 1 H-NMR measurement. GPC (gel permeation chromatography) measurement was performed using HLC-8320GPC manufactured by Tosoh Corporation, using tetrahydrofuran (THF) as the mobile phase, and determining the weight average molecular weight (Mw) in terms of polystyrene.

下記の例において、オルガノポリシロキサンの構成単位を表す記号は以下のとおりである。
ＭΦＶｉ：（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２
Ｄ２Φ：（Ｃ６Ｈ５）２ＳｉＯ２／２
Ｑ：ＳｉＯ４／２ In the examples below, the symbols representing the structural units of organopolysiloxane are as follows.
MΦVi : ( CH2 =CH)( C6H5 )( CH3 ) SiO1 /2
D2Φ : ( C6H5 )2SiO2 / 2
Q: SiO 4/2

［合成例１］付加反応物（Ａ－１）の調製
攪拌装置、冷却管、滴下ロートおよび温度計を備えた１Ｌの４つ口フラスコに、１，４－ビス（ジメチルシリル）ベンゼン（北興化学工業株式会社製）９４ｇ（０．５ モル）、５％Ｐｔカーボン粉末（エヌ・イーケムキャット株式会社製）０．０７ｇを加え、オイルバスを用いて８５℃に加熱した。これを撹拌しながらＭΦＶｉ ２で表されるジシロキサン（北興化学工業株式会社製）４７ｇ（０．１５モル）と、ＭΦＶｉ ０．２５Ｄ２Φ ０．３Ｑ０．４５で表される分岐状オルガノポリシロキサン（ビニル基：０．２モル／１００ｇ）の７５％キシレン溶液３１ｇ（ビニル基：０．０４７モル）との混合液を滴下した。滴下終了後、９０～１００℃の間で３時間撹拌した。撹拌終了後２５℃に戻し、１Ｈ－ＮＭＲスペクトル測定にてビニル基のピーク消失を確認した。活性炭を１．７ｇ加え１時間撹拌後、Ｐｔカーボン粉末、及び活性炭を濾別し、減圧濃縮により余剰の１，４－ビス（ジメチルシリル）ベンゼンを除去することで、付加反応物（Ａ－１）（無色透明、２３℃における粘度：１３Ｐａ・ｓ、Ｍｗ：３，０５０、ＳｉＨ基の含有割合：０．００１６６モル／ｇ）を得た。 [Synthesis Example 1] Preparation of addition reaction product (A-1) In a 1L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer, 1,4-bis(dimethylsilyl)benzene (Hokuko Chemical Co., Ltd.) was added. 94 g (0.5 mol) of 5% Pt carbon powder (manufactured by N.E. Chemcat Co., Ltd.) were added thereto, and the mixture was heated to 85° C. using an oil bath. While stirring this, add 47 g (0.15 mol) of disiloxane represented by M ΦVi 2 (manufactured by Hokuko Chemical Industry Co., Ltd.) and a branched product represented by M ΦVi 0.25 D 2Φ 0.3 Q 0.45 . A mixture of 31 g of a 75% xylene solution (vinyl group: 0.047 mol) of organopolysiloxane (vinyl group: 0.2 mol/100 g) was added dropwise. After the dropwise addition was completed, the mixture was stirred at 90 to 100°C for 3 hours. After the stirring was completed, the temperature was returned to 25°C, and disappearance of the vinyl group peak was confirmed by 1 H-NMR spectrum measurement. After adding 1.7 g of activated carbon and stirring for 1 hour, Pt carbon powder and activated carbon were filtered out, and excess 1,4-bis(dimethylsilyl)benzene was removed by vacuum concentration to obtain the addition reaction product (A-1). ) (colorless and transparent, viscosity at 23° C.: 13 Pa·s, Mw: 3,050, SiH group content: 0.00166 mol/g) was obtained.

［合成例２］付加反応物（Ａ－２）の調製
攪拌装置、冷却管、滴下ロートおよび温度計を備えた１Ｌの４つ口フラスコに、１，４－ビス（ジメチルシリル）ベンゼン（北興化学工業株式会社製）１０５ｇ（０．５４モル）、５％Ｐｔカーボン粉末（エヌ・イーケムキャット株式会社製）０．０９ｇを加え、オイルバスを用いて８５℃に加熱した。これを撹拌しながらＭΦＶｉ ２で表されるジシロキサン（北興化学工業株式会社製）４７ｇ（０．１５モル）と、ＭΦＶｉ ０．２５Ｄ２Φ ０．３Ｑ０．４５で表される分岐状オルガノポリシロキサン（ビニル基：０．２モル／１００ｇ）の７５％キシレン溶液６２ｇ（ビニル基：０．０９モル）との混合液を滴下した。滴下終了後、９０～１００℃の間で３時間撹拌した。撹拌終了後２５℃に戻し、１Ｈ－ＮＭＲスペクトル測定にてビニル基のピーク消失を確認した。活性炭を１．７ｇ加え１時間撹拌後、Ｐｔカーボン粉末、及び活性炭を濾別し、減圧濃縮により余剰の１，４－ビス（ジメチルシリル）ベンゼンを除去することで、付加反応物（Ａ－２）（無色透明、２３℃における粘度：４２Ｐａ・ｓ、Ｍｗ：４，３７０、ＳｉＨ基の含有割合：０．００１５７モル／ｇ）を得た。 [Synthesis Example 2] Preparation of addition reaction product (A-2) In a 1 L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer, 1,4-bis(dimethylsilyl)benzene (Hokuko Chemical Co., Ltd.) was added. 105 g (0.54 mol) of 5% Pt carbon powder (manufactured by N.E. Chemcat Co., Ltd.) were added thereto, and the mixture was heated to 85° C. using an oil bath. While stirring this, add 47 g (0.15 mol) of disiloxane represented by M ΦVi 2 (manufactured by Hokuko Chemical Industry Co., Ltd.) and a branched product represented by M ΦVi 0.25 D 2Φ 0.3 Q 0.45 . A mixture of 62 g of a 75% xylene solution (vinyl group: 0.09 mol) of organopolysiloxane (vinyl group: 0.2 mol/100 g) was added dropwise. After the dropwise addition was completed, the mixture was stirred at 90 to 100°C for 3 hours. After the stirring was completed, the temperature was returned to 25°C, and disappearance of the vinyl group peak was confirmed by 1 H-NMR spectrum measurement. After adding 1.7 g of activated carbon and stirring for 1 hour, the Pt carbon powder and activated carbon were filtered out, and excess 1,4-bis(dimethylsilyl)benzene was removed by vacuum concentration to obtain the addition reaction product (A-2). ) (colorless and transparent, viscosity at 23° C.: 42 Pa·s, Mw: 4,370, SiH group content: 0.00157 mol/g) was obtained.

［合成例３］付加反応物（Ａ－３）の調製
攪拌装置、冷却管、滴下ロートおよび温度計を備えた１Ｌの４つ口フラスコに、１，４－ビス（ジメチルシリル）ベンゼン（北興化学工業株式会社製）１２２ｇ（０．６３モル）、５％Ｐｔカーボン粉末（エヌ・イーケムキャット株式会社製）０．１０ｇを加え、オイルバスを用いて８５℃に加熱した。これを撹拌しながらＭΦＶｉ ２で表されるジシロキサン（北興化学工業株式会社製）４７ｇ（０．１５モル）と、ＭΦＶｉ ０．２５Ｄ２Φ ０．３Ｑ０．４５で表される分岐状オルガノポリシロキサン（ビニル基：０．２モル／１００ｇ）の７５％キシレン溶液９３ｇ（ビニル基：０．１３５モル）の混合液を滴下した。滴下終了後、９０～１００℃の間で３時間撹拌した。撹拌終了後２５℃に戻し、１Ｈ－ＮＭＲスペクトル測定にてビニル基のピーク消失を確認した。活性炭を２．６ｇ加え１時間撹拌後、Ｐｔカーボン粉末、及び活性炭を濾別し、減圧濃縮により余剰の１，４－ビス（ジメチルシリル）ベンゼンを除去することで、付加反応物（Ａ－３）（無色透明、２３℃における粘度：１４０Ｐａ・ｓ、Ｍｗ：５，０００、ＳｉＨ基の含有割合：０．００１４５モル／ｇ）を得た。 [Synthesis Example 3] Preparation of addition reaction product (A-3) In a 1 L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel, and a thermometer, 1,4-bis(dimethylsilyl)benzene (Hokuko Chemical Co., Ltd.) was added. 122 g (0.63 mol) of 5% Pt carbon powder (manufactured by N.E. Chemcat Co., Ltd.) were added thereto, and the mixture was heated to 85° C. using an oil bath. While stirring this, add 47 g (0.15 mol) of disiloxane represented by M ΦVi 2 (manufactured by Hokuko Chemical Industry Co., Ltd.) and a branched product represented by M ΦVi 0.25 D 2Φ 0.3 Q 0.45 . A mixture of 93 g (vinyl group: 0.135 mol) of a 75% xylene solution of organopolysiloxane (vinyl group: 0.2 mol/100 g) was added dropwise. After the dropwise addition was completed, the mixture was stirred at 90 to 100°C for 3 hours. After the stirring was completed, the temperature was returned to 25°C, and disappearance of the vinyl group peak was confirmed by 1 H-NMR spectrum measurement. After adding 2.6 g of activated carbon and stirring for 1 hour, Pt carbon powder and activated carbon were filtered out, and excess 1,4-bis(dimethylsilyl)benzene was removed by vacuum concentration to obtain the addition reaction product (A-3). ) (colorless and transparent, viscosity at 23° C.: 140 Pa·s, Mw: 5,000, SiH group content: 0.00145 mol/g) was obtained.

［比較合成例１］付加反応物（Ａ－４）の調製
攪拌装置、冷却管、滴下ロートおよび温度計を備えた１Ｌの４つ口フラスコに、１，４－ビス（ジメチルシリル）ベンゼン（信越化学工業株式会社製）２６２．８ｇ（１．３５モル）、５％Ｐｔカーボン粉末（エヌ・イーケムキャット株式会社製）０．１２ｇを加え、オイルバスを用いて８５℃に加熱した。これを撹拌しながらトリビニルフェニルシラン（信越化学工業株式会社製）を２８．０ｇ（０．１５モル）滴下した。滴下終了後、９０～１００℃の間で５時間撹拌した。撹拌終了後２５℃に戻し、１Ｈ－ＮＭＲスペクトル測定にてビニル基のピーク消失を確認した。活性炭を２．９ｇ加え１時間撹拌後、Ｐｔカーボン粉末、及び活性炭を濾別し、減圧濃縮により余剰の１，４－ビス（ジメチルシリル）ベンゼンを除去することで、付加反応物（Ａ－４）９９．７ｇ（無色透明、２５℃における粘度：３０Ｐａ・ｓ、Ｍｗ：１，５００、ＳｉＨ基の含有割合：０．００３５モル／ｇ、下記式で表される構成単位比を有するオリゴマーの混合物）を得た。 [Comparative Synthesis Example 1] Preparation of addition reaction product (A-4) 1,4-bis(dimethylsilyl)benzene (Shin-Etsu 262.8 g (1.35 mol) of Kagaku Kogyo Co., Ltd.) and 0.12 g of 5% Pt carbon powder (manufactured by N.E. Chemcat Co., Ltd.) were added, and the mixture was heated to 85° C. using an oil bath. While stirring this, 28.0 g (0.15 mol) of trivinylphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise. After the addition was completed, the mixture was stirred at 90 to 100°C for 5 hours. After the stirring was completed, the temperature was returned to 25°C, and disappearance of the vinyl group peak was confirmed by 1 H-NMR spectrum measurement. After adding 2.9 g of activated carbon and stirring for 1 hour, Pt carbon powder and activated carbon were filtered out, and excess 1,4-bis(dimethylsilyl)benzene was removed by vacuum concentration to obtain the addition reaction product (A-4). ) 99.7g (colorless and transparent, viscosity at 25°C: 30 Pa・s, Mw: 1,500, SiH group content: 0.0035 mol/g, mixture of oligomers having a constituent unit ratio represented by the following formula) ) was obtained.

Figure 0007388865000013
（式中、ｎは１以上の整数であり、破線は結合手を表す。）
Figure 0007388865000013
 (In the formula, n is an integer of 1 or more, and the broken line represents a bond.)

［実施例１～４、比較例１、２］
表１に示す組成比（数値は質量部を表す）で下記の各成分を混合し、組成物中のアルケニル基に対するＳｉＨ基のモル比（［ＳｉＨ基］／［アルケニル基］）が０．９となるように付加硬化型シリコーン組成物を調製した。混合後の外観を目視にて確認した結果を表１に示す。 [Examples 1 to 4, Comparative Examples 1 and 2]
The following components were mixed at the composition ratios shown in Table 1 (numbers represent parts by mass), and the molar ratio of SiH groups to alkenyl groups in the composition ([SiH groups]/[alkenyl groups]) was 0.9. An addition-curing silicone composition was prepared as follows. Table 1 shows the results of visual confirmation of the appearance after mixing.

（Ａ）成分
（Ａ－１）上記合成例１で得られた付加反応物
（Ａ－２）上記合成例２で得られた付加反応物
（Ａ－３）上記合成例３で得られた付加反応物
比較成分
（Ａ－４）上記比較合成例１で得られた付加反応物 (A) Component (A-1) Addition reaction product obtained in the above Synthesis Example 1 (A-2) Addition reaction product obtained in the above Synthesis Example 2 (A-3) Addition reaction product obtained in the above Synthesis Example 3 Reactant comparison component (A-4) Addition reaction product obtained in Comparative Synthesis Example 1 above

（Ｂ）成分
（Ｂ－１）ＭΦＶｉ ２Ｄ２Φ ３で表される直鎖状オルガノポリシロキサン
（Ｂ－２）ＭΦＶｉ ０．２５Ｄ２Φ ０．３Ｑ０．４５で表される三次元網状オルガノポリシロキサン（ビニル基：０．２モル／１００ｇ） (B) Component (B-1) Linear organopolysiloxane represented by M ΦVi 2 D 2Φ 3 (B-2) Three-dimensional represented by M ΦVi 0.25 D 2Φ 0.3 Q 0.45 Reticulated organopolysiloxane (vinyl group: 0.2 mol/100g)

（Ｃ）成分
白金１，３－ジビニル－１，１，３，３－テトラメチルジシロキサン錯体のポリシロキサン希釈品（白金含有量：１重量％） (C) Component Polysiloxane diluted product of platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum content: 1% by weight)

（Ｄ）成分
下記構造式で表される接着性向上剤

Figure 0007388865000014
(D) Component Adhesiveness improver represented by the following structural formula
Figure 0007388865000014

（Ｅ）成分
酸化防止剤：２，６－ジ－ｔ－ブチル－４－メチルフェノール (E) Component Antioxidant: 2,6-di-t-butyl-4-methylphenol

（Ｆ）成分
付加反応制御剤：１－エチニルシクロヘキサノール (F) Component Addition reaction control agent: 1-ethynylcyclohexanol

Figure 0007388865000015
Figure 0007388865000015

［性能評価手法］
上記実施例および比較例で得られた付加硬化型シリコーン組成物について、下記手法に従い、その硬化物の性能を評価した。なお、比較例２については組成物が相溶せず、硬化物を得ることが出来なかった。 [Performance evaluation method]
Regarding the addition-curing silicone compositions obtained in the above examples and comparative examples, the performance of the cured products was evaluated according to the following method. Note that in Comparative Example 2, the compositions were not compatible and a cured product could not be obtained.

（１）硬度
ガラス板で組んだ型の中に付加硬化型シリコーン組成物を流し込み、１５０℃で４時間硬化を行い、６ｍｍ厚の硬化物を得た。ＡＳＴＭ Ｄ ２２４０に準じて、各硬化物のＳｈｏｒｅ Ｄ硬度を２３℃で測定した結果を表２に示す。 (1) Hardness An addition-curing silicone composition was poured into a mold made of glass plates and cured at 150° C. for 4 hours to obtain a cured product with a thickness of 6 mm. The Shore D hardness of each cured product was measured at 23°C in accordance with ASTM D 2240, and the results are shown in Table 2.

（２）光透過率（耐熱変色性）
上記硬度測定と同様に調製した２ｍｍ厚の硬化物について、作成直後（初期）および１８０℃のオーブン内に１，０００時間置いた後における各硬化物の４００ｎｍ光透過率を分光光度計を用いて測定した。測定結果を表２に示す。 (2) Light transmittance (thermal discoloration resistance)
For 2 mm thick cured products prepared in the same manner as the hardness measurement above, the 400 nm light transmittance of each cured product immediately after creation (initial stage) and after being placed in an oven at 180°C for 1,000 hours was measured using a spectrophotometer. It was measured. The measurement results are shown in Table 2.

（３）靭性評価
上記硬度測定と同様に、２ｍｍ厚の硬化物を作成し、それぞれの硬化物を直径１ｍｍの金属棒に沿って２３℃で直角に折り曲げた時の状態を、〇（割れずに曲がる）、×（割れる）で評価した。 (3) Toughness evaluation In the same way as the hardness measurement above, cured products with a thickness of 2 mm were made, and when each cured product was bent at right angles at 23°C along a metal rod with a diameter of 1 mm, the state was 〇 (without cracking). It was evaluated as (bending) and × (breaking).

Figure 0007388865000016
Figure 0007388865000016

表１および表２に示されるように、本発明の付加硬化型シリコーン組成物は（Ａ）成分及び（Ｂ）成分の相溶性が良好なものであり、透明性、硬度、耐熱変色性、靱性に優れた硬化物を与えた。 As shown in Tables 1 and 2, the addition-curable silicone composition of the present invention has good compatibility between component (A) and component (B), and has good transparency, hardness, heat discoloration resistance, and toughness. It gave an excellent cured product.

一方、本発明の（Ａ）成分に代えてトリビニルフェニルシランと１，４－ビス（ジメチルシリル）ベンゼンとの付加反応物を用いた組成物は耐熱変色性に劣り（比較例１）、更に（Ｂ）成分として三次元網状オルガノポリシロキサンを含む場合の相溶性が不十分であった（比較例２）。 On the other hand, a composition using an addition reaction product of trivinylphenylsilane and 1,4-bis(dimethylsilyl)benzene in place of component (A) of the present invention has poor heat discoloration resistance (Comparative Example 1), and When the component (B) contained a three-dimensional network organopolysiloxane, the compatibility was insufficient (Comparative Example 2).

なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。 Note that the present invention is not limited to the above embodiments. The above-mentioned embodiments are illustrative, and any embodiment having substantially the same configuration as the technical idea stated in the claims of the present invention and having similar effects may be included in the present invention. covered within the technical scope of.

１…半導体装置、 ２…銀メッキ基板、 ３…パッケージ、 ４…半導体チップ、
５…ボンディングワイヤ、 ６…付加硬化型シリコーン組成物の硬化物。 1... Semiconductor device, 2... Silver plated substrate, 3... Package, 4... Semiconductor chip,
5... Bonding wire, 6... Cured product of addition-curable silicone composition.

Claims (4)

下記（Ａ）、（Ｂ）及び（Ｃ）を含む付加硬化型シリコーン組成物。
（Ａ）下記式（１）で表される有機ケイ素化合物と、下記式（２）で表される直鎖状シロキサン及び下記式（３）で表される三次元網状シロキサンとの付加反応物であって、１分子中にＳｉＨ基を２個以上有し、
Figure 0007388865000017
 （式中、Ｒ１は置換または非置換の炭素原子数１～１２の２価炭化水素基である。）
Figure 0007388865000018
 （式中、Ｒ２、Ｒ４は独立に置換または非置換の炭素原子数１～１２の１価炭化水素基であり、Ｒ３は独立に単結合または非置換の炭素数１～４の２価炭化水素基である。ａは１～３の整数であり、ｂは０～１００の整数である。）
（Ｒ５ ３ＳｉＯ１／２）ｃ（Ｒ５ ２ＳｉＯ２／２）ｄ（ＳｉＯ４／２）ｅ（ＸＯ１／２）ｆ （３）
（式中、Ｒ５は独立に置換または非置換の炭素原子数１～１２の１価炭化水素基であり、但し、Ｒ５の全数のうち０．１～４０％はアルケニル基であり、かつ、１０～９９．９％はアリール基である。Ｘは水素原子またはアルキル基であり、ｃは０．１～０．５の数であり、ｄは０．１～０．６の数であり、ｅは０．２～０．８の数であり、ｆは０～０．２の数であり、ｃ＋ｄ＋ｅ＋ｆ＝１である。）
上記式（１）で表される前記有機ケイ素化合物が、１，４－ビス（ジメチルシリル）ベンゼンであり、
上記式（２）で表される前記直鎖状シロキサンが、ＭΦＶｉ ２で表されるジシロキサンであり、
上記式（３）で表される前記三次元網状シロキサンが、ＭΦＶｉ ０．２５Ｄ２Φ ０．３Ｑ０．４５で表される分岐状オルガノポリシロキサンであり、
ＭΦＶｉが、（ＣＨ２＝ＣＨ）（Ｃ６Ｈ５）（ＣＨ３）ＳｉＯ１／２であり、
Ｄ２Φが、（Ｃ６Ｈ５）２ＳｉＯ２／２であり、
Ｑが、ＳｉＯ４／２である、付加反応物、
（Ｂ）アルケニル基を１分子中に２個以上有する化合物であって、
Ｍ ΦＶｉ ２ Ｄ ２Φ ３ で表される直鎖状オルガノポリシロキサン、又は
Ｍ ΦＶｉ ２ Ｄ ２Φ ３ で表される直鎖状オルガノポリシロキサンとＭ ΦＶｉ ０．２５ Ｄ ２Φ ０．３ Ｑ ０．４５ で表される三次元網状オルガノポリシロキサンとの混合物
（Ｍ ΦＶｉ が、（ＣＨ ２ ＝ＣＨ）（Ｃ ６ Ｈ ５ ）（ＣＨ ３ ）ＳｉＯ １／２ であり、Ｄ ２Φ が、（Ｃ ６ Ｈ ５ ） ２ ＳｉＯ ２／２ であり、Ｑが、ＳｉＯ ４／２ である）、
（Ｃ）ヒドロシリル化反応触媒 An addition-curing silicone composition comprising the following (A), (B) and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1), a linear siloxane represented by the following formula (2), and a three-dimensional network siloxane represented by the following formula (3). and has two or more SiH groups in one molecule,
Figure 0007388865000017
 (In the formula, R 1 is a substituted or unsubstituted divalent hydrocarbon group having 1 to 12 carbon atoms.)
Figure 0007388865000018
 (In the formula, R 2 and R 4 are independently substituted or unsubstituted monovalent hydrocarbon groups having 1 to 12 carbon atoms, and R 3 is independently a single bond or unsubstituted 2 to 4 carbon atoms. It is a valence hydrocarbon group. a is an integer of 1 to 3, and b is an integer of 0 to 100.)
(R 5 3 SiO 1/2 ) c (R 5 2 SiO 2/2 ) d (SiO 4/2 ) e (XO 1/2 ) f (3)
(In the formula, R 5 is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 12 carbon atoms, provided that 0.1 to 40% of the total number of R 5 is an alkenyl group, and , 10 to 99.9% are aryl groups. X is a hydrogen atom or an alkyl group, c is a number from 0.1 to 0.5, and d is a number from 0.1 to 0.6. , e is a number from 0.2 to 0.8, f is a number from 0 to 0.2, and c+d+e+f=1.)
The organosilicon compound represented by the above formula (1) is 1,4-bis(dimethylsilyl)benzene,
The linear siloxane represented by the above formula (2) is a disiloxane represented by M ΦVi 2 ,
The three-dimensional network siloxane represented by the above formula (3) is a branched organopolysiloxane represented by M ΦVi 0.25 D 2Φ 0.3 Q 0.45 ,
M ΦVi is (CH 2 =CH) (C 6 H 5 ) (CH 3 )SiO 1/2 ,
D 2Φ is (C 6 H 5 ) 2 SiO 2/2 ,
an addition reactant, where Q is SiO 4/2 ;
(B) a compound having two or more alkenyl groups in one molecule ,
Linear organopolysiloxane represented by M ΦVi 2 D 2Φ 3 , or
A mixture of a linear organopolysiloxane represented by M ΦVi 2 D 2Φ 3 and a three-dimensional network organopolysiloxane represented by M ΦVi 0.25 D 2Φ 0.3 Q 0.45
( M ΦVi is (CH 2 = CH) (C 6 H 5 ) (CH 3 ) SiO 1/2 , D 2Φ is (C 6 H 5 ) 2 SiO 2/2 , and Q is SiO 4/2 ) ,
(C) Hydrosilylation reaction catalyst 請求項１に記載の付加硬化型シリコーン組成物を硬化してなることを特徴とする硬化物。 A cured product obtained by curing the addition-curing silicone composition according to claim 1 . １８０℃で１，０００時間静置後、厚さ２ｍｍにおける波長４００ｎｍの光透過率（２５℃）が６０％以上であることを特徴とする請求項２に記載の硬化物。 The cured product according to claim 2, wherein the cured product has a light transmittance (25°C) at a wavelength of 400 nm at a thickness of 2 mm of 60% or more after being left at 180°C for 1,000 hours. 請求項２又は３に記載の硬化物により半導体素子が被覆されたものであることを特徴とする半導体装置。
A semiconductor device comprising a semiconductor element coated with the cured product according to claim 2 or 3 .
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