JP2020026502A - Curable composition, cured product of the composition, and semiconductor device using the cured product - Google Patents
Curable composition, cured product of the composition, and semiconductor device using the cured product Download PDFInfo
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- JP2020026502A JP2020026502A JP2018152932A JP2018152932A JP2020026502A JP 2020026502 A JP2020026502 A JP 2020026502A JP 2018152932 A JP2018152932 A JP 2018152932A JP 2018152932 A JP2018152932 A JP 2018152932A JP 2020026502 A JP2020026502 A JP 2020026502A
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- curable composition
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- H—ELECTRICITY
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- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
Description
本発明は、硬化性組成物、その硬化物、及び前記硬化物を用いた半導体装置に関する。 The present invention relates to a curable composition, a cured product thereof, and a semiconductor device using the cured product.
従来、光学デバイスまたは光学部品用材料、特に発光ダイオード(LED)素子の封止材料としては、一般的にエポキシ樹脂が用いられている。また、シリコーン樹脂に関しても、LED素子のモールド部材等として用いること(特許文献1、2)、またカラーフィルター材料として用いること(特許文献3)が試みられているが、実際上の使用例は少ない。
2. Description of the Related Art Conventionally, an epoxy resin is generally used as a material for an optical device or an optical component, particularly as a sealing material for a light emitting diode (LED) element. In addition, silicone resin has been tried to be used as a mold member or the like of an LED element (
近年、白色LEDが注目される中で、これまで問題とされなかったエポキシ封止材の紫外線等による黄変や、小型化に伴う発熱量の増加によるクラックの発生等が問題となっており対応が急務となっている。これらの対応策としては、分子中に多量のフェニル基を持つシリコーンレジン硬化物を用いることが検討されている。しかしながら、現状のLEDに使用されている基板は銀基板が使用されている事が多く、銀は空気中に存在する硫黄化合物により腐食され、これによりLEDの発光効率が落ちる場合がある。この現象はフェニル基を持つシリコーンレジン硬化物でもある程度は抑えられるが、エポキシ封止材には劣る。この対策として多環式炭化水素基を有する硬化組成物を用いることで、銀の腐食と耐熱性を両立した材料が提案されている(特許文献4)。しかしながら、この組成物は樹脂としての変化点が室温付近にあるため、高温・低温の温度変化により、クラックが発生しやすい。 In recent years, while white LEDs have attracted attention, yellowing of epoxy encapsulant, which has not been a problem until now, has become a problem due to yellowing due to ultraviolet rays, etc., and cracking due to increased heat generation due to miniaturization. Is urgently needed. As a countermeasure for these, use of a cured silicone resin having a large amount of phenyl groups in the molecule has been studied. However, silver substrates are often used as substrates used in current LEDs, and silver is corroded by sulfur compounds present in the air, which may reduce the luminous efficiency of the LED. This phenomenon can be suppressed to some extent even with a cured silicone resin having a phenyl group, but is inferior to an epoxy sealing material. As a countermeasure, there has been proposed a material that achieves both corrosion of silver and heat resistance by using a cured composition having a polycyclic hydrocarbon group (Patent Document 4). However, since this composition has a changing point near room temperature as a resin, cracks are likely to occur due to temperature changes at high and low temperatures.
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、硬度、機械的強度、および耐クラック性が高く、短波長領域の光透過性、ガスバリア性に優れた硬化物を与える硬化性組成物を提供することを目的とする。 The present invention has been made to solve the above problems, and has a high hardness, a high mechanical strength, and a high crack resistance, and has a light transmittance in a short wavelength region and a curable composition which gives a cured product having excellent gas barrier properties. The purpose is to provide things.
上記課題を達成するために、本発明では、下記(A)、(B)及び(C)を含む硬化性組成物を提供する。
(A)下記式(1)で表される有機ケイ素化合物と、下記式(2)で表される有機ケイ素化合物との付加反応物であって、1分子中にSiH基を3個以上有する付加反応物、
(B)アルケニル基を1分子中に2個以上有するオルガノシロキサン化合物、
(C)ヒドロシリル化反応触媒:組成物全体の質量に対して白金族金属原子として1〜500ppm
In order to achieve the above object, the present invention provides a curable composition containing the following (A), (B) and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), wherein the addition reaction has three or more SiH groups in one molecule. Reactants,
(B) an organosiloxane compound having two or more alkenyl groups in one molecule,
(C) Hydrosilylation reaction catalyst: 1 to 500 ppm as a platinum group metal atom based on the total mass of the composition
本発明の硬化性組成物であれば、硬度、機械的強度、および耐クラック性が高く、短波長領域の光透過性、ガスバリア性に優れた硬化物を与える硬化性組成物を提供できる。 The curable composition of the present invention can provide a curable composition having high hardness, mechanical strength, and crack resistance, and providing a cured product having excellent light transmittance in a short wavelength region and excellent gas barrier properties.
本発明の硬化性組成物は、上記R1がフェニレン基、上記R2がメチル基又はフェニル基であることができる。 In the curable composition of the present invention, R 1 may be a phenylene group, and R 2 may be a methyl group or a phenyl group.
本発明の硬化性組成物は、さらに前記(B)が下記式(3)で表される化合物であることが好ましい。
また本発明は、前記硬化性組成物を硬化してなる硬化物を提供する。 Further, the present invention provides a cured product obtained by curing the curable composition.
本発明の硬化物であれば、硬度、機械的強度、および耐クラック性が高く、短波長領域の光透過性、ガスバリア性に優れる。 The cured product of the present invention has high hardness, mechanical strength, and crack resistance, and is excellent in light transmittance in a short wavelength region and gas barrier properties.
本発明の硬化物は、厚さ2mmにおける波長400nmの光透過率(25℃)が80%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 a wavelength of 400 nm (25 ° C.) at a thickness of 2 mm of 80% or more.
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。 A cured product having such light transmittance can be suitably used for applications such as protection, sealing or adhesion, wavelength change or adjustment, or lens of a light emitting diode element.
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。 Further, the present invention provides a semiconductor device in which a semiconductor element is covered with the cured product.
本発明の半導体装置であれば、使用する硬化物の硬度、機械的強度、および耐クラック性が高く、そのガスバリア性が優れているため、高い耐久性を有する半導体装置となる。さらに、短波長領域の光透過性にも優れるため、発光ダイオード素子などの光透過性を要する半導体装置としても有用である。 According to the semiconductor device of the present invention, the hardness, mechanical strength, and crack resistance of the cured product used are high, and the gas barrier property thereof is excellent, so that the semiconductor device has high durability. Further, since it has excellent light transmittance in a short wavelength region, it is useful as a semiconductor device requiring light transmittance such as a light emitting diode element.
本発明の硬化性組成物であれば、硬度、機械的強度、および耐クラック性が高く、短波長領域の光透過性、ガスバリア性に優れた硬化物を与えることができる。このため、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。 The curable composition of the present invention can provide a cured product having high hardness, mechanical strength, and crack resistance, and excellent in light transmittance in a short wavelength region and gas barrier properties. For this reason, it can be suitably used for applications such as protection, sealing or adhesion of light emitting diode elements, wavelength change or adjustment, and 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.
上述のように、硬度、機械的強度、および耐クラック性が高く、短波長領域の光透過性、ガスバリア性に優れた硬化物を与える硬化性組成物の開発が求められていた。 As described above, there has been a demand for the development of a curable composition that has high hardness, mechanical strength, and crack resistance, and that provides a cured product having excellent light transmittance in a short wavelength region and excellent gas barrier properties.
本発明者らは、上記課題について鋭意検討を重ねた結果、特定の成分を含む硬化性組成物であれば、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。 The present inventors have conducted intensive studies on the above problems, and as a result, have found that a curable composition containing a specific component can solve the above problems, and have completed the present invention.
即ち、本発明は、下記(A)、(B)及び(C)を含む硬化性組成物である。
(A)下記式(1)で表される有機ケイ素化合物と、下記式(2)で表される有機ケイ素化合物との付加反応物であって、1分子中にSiH基を3個以上有する付加反応物、
(B)アルケニル基を1分子中に2個以上有するオルガノシロキサン化合物、
(C)ヒドロシリル化反応触媒:組成物全体の質量に対して白金族金属原子として1〜500ppm
That is, the present invention is a curable composition containing the following (A), (B) and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), wherein the addition reaction has three or more SiH groups in one molecule. Reactants,
(B) an organosiloxane compound having two or more alkenyl groups in one molecule,
(C) Hydrosilylation reaction catalyst: 1 to 500 ppm as a platinum group metal atom based on the total mass of the composition
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 described in detail, but the present invention is not limited thereto.
[硬化性組成物]
本発明の硬化性組成物は下記(A)〜(C)成分を含有してなる。本発明の硬化性組成物(付加硬化型シリコーン組成物)は、下記(A)〜(C)成分及び、必要に応じてその他の成分を、従来公知の方法で混合して調製することができる。
以下、各成分について詳細に説明する。
[Curable composition]
The curable composition of the present invention contains the following components (A) to (C). The curable composition (addition-curable silicone composition) of the present invention can be prepared by mixing the following components (A) to (C) and, if necessary, other components by a conventionally known method. .
Hereinafter, each component will be described in detail.
[(A)成分]
本発明の硬化性組成物における(A)成分は、後述の(B)成分とヒドロシリル化反応を起こすことにより、架橋剤として機能する。
[(A) component]
The component (A) in the curable composition of the present invention functions as a crosslinking agent by causing a hydrosilylation reaction with the component (B) described below.
(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)で表される有機ケイ素化合物との付加反応物であって、1分子中にSiH基を3個以上有する付加反応物である。 The component (A) is an addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), and has three SiH groups in one molecule. It is an addition reaction product having the above.
R1で表される炭素数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。 Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms represented by R 1 include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, a cyclohexylene group, Alkylene groups such as n-octylene group, arylene groups such as phenylene group and naphthylene group, and those in which part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, and chlorine are included. R 1 is particularly preferably a phenylene group.
R2で表される炭素数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、R2としてはメチル又はフェニル基が好ましく、フェニル基が特に好ましい。 Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms represented by R 2 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl. Group, alkyl group such as octyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group, propenyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenyl Ethyl groups, aralkyl groups such as phenylpropyl group and the like, and those in which part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine and chlorine, and R 2 is methyl or A phenyl group is preferred, and a phenyl group is particularly preferred.
R3で表される非置換の炭素数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としては単結合又はエチレン基が特に好ましい。 Examples of the unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms represented by R 3 include an alkylene group such as a methylene group, an ethylene group, an n-propylene group, and an 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. As R 3 , a single bond or an ethylene group is particularly preferred.
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。
上記式(2)で表される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(2)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。
上記式(1)で表される有機ケイ素化合物と、上記式(2)で表される有機ケイ素化合物との付加反応物である(A)成分の好ましい例としては下記単位式で表される化合物が挙げられる。
前記単位式で表される化合物の具体例としては、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。
また、(A)成分は上記単位式で表される化合物の1種単独でも2種以上の組み合わせでも使用することができる。 The component (A) can be used alone or in combination of two or more of the compounds represented by the above unit formula.
[(A)成分の調製]
本発明の硬化性組成物における(A)成分は、上記式(2)で表される化合物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3モルを越え30モル以下、より好ましくは4.5モルを越え15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 (A) component]
The component (A) in the curable composition of the present invention contains the compound represented by the formula (1) in an excess amount, preferably 3 mol, per 1 mol of the compound represented by the formula (2). More than 30 moles, more preferably more than 4.5 moles and 15 moles or less, can be obtained by performing a hydrosilylation reaction in the presence of both.
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 for the hydrosilylation reaction, a known catalyst can be used. For example, carbon powder carrying platinum metal, platinum black, platinic chloride, chloroplatinic acid, a reaction product of chloroplatinic acid with a monohydric alcohol, a complex of chloroplatinic acid with olefins, platinum bisacetoacetate, etc. And platinum group metal catalysts such as palladium catalysts and rhodium catalysts. In addition, the addition reaction conditions, purification conditions, use of a solvent, and the like are not particularly limited, and a known method may be used.
本発明の硬化性組成物における(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。 The component (A) in the curable composition of the present invention may be composed of one compound or a combination (mixture) of two or more compounds.
(A)成分を構成する化合物1分子中にSiH基を3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3個以上有することを確認できる。 The presence of three or more SiH groups in one molecule of the compound constituting the component (A) can be confirmed by selecting an appropriate measuring means. When two or more compounds constitute the component (A), an appropriate combination of measurement means (for example, 1 H-NMR and GPC) is selected so that each compound has an SiH group in one molecule. It can be confirmed that there are three or more.
[(B)成分]
本発明の硬化性組成物における(B)成分は、アルケニル基を1分子中に2個以上有するオルガノシロキサン化合物である。
[Component (B)]
The component (B) in the curable composition of the present invention is an organosiloxane compound having two or more alkenyl groups in one molecule.
(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、(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。 Specific examples of the component (B) include, but are not particularly limited to, a dimethylsiloxane / methylvinylsiloxane copolymer having a trimethylsiloxy group at both ends of a molecular chain, a dimethylsiloxane, a diphenylsiloxane, and a methylvinylsiloxane having a trimethylsiloxy group at both ends of a molecular chain. Copolymers, dimethylvinylsiloxy group-blocked dimethylsiloxane / diphenylsiloxane copolymers having both ends of the molecular chain, and the like, and the component (B) can be used alone or in combination of two or more.
(B)成分としては、下記式(3)で表される直鎖状のオルガノポリシロキサンであることが好ましい。
R4で表される非置換または置換の1価炭化水素基としては、前記脂肪族不飽和基、及び前記脂肪族不飽和基以外の1価炭化水素基、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;フェニル基、トリル基等の炭素原子数6〜10のアリール基が挙げられる。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。 Examples of the unsubstituted or substituted monovalent hydrocarbon group represented by R 4 include the above-mentioned aliphatic unsaturated group and a monovalent hydrocarbon group other than the above-mentioned aliphatic unsaturated group, for example, a methyl group, an ethyl group, a propyl group. An alkyl group having 1 to 6 carbon atoms such as a group, isopropyl group, butyl group, isobutyl group, sec-butyl group, t-butyl group; a carbon atom such as chloromethyl group, 3,3,3-trifluoropropyl group A haloalkyl group having 1 to 4; an aryl group having 6 to 10 carbon atoms such as a phenyl group and a tolyl group. Among them, an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a vinyl group are preferable, and a methyl group is particularly preferable.
上記式(3)において、aは0〜50の整数であり、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、2〜4であることが更に好ましい。bは0〜100の整数であり、0〜50であることが好ましく、1〜10であることがより好ましく、2〜4であることが更に好ましい。 In the above formula (3), a is an integer of 0 to 50, preferably 1 to 10, more preferably 1 to 7, and even more preferably 2 to 4. b is an integer of 0 to 100, preferably 0 to 50, more preferably 1 to 10, and even more preferably 2 to 4.
式(3)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、脂肪族不飽和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 the formula (3) is obtained by, for example, hydrolyzing and condensing a bifunctional silane such as dichlorodiphenylsilane and dialkoxydiphenylsilane, or simultaneously with hydrolyzing and condensing the aliphatic unsaturation. It is obtained by blocking the terminal with a siloxane unit containing a group.
(B)成分の配合量は、組成物中の脂肪族不飽和基に対するSiH基のモル比(SiH基/脂肪族不飽和基)が0.5以上5以下であるようにすることができ、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 amount of the component (B) can be adjusted so that the molar ratio of SiH groups to aliphatic unsaturated groups in the composition (SiH group / aliphatic unsaturated group) is from 0.5 to 5, Preferably, the amount is 0.8 or more and 2 or less. 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]
As the hydrosilylation reaction catalyst which is the component (C) of the present invention, the same catalyst as that used for the preparation of the component (A) can be used.
本発明の硬化性組成物への(C)成分の配合量は、組成物全体の質量に対して、白金族金属原子として1〜500ppm、好ましくは1〜100ppm程度、さらに好ましくは2〜12ppmとなる量である。(C)成分の配合量を、組成物全体の質量に対して白金族金属原子として1ppm未満としたり、500ppmを超えるものとすると、硬化反応に要する時間が長くなりすぎたり、短すぎたりするうえ、硬化物が着色する等の問題を生じることがある。 The compounding amount of the component (C) in the curable composition of the present invention is 1 to 500 ppm, preferably about 1 to 100 ppm, and more preferably 2 to 12 ppm as a platinum group metal atom based on the mass of the whole composition. Amount. If the amount of the component (C) is less than 1 ppm or more than 500 ppm as a platinum group metal atom with respect to the mass of the whole composition, the time required for the curing reaction becomes too long or too short. In some cases, the cured product may be colored.
[その他の成分]
本発明の硬化性組成物には、上記(A)〜(C)成分に加え、必要に応じて酸化防止剤、無機充填剤等の成分を配合してもよい。
[Other ingredients]
The curable composition of the present invention may contain components such as an antioxidant and an inorganic filler, if necessary, in addition to the components (A) to (C).
[酸化防止剤]
本発明の硬化性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、本発明の硬化性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 curable composition of the present invention, the addition-reactive carbon-carbon double bond in the component (B) may remain unreacted in some cases. Oxidation may cause the cured product to be colored. Thus, if necessary, such coloring can be prevented beforehand by adding an antioxidant to the curable composition of the present invention.
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 ones can be used. For example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2,5-di- 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。 In addition, when this antioxidant is used, its compounding amount is not particularly limited, but is usually 1 to 10,000 ppm, particularly preferably 10 to 1 ppm with respect to the total mass of the above components (A) and (B). It is preferable to add about 2,000 ppm. When the amount is within the above range, the antioxidant ability is sufficiently exhibited, and a cured product having excellent optical characteristics without coloring, turbidity, and oxidative deterioration is obtained.
[無機充填剤]
本発明の硬化性組成物の粘度や、本発明の硬化性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]
The viscosity of the curable composition of the present invention, or adjust the hardness and the like of the cured product obtained from the curable composition of the present invention, to improve the strength, to improve the dispersion of the phosphor, nano silica, An inorganic filler such as fused silica, crystalline silica, titanium oxide, nano-alumina, and alumina may be added.
[接着性向上剤]
本発明の硬化性組成物には、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 curable composition of the present invention may contain an adhesiveness improver. Examples of the adhesion improver include a silane coupling agent and its oligomer, and a polysiloxane having the same reactive group as the silane coupling agent.
接着性向上剤は、下記式(4)で表される化合物が好ましい。
接着性向上剤は、本発明の硬化性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 curable composition of the present invention and the cured product thereof in order to improve the adhesion to the substrate. Here, the base material refers to a metal material such as gold, silver, copper, and nickel; a ceramic material such as aluminum oxide, aluminum nitride, and titanium oxide; and a polymer material such as a silicone resin and an epoxy resin. The adhesion improver 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 the adhesion improver is used, the amount is preferably 1 to 30 parts by mass, more preferably 1 to 10 parts by mass, based on 100 parts by mass of the above components (A) and (B) in total. is there. With such a compounding amount, the thermosetting silicone composition of the present invention and the cured product thereof effectively improve the adhesiveness to the substrate, and hardly causes coloring.
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。
[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 secure a pot life, an addition reaction controlling agent such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyn-3-ol can be blended.
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。 Further, it is also possible to use a light stabilizer for imparting resistance to light deterioration due to light energy such as sunlight or fluorescent light. As this light stabilizer, a hindered amine-based stabilizer that captures radicals generated by photo-oxidation degradation 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.
[硬化物]
本発明の硬化性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、機械的強度、および耐クラック性が高く、短波長領域の光透過性、ガスバリア性に優れる。なお、本発明の硬化性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 curable composition of the present invention is cured to obtain a cured product of the present invention. The cured product has high hardness, mechanical strength, and crack resistance, and is excellent in light transmittance in a short wavelength region and gas barrier properties. The curing conditions of the curable composition of the present invention are not particularly limited, but are preferably 60 to 180 ° C. for 5 to 180 minutes.
本発明の硬化性組成物から得られる硬化物において、波長589nmの光の屈折率(25℃)が1.5以上である事が好ましい。 In the cured product obtained from the curable composition of the present invention, the refractive index (25 ° C.) of light having a wavelength of 589 nm is preferably 1.5 or more.
また、本発明の硬化性組成物から得られる硬化物は、厚さ2mmにおける波長400nmの光透過率(25℃)が80%以上である事が好ましい。 The cured product obtained from the curable composition of the present invention preferably has a light transmittance (25 ° C.) at a wavelength of 400 nm at a thickness of 2 mm of 80% or more.
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 a light emitting diode element, wavelength change or adjustment, or use for a lens, etc., as well as a lens material, an optical device or an optical device. Various materials for optical parts such as sealing materials for parts and display materials, insulating materials for electronic devices or electronic parts, and also useful materials as coating materials.
[半導体装置]
本発明では更に、上記の硬化性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 covered with a cured product obtained from the curable composition.
以下、図1を参照して、本発明の硬化性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, a semiconductor device using a cured product of the curable composition of the present invention (hereinafter, also referred to as “semiconductor device of the present invention”) will be described with reference to FIG. 1, but the present invention is not limited thereto. Not something.
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、上述した本発明の硬化性組成物の硬化物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、上述した本発明の硬化性組成物(付加硬化型シリコーン組成物)を塗布し、加熱により硬化性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 sectional view showing an example of the semiconductor device of the present invention. In the
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、上記硬化性組成物は、硬化により、JISに規定の硬さがShoreD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 hardly being affected by external stress and minimizing the adhesion of dust and the like, the curable composition forms a cured product having a hardness of 30 or more according to JIS in ShoreD by curing. It is preferable that
本発明の硬化性組成物は、硬度および耐クラック性が高く、短波長領域の光透過性、ガスバリア性に優れた硬化物を形成するため、この硬化性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。 The curable composition of the present invention has high hardness and crack resistance, and forms a cured product excellent in light transmittance and gas barrier properties in a short wavelength region. Therefore, the semiconductor device of the present invention using this curable composition Is excellent in reliability.
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 described specifically with reference to 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、ポリスチレン換算で行った。 In the examples, 1 H-NMR measurement used AVANCE III manufactured by Bruker BioSpin. The GPC (gel permeation chromatography) measurement was performed using HLC-8320GPC manufactured by Tosoh Corporation and using tetrahydrofuran (THF) as a mobile phase, in terms of polystyrene.
[合成例1](A−1)成分の調製
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)350.0g(1.8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)0.18gを加え、オイルバスを用いて85℃に加熱した。これにトリビニルフェニルシラン(信越化学工業株式会社製)を74.5g(0.4モル)滴下した。滴下終了後、90〜100℃の間で5時間撹拌した。撹拌後終了後25℃に戻し、活性炭を4.2g加え1時間撹拌した。撹拌後ろ過、減圧濃縮し、(A−1)成分250.7g(無色透明、収率81%、25℃における粘度:400Pa・s)を得た。
[Synthesis Example 1] Preparation of component (A-1) 1,4-bis (dimethylsilyl) benzene (Shin-Etsu Chemical Co., Ltd.) was placed in a 1-L four-necked flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer. 350.0 g (1.8 mol) and 0.18 g of 5% Pt carbon powder (manufactured by NE Chemcat Corporation) were added, and heated to 85 ° C. using an oil bath. To this, 74.5 g (0.4 mol) of trivinylphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise. After completion of the dropwise addition, the mixture was stirred at 90 to 100 ° C for 5 hours. After completion of the stirring, the temperature was returned to 25 ° C., 4.2 g of activated carbon was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered and concentrated under reduced pressure to obtain 250.7 g of the component (A-1) (colorless and transparent, yield: 81%, viscosity at 25 ° C: 400 Pa · s).
反応生成物を1H−NMR(図2)、GPC(図3)等により分析した結果、得られた反応生成物は、下記式(a)〜(e)で表される構造を有する化合物の混合物であり、各化合物の割合は(a):(b):(c):(d):(e)=30:20:15:10:25(mol%)であった。また、前記化合物はそれぞれ1分子中にSiH基を3個以上有する化合物であり、混合物全体のSiH基の含有割合は、0.0030mol/gであった。 As a result of analyzing the reaction product by 1 H-NMR (FIG. 2), GPC (FIG. 3), and the like, the obtained reaction product was obtained from a compound having a structure represented by the following formulas (a) to (e). It was a mixture, and the ratio of each compound was (a) :( b) :( c) :( d) :( e) = 30: 20: 15: 10: 25 (mol%). In addition, each of the compounds was a compound having three or more SiH groups in one molecule, and the content ratio of the SiH groups in the entire mixture was 0.0030 mol / g.
[合成例2](A−2)成分の調製
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)194.4g(1.0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)0.097gを加え、オイルバスを用いて85℃に加熱した。これにトリビニルフェニルシラン(信越化学工業株式会社製)を37.3g(0.2モル)滴下した。滴下終了後、90〜100℃の間で5時間撹拌した。撹拌後終了後25℃に戻し、活性炭を4.2g加え1時間撹拌した。撹拌後ろ過、減圧濃縮し、(A−2)成分131.0g(無色透明、収率85%、25℃における粘度:150Pa・s)を得た。
[Synthesis Example 2] Preparation of component (A-2) 1,4-bis (dimethylsilyl) benzene (Shin-Etsu Chemical Co., Ltd.) was placed in a 1-L four-necked flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer. 194.4 g (1.0 mol) (made by the company) and 0.097 g of 5% Pt carbon powder (manufactured by NEC Chemcat Corporation) were added, and the mixture was heated to 85 ° C. using an oil bath. To this, 37.3 g (0.2 mol) of trivinylphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise. After completion of the dropwise addition, the mixture was stirred at 90 to 100 ° C for 5 hours. After completion of the stirring, the temperature was returned to 25 ° C., 4.2 g of activated carbon was added, and the mixture was stirred for 1 hour. After stirring, filtration and concentration under reduced pressure were performed to obtain 131.0 g of the component (A-2) (colorless and transparent, yield: 85%, viscosity at 25 ° C: 150 Pa · s).
反応生成物を、1H−NMR(図4)、GPC(図5)等により分析した結果、得られた反応生成物は、上記式(a)〜(e)で表される構造を有する化合物の混合物であり、各化合物の割合は(a):(b):(c):(d):(e)=36:24:15:10:15(mol%)であった。また、前記化合物はそれぞれ1分子中にSiH基を3個以上有する化合物であり、混合物全体のSiH基の含有割合は、0.0032mol/gであった。 The reaction product was analyzed by 1 H-NMR (FIG. 4), GPC (FIG. 5), and the like. As a result, the obtained reaction product was a compound having a structure represented by the above formulas (a) to (e). And the ratio of each compound was (a) :( b) :( c) :( d) :( e) = 36: 24: 15: 10: 15 (mol%). Further, each of the compounds was a compound having three or more SiH groups in one molecule, and the content ratio of the SiH groups in the whole mixture was 0.0032 mol / g.
[合成例3](A−3)成分の調製
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。これに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。撹拌後終了後25℃に戻し、活性炭を2.9g加え1時間撹拌した。撹拌後ろ過、減圧濃縮し、(A−3)成分99.7g(無色透明、収率87%、25℃における粘度:30Pa・s)を得た。
[Synthesis Example 3] Preparation of Component (A-3) 1,4-bis (dimethylsilyl) benzene (Shin-Etsu Chemical Co., Ltd.) was placed in a 1-L four-necked flask equipped with a stirrer, a condenser, a dropping funnel, and a thermometer. 262.8 g (1.35 mol), 0.12 g of 5% Pt carbon powder (manufactured by NEC Chemcat Corporation) was added, and the mixture was heated to 85 ° C. using an oil bath. To this, 28.0 g (0.15 mol) of trivinylphenylsilane (manufactured by Shin-Etsu Chemical Co., Ltd.) was added dropwise. After completion of the dropwise addition, the mixture was stirred at 90 to 100 ° C for 5 hours. After completion of the stirring, the temperature was returned to 25 ° C., 2.9 g of activated carbon was added, and the mixture was stirred for 1 hour. After stirring, the mixture was filtered and concentrated under reduced pressure to obtain 99.7 g of component (A-3) (colorless and transparent, yield: 87%, viscosity at 25 ° C: 30 Pa · s).
反応生成物を、1H−NMR(図6)、GPC(図7)等により分析した結果、このものは、下記式(a)〜(c)、(f)で表される構造を有する化合物の混合物であり、各化合物の割合は(a):(b):(c):(f)=55:25:10:10(mol%)であった。また、前記化合物はそれぞれ1分子中にSiH基を3個以上有する化合物であり、前記混合物全体としてSiH基の含有割合は、0.0035モル/gであった。 The reaction product was analyzed by 1 H-NMR (FIG. 6), GPC (FIG. 7), and the like. As a result, the product was a compound having a structure represented by the following formulas (a) to (c) and (f). And the ratio of each compound was (a) :( b) :( c) :( f) = 55: 25: 10: 10 (mol%). Further, each of the compounds was a compound having three or more SiH groups in one molecule, and the content of SiH groups in the entire mixture was 0.0035 mol / g.
[実施例1〜4、比較例1〜3]
表1、2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、シリコーン組成物を調製した。下記の例において、オルガノポリシロキサンの組成を表す記号は以下のとおりである。
MVi:(CH2=CH)(CH3)2SiO1/2
MΦVi:(CH2=CH)(CH3)(C6H5)SiO1/2
MH:H(CH3)2SiO1/2
D2Φ:(C6H5)2SiO2/2
TΦ:(C6H5)SiO3/2
Q:SiO4/2
[Examples 1 to 4, Comparative Examples 1 to 3]
The following components were mixed at the composition ratios shown in Tables 1 and 2 (the numerical values represent parts by mass) to prepare silicone compositions. In the following examples, the symbols representing the composition of the organopolysiloxane are as follows.
M Vi : (CH 2 CHCH) (CH 3 ) 2 SiO 1/2
MΦVi : (CH 2 CH) (CH 3 ) (C 6 H 5 ) SiO 1/2
MH : H (CH 3 ) 2 SiO 1/2
D 2Φ : (C 6 H 5 ) 2 SiO 2/2
T Φ : (C 6 H 5 ) SiO 3/2
Q: SiO 4/2
(A)成分
(A−1)上記合成例1で得られた化合物
(A−2)上記合成例2で得られた化合物
(A−3)上記合成例3で得られた化合物
比較成分
(A−4)MH 3TΦ 1で表される分岐型オルガノポリシロキサン
(A) Component (A-1) Compound obtained in Synthesis Example 1 above (A-2) Compound obtained in Synthesis Example 2 above (A-3) Compound obtained in Synthesis Example 3 above Comparison Component (A -4) represented by M H 3 T Φ 1 branched organopolysiloxane
(B)成分
(B−1)平均単位式MΦVi 2D2Φ 3で表される、100gあたりビニル基を0.23モル有する粘度2,000mPa・sのオルガノポリシロキサン
(B−2)平均単位式MVi 2D2Φで表される、100gあたりビニル基を0.50モル有する粘度10mPa・sのオルガノポリシロキサン
(B−3)平均単位式MΦVi 20D2Φ 37.5Q42.5で表される、100gあたりビニル基を0.16モル有する25℃において固体のオルガノポリシロキサン
(B) Component (B-1) Average unit represented by the formula M ΦVi 2 D 2Φ 3 Organopolysiloxane having a viscosity of 2,000 mPa · s and having a vinyl group of 0.23 mol per 100 g (B-2) Average unit Organopolysiloxane having a viscosity of 10 mPa · s and having a vinyl group content of 0.50 mol per 100 g and represented by the formula M Vi 2 D 2Φ (B-3) Average unit formula MΦVi 20 D 2Φ 37.5 Q 42.5 Represented organopolysiloxane solid at 25 ° C. having 0.16 mol of vinyl groups per 100 g
(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%)
Component (C) Platinum-diluted product of
(D)成分
下記構造式(5)で表される接着性向上剤
<性能評価手法>
上記実施例および比較例で得られた硬化性組成物について、下記手法に従い、その硬化物の性能を評価した。
<Performance evaluation method>
For the curable compositions obtained in the above Examples and Comparative Examples, the performance of the cured products was evaluated according to the following method.
(1)硬度
ガラス板で組んだ型の中に硬化性組成物を6mm厚になるように流し込み、150℃で4時間ポストキュアーを行い、硬化物を得た。ASTM D 2240に準じて、各硬化物の硬度(Shore DまたはType A)を23℃で測定した結果を表3に示す。なお、Shore D硬度は値の前にDを、Type A硬度は値の前にAをそれぞれ付記した。
(1) Hardness The curable composition was poured into a mold formed of glass plates so as to have a thickness of 6 mm, and was post-cured at 150 ° C. for 4 hours to obtain a cured product. Table 3 shows the results of measuring the hardness (Shore D or Type A) of each cured product at 23 ° C. according to ASTM D 2240. The Shore D hardness is indicated by D before the value, and the Type A hardness is indicated by A before the value.
(2)光透過率
上記硬度測定と同様に調製した2mm厚の硬化物について、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3に示す。
(2) Light Transmittance For a cured product having a thickness of 2 mm prepared in the same manner as in the hardness measurement, the light transmittance of each cured product at 400 nm was measured using a spectrophotometer. Table 3 shows the measurement results.
(3)伸び、引張強度
上記硬度測定と同様に調製した2mm厚の硬化物について、各硬化物の伸び、及び引張強度をJIS−K−6249に準じて23℃で測定した。測定結果を表3に示す。
(3) Elongation and Tensile Strength For the cured product having a thickness of 2 mm prepared in the same manner as in the hardness measurement, the elongation and tensile strength of each cured product were measured at 23 ° C. according to JIS-K-6249. Table 3 shows the measurement results.
(4)耐クラック性
図1に示した半導体装置(LEDデバイス)に硬化性組成物を流し込み、100℃で1時間保持した後、150℃で4時間の条件で硬化を行った。得られたLEDデバイスを260℃に3分間曝し、硬化物のクラックの有無を確認した。その後、各LEDデバイスを−40℃15分、125℃15分を1サイクルとする熱衝撃試験機に入れ、500サイクル後の各LEDデバイスにおける硬化性組成物の硬化物部分のクラックの有無を確認した。その結果を表3に示す。
(4) Crack resistance The curable composition was poured into the semiconductor device (LED device) shown in FIG. 1, held at 100 ° C. for 1 hour, and then cured at 150 ° C. for 4 hours. The obtained LED device was exposed to 260 ° C. for 3 minutes, and the presence or absence of cracks in the cured product was confirmed. Thereafter, each LED device was placed in a thermal shock tester in which -40 ° C. for 15 minutes and 125 ° C. for 15 minutes as one cycle, and the presence or absence of cracks in the cured product portion of the curable composition in each LED device after 500 cycles was confirmed did. Table 3 shows the results.
(5)酸素ガス透過性
ガラス板で組んだ型の中に硬化性組成物を1mm厚になるように流し込み、150℃で4時間ポストキュアーを行って得られた硬化物について、酸素ガス透過装置(イリノイインスツルメンツ社製モデル8000)を用いて測定を行った。その結果を表3に示す。
(5) Oxygen gas permeability The curable composition was poured into a mold formed of glass plates so as to have a thickness of 1 mm, and was post-cured at 150 ° C. for 4 hours. (Illinois Instruments Model 8000) was used for the measurement. Table 3 shows the results.
表3より、本発明の硬化性組成物の硬化物が、透明性、伸び、引っ張り強度、耐クラック性、ガスバリア性に優れることを示している。よって、本発明の透明熱硬化性シリコーン組成物の硬化物は、光学素子封止材料、特に白色LED用の封止材料として有用である。 Table 3 shows that the cured product of the curable composition of the present invention is excellent in transparency, elongation, tensile strength, crack resistance, and gas barrier properties. Therefore, the cured product of the transparent thermosetting silicone composition of the present invention is useful as a sealing material for optical elements, particularly for white LEDs.
比較例1〜3に示したように、シロキサン結合を有する架橋剤である(A−4)を用いた場合は、本発明の硬化性組成物と比較して伸び及び酸素ガス透過率において劣る結果となった。 As shown in Comparative Examples 1 to 3, when (A-4), which is a crosslinking agent having a siloxane bond, was used, the results were inferior in elongation and oxygen gas permeability as compared with the curable composition of the present invention. It became.
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 embodiment. The above embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and has the same effect. 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…硬化性組成物の硬化物
1: semiconductor device, 2: silver-plated substrate, 3: package, 4: semiconductor chip,
5: bonding wire, 6: cured product of curable composition
Claims (6)
(A)下記式(1)で表される有機ケイ素化合物と、下記式(2)で表される有機ケイ素化合物との付加反応物であって、1分子中にSiH基を3個以上有する付加反応物、
(B)アルケニル基を1分子中に2個以上有するオルガノシロキサン化合物、
(C)ヒドロシリル化反応触媒:組成物全体の質量に対して白金族金属原子として1〜500ppm A curable composition containing the following (A), (B) and (C).
(A) An addition reaction product of an organosilicon compound represented by the following formula (1) and an organosilicon compound represented by the following formula (2), wherein the addition reaction has three or more SiH groups in one molecule. Reactants,
(B) an organosiloxane compound having two or more alkenyl groups in one molecule,
(C) Hydrosilylation reaction catalyst: 1 to 500 ppm as a platinum group metal atom based on the total mass of the composition
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JP2021059682A (en) * | 2019-10-08 | 2021-04-15 | 信越化学工業株式会社 | Curable composition, cured product thereof, and semiconductor device |
JP2021059684A (en) * | 2019-10-08 | 2021-04-15 | 信越化学工業株式会社 | Curable composition, cured product thereof, and semiconductor device |
WO2024029406A1 (en) * | 2022-08-01 | 2024-02-08 | 信越化学工業株式会社 | Low-dielectric-constant insulating coating composition, cured product of same, and display device |
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