JP4841529B2 - Modified polysiloxane - Google Patents
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Description
本発明は、発光ダイオード、フォトダイオード等の光半導体の封止剤、電子部品用の接着剤、シール剤等として有用な硬化性樹脂組成物及びそれを調製する為の変性ポリシロキサンに関するものである。 The present invention relates to a curable resin composition useful as a sealing agent for optical semiconductors such as light emitting diodes and photodiodes, an adhesive for electronic parts, a sealing agent, and the like, and a modified polysiloxane for preparing the same. .
一般に、光半導体装置は発光ダイオード、フォトダイオード等の光半導体素子をエポキシ樹脂組成物によって樹脂封止することにより構成されている。一方、近年注目されている青色ＬＥＤや白色ＬＥＤの場合、封止剤として従来のエポキシ組成物を用いると耐光性が不充分であり、短期間に輝度の低下が起こる。耐光性を向上させる手段として脂環式のエポキシ樹脂を用いる検討が、例えば特許文献１等に開示されているが、未だ不充分であり、更なる耐光性の向上が強く求められている。
一方、エポキシ基を有するシリコーン樹脂を含有するエポキシ樹脂組成物を光半導体の封止剤として用いる検討が、例えば特許文献２等に開示されている。しかしながら、一般にエポキシ基を有するシリコーン樹脂はガラス転移温度が低く、それを用いた組成物で青色ＬＥＤや白色ＬＥＤを封止すると通電による発熱により封止剤が軟化すると言う課題を有し、耐熱性の向上が強く求められている。
On the other hand, a study of using an epoxy resin composition containing a silicone resin having an epoxy group as a sealing agent for an optical semiconductor is disclosed in, for example, Patent Document 2. However, in general, silicone resins having an epoxy group have a low glass transition temperature, and there is a problem that when a blue LED or white LED is sealed with a composition using the epoxy resin, the sealant softens due to heat generated by energization. Improvement is strongly demanded.
本発明は、高い耐光性と耐熱性を有する硬化物を与える変性ポリシロキサンおよび硬化性樹脂組成物を提供することを目的とする。 An object of this invention is to provide the modified polysiloxane and curable resin composition which give the hardened | cured material which has high light resistance and heat resistance.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、脂環式炭化水素基と架橋点となる置換基を特定割合で導入した変性ポリシロキサンを硬化性樹脂組成物の一成分として使用することにより、上記の目的が達成されることを見出し、本発明を完成した。
即ち、本発明は下記の通りである。１）平均組成式（１）
As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are a component of a curable resin composition containing a modified polysiloxane introduced with a specific ratio of a substituent that becomes an alicyclic hydrocarbon group and a crosslinking point. As a result, the present inventors have found that the above object can be achieved and completed the present invention.
That is, the present invention is as follows. 1) Average composition formula (1)
（但し、Ｒ１は水素基あるいは炭素数が１〜６の脂肪族炭化水素基、Ｒ２は化学式（２）あるいは化学式（３）で示される置換基、Ｒ３は炭素数が５〜２０の多環脂環式炭化水素基である。Ｒ４はＲ１〜Ｒ３の何れかの基である。ｘ,ｙ,ｚはそれぞれ、０≦ｘ≦５０，１≦ｙ≦５０，１≦ｚ≦５０の整数である。）
化学式（２）
(However, R 1 is a hydrogen group or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, R 2 is a substituent represented by chemical formula (2) or chemical formula (3), and R 3 has 5 to 20 carbon atoms. R 4 is a polycyclic alicyclic hydrocarbon group, R 4 is any group of R 1 to R 3. x, y, z are 0 ≦ x ≦ 50, 1 ≦ y ≦ 50, 1 ≦ z, respectively. ≦ An integer of 50.)
Chemical formula (2)
化学式（３） Chemical formula (3)
(但しＲ５は炭素数が１〜１０，酸素数が０〜２の２価の有機基)
で示される変性ポリシロキサン。
２）ｘ、ｙ、ｚの合計に対するｙの比率が５〜８０％である上記１）記載の変性ポリシロキサン。
３）ｘ、ｙ、ｚの合計に対するｚの比率が５〜５０％である上記１）記載の変性ポリシロキサン。
４）上記１）〜３）に記載の変性ポリシロキサンとエポキシ樹脂用硬化剤を含有する硬化性樹脂組成物。
５）さらに芳香環を有さないエポキシ樹脂を含有する上記４）記載の硬化性樹脂組成物。
６）硬化剤が酸無水物系硬化剤である上記４），５）記載の硬化性樹脂組成物。
(However, R 5 is a divalent organic group having 1 to 10 carbon atoms and 0 to 2 oxygen atoms)
Modified polysiloxane represented by
2) The modified polysiloxane as described in 1) above, wherein the ratio of y to the total of x, y and z is 5 to 80%.
3) The modified polysiloxane as described in 1) above, wherein the ratio of z to the total of x, y and z is 5 to 50%.
4) A curable resin composition containing the modified polysiloxane as described in 1) to 3) above and a curing agent for epoxy resin.
5) The curable resin composition according to 4) above, further comprising an epoxy resin having no aromatic ring.
6) The curable resin composition according to 4) or 5) above, wherein the curing agent is an acid anhydride curing agent.
本発明の変性ポリシロキサンを用いた硬化性樹脂組成物は、エポキシ基を含有する置換基と多環脂環式炭化水素を含有する置換基の両方を有する変性ポリシロキサンを用いているため、耐光性に優れると共に高い耐熱性を有する。これを封止剤として用いて得られる光半導体装置は、半導体素子の特性低下が少なく信頼性が高い。 The curable resin composition using the modified polysiloxane of the present invention uses a modified polysiloxane having both a substituent containing an epoxy group and a substituent containing a polycyclic alicyclic hydrocarbon. Excellent heat resistance and high heat resistance. An optical semiconductor device obtained by using this as a sealant is highly reliable with little deterioration in characteristics of the semiconductor element.
以下、本発明を詳細に説明する。
本発明の変性ポリシロキサンは、平均組成式（１）に示す構造を有する。
Hereinafter, the present invention will be described in detail.
The modified polysiloxane of the present invention has a structure represented by an average composition formula (1).
（但し、Ｒ１は水素基あるいは炭素数が１〜６の脂肪族炭化水素基、Ｒ２は化学式（２）あるいは化学式（３）で示される置換基、Ｒ３は炭素数が５〜２０の脂環式炭化水素基である。Ｒ４はＲ１〜Ｒ３の何れかの基である。ｘ,ｙ,ｚはそれぞれ、０≦ｘ≦５０，１≦ｙ≦５０，１≦ｚ≦５０の整数である。）
化学式（２）
(However, R 1 is a hydrogen group or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, R 2 is a substituent represented by chemical formula (2) or chemical formula (3), and R 3 has 5 to 20 carbon atoms. An alicyclic hydrocarbon group, R 4 is any group of R 1 to R 3. x, y, and z are 0 ≦ x ≦ 50, 1 ≦ y ≦ 50, and 1 ≦ z ≦ 50, respectively. Is an integer.)
Chemical formula (2)
化学式（３） Chemical formula (3)
(但しＲ５は炭素数が１〜１０，酸素数が０〜２の２価の有機基)
Ｒ１は具体的には水素基、メチル基、エチル基、プロピル基、ブチル基等があげられる。好ましくはメチル基である。該置換基は１種類でも数種の混合でも良い。
Ｒ２は反応して架橋点となる置換基であり、具体的にはグリシジル基、エチニルグリシジルエーテル基、プロピレニルグリシジルエーテル基、エチニルシクロヘキセンオキシド基等があげられる。特にエチニルシクロヘキセンオキシド基が好ましい。該置換基は１種類でも数種の混合でも良い。ｙは硬化が十分にできる量あればよく２以上である事が好ましい。ｘ、ｙ、ｚの合計に対するｙの比率は好ましくは５〜８０％である。更に好ましくは１０〜６０％、一層好ましくは１５〜５０％、更に一層好ましくは２０〜４０％である。ｙの比率が５％以上有する事で、十分な低吸水性が得られ、また、硬化剤等との高い相溶性が得られる。一方、ｙの比率が８０％以下で、高い耐クラック性が得られる。
(However, R 5 is a divalent organic group having 1 to 10 carbon atoms and 0 to 2 oxygen atoms)
Specific examples of R 1 include a hydrogen group, a methyl group, an ethyl group, a propyl group, and a butyl group. A methyl group is preferred. The substituent may be one kind or a mixture of several kinds.
R 2 is a substituent that reacts to form a crosslinking point, and specific examples thereof include a glycidyl group, an ethynyl glycidyl ether group, a propylenyl glycidyl ether group, and an ethynyl cyclohexene oxide group. An ethynylcyclohexene oxide group is particularly preferable. The substituent may be one kind or a mixture of several kinds. y may be an amount that can be sufficiently cured, and is preferably 2 or more. The ratio of y to the sum of x, y and z is preferably 5 to 80%. More preferably, it is 10 to 60%, more preferably 15 to 50%, and still more preferably 20 to 40%. When the ratio of y is 5% or more, sufficient low water absorption can be obtained, and high compatibility with a curing agent or the like can be obtained. On the other hand, when the ratio of y is 80% or less, high crack resistance is obtained.
Ｒ３は耐熱性を付与する置換基であり、具体的には、ノルボルナニル基、ノルボルネニル基、ジシクロペンタジエニル基、エチニルデカヒドロナフタレン基等があげられる。特にノルボルナニル基が好ましい。該置換基は１種類でも数種の混合でも良い。ｚは耐熱性を向上させる効果が発現できる量あればよい。ｘ、ｙ、ｚの合計に対するｚの比率は好ましくは５〜５０％であり、更に好ましくは１０〜４０％一層好ましくは１５〜３０％である。ｚの比率が５％以上で高い耐熱性が得られ、一方、ｚの比率が５０％以下で、高い耐光性が得られる。
Ｒ５は、具体的には−ＣＨ２−、−ＣＨ２−ＣＨ２−、−Ｏ−ＣＨ２−ＣＨ２−、−ＣＨ２−ＣＨ２−Ｏ−、−ＣＨ２−ＣＨ２−ＣＨ２−Ｏ−等が挙げられる。
R 3 is a substituent that imparts heat resistance, and specific examples include a norbornanyl group, a norbornenyl group, a dicyclopentadienyl group, an ethynyldecahydronaphthalene group, and the like. A norbornanyl group is particularly preferable. The substituent may be one kind or a mixture of several kinds. z should just be the quantity which can express the effect which improves heat resistance. The ratio of z to the sum of x, y and z is preferably 5 to 50%, more preferably 10 to 40%, and even more preferably 15 to 30%. High heat resistance is obtained when the z ratio is 5% or more, while high light resistance is obtained when the z ratio is 50% or less.
R 5 is specifically -CH 2 -, - CH 2 -CH 2 -, - O-CH 2 -CH 2 -, - CH 2 -CH 2 -O -, - CH 2 -CH 2 -CH 2 -O- etc. are mentioned.
本発明の変性ポリシロキサンは従来周知の方法で合成する事ができる。具体的には、ＳｉＨ基を含有するオルガノポリシロキサンにハイドロシリレーション反応によって置換基を導入する方法、オルガノハロシラン及びオルガノアルコキシシランを単独にあるいは混合して加水分解する方法や、さらに再平衡化重合する方法、環状オルガノシロキサンを開環重合する方法等があげられる。なかでもＳｉＨ基を含有するオルガノポリシロキサンにハイドロシリレーション反応によって置換基を導入する方法が簡便であり好ましい。以下、具体的にこの方法について述べる。
ハイドロシリレーション反応は、必要に応じて触媒の存在下、ＳｉＨ基含有オルガノポリシロキサンに置換基となるビニル基を含有する不飽和化合物を段階的にあるいは一度に反応させる方法である。
The modified polysiloxane of the present invention can be synthesized by a conventionally known method. Specifically, a method of introducing a substituent into an organopolysiloxane containing a SiH group by a hydrosilation reaction, a method of hydrolyzing an organohalosilane and an organoalkoxysilane alone or mixed, and further re-equilibration Examples thereof include a polymerization method and a ring-opening polymerization method of a cyclic organosiloxane. Among them, a method of introducing a substituent into an organopolysiloxane containing a SiH group by a hydrosilylation reaction is simple and preferable. Hereinafter, this method will be specifically described.
The hydrosilylation reaction is a method in which an unsaturated compound containing a vinyl group serving as a substituent is reacted stepwise or at a time with a SiH group-containing organopolysiloxane in the presence of a catalyst as necessary.
置換基となるビニル基を含有する不飽和化合物としては以下のものが挙げられる。
反応してＲ２になる化合物としては、ビニルグリシジルエーテル、アリルグリシジルエーテル、ビニルシクロヘキセンオキシド等が挙げられる。
反応してＲ３になる化合物としては、ノルボルネン、ノルボルナジエン、ジシクロペンタジエン、ビニルシクロヘキサン、ビニルシクロヘキセン、ビニルデカヒドロナフタレン等があげられる。
反応温度は特に制限はないが、反応の速度と収率の観点から１０〜２００℃、好ましくは３０〜１５０℃、特に好ましくは、５０〜１２０℃である。反応は無溶媒下でも進行するが溶媒を使用しても良い。溶媒として、ジオキサン、メチルイソブチルケトン、トルエン、キシレン、酢酸ブチル等が使用される。
シロキサン骨格は本質的に耐光性を有する。しかしながら耐熱性をあげるために一般的に用いられるフェニル基を置換基として用いると、このフェニル基が耐光性を低下させてしまう。よって、これまでに耐光性と耐熱性に優れたポリシロキサンは提供されていなかった。本発明者らは、脂環式炭化水素基とエポキシ基を特定割合で導入した変性ポリシロキサンを硬化性樹脂組成物の一成分として使用することにより、上記の目的が達成されることを見出し本発明を完成した。
Examples of the unsaturated compound containing a vinyl group serving as a substituent include the following.
Examples of the compound that reacts to R 2 include vinyl glycidyl ether, allyl glycidyl ether, vinyl cyclohexene oxide, and the like.
Examples of the compound that reacts to R 3 include norbornene, norbornadiene, dicyclopentadiene, vinylcyclohexane, vinylcyclohexene, vinyldecahydronaphthalene, and the like.
The reaction temperature is not particularly limited, but is 10 to 200 ° C., preferably 30 to 150 ° C., particularly preferably 50 to 120 ° C. from the viewpoint of reaction rate and yield. The reaction proceeds even without solvent, but a solvent may be used. As the solvent, dioxane, methyl isobutyl ketone, toluene, xylene, butyl acetate or the like is used.
The siloxane skeleton is inherently light resistant. However, when a phenyl group generally used for increasing heat resistance is used as a substituent, the phenyl group reduces light resistance. Therefore, so far, no polysiloxane excellent in light resistance and heat resistance has been provided. The present inventors have found that the above object can be achieved by using, as a component of a curable resin composition, a modified polysiloxane having an alicyclic hydrocarbon group and an epoxy group introduced at a specific ratio. Completed the invention.
本発明で使用されるエポキシ樹脂用硬化剤は、例えば、エチレンジアミン、トリエチレンペンタミン、ヘキサメチレンジアミン、ダイマー酸変性エチレンジアミン、Ｎ−エチルアミノピペラジン、イソホロンジアミン等の脂肪族アミン類、メタフェニレンジアミン、パラフェニレンジアミン、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノジフェノルスルホン、４，４’−ジアミノジフェノルメタン、４，４’−ジアミノジフェノルエーテル等の芳香族アミン類、メルカプトプロピオン酸エステル、エポキシ樹脂の末端メルカプト化合物等のメルカプタン類、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、ビスフェノールＳ、テトラメチルビスフェノールＡ、テトラメチルビスフェノールＦ、テトラメチルビスフェノールＡＤ、テトラメチルビスフェノールＳ、テトラブロモビスフェノールＡ、テトラクロロビスフェノールＡ、テトラフルオロビスフェノールＡ、ビフェノール、ジヒドロキシナフタレン、１，１，１−トリス（４−ヒドロキシフェニル）メタン、４，４−（１−（４−（１−（４−ヒドロキシフェニル）−１−メチルエチル）フェニル）エチリデン）ビスフェノール、フェノールノボラック、クレゾールノボラック、ビスフェノールＡノボラック、臭素化フェノールノボラック、臭素化ビスフェノールＡノボラック等のフェノール樹脂類、これらフェノール樹脂類芳香環を水素化したポリオール類、ポリアゼライン酸無水物、メチルテトラヒドロ無水フタル酸、テトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、５−ノルボルネン−２，３−ジカルボン酸無水物、ノルボルナン−２，３−ジカルボン酸無水物、メチル−５−ノルボルネン−２，３−ジカルボン酸無水物、メチル−ノルボルナン−２，３−ジカルボン酸無水物等の脂環式酸無水物類、無水フタル酸、無水トリメリット酸、無水ピロメリット酸等の芳香族酸無水物類、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール等のイミダゾール類およびその塩類、上記脂肪族アミン類、芳香族アミン類、及び／またはイミダゾール類とエポキシ樹脂との反応により得られるアミンアダクト類、アジピン酸ジヒドラジド等のヒドラジン類、ジメチルベンジルアミン、１，８−ジアザビシクロ［５．４．０］ウンデセン−７等の第３級アミン類、トリフェニルホスフィン等の有機ホスフィン類、ジシアンジアミド等が挙げられる。中でも酸無水物類が好ましく、より好ましくは、脂環式酸無水物類であり、特に好ましくは、メチルヘキサヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、ノルボルナン−２，３−ジカルボン酸無水物、メチル−ノルボルナン−２，３−ジカルボン酸無水物である。 Examples of the curing agent for epoxy resin used in the present invention include aliphatic amines such as ethylenediamine, triethylenepentamine, hexamethylenediamine, dimer acid-modified ethylenediamine, N-ethylaminopiperazine, and isophoronediamine, metaphenylenediamine, Aromatic amines such as paraphenylenediamine, 3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenol sulfone, 4,4′-diaminodiphenol methane, 4,4′-diaminodiphenol ether , Mercaptans such as mercaptopropionic acid esters, terminal mercapto compounds of epoxy resins, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbis Enol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) phenol resins such as bisphenol, phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, These phenol resins aromatic polyol hydrogenated polyols, polyazeline acid anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexa Drophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, methyl-norbornane-2, Alicyclic acid anhydrides such as 3-dicarboxylic acid anhydride, aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 2-methylimidazole, 2-ethyl-4-methyl Imidazoles such as imidazole and 2-phenylimidazole and their salts, aliphatic amines, aromatic amines, and / or amine adducts obtained by reacting imidazoles with epoxy resins, and hydrazines such as adipic acid dihydrazide. , Tertiary amide such as dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] undecene-7 And organic phosphines such as triphenylphosphine, dicyandiamide and the like. Among them, acid anhydrides are preferable, and alicyclic acid anhydrides are more preferable, and methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, norbornane-2,3-dicarboxylic acid anhydride, methyl are particularly preferable. -Norbornane-2,3-dicarboxylic acid anhydride.
硬化剤の使用量は変性ポリシロキサン１００部に対して、任意に選択できるが、好ましくは、０．１〜２００質量部である。より好ましくは０．２〜１００質量部である。これらの硬化剤は単独で用いても良く、２種以上を併用しても良い。
本発明の芳香環を有さないエポキシ樹脂とは、脂環式エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、水添ビスフェノールＦ型エポキシ樹脂等が挙げられる。芳香環を水添したエポキシ樹脂では、本質的に芳香環を有していない事が必須であり、このエポキシ樹脂の組成物への添加量にもよるが、その水添率が好ましくは９０モル％以上、さらに好ましくは９５モル％以上である。また、その添加量は本発明の変性ポリシロキサンに対して１００重量％以下であり、より好ましくは５０重量％以下である。
Although the usage-amount of a hardening | curing agent can be arbitrarily selected with respect to 100 parts of modified polysiloxane, Preferably it is 0.1-200 mass parts. More preferably, it is 0.2-100 mass parts. These curing agents may be used alone or in combination of two or more.
Examples of the epoxy resin having no aromatic ring of the present invention include alicyclic epoxy resins, hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol F type epoxy resins and the like. An epoxy resin hydrogenated with an aromatic ring must have essentially no aromatic ring, and the hydrogenation rate is preferably 90 mol, depending on the amount of epoxy resin added to the composition. % Or more, more preferably 95 mol% or more. Moreover, the addition amount is 100 weight% or less with respect to the modified polysiloxane of this invention, More preferably, it is 50 weight% or less.
本発明の硬化性樹脂組成物は、上記成分以外に必要に応じて、硬化促進剤、染料、変性剤、変色防止剤等の従来公知の添加剤を適宜配合することができる。
硬化促進剤としては、例えば、２−メチルイミダゾール、２−エチル−４−メチルイミダゾール等のイミダゾール類、１，８−ジアザビシクロ（５，４，０）ウンデセン−７等の第３級アミン類、トリフェニルホスフィン等のホスフィン類、トリフェニルホスホニウムブロマイド等のホスホニウム塩類、アミノトリアゾール類、オクチル酸錫、ジブチル錫ジラウレート等の錫系、オクチル酸亜鉛等の亜鉛系、アルミニウム、クロム、コバルト、ジルコニウム等のアセチルアセトナート等の金属触媒類等が用いられる。これらの硬化促進剤は単独で用いても良く、２種以上を併用しても良い。
本発明のエポキシ樹脂組成物を用いての光半導体素子の封止は、特に限定されることなく、通常の注型等の公知のモールド方法により行うことができる。
The curable resin composition of this invention can mix | blend conventionally well-known additives, such as a hardening accelerator, a dye, a modifier, and a discoloration prevention agent suitably, other than the said component as needed.
Examples of the curing accelerator include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, tertiary amines such as 1,8-diazabicyclo (5,4,0) undecene-7, Phosphines such as phenylphosphine, phosphonium salts such as triphenylphosphonium bromide, tins such as aminotriazoles, tin octylate and dibutyltin dilaurate, zincs such as zinc octylate, acetyls such as aluminum, chromium, cobalt and zirconium Metal catalysts such as acetonate are used. These curing accelerators may be used alone or in combination of two or more.
Sealing of the optical semiconductor element using the epoxy resin composition of the present invention is not particularly limited and can be performed by a known molding method such as ordinary casting.
本発明について、以下具体的に説明する。
評価方法は以下の通りとする。
透過率
厚さ２ｍｍの硬化物を用いて、（株）島津製作所のＵＶ−２５００ＰＣを用いて４３０ｎｍの光透過率を測定した。
透過率保持率
厚さ２ｍｍの硬化物に、高圧水銀ランプを用いて５００時間紫外線を照射する。紫外線照射前後の４３０ｎｍの光透過率を（株）島津製作所のＵＶ−２５００ＰＣを用いて測定し、その保持率が８０％以上を○とし、６０〜８０％を△、それ以下を×とした。
耐熱性
厚さ２ｍｍの硬化物を１５０℃で１０時間保持した時に軟化しないものを○とした。
本発明を実施例に基づいて説明する。
The present invention will be specifically described below.
The evaluation method is as follows.
Transmittance Using a cured product having a thickness of 2 mm, a light transmittance of 430 nm was measured using UV-2500PC manufactured by Shimadzu Corporation.
Transmittance retention rate A cured product having a thickness of 2 mm is irradiated with ultraviolet rays for 500 hours using a high-pressure mercury lamp. The light transmittance at 430 nm before and after the ultraviolet irradiation was measured using UV-2500PC manufactured by Shimadzu Corporation, and the retention rate was 80% or more as ◯, 60 to 80% as Δ, and the lower as x.
Heat resistance A cured product having a thickness of 2 mm was evaluated as ◯ if it was not softened when held at 150 ° C. for 10 hours.
The present invention will be described based on examples.
[実施例１]
還流冷却器、温度計及び撹拌装置を有する１Ｌの反応器にメチルハイドロジェンシロキサン−ジメチルシロキサンコポリマー（旭化成ワッカーシリコーン社製：Ｖ５８）１００ｇ、ジオキサン１００ｇを入れ、撹拌下６０℃に加熱した。これにジシクロペンタジエニル白金ジクロライドの０．５重量％ジオキサン溶液を０．４５ｇ添加した後、ノルボルネン（和光純薬株式会社製：試薬特級）の２０重量％ジオキサン溶液１６５ｇを１２０分かけて滴下し、さらに６０℃で１時間撹拌を続けた。これにジシクロペンタジエニル白金ジクロライドの０．５重量％ジオキサン溶液を０．２ｇ追加添加した後、続けてビニルシクロヘキセンオキシド（ダイセル化学工業株式会社製：セロキサイド２０００）の２０重量％ジオキサン溶液２１７ｇを１２０分かけて滴下し、さらに６０℃で１時間撹拌を続けた。
この反応液を加熱減圧下、溶媒等を留去することにより本発明の変性ポリシロキサン１６８ｇを得た。なお、各ステップで反応液をサンプリングし、アルカリで分解して水素ガスの発生を確認することにより、反応が定量的に進行している事を確認した。
[Example 1]
100 g of methylhydrogensiloxane-dimethylsiloxane copolymer (Asahi Kasei Wacker Silicone Co., Ltd .: V58) and 100 g of dioxane were placed in a 1 L reactor having a reflux condenser, a thermometer, and a stirring device, and heated to 60 ° C. with stirring. After adding 0.45 g of a 0.5 wt% dioxane solution of dicyclopentadienylplatinum dichloride, 165 g of a 20 wt% dioxane solution of norbornene (manufactured by Wako Pure Chemical Industries, Ltd .: reagent grade) was added dropwise over 120 minutes. Further, stirring was continued at 60 ° C. for 1 hour. After adding 0.2 g of a 0.5 wt% dioxane solution of dicyclopentadienyl platinum dichloride to this, 217 g of a 20 wt% dioxane solution of vinylcyclohexene oxide (manufactured by Daicel Chemical Industries, Ltd .: Celoxide 2000) was subsequently added. The solution was added dropwise over 120 minutes, and stirring was further continued at 60 ° C. for 1 hour.
168 g of the modified polysiloxane of the present invention was obtained by distilling off the solvent and the like while heating the reaction solution under reduced pressure. The reaction solution was sampled at each step and decomposed with alkali to confirm the generation of hydrogen gas, thereby confirming that the reaction was proceeding quantitatively.
[参考例１]
実施例１で得られた変性ポリシロキサンとメチルヘキサヒドロ無水フタル酸をエポキシ基と無水カルボン酸が当量となるように混合し、変性ポリシロキサンに対して０．５重量％のナフテン酸コバルトを混合し、全体が均一になるまで撹拌して硬化性樹脂組成物を得た。この組成物を深さ２ｍｍの型に流し込み、１２０℃で２時間、更に１５０℃で６時間硬化反応を行い、硬化物を得た。物性を表１に示す。
[Reference Example 1]
The modified polysiloxane obtained in Example 1 and methylhexahydrophthalic anhydride are mixed so that the epoxy group and carboxylic anhydride are equivalent, and 0.5% by weight of cobalt naphthenate is mixed with the modified polysiloxane. The mixture was stirred until the whole became uniform to obtain a curable resin composition. This composition was poured into a mold having a depth of 2 mm and subjected to a curing reaction at 120 ° C. for 2 hours and further at 150 ° C. for 6 hours to obtain a cured product. The physical properties are shown in Table 1.
[参考例２]
変性ポリシロキサンに対して１０重量％の脂環式エポキシ樹脂である３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート（東京化成株式会社製）を添加し、両方のエポキシ基に対して無水カルボン酸が当量となるように混合した以外は参考例１と同様にして硬化物を得た。物性を表１に示す。
[Reference Example 2]
3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.), which is a 10% by weight alicyclic epoxy resin, is added to the modified polysiloxane, and both epoxy groups are Then, a cured product was obtained in the same manner as in Reference Example 1 except that the carboxylic anhydride was mixed in an equivalent amount. The physical properties are shown in Table 1.
[参考例３]
３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレートのみを用いて、このエポキシ基に対して無水カルボン酸が当量となるように混合した以外は参考例１と同様にして硬化物を得た。物性を表１に示す。
[Reference Example 3]
A cured product was obtained in the same manner as in Reference Example 1 except that only 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate was mixed so that the carboxylic anhydride was equivalent to this epoxy group. Obtained. The physical properties are shown in Table 1.
本発明の変性ポリシロキサンを用いた硬化性樹脂組成物は、エポキシ基を含有する置換基と多環脂環式炭化水素を含有する置換基の両方を有する変性ポリシロキサンを用いているため、耐光性に優れると共に高い耐熱性を有する。これを封止剤として用いて得られる光半導体装置は、半導体素子の特性低下が少なく信頼性が高い。
The curable resin composition using the modified polysiloxane of the present invention uses a modified polysiloxane having both a substituent containing an epoxy group and a substituent containing a polycyclic alicyclic hydrocarbon. Excellent heat resistance and high heat resistance. An optical semiconductor device obtained by using this as a sealant is highly reliable with little deterioration in characteristics of the semiconductor element.
Claims (3)
化学式（２）
で示される変性ポリシロキサン。 Average composition formula (1)
Chemical formula (2)
Modified polysiloxane represented by
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| JP5305452B2 (en) * | 2009-06-12 | 2013-10-02 | 信越化学工業株式会社 | Resin composition for optical semiconductor element sealing |
| CN115449228B (en) * | 2022-09-28 | 2023-11-10 | 汇涌进光电(浙江)有限公司 | High-temperature-resistant, high-humidity-resistant and photo-aging-resistant photoelectric packaging material as well as preparation method and application thereof |
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| JPS5133540B2 (en) * | 1973-10-08 | 1976-09-20 | ||
| US4576999A (en) * | 1982-05-06 | 1986-03-18 | General Electric Company | Ultraviolet radiation-curable silicone release compositions with epoxy and/or acrylic functionality |
| DE3431075A1 (en) * | 1984-08-23 | 1986-02-27 | Wacker-Chemie GmbH, 8000 München | ORGANOPOLYSILOXANES WITH SI-TIED HYDROGEN AND SIC-TIED EPOXY GROUPS, METHOD FOR THE PRODUCTION THEREOF AND THE USE OF THESE ORGANOPOLYSILOXANS |
| JPS6198735A (en) * | 1984-10-22 | 1986-05-17 | Toshiba Silicone Co Ltd | Polysiloxane containing ethylidenenorbornyl group |
| JPH02168654A (en) * | 1988-12-21 | 1990-06-28 | Nitto Denko Corp | Semiconductor device |
| US5037861A (en) * | 1989-08-09 | 1991-08-06 | General Electric Company | Novel highly reactive silicon-containing epoxides |
| JP2933744B2 (en) * | 1991-04-23 | 1999-08-16 | 日東電工株式会社 | Curable silicone release agent and its separator |
| ATE158001T1 (en) * | 1992-03-23 | 1997-09-15 | Siemens Ag | POLYSILOXANES |
| JP3283606B2 (en) * | 1993-02-17 | 2002-05-20 | 日本化薬株式会社 | Organopolysiloxane and epoxy resin composition containing the same |
| JPH07133351A (en) * | 1993-11-08 | 1995-05-23 | Shin Etsu Chem Co Ltd | Production of epoxy-modified silicone |
| US5492994A (en) * | 1995-01-12 | 1996-02-20 | Dow Corning Corporation | Adhesion additives and curable organosiloxane compositions containing same |
| JP3602619B2 (en) * | 1995-08-17 | 2004-12-15 | 日本ユニカー株式会社 | Novel modified organopolysiloxane compound and epoxy resin composition for semiconductor encapsulation using the same |
| JPH10168282A (en) * | 1996-12-12 | 1998-06-23 | Sumitomo Bakelite Co Ltd | Semiconductor sealing epoxy resin composition |
| US6414175B1 (en) * | 1997-03-29 | 2002-07-02 | Th. Goldschmidt Agh | Innovative siloxane block copolymers with rigid spacers and their use |
| JP3063712B2 (en) * | 1997-11-10 | 2000-07-12 | 信越化学工業株式会社 | Method for producing organopolysiloxane |
| JP2003192790A (en) * | 2001-12-27 | 2003-07-09 | Dow Corning Toray Silicone Co Ltd | Radically polymerizable organopolysiloxane mixture and method for producing the same |
| JP2003252994A (en) * | 2002-02-28 | 2003-09-10 | Dow Corning Toray Silicone Co Ltd | Method for manufacturing emulsion-polymerized diorganopolysiloxane emulsion composition |
| JP4088697B2 (en) * | 2002-11-05 | 2008-05-21 | 旭化成株式会社 | Modified polysiloxane and curable resin composition using the same |
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