JP2005343984A - Curable composition and semiconductor device encapsulated with the curable composition - Google Patents
Curable composition and semiconductor device encapsulated with the curable composition Download PDFInfo
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- JP2005343984A JP2005343984A JP2004164165A JP2004164165A JP2005343984A JP 2005343984 A JP2005343984 A JP 2005343984A JP 2004164165 A JP2004164165 A JP 2004164165A JP 2004164165 A JP2004164165 A JP 2004164165A JP 2005343984 A JP2005343984 A JP 2005343984A
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
Abstract
Description
本発明は、硬化性組成物、その硬化物及び該硬化性組成物により封止された半導体装置に関するものである。 The present invention relates to a curable composition, a cured product thereof, and a semiconductor device sealed with the curable composition.
IC、LSI、LED等の半導体素子を用いた部品は空気酸化や湿気等による性能低下を防止するため、これらの素子を樹脂パッケージやセラミックパッケージの内部に装着後、エポキシ樹脂等により封止されることが多い。最近は、耐熱性、耐透湿性に優れるセラミックパッケージが多用されるようになってきたが、パッケージの線膨張係数に比べて、封止樹脂の線膨張係数が大きいことから、210〜280℃程度の高温に曝される表面実装時や冷熱試験時に封止樹脂にクラックが発生し易い。耐クラック性を改良する方法としては、封止樹脂にシリカ等の無機フィラーを高充填して線膨張係数を低下させたり、ゴム粒子やオルガノポリシロキサンを配合して低応力化することが従来技術にある(例えば、特許文献1、特許文献2参照。)。しかしながら、シリカ等の無機フィラーを多量に使用すると樹脂組成物が高粘度になるため作業性が劣ったり、封止樹脂が高弾性化して応力が高くなったりする。また、ゴム粒子やオルガノポリシロキサンを配合すると低弾性化して低応力化することは可能であるが、半導体素子の動作時に100℃を越えるような高温になる場合、例えば、封止にエポキシ樹脂を用いた時は、封止樹脂が熱劣化して変色するという問題が発生し、LEDの封止の場合には輝度を低下させる。
本発明の目的は、熱衝撃が加わっても耐クラック性、耐変色性に優れた硬化物の得られる硬化性組成物及び該硬化性組成物を用いて封止した半導体装置を提供することである。 An object of the present invention is to provide a curable composition capable of obtaining a cured product excellent in crack resistance and discoloration resistance even when a thermal shock is applied, and a semiconductor device encapsulated using the curable composition. is there.
このような課題を解決するために本発明者らは鋭意研究の結果、(A)SiH基と反応性を有する炭素−炭素二重結合を含有する有機化合物、(B)1分子中に少なくとも2個のSiH基を含有するケイ素化合物、(C)ヒドロシリル化触媒、(E)SiH基と反応性を有する炭素−炭素二重結合を1分子中に少なくとも2個含有するオルガノポリシロキサンを必須成分とする硬化性組成物とすることにより上記課題を解決できることを見出し、本発明に至った。 In order to solve such problems, the present inventors have conducted intensive research, and as a result, (A) an organic compound containing a carbon-carbon double bond reactive with a SiH group, (B) at least 2 in one molecule. An essential component is a silicon compound containing one SiH group, (C) a hydrosilylation catalyst, (E) an organopolysiloxane containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule. The present inventors have found that the above-mentioned problems can be solved by using a curable composition to achieve the present invention.
すなわち、本発明は、
(A)SiH基と反応性を有する炭素−炭素二重結合を含有する有機化合物、(B)1分子中に少なくとも2個のSiH基を含有するケイ素化合物、(C)ヒドロシリル化触媒、(E)SiH基と反応性を有する炭素−炭素二重結合を1分子中に少なくとも2個含有するオルガノポリシロキサンを必須成分とする硬化性組成物(請求項1)であり、
(A)成分と(E)成分の合計100重量部に対する(E)成分の割合が下限5重量部、上限65重量部であることを特徴とする請求項1記載の硬化性組成物(請求項2)であり、
請求項1又は請求項2記載の硬化性組成物を硬化してなる硬化物(請求項3)であり、
請求項1又は請求項2記載の硬化性組成物で半導体を封止してなることを特徴とする半導体装置(請求項4)であり、
半導体が発光ダイオード(LED)用素子であることを特徴とする請求項4記載の半導体装置(請求項5)である。
That is, the present invention
(A) an organic compound containing a carbon-carbon double bond reactive with SiH groups, (B) a silicon compound containing at least two SiH groups in one molecule, (C) a hydrosilylation catalyst, (E ) A curable composition comprising as an essential component an organopolysiloxane containing at least two carbon-carbon double bonds reactive with SiH groups in one molecule (claim 1).
The curable composition according to claim 1, wherein the ratio of the component (E) to the total of 100 parts by weight of the component (A) and the component (E) is 5 parts by weight as a lower limit and 65 parts by weight as an upper limit. 2)
A cured product obtained by curing the curable composition according to claim 1 or claim 2 (claim 3),
A semiconductor device (Claim 4) comprising a semiconductor sealed with the curable composition according to Claim 1 or Claim 2,
5. The semiconductor device according to claim 4, wherein the semiconductor is a light emitting diode (LED) element.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
まず、本発明における(A)成分について説明する。 First, the component (A) in the present invention will be described.
(A)成分は、SiH基と反応性を有する炭素−炭素二重結合を含有する有機化合物である。 The component (A) is an organic compound containing a carbon-carbon double bond that is reactive with the SiH group.
(A)成分の有機化合物は、それを構成する有機系骨格としては特に限定はなく、例えば、ポリエーテル系、ポリエステル系、ポリアリレート系、ポリカーボネート系、飽和炭化水素系、ポリアクリル酸エステル系、ポリアミド系、フェノール−ホルムアルデヒド系(フェノール樹脂系)、ポリイミド系等の有機重合体骨格;フェノール系、ビスフェノール系、ベンゼン、ナフタレン等の芳香族炭化水素系、脂肪族炭化水素系、脂肪族アルコール系等及びこれらの2種以上からなる有機単量体骨格が挙げられる。 The organic compound of the component (A) is not particularly limited as an organic skeleton constituting the component, for example, polyether-based, polyester-based, polyarylate-based, polycarbonate-based, saturated hydrocarbon-based, polyacrylate-based, Organic polymer skeletons such as polyamides, phenol-formaldehydes (phenolic resins), polyimides; aromatic hydrocarbons such as phenols, bisphenols, benzene, naphthalene, aliphatic hydrocarbons, aliphatic alcohols, etc. And an organic monomer skeleton composed of two or more of these.
また、(A)成分の有機化合物は、上記有機系骨格部分と、その有機系骨格部分に共有結合するSiH基と反応性を有する炭素−炭素二重結合を有する基とからなる。このように表した場合、SiH基と反応性を有する炭素−炭素二重結合を有する基は、有機系骨格のどの部位に共有結合していてもよい。 The organic compound of component (A) is composed of the organic skeleton portion and a group having a carbon-carbon double bond that is reactive with the SiH group covalently bonded to the organic skeleton portion. When expressed in this way, the group having a carbon-carbon double bond that is reactive with the SiH group may be covalently bonded to any part of the organic skeleton.
(A)成分の有機化合物が含有する、SiH基と反応性を有する炭素−炭素二重結合を有する基は、SiH基と反応性を有するものであれば特に制限されない。 The group having a carbon-carbon double bond reactive with the SiH group contained in the organic compound (A) is not particularly limited as long as it has reactivity with the SiH group.
例えば、下記一般式(I) For example, the following general formula (I)
原料の入手の容易さからは、 From the availability of raw materials,
(A)成分の有機化合物が含有するアルケニル基としては、下記一般式(II) As the alkenyl group contained in the organic compound (A), the following general formula (II)
また、原料の入手の容易さからは、 In addition, from the availability of raw materials,
アルケニル基は2価以上の置換基を介して、(A)成分の有機系骨格部分に共有結合していても良い。 The alkenyl group may be covalently bonded to the organic skeleton portion of the component (A) via a divalent or higher substituent.
2価以上の置換基としては炭素数0〜10の置換基であれば特に制限はない。このような置換基の例としては、 The divalent or higher valent substituent is not particularly limited as long as it is a substituent having 0 to 10 carbon atoms. Examples of such substituents include
また、これらの置換基の2つ以上が共有結合によりつながって1つの2価以上の置換基を構成していてもよい。 Two or more of these substituents may be connected by a covalent bond to form one divalent or higher substituent.
以上のような有機系骨格部分に共有結合する基としては、例えば、ビニル基、アリル基、メタリル基、アクリル基、メタクリル基、2−アリルフェニル基、3−アリルフェニル基、4−アリルフェニル基、2−(アリルオキシ)フェニル基、3−(アリルオキシ)フェニル基、4−(アリルオキシ)フェニル基、2−(アリルオキシ)エチル基、3−(アリルオキシ)プロピル基、2、2−ビス(アリルオキシメチル)ブチル基、3−アリルオキシ−2、2−ビス(アリルオキシメチル)プロピル基、 Examples of the group covalently bonded to the organic skeleton portion as described above include a vinyl group, an allyl group, a methallyl group, an acrylic group, a methacryl group, a 2-allylphenyl group, a 3-allylphenyl group, and a 4-allylphenyl group. 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group, 3- (allyloxy) propyl group, 2,2-bis (allyloxymethyl) ) Butyl group, 3-allyloxy-2, 2-bis (allyloxymethyl) propyl group,
(A)成分の有機化合物の具体的な例としては、ジアリルフタレート、トリアリルトリメリテート、ジエチレングリコールビスアリルカーボネート、トリメチロールプロパンジアリルエーテル、ペンタエリスリトールトリアリルエーテル、1,1,2,2−テトラアリロキシエタン、ジアリリデンペンタエリスリット、トリアリルシアヌレート、トリアリルイソシアヌレート、1,2,4−トリビニルシクロヘキサン、ジビニルベンゼン類(純度50〜100%のもの、好ましくは純度80〜100%のもの)、ジビニルビフェニル、1,3−ジイソプロペニルベンゼン、1,4−ジイソプロペニルベンゼン、及びそれらのオリゴマー、1,2−ポリブタジエン(1、2比率10〜100%のもの、好ましくは1、2比率50〜100%のもの)、ノボラックフェノールのアリルエーテル、アリル化ポリフェニレンオキサイド、 Specific examples of the organic compound (A) include diallyl phthalate, triallyl trimellitate, diethylene glycol bisallyl carbonate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, 1,1,2,2-tetra Allyloxyethane, diarylidenepentaerythritol, triallyl cyanurate, triallyl isocyanurate, 1,2,4-trivinylcyclohexane, divinylbenzenes (having a purity of 50 to 100%, preferably a purity of 80 to 100% ), Divinylbiphenyl, 1,3-diisopropenylbenzene, 1,4-diisopropenylbenzene, and oligomers thereof, 1,2-polybutadiene (1,2 ratio of 10 to 100%, preferably 1) 2 ratio of 50-100% ), Allyl ether of novolak phenol, allylated polyphenylene oxide,
(A)成分の有機化合物としては、上記有機系骨格部分と、その有機系骨格部分に共有結合するSiH基と反応性を有する炭素−炭素二重結合を有する基とに分けて表現しがたい低分子量化合物も用いることができる。これらの低分子量化合物の具体例としては、ブタジエン、イソプレン、オクタジエン、デカジエン等の脂肪族鎖状ポリエン化合物系;シクロペンタジエン、シクロオクタジエン、ジシクロペンタジエン、トリシクロペンタジエン、ノルボルナジエン等の脂肪族環状ポリエン化合物系;ビニルシクロペンテン、ビニルシクロヘキセン等の置換脂肪族環状オレフィン化合物系等が挙げられる。 As the organic compound of component (A), it is difficult to express the organic compound divided into the organic skeleton part and a group having a carbon-carbon double bond that is reactive with the SiH group covalently bonded to the organic skeleton part. Low molecular weight compounds can also be used. Specific examples of these low molecular weight compounds include aliphatic chain polyene compound systems such as butadiene, isoprene, octadiene and decadiene; aliphatic cyclic polyenes such as cyclopentadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene and norbornadiene. Compound systems: Substituted aliphatic cyclic olefin compound systems such as vinylcyclopentene and vinylcyclohexene.
(A)成分の有機化合物としては、耐熱性の観点からは、下記一般式(III) As the organic compound (A), from the viewpoint of heat resistance, the following general formula (III)
上記一般式(III)のR4、R5、R6としては、得られる硬化物の耐熱性がより高くなりうるという観点からは、炭素数1〜20の一価の有機基であることが好ましく、炭素数1〜10の一価の有機基であることがより好ましく、炭素数1〜4の一価の有機基であることがさらに好ましい。これらの好ましいR4、R5、R6の例としては、メチル基、エチル基、プロピル基、ブチル基、フェニル基、ベンジル基、フェネチル基、ビニル基、アリル基、グリシジル基、 R 4 , R 5 and R 6 in the general formula (III) are monovalent organic groups having 1 to 20 carbon atoms from the viewpoint that the heat resistance of the obtained cured product can be further increased. The monovalent organic group having 1 to 10 carbon atoms is more preferable, and the monovalent organic group having 1 to 4 carbon atoms is more preferable. Examples of these preferable R 4 , R 5 and R 6 include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,
上記一般式(III)のR4、R5、R6としては、得られる硬化物の各種材料との接着性が良好になりうるという観点からは、これらのうち少なくとも1つがエポキシ基を一つ以上含む炭素数1〜50の一価の有機基であることが好ましく、 As R 4 , R 5 , and R 6 in the general formula (III), at least one of them has one epoxy group from the viewpoint that adhesion of the obtained cured product to various materials can be improved. It is preferably a monovalent organic group having 1 to 50 carbon atoms,
上記一般式(III)のR4、R5、R6としては、得られる硬化物の化学的な熱安定性が良好になりうるという観点からは、これらのうち少なくとも1つが2個以下の酸素原子を含みかつ構成元素としてC、H、Oのみを含む炭素数1〜50の一価の有機基であることが好ましく、炭素数1〜50の一価の炭化水素基であることがより好ましい。これらの好ましいR4、R5、R6の例としては、メチル基、エチル基、プロピル基、ブチル基、フェニル基、ベンジル基、フェネチル基、ビニル基、アリル基、グリシジル基、 As R 4 , R 5 , and R 6 in the general formula (III), at least one of them is oxygen of 2 or less from the viewpoint that chemical thermal stability of the resulting cured product can be improved. It is preferably a monovalent organic group having 1 to 50 carbon atoms and containing only C, H and O as constituent elements, and more preferably a monovalent hydrocarbon group having 1 to 50 carbon atoms. . Examples of these preferable R 4 , R 5 and R 6 include methyl group, ethyl group, propyl group, butyl group, phenyl group, benzyl group, phenethyl group, vinyl group, allyl group, glycidyl group,
上記一般式(III)のR4、R5、R6としては、反応性が良好になるという観点からは、これらのうち少なくとも1つが As R 4 , R 5 and R 6 in the general formula (III), at least one of them is selected from the viewpoint of good reactivity.
上記一般式(V)のR8は、直接結合あるいは炭素数1〜48の二価の有機基であるが、得られる硬化物の耐熱性がより高くなりうるという観点からは、直接結合あるいは炭素数1〜20の二価の有機基であることが好ましく、直接結合あるいは炭素数1〜10の二価の有機基であることがより好ましく、直接結合あるいは炭素数1〜4の二価の有機基であることがさらに好ましい。これらの好ましいR8の例としては、 R 8 in the general formula (V) is a direct bond or a divalent organic group having 1 to 48 carbon atoms. From the viewpoint that the heat resistance of the obtained cured product can be further increased, the direct bond or carbon It is preferably a divalent organic group having 1 to 20 carbon atoms, more preferably a direct bond or a divalent organic group having 1 to 10 carbon atoms, and a direct bond or a divalent organic group having 1 to 4 carbon atoms. More preferably, it is a group. Examples of these preferred R 8 include
上記一般式(V)のR8としては、得られる硬化物の化学的な熱安定性が良好になりうるという観点からは、直接結合あるいは2個以下の酸素原子を含みかつ構成元素としてC、H、Oのみを含む炭素数1〜48の二価の有機基であることが好ましく、直接結合あるいは炭素数1〜48の二価の炭化水素基であることがより好ましい。これらの好ましいR8の例としては、 As R 8 of the general formula (V), from the viewpoint that the chemical thermal stability of the resulting cured product can be improved, it is a direct bond or contains 2 or less oxygen atoms and contains C as a constituent element. It is preferably a C1-C48 divalent organic group containing only H and O, more preferably a direct bond or a C1-C48 divalent hydrocarbon group. Examples of these preferred R 8 include
上記一般式(V)のR9は、水素原子又はメチル基であるが、反応性が良好であるという観点からは、水素原子が好ましい。 R 9 in the general formula (V) is a hydrogen atom or a methyl group, and a hydrogen atom is preferable from the viewpoint of good reactivity.
また、耐熱性をより向上し得るという観点からは、一般式(III)において、SiH基と反応性を有する炭素−炭素二重結合を1分子中に2個以上含有することが好ましく、3個以上含有することがより好ましい。 Moreover, from the viewpoint that heat resistance can be further improved, in the general formula (III), it is preferable that two or more carbon-carbon double bonds having reactivity with the SiH group are contained in one molecule. It is more preferable to contain above.
以上のような一般式(III)で表される有機化合物の好ましい具体例としては、トリアリルイソシアヌレート、 Preferable specific examples of the organic compound represented by the general formula (III) as described above include triallyl isocyanurate,
また、(A)成分の有機化合物としては、有機重合体骨格に、SiH基と反応性を有する炭素−炭素二重結合を含有する基が共有結合したものも好ましい。 In addition, as the organic compound of the component (A), a compound in which a group containing a carbon-carbon double bond having reactivity with the SiH group is covalently bonded to the organic polymer skeleton is also preferable.
有機重合体骨格としては、例えば、ポリオキシエチレン、ポリオキシプロピレン、ポリオキシテトラメチレン、ポリオキシエチレン−ポリオキシプロピレン共重合体等のポリエーテル系重合体が挙げられる。さらに具体的な例を示すと、 Examples of the organic polymer skeleton include polyether polymers such as polyoxyethylene, polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-polyoxypropylene copolymer. More specific examples:
なお、R10、R11は好ましくは炭素数1〜200の二価の炭化水素基、より好ましくは炭素数1〜200のアルキレン基である。 R 10 and R 11 are preferably a divalent hydrocarbon group having 1 to 200 carbon atoms, more preferably an alkylene group having 1 to 200 carbon atoms.
有機重合体骨格として用いられるその他の重合体としては、例えば、アジピン酸、フタル酸、イソフタル酸、テレフタル酸、ヘキサヒドロフタル酸等の2塩基酸とエチレングリコール、ジエチレングリコール、プロピレングリコール、テトラメチレングリコール、ネオペンチルグリコール等のグリコールとの縮合またはラクトン類の開環重合で得られるポリエステル系重合体;エチレン−プロピレン系共重合体;ポリイソブチレン、イソブチレンとイソプレン等との共重合体;ポリクロロプレン;ポリイソプレン、イソプレンとブタジエン、アクリロニトリル、スチレン等との共重合体;ポリブタジエン、ブタジエンとスチレン、アクリロニトリル等との共重合体;ポリイソプレンを水素添加して得られるポリオレフィン系(飽和炭化水素系)重合体、ポリブタジエンを水素添加して得られるポリオレフィン系重合体、イソプレンとアクリロニトリル、スチレン等との共重合体を水素添加して得られるポリオレフィン系重合体、ブタジエンとアクリロニトリル、スチレン等との共重合体を水素添加して得られるポリオレフィン系重合体;エチルアクリレート、ブチルアクリレート等のモノマーをラジカル重合して得られるポリアクリル酸エステル;エチルアクリレート、ブチルアクリレート等のアクリル酸エステルと、酢酸ビニル、アクリロニトリル、メチルメタクリレート、スチレン等とのアクリル酸エステル系共重合体;前記有機重合体中でビニルモノマーを重合して得られるグラフト重合体;ポリサルファイド系重合体;ε−カプロラクタムの開環重合によるナイロン6、ヘキサメチレンジアミンとアジピン酸の重縮合によるナイロン66、ヘキサメチレンジアミンとセバシン酸の重縮合によるナイロン610、11−アミノウンデカン酸の重縮合によるナイロン11、ラウロラクタムの開環重合によるナイロン12、上記のナイロンのうち2成分以上の成分を有する共重合ナイロン等のポリアミド系重合体;ビスフェノールAと塩化カルボニルより重縮合して製造されたポリカーボネート系重合体;ジアリルフタレート系重合体;ノボラック型フェノール樹脂、レゾール型フェノール樹脂、アンモニアレゾール型フェノール樹脂、ベンジリックエーテル型フェノール樹脂等のフェノール系樹脂等が挙げられる。 Examples of other polymers used as the organic polymer skeleton include dibasic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and hexahydrophthalic acid, and ethylene glycol, diethylene glycol, propylene glycol, tetramethylene glycol, Polyester polymers obtained by condensation with glycols such as neopentyl glycol or ring-opening polymerization of lactones; ethylene-propylene copolymers; polyisobutylene, copolymers of isobutylene and isoprene, etc .; polychloroprene; polyisoprene , Copolymers of isoprene and butadiene, acrylonitrile, styrene, etc .; copolymers of polybutadiene, butadiene and styrene, acrylonitrile, etc .; polyolefins obtained by hydrogenating polyisoprene (saturated hydrocarbons) Polymers, polyolefin polymers obtained by hydrogenating polybutadiene, polyolefin polymers obtained by hydrogenating copolymers of isoprene and acrylonitrile, styrene, copolymers of butadiene, acrylonitrile, styrene, etc. Polyolefin polymer obtained by hydrogenation of polyacrylic acid ester obtained by radical polymerization of monomers such as ethyl acrylate and butyl acrylate; acrylic acid ester such as ethyl acrylate and butyl acrylate, vinyl acetate, acrylonitrile, methyl Acrylate ester copolymer with methacrylate, styrene, etc .; Graft polymer obtained by polymerizing vinyl monomer in the organic polymer; Polysulfide polymer; Nylon 6, hexene by ring-opening polymerization of ε-caprolactam Nylon 66 by polycondensation of samethylenediamine and adipic acid, nylon 610 by polycondensation of hexamethylenediamine and sebacic acid, nylon 11 by polycondensation of 11-aminoundecanoic acid, nylon 12 by ring-opening polymerization of laurolactam, Polyamide polymer such as copolymer nylon having two or more components of nylon; polycarbonate polymer produced by polycondensation from bisphenol A and carbonyl chloride; diallyl phthalate polymer; novolac type phenol resin, resole Examples thereof include phenolic resins such as type phenolic resin, ammonia resol type phenolic resin, and benzylic ether type phenolic resin.
また、SiH基と反応性を有する炭素−炭素二重結合を含有する基については、前記説明のものが挙げられる。 Examples of the group containing a carbon-carbon double bond having reactivity with the SiH group include those described above.
アルケニル基を前記重合体骨格に導入する方法については、種々提案されているものを用いることができるが、重合後にアルケニル基を導入する方法と重合中にアルケニル基を導入する方法に大別することができる。 Various methods for introducing an alkenyl group into the polymer skeleton can be used. However, the method can be roughly divided into a method for introducing an alkenyl group after polymerization and a method for introducing an alkenyl group during polymerization. Can do.
重合後にアルケニル基を導入する方法としては、例えば、末端、主鎖あるいは側鎖に水酸基、アルコキシド基、カルボキシル基、エポキシ基等の官能基を有する有機重合体に、その官能基に対して反応性を示す活性基とアルケニル基の両方を有する有機化合物を反応させることにより、アルケニル基を末端、主鎖あるいは側鎖に導入することができる。 As a method for introducing an alkenyl group after polymerization, for example, an organic polymer having a functional group such as a hydroxyl group, an alkoxide group, a carboxyl group, or an epoxy group at the terminal, main chain, or side chain is reactive with the functional group. By reacting an organic compound having both an active group having an alkenyl group and an alkenyl group, the alkenyl group can be introduced into the terminal, main chain or side chain.
上記官能基に対して反応性を示す活性基とアルケニル基の両方を有する有機化合物の例としては、アクリル酸、メタクリル酸、ビニル酢酸、アクリル酸クロライド、アクリル酸ブロマイド等の炭素数3〜20の不飽和脂肪酸、酸ハライド、酸無水物等;アリルクロロホルメート(CH2=CHCH2OCOCl)、アリルブロモホルメート(CH2=CHCH2OCOBr)等の炭素数3〜20の不飽和脂肪族アルコール置換炭酸ハライド;アリルクロライド、アリルブロマイド、ビニル(クロロメチル)ベンゼン、アリル(クロロメチル)ベンゼン、アリル(ブロモメチル)ベンゼン、アリル(クロロメチル)エーテル、アリル(クロロメトキシ)ベンゼン、1−ブテニル(クロロメチル)エーテル、1−ヘキセニル(クロロメトキシ)ベンゼン、アリルオキシ(クロロメチル)ベンゼン、アリルイソシアネート等が挙げられる。 Examples of organic compounds having both an active group and an alkenyl group that are reactive with respect to the functional group include 3 to 20 carbon atoms such as acrylic acid, methacrylic acid, vinyl acetic acid, acrylic acid chloride, and acrylic acid bromide. unsaturated fatty acids, acid halides, acid anhydrides and the like; allyl chloroformate (CH 2 = CHCH 2 OCOCl) , allyl bromo formate (CH 2 = CHCH 2 OCOBr) unsaturated aliphatic 3 to 20 carbon atoms such as alcohol Substituted carbonates; allyl chloride, allyl bromide, vinyl (chloromethyl) benzene, allyl (chloromethyl) benzene, allyl (bromomethyl) benzene, allyl (chloromethyl) ether, allyl (chloromethoxy) benzene, 1-butenyl (chloromethyl) ) Ether, 1-hexenyl (chloromethoxy) Zen, allyloxy (chloromethyl) benzene, allyl isocyanate.
また、エステル交換法を用いてアルケニル基を導入する方法がある。この方法はポリエステル樹脂やアクリル樹脂のエステル部分のアルコール残基を、エステル交換触媒を用いて、アルケニル基含有アルコール又はアルケニル基含有フェノール誘導体とエステル交換する方法である。 There is also a method of introducing an alkenyl group using a transesterification method. This method is a method in which an alcohol residue in an ester portion of a polyester resin or an acrylic resin is transesterified with an alkenyl group-containing alcohol or an alkenyl group-containing phenol derivative using a transesterification catalyst.
アルコール残基との交換に用いるアルケニル基含有アルコール又はアルケニル基含有フェノール誘導体は、少なくとも1個のアルケニル基を有し、かつ、少なくとも1個の水酸基を有するアルコール又はフェノール誘導体であれば良いが、水酸基を1個有する方が好ましい。触媒は、使用してもしなくても良いが、用いる場合にはチタン系及び錫系のものが良い。 The alkenyl group-containing alcohol or alkenyl group-containing phenol derivative used for exchange with an alcohol residue may be any alcohol or phenol derivative having at least one alkenyl group and having at least one hydroxyl group. It is preferable to have one. The catalyst may or may not be used, but when used, a titanium-based and tin-based catalyst is preferable.
上記のアルケニル基と水酸基をもつアルコール又はフェノール誘導体の例としては、アリルアルコール、3−ブテン−1−オール、4−ペンテン−1−オール、5−ヘキセン−1−オール、6−ヘプテン−1−オール、7−オクテン−1−オール、8−ノネン−1−オール、9−デセン−1−オール、2−(アリルオキシ)エタノール、ネオペンチルグリコールモノアリルエーテル、グリセリンジアリルエーテル、トリメチロールプロパントリアリルエーテル、トリメチロールエタントリアリルエーテル、ペンタエリスリトールテトラアリルエーテル、1,2,6−ヘキサントリオールトリアリルエーテル、ソルビタントリアリルエーテル、 Examples of the alcohol or phenol derivative having an alkenyl group and a hydroxyl group include allyl alcohol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, and 6-heptene-1-. All, 7-octen-1-ol, 8-nonen-1-ol, 9-decen-1-ol, 2- (allyloxy) ethanol, neopentyl glycol monoallyl ether, glyceryl diallyl ether, trimethylolpropane triallyl ether , Trimethylolethane triallyl ether, pentaerythritol tetraallyl ether, 1,2,6-hexanetriol triallyl ether, sorbitan triallyl ether,
さらに、上記アルコール又はフェノール誘導体の酢酸エステル等のエステル化物と、ポリエステル樹脂やアクリル樹脂のエステル部分を、エステル交換触媒を用いてエステル交換しながら、生成するポリエステル樹脂やアクリル樹脂のエステル部分のアルコール残基との酢酸エステル等の低分子量エステル化物を、減圧脱揮等で系外に留去する方法でアルケニル基を導入する方法もある。 Further, the ester residue of the above alcohol or phenol derivative such as acetate ester and the ester portion of the polyester resin or acrylic resin are transesterified using a transesterification catalyst, and the alcohol residue in the ester portion of the polyester resin or acrylic resin to be produced is obtained. There is also a method of introducing an alkenyl group by a method in which a low molecular weight esterified product such as an acetic ester with a group is distilled out of the system by vacuum devolatilization or the like.
また、リビング重合によりメチル(メタ)アクリレート等の重合を行った後、リビング末端をアルケニル基を有する化合物によって停止させる方法により、末端にアルケニル基を導入することもできる。 Moreover, after polymerizing methyl (meth) acrylate etc. by living polymerization, an alkenyl group can also be introduce | transduced into the terminal by the method of stopping a living terminal with the compound which has an alkenyl group.
重合中にアルケニル基を導入する方法としては、例えば、ラジカル重合法で本発明に用いる(A)成分の有機重合体骨格を製造する場合に、アリルメタクリレート、アリルアクリレート等の分子中にラジカル反応性の低いアルケニル基を有するビニルモノマーや、アリルメルカプタン等のラジカル反応性の低いアルケニル基を有するラジカル連鎖移動剤を用いることにより、有機重合体骨格の側鎖や末端にアルケニル基を導入することができる。 As a method for introducing an alkenyl group during the polymerization, for example, in the case of producing the organic polymer skeleton of the component (A) used in the present invention by radical polymerization, radical reactivity in the molecule of allyl methacrylate, allyl acrylate, etc. By using a vinyl monomer having a low alkenyl group or a radical chain transfer agent having a low alkenyl group such as allyl mercaptan, an alkenyl group can be introduced into the side chain or terminal of the organic polymer skeleton. .
上記の重合体骨格の側鎖又は末端にアルケニル基を導入した(A)成分の有機化合物の具体的な例としては、 As a specific example of the organic compound of the component (A) in which an alkenyl group is introduced into the side chain or terminal of the polymer skeleton,
等が挙げられる。
Etc.
なお、R13、R14、R16、R17、R19、R20は、好ましくは炭素数1〜200の二価の炭化水素基、より好ましくは炭素数1〜200のアルキレン基である。R22、R23、R25、R26、R27は、好ましくは炭素数1〜6の二価の炭化水素基、より好ましくは炭素数1〜6のアルキレン基である。X、Yは、好ましくは直接結合又は炭素数1〜48の二価の炭化水素基、より好ましくは直接結合又は炭素数1〜48のアルキレン基である。 R 13 , R 14 , R 16 , R 17 , R 19 , and R 20 are preferably a divalent hydrocarbon group having 1 to 200 carbon atoms, more preferably an alkylene group having 1 to 200 carbon atoms. R 22 , R 23 , R 25 , R 26 and R 27 are preferably a divalent hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms. X and Y are preferably a direct bond or a divalent hydrocarbon group having 1 to 48 carbon atoms, more preferably a direct bond or an alkylene group having 1 to 48 carbon atoms.
(A)成分としては、他の成分との均一な混合、及び良好な作業性を得るためには、100℃以下の温度において流動性があるものが好ましく、線状でも枝分かれ状でもよい。分子量としては、好ましい下限は50、好ましい上限は100,000であり、より好ましい下限は54、より好ましい上限は70,000であり、さらに好ましい下限は68、さらに好ましい上限は50,000である。分子量が50より低いものは揮発性が大となる傾向があり、分子量が100,000を越えるものでは一般に原料が高粘度となり作業性が低下する傾向があるとともに、アルケニル基とSiH基との反応による架橋の効果が発現し難い傾向がある。なお、当該分子量は、ゲル浸透クロマトグラフィー(GPC)法により測定した値である。 As the component (A), in order to obtain uniform mixing with other components and good workability, a component having fluidity at a temperature of 100 ° C. or lower is preferable, and may be linear or branched. As a molecular weight, a preferable lower limit is 50, a preferable upper limit is 100,000, a more preferable lower limit is 54, a more preferable upper limit is 70,000, a further preferable lower limit is 68, and a further preferable upper limit is 50,000. When the molecular weight is lower than 50, the volatility tends to increase. When the molecular weight exceeds 100,000, the raw material generally has a high viscosity and the workability tends to decrease, and the reaction between the alkenyl group and the SiH group. There is a tendency that the effect of cross-linking by is hardly expressed. The molecular weight is a value measured by a gel permeation chromatography (GPC) method.
また、本発明では、上記(A)成分を単独で用いても2種以上を混合使用してもよい。 Moreover, in this invention, the said (A) component may be used independently, or 2 or more types may be mixed and used.
次に、(B)成分である1分子中に少なくとも2個のSiH基を含有するケイ素化合物について説明する。 Next, the silicon compound containing at least two SiH groups in one molecule as the component (B) will be described.
本発明に使用できる1分子中に少なくとも2個のSiH基を含有するケイ素化合物については、特に制限がなく、例えば国際公開第96/15194号パンフレットに記載される化合物で、1分子中に少なくとも2個のSiH基を有するもの等が使用できる。 The silicon compound containing at least two SiH groups in one molecule that can be used in the present invention is not particularly limited, and is a compound described in, for example, WO 96/15194, and at least 2 in one molecule. Those having a single SiH group can be used.
これらのうち、入手性の面からは、1分子中に少なくとも2個のSiH基を有する鎖状及び/又は環状ポリオルガノシロキサンが好ましい。 Among these, from the viewpoint of availability, a linear and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule is preferable.
上記鎖状ポリオルガノシロキサンとしては、例えば、1,1,3,3−テトラメチルジシロキサン、1,1,3,3,5,5−ヘキサメチルトリシロキサン、1,1,3,3,5,5,7,7−オクタメチルテトラシロキサン等の両末端水素化ポリジメチルシロキサン;ポリメチル水素シロキサン;メチル水素シロキサンとジメチルシロキサンとの共重合体;ポリエチル水素シロキサン等が挙げられる。 Examples of the chain polyorganosiloxane include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, and 1,1,3,3,5. , 5,7,7-octamethyltetrasiloxane, etc., hydrogenated polydimethylsiloxane; polymethylhydrogensiloxane; copolymer of methylhydrogensiloxane and dimethylsiloxane; polyethylhydrogensiloxane.
上記環状ポリオルガノシロキサンとしては、例えば、下記一般式(VI) Examples of the cyclic polyorganosiloxane include the following general formula (VI):
また、(A)成分との相溶性が良いという観点から、上記一般式(VI)で表される、
1分子中に少なくとも2個のSiH基を有する環状ポリオルガノシロキサンがより好ましい。なお、上記一般式(VI)におけるR28は、C、H、Oから構成される炭素数1〜6の有機基であることが好ましく、炭素数1〜6の炭化水素基であることがより好ましく、炭素数1〜6のアルキル基であることがさらに好ましい。また、nは3〜10の数であることが好ましい。
In addition, from the viewpoint of good compatibility with the component (A), it is represented by the above general formula (VI).
A cyclic polyorganosiloxane having at least two SiH groups in one molecule is more preferred. R 28 in the general formula (VI) is preferably an organic group having 1 to 6 carbon atoms composed of C, H, and O, and more preferably a hydrocarbon group having 1 to 6 carbon atoms. An alkyl group having 1 to 6 carbon atoms is more preferable. N is preferably a number of 3 to 10.
一般式(VI)で表される環状ポリオルガノシロキサンの好ましい具体例としては、1,3,5−トリメチルシクロトリシロキサン、1,3,5,7−テトラメチルシクロテトラシロキサン、1,3,5,7,9−ペンタメチルシクロペンタシロキサン等が挙げられる。 Preferable specific examples of the cyclic polyorganosiloxane represented by the general formula (VI) include 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5 , 7,9-pentamethylcyclopentasiloxane and the like.
さらに、1分子中に少なくとも2個のSiH基を有する鎖状及び/又は環状ポリオルガノシロキサンと、炭素−炭素二重結合を有する有機化合物から選ばれた1種以上の化合物(以降(F)成分と称する)との反応物も好ましい。 Furthermore, at least one compound selected from a chain and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule and an organic compound having a carbon-carbon double bond (hereinafter referred to as component (F)) And the reaction product thereof is also preferred.
1分子中に少なくとも2個のSiH基を有する鎖状及び/又は環状ポリオルガノシロキサンとしては、上記と同様のものが挙げられる。 Examples of the linear and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule include those described above.
(F)成分は、SiH基と反応性を有する炭素−炭素二重結合を1分子中に少なくとも1個含有する有機系骨格からなる有機化合物であって、前記(A)成分で説明したものと同じものが使用できる。 The component (F) is an organic compound composed of an organic skeleton containing at least one carbon-carbon double bond having reactivity with the SiH group in one molecule, as described in the component (A). The same can be used.
(F)成分の好ましい具体例としては、ノボラックフェノールのアリルエーテル、ビスフェノールAジアリルエーテル、水添ビスフェノールAのジアリルエーテル、2、2’−ジアリルビスフェノールA、ジアリルフタレート、フタル酸のビス(2−アリルオキシエチル)エステル、トリアリルイソシアヌレート、スチレン、α−メチルスチレン、ジビニルベンゼン、アリル末端ポリプロピレンオキシド、アリル末端ポリエチレンオキシド等が挙げられる。(F)成分の有機化合物は、単独もしくは2種以上のものを混合して用いることが可能である。 Preferred examples of the component (F) include novolak phenol allyl ether, bisphenol A diallyl ether, hydrogenated bisphenol A diallyl ether, 2,2'-diallyl bisphenol A, diallyl phthalate, phthalic acid bis (2-allyl). Oxyethyl) ester, triallyl isocyanurate, styrene, α-methylstyrene, divinylbenzene, allyl-terminated polypropylene oxide, allyl-terminated polyethylene oxide, and the like. The organic compound (F) can be used alone or in combination of two or more.
上記(F)成分と、1分子中に少なくとも2個のSiH基を有する鎖状及び/又は環状ポリオルガノシロキサンの反応は、本発明の(C)成分であるヒドロシリル化触媒を用いて実施することができる。 The reaction of the component (F) with a linear and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule is carried out using the hydrosilylation catalyst which is the component (C) of the present invention. Can do.
ヒドロシリル化触媒としては、触媒活性の点から、塩化白金酸、白金−オレフィン錯体、白金−ビニルシロキサン錯体等が好ましい。また、これらの触媒は単独で使用してもよく、2種以上併用してもよい。触媒の添加量は特に限定されないが、十分な反応性を有し、かつコストを比較的低く抑えるために、SiH基1モルに対して、下限10-8モル、上限10-1モルの範囲が好ましく、より好ましくは、下限10-6モル、上限10-2モルの範囲である。 As the hydrosilylation catalyst, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types. The addition amount of the catalyst is not particularly limited, but in order to have sufficient reactivity and keep the cost relatively low, the range of the lower limit of 10 -8 mol and the upper limit of 10 -1 mol per 1 mol of SiH group. More preferably, the lower limit is 10 −6 mol and the upper limit is 10 −2 mol.
上記(F)成分と1分子中に少なくとも2個のSiH基を有する鎖状及び/又は環状ポリオルガノシロキサンの反応に使用できる溶媒としては、特に限定されるものではなく、具体的に例示すれば、ベンゼン、トルエン、ヘキサン、ヘプタン等の炭化水素系溶媒;テトラヒドロフラン、1, 4−ジオキサン、ジエチルエーテル等のエーテル系溶媒;アセトン、メチルエチルケトン等のケトン系溶媒;クロロホルム、塩化メチレン、1, 2−ジクロロエタン等のハロゲン系溶媒等を好適に用いることができる。当該溶媒は、単独で用いてもよいし、2種類以上の混合溶媒として用いることもできる。溶媒としては、トルエン、テトラヒドロフラン、クロロホルムが好ましい。 The solvent that can be used in the reaction of the component (F) and the chain and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule is not particularly limited, and is specifically exemplified. Hydrocarbon solvents such as benzene, toluene, hexane and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane and diethyl ether; ketone solvents such as acetone and methyl ethyl ketone; chloroform, methylene chloride and 1,2-dichloroethane A halogen-based solvent such as can be suitably used. The said solvent may be used independently and can also be used as 2 or more types of mixed solvents. As the solvent, toluene, tetrahydrofuran and chloroform are preferable.
使用する溶媒量は、用いる反応性[(F)+(1分子中に少なくとも2個のSiH基を有する鎖状及び/又は環状ポリオルガノシロキサン)]成分1gに対し、下限0mL、上限10 mLの範囲で用いるのが好ましく、下限0.5mL、上限5mLの範囲で用いるのがより好ましく、下限1mL、上限3mLの範囲で用いるのがさらに好ましい。 The amount of the solvent to be used is a lower limit of 0 mL and an upper limit of 10 mL with respect to 1 g of the reactive [(F) + (chain and / or cyclic polyorganosiloxane having at least two SiH groups in one molecule)] component. It is preferably used in a range, more preferably in a range of a lower limit of 0.5 mL and an upper limit of 5 mL, and further preferably in a range of a lower limit of 1 mL and an upper limit of 3 mL.
(F)成分と、1分子中に少なくとも2個のSiH基を有する鎖状及び/又は環状ポリオルガノシロキサンとのモル比[(F)成分/1分子中に少なくとも2個のSiH基を有する鎖状及び/又は環状ポリオルガノシロキサン]は、収率の点から、下限5、上限100であることが好ましく、下限7、上限50であることがより好ましく、下限8、上限20であることがさらに好ましい。 Mole ratio of (F) component to chain and / or cyclic polyorganosiloxane having at least 2 SiH groups in one molecule [(F) component / chain having at least 2 SiH groups in 1 molecule The shape and / or cyclic polyorganosiloxane] is preferably the lower limit 5 and the upper limit 100 in terms of yield, more preferably the lower limit 7 and the upper limit 50, and further preferably the lower limit 8 and the upper limit 20. preferable.
また、上記したような各種(B)成分は、単独もしくは2種以上のものを混合して用いることが可能である。 Moreover, various (B) components as described above can be used alone or in combination of two or more.
なお、硬化性組成物中の(A)成分と(B)成分の比率としては、[硬化性組成物中の(A)成分のアルケニル基のモル数/硬化性組成物中の(B)成分のSiH基のモル数]の値が、下限0.25、上限30の範囲となる比率であることが好ましく、下限0.33、上限20の範囲となる比率であることがより好ましい。上記値が0.25より小さい場合はアルケニル基とSiH基との反応による架橋の効果が不十分になる傾向にあり、30より大きい場合は硬化物から未反応の(A)成分がブリードしてくる傾向にある。 The ratio of the component (A) to the component (B) in the curable composition is [number of moles of alkenyl group of the component (A) in the curable composition / component (B) in the curable composition. The value of the number of moles of SiH groups] is preferably a ratio that is in the range of a lower limit of 0.25 and an upper limit of 30, and more preferably a ratio that is in the range of a lower limit of 0.33 and an upper limit of 20. When the above value is smaller than 0.25, the effect of crosslinking due to the reaction between the alkenyl group and the SiH group tends to be insufficient, and when larger than 30, the unreacted component (A) is bleed from the cured product. Tend to come.
次に、(C)成分であるヒドロシリル化触媒について説明する。 Next, the hydrosilylation catalyst as component (C) will be described.
ヒドロシリル化触媒としては、ヒドロシリル化反応の触媒活性があれば特に限定されないが、例えば、白金の単体;アルミナ、シリカ、カーボンブラック等の担体に固体白金を担持させたもの;塩化白金酸;塩化白金酸とアルコール、アルデヒド、ケトン等との錯体;白金−オレフィン錯体(例えば、Pt(CH2=CH2)2(PPh3)2、Pt(CH2=CH2)2Cl2);白金−ビニルシロキサン錯体(例えば、Pt(ViMe2SiOSiMe2Vi)a、Pt[(MeViSiO)4]b);白金−ホスフィン錯体(例えば、Pt(PPh3)4、Pt(PBu3)4);白金−ホスファイト錯体(例えば、Pt[P(OPh)3]4、Pt[P(OBu)3]4)(式中、Meはメチル基、Buはブチル基、Viはビニル基、Phはフェニル基を表し、a、bは、整数を示す。);ジカルボニルジクロロ白金;カールシュテト(Karstedt)触媒;アシュビー(Ashby)の米国特許第3159601号及び第3159662号明細書中に記載された白金−炭化水素複合体;ラモロー(Lamoreaux)の米国特許第3220972号明細書中に記載された白金アルコラート触媒等が挙げられる。さらに、モディック(Modic)の米国特許第3516946号明細書中に記載された塩化白金−オレフィン複合体も本発明において有用である。 The hydrosilylation catalyst is not particularly limited as long as it has catalytic activity for the hydrosilylation reaction. For example, platinum alone; solid platinum supported on a support such as alumina, silica, carbon black; chloroplatinic acid; platinum chloride Complexes of acids with alcohols, aldehydes, ketones, etc .; platinum-olefin complexes (for example, Pt (CH 2 ═CH 2 ) 2 (PPh 3 ) 2 , Pt (CH 2 ═CH 2 ) 2 Cl 2 ); platinum-vinyl Siloxane complexes (eg, Pt (ViMe 2 SiOSiMe 2 Vi) a , Pt [(MeViSiO) 4 ] b ); platinum-phosphine complexes (eg, Pt (PPh 3 ) 4 , Pt (PBu 3 ) 4 ); platinum-phos Fight complexes (e.g., Pt [P (OPh) 3 ] 4, Pt [P (OBu) 3] 4) ( in the formula, Me represents a methyl group, Bu a butyl group, Vi represents a vinyl group Ph represents a phenyl group, and a and b represent integers.); Dicarbonyldichloroplatinum; Karlstedt catalyst; described in Ashby US Pat. Nos. 3,159,601 and 3,159,662 Platinum-hydrocarbon composites; platinum alcoholate catalysts described in US Pat. No. 3,220,972 to Lamoreaux. In addition, platinum chloride-olefin complexes described in Modic US Pat. No. 3,516,946 are also useful in the present invention.
また、白金化合物以外の触媒の例としては、RhCl(PPh)3、RhCl3、RhAl2O3、RuCl3、IrCl3、FeCl3、AlCl3、PdCl2・2H2O、NiCl2、TiCl4等が挙げられる。 Examples of catalysts other than platinum compounds include RhCl (PPh) 3 , RhCl 3 , RhAl 2 O 3 , RuCl 3 , IrCl 3 , FeCl 3 , AlCl 3 , PdCl 2 .2H 2 O, NiCl 2 , TiCl 4. Etc.
これらの中では、触媒活性の点から、塩化白金酸、白金−オレフィン錯体、白金−ビニルシロキサン錯体等が好ましい。また、これらの触媒は単独で使用してもよく、2種以上併用してもよい。 Of these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes and the like are preferable from the viewpoint of catalytic activity. Moreover, these catalysts may be used independently and may be used together 2 or more types.
(C)成分のヒドロシリル化触媒の添加量は特に限定されないが、十分な硬化性を有し、かつ硬化性組成物のコストを比較的低く抑えるために、SiH基1モルに対して、下限10-8モル、上限10-1モルの範囲が好ましく、より好ましくは、下限10-6モル、上限10-2モルの範囲である。 The addition amount of the hydrosilylation catalyst of component (C) is not particularly limited, but in order to have sufficient curability and keep the cost of the curable composition relatively low, the lower limit is 10 with respect to 1 mol of SiH groups. A range of -8 mol and an upper limit of 10 -1 mol is preferable, and a lower limit of 10 -6 mol and an upper limit of 10 -2 mol are more preferable.
なお、当該触媒は、(B)成分合成時に使用して残存している量で十分な硬化性を示す場合は必ずしも添加する必要はないが、硬化性を調整するために上記の範囲で新たに添加することもできる。 The catalyst does not necessarily need to be added if the remaining amount used at the synthesis of the component (B) shows sufficient curability, but is newly added in the above range in order to adjust curability. It can also be added.
また、上記触媒には助触媒を併用することが可能である。助触媒としては、例えば、単体の硫黄等の硫黄系化合物、トリエチルアミン等のアミン系化合物等が挙げられる。 In addition, a cocatalyst can be used in combination with the catalyst. Examples of the cocatalyst include a sulfur-based compound such as simple sulfur, and an amine-based compound such as triethylamine.
助触媒の添加量は特に限定されないが、上記ヒドロシリル化触媒1モルに対して、下限10-2モル、上限102モルの範囲が好ましく、より好ましくは下限10-1モル、上限10モルの範囲である。 The amount of the cocatalyst added is not particularly limited, but the lower limit is preferably 10 -2 mol and the upper limit is 10 2 mol, more preferably the lower limit is 10 -1 mol and the upper limit is 10 mol, relative to 1 mol of the hydrosilylation catalyst. It is.
さらに、本発明の組成物の保存安定性を改良する目的、又は、製造過程でのヒドロシリル化反応の反応性を調整する目的で、硬化遅延剤を使用することができる。硬化遅延剤としては、例えば、脂肪族不飽和結合を含有する化合物、有機リン化合物、有機硫黄化合物、窒素含有化合物、スズ系化合物、有機過酸化物等が挙げられる。これらは、単独で使用してもよく、2種以上併用してよい。 Furthermore, a retarder can be used for the purpose of improving the storage stability of the composition of the present invention or adjusting the reactivity of the hydrosilylation reaction during the production process. Examples of the curing retarder include a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, and an organic peroxide. These may be used alone or in combination of two or more.
脂肪族不飽和結合を含有する化合物としては、プロパルギルアルコール類、エン−イン化合物類、マレイン酸エステル類等が例示される。有機リン化合物としては、トリオルガノフォスフィン類、ジオルガノフォスフィン類、オルガノフォスフォン類、トリオルガノフォスファイト類等が例示される。有機硫黄化合物としては、オルガノメルカプタン類、ジオルガノスルフィド類、硫化水素、ベンゾチアゾール、チアゾール、ベンゾチアゾールジサルファイド等が例示される。窒素含有化合物としては、アンモニア、1〜3級アルキルアミン類、アリールアミン類、尿素、ヒドラジン等が例示される。スズ系化合物としては、ハロゲン化第一スズ2水和物、カルボン酸第一スズ等が例示される。有機過酸化物としては、ジ−tert−ブチルペルオキシド、ジクミルペルオキシド、ベンゾイルペルオキシド、過安息香酸tert−ブチル等が例示される。 Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, maleate esters and the like. Examples of the organophosphorus compound include triorganophosphine, diorganophosphine, organophosphon, and triorganophosphite. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, thiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound include ammonia, primary to tertiary alkylamines, arylamines, urea, hydrazine and the like. Examples of tin compounds include stannous halide dihydrate and stannous carboxylate. Examples of the organic peroxide include di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and tert-butyl perbenzoate.
これらの硬化遅延剤のうち、遅延活性が良好で原料入手性がよいという観点からは、ベンゾチアゾール、チアゾール、ジメチルマレート、3−ヒドロキシ−3−メチル−1−ブチン、1−エチニル−1−シクロヘキサノールが好ましい。 Among these curing retarders, from the viewpoint of good retarding activity and good raw material availability, benzothiazole, thiazole, dimethyl malate, 3-hydroxy-3-methyl-1-butyne, 1-ethynyl-1- Cyclohexanol is preferred.
硬化遅延剤の添加量は、使用するヒドロシリル化触媒1モルに対して、下限10-1モル、上限103モルの範囲が好ましく、より好ましくは下限1モル、上限50モルの範囲である。 The addition amount of the curing retardant is preferably in the range of the lower limit of 10 −1 mol and the upper limit of 10 3 mol, more preferably the lower limit of 1 mol and the upper limit of 50 mol, with respect to 1 mol of the hydrosilylation catalyst used.
本発明の硬化性組成物には、さらに(D)接着性改良剤を含有させてもよく、本発明の硬化性組成物で半導体を封止して半導体装置とする場合に、半導体との接着性が高くなり半導体装置としての信頼性が高くなるという観点から、(D)成分を含有させる方が好ましい。 The curable composition of the present invention may further contain (D) an adhesion improver, and when the semiconductor is sealed with the curable composition of the present invention to form a semiconductor device, adhesion to the semiconductor is achieved. From the viewpoint of improving the reliability and the reliability of the semiconductor device, it is preferable to contain the component (D).
次に、(D)成分である接着性改良剤について説明する。 Next, the adhesiveness improving agent which is (D) component is demonstrated.
接着性改良剤としては、一般に用いられている接着剤の他、例えば、種々のカップリング剤、エポキシ化合物、フェノール樹脂、クマロン−インデン樹脂、ロジンエステル樹脂、テルペン−フェノール樹脂、ポリスチレン系樹脂、芳香族ポリイソシアネート等を挙げることができる。 Examples of the adhesion improver include, in addition to commonly used adhesives, various coupling agents, epoxy compounds, phenol resins, coumarone-indene resins, rosin ester resins, terpene-phenol resins, polystyrene resins, aromatics, and the like. Group polyisocyanate and the like.
カップリング剤としては、例えばシランカップリング剤が挙げられる。シランカップリング剤としては、分子中に有機基と反応性のある官能基と加水分解性のケイ素基を各々少なくとも1個有する化合物であれば特に限定されない。有機基と反応性のある官能基としては、取扱い性の点からエポキシ基、メタクリル基、アクリル基、イソシアネート基、イソシアヌレート基、ビニル基、カルバメート基から選ばれる少なくとも1個の官能基が好ましく、硬化性及び接着性の点から、エポキシ基、メタクリル基、アクリル基が特に好ましい。加水分解性のケイ素基としては、取扱い性の点からアルコキシシリル基が好ましく、反応性の点からメトキシシリル基、エトキシシリル基が特に好ましい。 Examples of the coupling agent include a silane coupling agent. The silane coupling agent is not particularly limited as long as it is a compound having at least one functional group reactive with an organic group and one hydrolyzable silicon group in the molecule. The functional group reactive with the organic group is preferably at least one functional group selected from an epoxy group, a methacryl group, an acryl group, an isocyanate group, an isocyanurate group, a vinyl group, and a carbamate group from the viewpoint of handleability. From the viewpoints of curability and adhesiveness, an epoxy group, a methacryl group, and an acrylic group are particularly preferable. As the hydrolyzable silicon group, an alkoxysilyl group is preferable from the viewpoint of handleability, and a methoxysilyl group and an ethoxysilyl group are particularly preferable from the viewpoint of reactivity.
好ましいシランカップリング剤としては、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、2−(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、2−(3,4-エポキシシクロヘキシル)エチルトリエトキシシラン等のエポキシ官能基を有するアルコキシシラン類;3−メタクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルトリエトキシシラン、3−アクリロキシプロピルトリメトキシシラン、3−アクリロキシプロピルトリエトキシシラン、メタクリロキシメチルトリメトキシシラン、メタクリロキシメチルトリエトキシシラン、アクリロキシメチルトリメトキシシラン、アクリロキシメチルトリエトキシシラン等のメタクリル基あるいはアクリル基を有するアルコキシシラン類が例示できる。 Preferred silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4- (Epoxycyclohexyl) alkoxysilanes having an epoxy functional group such as ethyltriethoxysilane; 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Methacrylic or acrylic groups such as triethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane Alkoxysilanes which can be exemplified.
エポキシ化合物としては、例えば、ノボラックフェノール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビスフェノールFジグリシジルエーテル、ビスフェノールAジグリシジルエーテル、2,2’−ビス(4−グリシジルオキシシクロヘキシル)プロパン、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ーボキシレート、ビニルシクロヘキセンジオキシド、2−(3,4−エポキシシクロヘキシル)−5,5−スピロ−(3,4−エポキシシクロヘキサン)−1,3−ジオキサン、ビス(3,4−エポキシシクロヘキシル)アジペート、1,2−シクロプロパンジカルボン酸ビスグリシジルエステル、トリグリシジルイソシアヌレート、モノアリルジグリシジルイソシアヌレート、ジアリルモノグリシジルイソシアヌレート等を挙げることができる。 Examples of the epoxy compound include novolak phenol type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and 2,2′-bis (4-glycidyloxycyclohexyl). Propane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide, 2- (3,4-epoxycyclohexyl) -5,5-spiro- (3,4-epoxycyclohexane) -1,3-dioxane, bis (3,4-epoxycyclohexyl) adipate, 1,2-cyclopropanedicarboxylic acid bisglycidyl ester, triglycidyl isocyanurate, monoallyl diglycidyl isocyanate Isocyanurate, mention may be made of diallyl monoglycidyl isocyanurate and the like.
フェノール樹脂としては、例えば、フェノールとホルムアルデヒド、アセトアルデヒド等との重縮合体、クレゾールとホルムアルデヒド、アセトアルデヒド等との重縮合体等が挙げられる。 Examples of the phenol resin include polycondensates of phenol and formaldehyde, acetaldehyde, and the like, polycondensates of cresol and formaldehyde, acetaldehyde, and the like.
クマロン−インデン樹脂としては、例えば、石炭乾留ガス軽油及び/又はコールタールを蒸留して得られる沸点140〜200℃留分(クマロン、インデン、スチレン、フェノール等の混合物)を含む炭化水素油を、脱タール塩基処理した後、重合したもの等が挙げられる。 As the coumarone-indene resin, for example, a hydrocarbon oil containing a fraction having a boiling point of 140 to 200 ° C. (a mixture of coumarone, indene, styrene, phenol, etc.) obtained by distillation of coal dry gas gas oil and / or coal tar, Examples thereof include a polymerized product after the detar base treatment.
ロジンエステル樹脂としては、例えば、アビエチン酸、ネオアビエチン酸、レボビマル酸等の樹脂酸を主成分とする、ガムロジン、ウッドロジン、トール油ロジン等を、エチレングリコール、グリセリン、ペンタエリスリトール等のアルコールでエステル化したもの等が挙げられる。 Examples of rosin ester resins include esterification of gum rosin, wood rosin, tall oil rosin, etc., with alcohols such as ethylene glycol, glycerin, pentaerythritol, etc., which are mainly composed of resin acids such as abietic acid, neoabietic acid, and levobimaric acid. And the like.
テルペン−フェノール樹脂としては、例えば、α−ピネン、β−ピネン、ジペンテン等のテルペン類と、フェノール、クレゾール、ビスフェノールA等のフェノール類との共重合体等が挙げられる。 Examples of the terpene-phenol resin include copolymers of terpenes such as α-pinene, β-pinene, and dipentene with phenols such as phenol, cresol, and bisphenol A.
ポリスチレン系樹脂としては、例えば、α−メチルスチレン−ビニルトルエン共重合体、ポリエチルメチルスチレン等が挙げられる。 Examples of the polystyrene resin include α-methylstyrene-vinyltoluene copolymer, polyethylmethylstyrene, and the like.
芳香族ポリイソシアネートとしては、例えば、2,4−トルイレンジイソシアネート、2,6−トルイレンジイソシアネート、トリフェニルメタントリイソシアネート等が挙げられる。 Examples of the aromatic polyisocyanate include 2,4-toluylene diisocyanate, 2,6-toluylene diisocyanate, triphenylmethane triisocyanate, and the like.
また、接着性改良剤としての上記カップリング剤、エポキシ化合物、フェノール樹脂、クマロン−インデン樹脂、ロジンエステル樹脂、テルペン−フェノール樹脂、ポリスチレン系樹脂、芳香族ポリイソシアネートは、単独で使用してもよく、2種以上を併用してもよい。 In addition, the above-mentioned coupling agent, epoxy compound, phenol resin, coumarone-indene resin, rosin ester resin, terpene-phenol resin, polystyrene resin, and aromatic polyisocyanate as adhesion improvers may be used alone. Two or more kinds may be used in combination.
(D)成分の接着性改良剤の添加量としては、種々設定できるが、[(A)成分+(B)成分]100重量部に対して、下限は好ましくは0.1重量部、より好ましくは0.5重量部であり、上限は好ましくは50重量部、より好ましくは25重量部である。(D)成分の添加量が0.1重量部より少ないと接着性改良効果が十分ではなくなる傾向があり、添加量が50重量部より多いと硬化物中での相溶性が低下し易くなったり、硬化物からブリードし易くなったりする傾向がある。 The amount of the component (D) adhesion improver can be variously set, but the lower limit is preferably 0.1 parts by weight, more preferably 100 parts by weight of [(A) component + (B) component]. Is 0.5 part by weight, and the upper limit is preferably 50 parts by weight, more preferably 25 parts by weight. When the addition amount of the component (D) is less than 0.1 parts by weight, the effect of improving the adhesion tends to be insufficient, and when the addition amount is more than 50 parts by weight, the compatibility in the cured product tends to decrease. , Tend to bleed from the cured product.
また、本発明において、接着性改良剤として上記カップリング剤やエポキシ化合物を用いる場合には、その効果を高めるために、さらにシラノール縮合触媒を用いることができ、接着性の向上及び/又は安定化が可能である。このようなシラノール縮合触媒としては、特に限定されないが、アルミニウム系化合物、チタン系化合物、ホウ酸エステル等を好ましく用いることができる。 In the present invention, when the above coupling agent or epoxy compound is used as an adhesion improver, a silanol condensation catalyst can be further used in order to enhance the effect, thereby improving and / or stabilizing the adhesion. Is possible. Such a silanol condensation catalyst is not particularly limited, but an aluminum compound, a titanium compound, a borate ester, or the like can be preferably used.
シラノール縮合触媒となるアルミニウム系化合物としては、アルミニウムトリイソプロポキシド、sec−ブトキシアルミニウムジイソプロポキシド、アルミニウムトリsec−ブトキシド等のアルミニウムアルコキシド類;エチルアセトアセテートアルミニウムジイソプロポキシド、アルミニウムトリス(エチルアセトアセテート)、アルミキレートM(川研ファインケミカル製、アルキルアセトアセテートアルミニウムジイソプロポキシド)、アルミニウムトリス(アセチルアセトネート)、アルミニウムモノアセチルアセトネートビス(エチルアセトアセテート)等のアルミニウムキレート類等が例示できる。取扱い性の点からアルミニウムキレート類がより好ましい。 Examples of the aluminum compound used as a silanol condensation catalyst include aluminum alkoxides such as aluminum triisopropoxide, sec-butoxyaluminum diisopropoxide, aluminum trisec-butoxide; ethyl acetoacetate aluminum diisopropoxide, aluminum tris (ethyl Acetoacetate), aluminum chelate M (produced by Kawaken Fine Chemicals, alkyl acetoacetate aluminum diisopropoxide), aluminum tris (acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), etc. it can. From the viewpoint of handleability, aluminum chelates are more preferable.
シラノール縮合触媒となるチタン系化合物としては、テトライソプロポキシチタン、テトラブトキシチタン等のテトラアルコキシチタン類;チタンテトラアセチルアセトナート等のチタンキレート類;オキシ酢酸やエチレングリコール等の残基を有する一般的なチタネートカップリング剤が例示できる。 Titanium compounds used as silanol condensation catalysts include tetraalkoxy titaniums such as tetraisopropoxy titanium and tetrabutoxy titanium; titanium chelates such as titanium tetraacetylacetonate; and general residues having residues such as oxyacetic acid and ethylene glycol And titanate coupling agents.
また、シラノール縮合触媒となるホウ酸エステルとしては、ホウ酸トリ−2−エチルヘキシル、ホウ酸ノルマルトリオクタデシル、ホウ酸トリノルマルオクチル、ホウ酸トリフェニル、トリメチレンボレート、トリス(トリメチルシリル)ボレート、ホウ酸トリノルマルブチル、ホウ酸トリ−sec−ブチル、ホウ酸トリ−tert−ブチル、ホウ酸トリイソプロピル、ホウ酸トリノルマルプロピル、ホウ酸トリアリル、ホウ酸トリエチル、ホウ酸トリメチル、ホウ素メトキシエトキサイドが例示できる。入手性の点からホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリノルマルブチルが好ましい。 Further, as boric acid ester as a silanol condensation catalyst, tri-2-ethylhexyl borate, normal trioctadecyl borate, tri-octyl borate, triphenyl borate, trimethylene borate, tris (trimethylsilyl) borate, boric acid Examples thereof include tri-normal butyl, tri-sec-butyl borate, tri-tert-butyl borate, triisopropyl borate, tri-normal propyl borate, triallyl borate, triethyl borate, trimethyl borate, and boron methoxyethoxide. . From the viewpoint of availability, trimethyl borate, triethyl borate and trinormal butyl borate are preferable.
シラノール縮合触媒を用いる場合の使用量としては、種々設定できるが、カップリング剤及びエポキシ化合物の合計100重量部に対して、下限は好ましくは0.1重量部、より好ましくは1重量部であり、上限は好ましくは50重量部、より好ましくは30重量部である。添加量が0.1重量部より少ないと接着性向上効果が十分ではなくなる傾向があり、添加量が50重量部より多いと硬化物中での相溶性が低下し易くなる傾向がある。 The amount used in the case of using a silanol condensation catalyst can be variously set, but the lower limit is preferably 0.1 parts by weight, more preferably 1 part by weight with respect to a total of 100 parts by weight of the coupling agent and the epoxy compound. The upper limit is preferably 50 parts by weight, more preferably 30 parts by weight. When the addition amount is less than 0.1 parts by weight, the effect of improving the adhesiveness tends to be insufficient, and when the addition amount is more than 50 parts by weight, the compatibility in the cured product tends to decrease.
また、これらのシラノール縮合触媒は単独で使用してもよく、2種以上併用してもよい。 These silanol condensation catalysts may be used alone or in combination of two or more.
また、本発明において、接着性改良剤として上記カップリング剤やエポキシ化合物を用いる場合には、その接着性改良効果をさらに高めるために、さらにシラノール源化合物を用いることができ、接着性の向上及び/又は安定化が可能である。このようなシラノール源化合物としては、例えばトリフェニルシラノール、ジフェニルジヒドロキシシラン等のシラノール化合物、ジフェニルジメトキシシラン、テトラメトキシシラン、メチルトリメトキシシラン等のアルコキシシラン類等を挙げることができる。 In the present invention, when the above coupling agent or epoxy compound is used as an adhesion improver, a silanol source compound can be further used in order to further enhance the adhesion improvement effect. / Or stabilization is possible. Examples of such silanol source compounds include silanol compounds such as triphenylsilanol and diphenyldihydroxysilane, and alkoxysilanes such as diphenyldimethoxysilane, tetramethoxysilane, and methyltrimethoxysilane.
シラノール源化合物を用いる場合の使用量としては、種々設定できるが、カップリング剤及びエポキシ化合物の合計100重量部に対して、下限は好ましくは0.1重量部、より好ましくは1重量部であり、上限は好ましくは50重量部、より好ましくは30重量部である。添加量が0.1重量部より少ないと接着性改良効果が十分ではなくなる傾向があり、添加量が50重量部より多いと硬化物中での相溶性が低下し易くなる傾向がある。 The amount used in the case of using the silanol source compound can be variously set, but the lower limit is preferably 0.1 parts by weight, more preferably 1 part by weight with respect to 100 parts by weight of the total of the coupling agent and the epoxy compound. The upper limit is preferably 50 parts by weight, more preferably 30 parts by weight. When the addition amount is less than 0.1 parts by weight, the effect of improving the adhesiveness tends to be insufficient, and when the addition amount is more than 50 parts by weight, the compatibility in the cured product tends to decrease.
また、これらのシラノール源化合物は単独で使用してもよく、2種以上併用してもよい。 Moreover, these silanol source compounds may be used independently and may be used together 2 or more types.
次に、封止樹脂を低弾性化して低応力化することができる(E)成分について説明する。 Next, the component (E) capable of reducing the stress by reducing the elasticity of the sealing resin will be described.
本発明に使用できる、SiH基と反応性を有する炭素−炭素二重結合を1分子中に少なくとも2個含有するオルガノポリシロキサンの具体的な例としては、下記一般式(VII) Specific examples of the organopolysiloxane containing at least two carbon-carbon double bonds having reactivity with SiH groups that can be used in the present invention include the following general formula (VII).
R29、R30、R31、R32、R33、R34、R35、R36、R37、R38、R39、R40としては、得られる硬化物の耐熱性がより高くなりうるという観点からは、炭素数1〜20の一価の有機基であることが好ましく、炭素数1〜15の一価の有機基であることがより好ましく、炭素数1〜10の一価の有機基であることがさらに好ましい。これらの好ましいR29、R30、R31、R32、R33、R34、R35、R36、R37、R38、R39、R40の例としては、メチル基、エチル基、プロピル基、ブチル基、フェニル基、ベンジル基、フェネチル基、メトキシ基、エトキシ基、ビニル基、アリル基、グリシジル基等が挙げられる。
As R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , the resulting cured product can have higher heat resistance. From the viewpoint, it is preferably a monovalent organic group having 1 to 20 carbon atoms, more preferably a monovalent organic group having 1 to 15 carbon atoms, and a monovalent organic group having 1 to 10 carbon atoms. More preferably, it is a group. Examples of these preferable R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 include methyl group, ethyl group, propyl Group, butyl group, phenyl group, benzyl group, phenethyl group, methoxy group, ethoxy group, vinyl group, allyl group, glycidyl group and the like.
本発明では、(A)成分と(E)成分の合計100重量部に対する、一般式(VII)で表される化合物の割合が下限5重量部、上限65重量部であることが好ましく、下限10重量部、上限60重量部であることがより好ましく、下限15重量部、上限55重量部であることがさらに好ましい。一般式(VII)で表される化合物の割合が5重量部より少ないと封止樹脂の低弾性化が十分ではなくなる傾向があり、65重量部より多いと硬化性組成物中での相溶性が低下する傾向がある。 In the present invention, the ratio of the compound represented by the general formula (VII) to the total of 100 parts by weight of the component (A) and the component (E) is preferably 5 parts by weight as the lower limit and 65 parts by weight as the upper limit. More preferably, the upper limit is 60 parts by weight, and the lower limit is 15 parts by weight, and the upper limit is more preferably 55 parts by weight. If the ratio of the compound represented by the general formula (VII) is less than 5 parts by weight, the reduction in elasticity of the sealing resin tends to be insufficient, and if it exceeds 65 parts by weight, the compatibility in the curable composition is poor. There is a tendency to decrease.
また、本発明では、上記SiH基と反応性を有する炭素−炭素二重結合を1分子中に少なくとも2個含有するオルガノポリシロキサンを単独で用いても2種以上を混合使用してもよい。 In the present invention, an organopolysiloxane containing at least two carbon-carbon double bonds having reactivity with the SiH group may be used alone, or two or more kinds may be used in combination.
次に、本発明の組成物の特性を改質する目的で添加することが可能な種々の樹脂について説明する。当該樹脂としては、ポリカーボネート樹脂、ポリエーテルスルホン樹脂、ポリアリレート樹脂、エポキシ樹脂、シアナート樹脂、フェノール樹脂、アクリル樹脂、ポリイミド樹脂、ポリビニルアセタール樹脂、ウレタン樹脂、ポリエステル樹脂等が例示されるが、これらに限定されるものではない。 Next, various resins that can be added for the purpose of modifying the properties of the composition of the present invention will be described. Examples of the resin include polycarbonate resin, polyethersulfone resin, polyarylate resin, epoxy resin, cyanate resin, phenol resin, acrylic resin, polyimide resin, polyvinyl acetal resin, urethane resin, polyester resin, and the like. It is not limited.
また、本発明の組成物は、溶剤を添加して粘度を調整し、作業性を向上させたペーストとすることも可能である。使用できる溶剤としては、特に限定されるものではないが、具体的に例示すれば、ベンゼン、トルエン、ヘキサン、ヘプタン等の炭化水素系溶剤;テトラヒドロフラン、1, 4−ジオキサン、ジエチルエーテル等のエーテル系溶剤;アセトン、メチルエチルケトン、シクロヘキサノン等のケトン系溶剤;酢酸n−ブチル、エチルセロソルブアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のエステル系溶剤;クロロホルム、塩化メチレン、1, 2−ジクロロエタン等のハロゲン系溶剤等を好適に用いることができる。また、当該溶剤は単独で使用してもよく、2種類以上の混合溶剤として用いることもできる。 In addition, the composition of the present invention can be made into a paste having a workability improved by adding a solvent to adjust the viscosity. Solvents that can be used are not particularly limited, but specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane; ether solvents such as tetrahydrofuran, 1,4-dioxane, and diethyl ether. Solvents; Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone; ester solvents such as n-butyl acetate, ethyl cellosolve acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate; chloroform, methylene chloride, 1,2-dichloroethane, etc. These halogen solvents can be suitably used. Moreover, the said solvent may be used independently and can also be used as 2 or more types of mixed solvents.
使用する溶剤量は、[(A)成分+(B)成分]100重量部に対して、下限0.1重量部、上限100重量部の範囲で用いるのが好ましく、下限0.5重量部、上限50重量部の範囲で用いるのがより好ましく、下限1重量部、上限30重量部の範囲で用いるのがさらに好ましい。使用量が0.1重量部より少ないと、低粘度化の効果が得られにくくなる傾向があり、使用量が100重量部より多いと、材料に溶剤が残留して熱クラック等の問題となり易く、またコスト的にも不利になり易い傾向がある。 The amount of solvent to be used is preferably 0.1 parts by weight at the lower limit and 100 parts by weight at the upper limit with respect to 100 parts by weight of [(A) component + (B) component], and the lower limit is 0.5 parts by weight. The upper limit is more preferably 50 parts by weight, and the lower limit is more preferably 1 part by weight and the upper limit is preferably 30 parts by weight. If the amount used is less than 0.1 parts by weight, the effect of lowering the viscosity tends to be difficult to obtain. If the amount used is more than 100 parts by weight, the solvent remains in the material and easily causes problems such as thermal cracks. Also, it tends to be disadvantageous in terms of cost.
本発明の組成物には、その他、老化防止剤、ラジカル禁止剤、紫外線吸収剤、難燃剤、界面活性剤、オゾン劣化防止剤、光安定剤、増粘剤、可塑剤、酸化防止剤、熱安定剤、加工安定剤、帯電防止剤、放射線遮断剤、核剤、リン系過酸化物分解剤、滑剤、顔料、金属不活性化剤、物性調整剤等を、本発明の目的及び効果を損なわない範囲において添加することができる。 In addition, the composition of the present invention includes an antioxidant, a radical inhibitor, an ultraviolet absorber, a flame retardant, a surfactant, an ozone degradation inhibitor, a light stabilizer, a thickener, a plasticizer, an antioxidant, a heat Stabilizers, processing stabilizers, antistatic agents, radiation blocking agents, nucleating agents, phosphorus peroxide decomposing agents, lubricants, pigments, metal deactivators, physical property modifiers, etc. It is possible to add in the range which is not.
本発明の組成物には、必要に応じて無機フィラーを添加してもよい。無機フィラーを添加すると、材料の高強度化に効果がある。無機フィラーとしては、微粒子状のものが好ましく、アルミナ、水酸化アルミニウム、溶融シリカ、結晶性シリカ、超微粉無定型シリカ、疎水性超微粉シリカ、タルク、硫酸バリウム等を挙げることができる。 You may add an inorganic filler to the composition of this invention as needed. Addition of an inorganic filler is effective in increasing the strength of the material. The inorganic filler is preferably in the form of fine particles, and examples thereof include alumina, aluminum hydroxide, fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, talc, and barium sulfate.
フィラーを添加する方法としては、例えば、アルコキシシラン、アシロキシシラン、ハロゲン化シラン等の加水分解性シランモノマー又はオリゴマーや、チタン、アルミニウム等の金属のアルコキシド、アシロキシド又はハロゲン化物等を、本発明の組成物に添加して、組成物中あるいは組成物の部分反応物中で反応させ、組成物中で無機フィラーを生成させる方法等も挙げることができる。 Examples of the method for adding the filler include hydrolyzable silane monomers or oligomers such as alkoxysilanes, acyloxysilanes, and halogenated silanes, and metal alkoxides, acyloxides, and halides such as titanium and aluminum. Examples thereof include a method in which an inorganic filler is produced in the composition by adding it to the composition and reacting in the composition or a partial reaction product of the composition.
さらに、本発明の組成物には接着剤の特性改善のための添加剤を加えてもよい。添加剤としては、例えば、酸化チタン、酸化アルミニウム、シリカ、石英ガラス、タルク、炭酸カルシウム等の無機充填材、窒化アルミニウム、窒化ボロン等の金属窒化物熱伝導性フィラー等を挙げることができる。 Furthermore, an additive for improving adhesive properties may be added to the composition of the present invention. Examples of the additive include inorganic fillers such as titanium oxide, aluminum oxide, silica, quartz glass, talc, and calcium carbonate, and metal nitride thermally conductive fillers such as aluminum nitride and boron nitride.
本発明の組成物は、上記各成分を混合等することにより得られる。 The composition of the present invention can be obtained by mixing the above components.
また、本発明の組成物を硬化させる方法としては、特に限定されないが、各成分を単に混合するだけで反応させることもできるし、加熱して反応させることもできる。反応が速く、一般に耐熱性の高い材料が得られ易いという観点から、加熱して反応させる方法が好ましい。 In addition, the method for curing the composition of the present invention is not particularly limited, but the reaction can be performed by simply mixing the components, or the reaction can be performed by heating. From the viewpoint that the reaction is fast and generally a material having high heat resistance is easily obtained, a method of heating and reacting is preferable.
反応温度としては種々設定できるが、下限25℃、上限300℃の温度範囲が好ましく、下限50℃、上限280℃がより好ましく、下限100℃、上限260℃がさらに好ましい。反応温度が25℃より低いと十分に反応させるための反応時間が長くなる傾向があり、反応温度が300℃より高いと製品の熱劣化が生じ易くなる傾向がある。 The reaction temperature can be variously set, but a temperature range with a lower limit of 25 ° C. and an upper limit of 300 ° C. is preferable, a lower limit of 50 ° C. and an upper limit of 280 ° C. are more preferable, and a lower limit of 100 ° C. and an upper limit of 260 ° C. are more preferable. When the reaction temperature is lower than 25 ° C, the reaction time for sufficient reaction tends to be long, and when the reaction temperature is higher than 300 ° C, the product tends to be thermally deteriorated.
反応は一定の温度で行ってもよいが、必要に応じて多段階あるいは連続的に温度を変化させてもよい。一定の温度で行うより、多段階的あるいは連続的に温度を上昇させながら反応させた方が、歪のない均一な硬化物が得られ易いという点で好ましい。 The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as required. Rather than carrying out the reaction at a constant temperature, the reaction is preferably carried out while raising the temperature in a multistage manner or continuously in that a uniform cured product without distortion can be easily obtained.
反応時の圧力も必要に応じて種々設定でき、常圧、高圧又は減圧状態で反応させることもできる。 The pressure during the reaction can be variously set as required, and the reaction can be carried out at normal pressure, high pressure or reduced pressure.
また、本発明の硬化性組成物は、IC、LSI、LED等の半導体素子の封止剤として使用することができる。具体的には、BGA(ボール・グリッド・アレイ)、CSP(チップ・サイズ・パッケージ)、ベアチップ実装のような高密度実装が可能なパッケージ封止等である。これらは、ビデオ、カメラ、携帯電話、パソコン等の電子部品、自動車の各種制御システム部品やランプ等に使用される。 Moreover, the curable composition of this invention can be used as sealing agent of semiconductor elements, such as IC, LSI, and LED. Specifically, it is package sealing capable of high-density mounting such as BGA (ball grid array), CSP (chip size package), and bare chip mounting. These are used for electronic parts such as video, cameras, mobile phones and personal computers, various control system parts for automobiles, lamps and the like.
本発明の硬化性組成物を用いて製造した材料は、熱衝撃が加わっても耐クラック性、耐変色性に優れていることから、工業的に極めて有用である。 The material produced using the curable composition of the present invention is extremely useful industrially because it is excellent in crack resistance and discoloration resistance even when subjected to thermal shock.
以下に、本発明をより詳細に説明するために実施例を示すが、本発明はこれら実施例によって限定されるものではない。 Examples are shown below to describe the present invention in more detail, but the present invention is not limited to these Examples.
(合成例1)トリアリルイソシアヌレートによる1,3,5,7−テトラメチルシクロテトラシロキサン変性体(1)の合成
冷却管、攪拌機、温度計を備えた1Lの4つ口フラスコに信越化学工業製1,3,5,7−テトラメチルシクロテトラシロキサン288gを入れ、トルエン360gを加えて溶解した後、110℃に保った。別途、トリアリルイソシアヌレート40gをトルエン40gに溶かし、白金−ジビニルテトラメチルジシロキサン錯体のキシレン溶液(白金3重量%含有)0.3gを加えた溶液を用意し、これを4つ口フラスコ中の溶液に10分かけて滴下した後、攪拌しながら6時間反応させた。反応後、1−エチニル−1−シクロヘキサノール0.6gを加えて溶解した後、25℃まで放冷した。その後、反応液を1Lのナスフラスコに移し、減圧下、60℃で揮発分を留去することによって、130gの変性体(1)を得た。変性体(1)のヒドロシリル基含有量はプロトンNMR分析の結果、8.04mmol/gであった。また、同分析の結果、アリル基残存量は0.10mmol/gであった。なお、ヒドロシリル基含有量及びアリル基残存量は、1,2−ジブロモエタンを内部標準とし、この標準物質のプロトンの化学シフト(3.65ppm)面積とヒドロシリル基のプロトンの化学シフト(4.7ppm)面積またはアリル基のプロトンの化学シフト(4.5ppm)面積を比較することによって決定した。
(実施例1)
2,2−ビス(4−アリルオキシシクロヘキシル)プロパン9.396g、ジアリルモノグリシジルイソシアヌレート7.777g、ビニル両末端(ジフェニルシロキサン/ジメチルシロキサン共重合体)(GELEST製PDV−2331)0.903g((A)成分と(E)成分の合計100重量部に対して5重量部)、ホウ酸トリメチル0.169g、白金−ジビニルテトラメチルジシロキサン錯体のキシレン溶液(白金3重量%含有)0.040g、イルガノックス1010(チバ・スペシャルティ・ケミカルズ製酸化防止剤)0.675gを混合し、攪拌溶解した。次に、合成例1で調製した変性体(1)15.673g、1−エチニル−1−シクロヘキサノール0.101g、3−グリシドキシプロピルトリメトキシシラン(日本ユニカー製A−187)0.844gを混合し、攪拌溶解した。この混合液20gを、2枚のガラス板に3mm厚みのシリコーンゴムシートをスペーサーとしてはさみこんで作製したセルに流し込み、60℃で6時間、続いて70℃で1時間、80℃で1時間、120℃で1時間、150℃で1時間、さらに180℃で30分間、空気中で加熱を行い、硬化させた。
別途、前記混合液10gにフィラーとしてシリカ4gを加え、攪拌、脱泡した。このフィラー入り組成物9.2gを66.5mmφの軟膏缶に注ぎ込み、前記条件で硬化させた。また、このフィラー入り組成物は、シリコンチップの装着された4mm□のセラミックパッケージにもディスペンスし、前記条件で硬化させた。
次に、上記によって得られた硬化物の物性測定を下記の方法によって行い、結果を表1に示した。
(1)引張貯蔵弾性率の測定
66.5mmφの軟膏缶で作製した硬化物から、幅5mm、長さ3cmの大きさのサンプルを切り出し、アイティー計測制御製動的粘弾性測定装置DVA−200を用い、昇温速度:5℃/分、周波数:10Hzで測定した。
(2)高温着色性試験
ガラスセルで作製した硬化物から、幅1.5cm、長さ3cmの大きさのサンプルを切り出し、200℃で24時間、空気中で加熱した。その後、25℃まで冷却した後、470nmにおける透過率を測定し、加熱前の透過率の50%以上を保持したものを合格とした。
(3)耐ハンダクラック試験
上記により封止されたセラミックパッケージを250℃のハンダ浴に10秒間浸した後、すぐに25℃の純水に3秒間浸け、封止樹脂のクラック発生の有無を観察した。クラックが発生しないものを合格とした。
(実施例2)
2,2−ビス(4−アリルオキシシクロヘキシル)プロパン7.863g、ジアリルモノグリシジルイソシアヌレート6.508g、ビニル両末端(ジフェニルシロキサン/ジメチルシロキサン共重合体)(GELEST製PDV−2331)6.153g((A)成分と(E)成分の合計100重量部に対して30重量部)、ホウ酸トリメチル0.169g、白金−ジビニルテトラメチルジシロキサン錯体のキシレン溶液(白金3重量%含有)0.040g、イルガノックス1010(チバ・スペシャルティ・ケミカルズ製酸化防止剤)0.675gを混合し、攪拌溶解した。次に、合成例1で調製した変性体(1)13.225g、1−エチニル−1−シクロヘキサノール0.101g、3−グリシドキシプロピルトリメトキシシラン(日本ユニカー製A−187)0.844gを混合し、攪拌溶解した。この混合液20gを、2枚のガラス板に3mm厚みのシリコーンゴムシートをスペーサーとしてはさみこんで作製したセルに流し込み、60℃で6時間、続いて70℃で1時間、80℃で1時間、120℃で1時間、150℃で1時間、さらに180℃で30分間、空気中で加熱を行い、硬化させた。
別途、前記混合液10gにフィラーとしてシリカ4gを加え、攪拌、脱泡した。このフィラー入り組成物9.2gを66.5mmφの軟膏缶に注ぎ込み、前記条件で硬化させた。また、このフィラー入り組成物は、シリコンチップの装着された4mm□のセラミックパッケージにもディスペンスし、前記条件で硬化させた。
次に、上記によって得られた硬化物の物性測定を実施例1記載の方法によって行い、結果を表1に示した。
(実施例3)
2,2−ビス(4−アリルオキシシクロヘキシル)プロパン4.849g、ジアリルモノグリシジルイソシアヌレート4.014g、ビニル両末端(ジフェニルシロキサン/ジメチルシロキサン共重合体)(GELEST製PDV−2331)16.475g((A)成分と(E)成分の合計100重量部に対して65重量部)、ホウ酸トリメチル0.169g、白金−ジビニルテトラメチルジシロキサン錯体のキシレン溶液(白金3重量%含有)0.040g、イルガノックス1010(チバ・スペシャルティ・ケミカルズ製酸化防止剤)0.675gを混合し、攪拌溶解した。次に、合成例1で調製した変性体(1)8.411g、1−エチニル−1−シクロヘキサノール0.101g、3−グリシドキシプロピルトリメトキシシラン(日本ユニカー製A−187)0.844gを混合し、攪拌溶解した。この混合液20gを、2枚のガラス板に3mm厚みのシリコーンゴムシートをスペーサーとしてはさみこんで作製したセルに流し込み、60℃で6時間、続いて70℃で1時間、80℃で1時間、120℃で1時間、150℃で1時間、さらに180℃で30分間、空気中で加熱を行い、硬化させた。
別途、前記混合液10gにフィラーとしてシリカ4gを加え、攪拌、脱泡した。このフィラー入り組成物9.2gを66.5mmφの軟膏缶に注ぎ込み、前記条件で硬化させた。また、このフィラー入り組成物は、シリコンチップの装着された4mm□のセラミックパッケージにもディスペンスし、前記条件で硬化させた。
次に、上記によって得られた硬化物の物性測定を実施例1記載の方法によって行い、結果を表1に示した。
(実施例4)
2,2−ビス(4−アリルオキシフェニル)プロパン6.146g、ジアリルモノグリシジルイソシアヌレート5.286g、ビニル両末端(ジフェニルシロキサン/ジメチルシロキサン共重合体)(GELEST製PDV−2331)11.447g((A)成分と(E)成分の合計100重量部に対して50重量部)、ホウ酸トリメチル0.169g、白金−ジビニルテトラメチルジシロキサン錯体のキシレン溶液(白金3重量%含有)0.040g、イルガノックス1010(チバ・スペシャルティ・ケミカルズ製酸化防止剤)0.675gを混合し、攪拌溶解した。次に、合成例1で調製した変性体(1)10.871g、1−エチニル−1−シクロヘキサノール0.101g、3−グリシドキシプロピルトリメトキシシラン(日本ユニカー製A−187)0.844gを混合し、攪拌溶解した。この混合液20gを、2枚のガラス板に3mm厚みのシリコーンゴムシートをスペーサーとしてはさみこんで作製したセルに流し込み、60℃で6時間、続いて70℃で1時間、80℃で1時間、120℃で1時間、150℃で1時間、さらに180℃で30分間、空気中で加熱を行い、硬化させた。
別途、前記混合液10gにフィラーとしてシリカ4gを加え、攪拌、脱泡した。このフィラー入り組成物9.2gを66.5mmφの軟膏缶に注ぎ込み、前記条件で硬化させた。また、このフィラー入り組成物は、シリコンチップの装着された4mm□のセラミックパッケージにもディスペンスし、前記条件で硬化させた。
次に、上記によって得られた硬化物の物性測定を実施例1記載の方法によって行い、結果を表1に示した。
(比較例1)
2,2−ビス(4−アリルオキシフェニル)プロパン9.397g、ジアリルモノグリシジルイソシアヌレート8.083g、ホウ酸トリメチル0.169g、白金−ジビニルテトラメチルジシロキサン錯体のキシレン溶液(白金3重量%含有)0.040g、イルガノックス1010(チバ・スペシャルティ・ケミカルズ製酸化防止剤)0.675gを混合し、攪拌溶解した。次に、合成例1で調製した変性体(1)16.270g、1−エチニル−1−シクロヘキサノール0.101g、3−グリシドキシプロピルトリメトキシシラン(日本ユニカー製A−187)0.844gを混合し、攪拌溶解した。この混合液20gを、2枚のガラス板に3mm厚みのシリコーンゴムシートをスペーサーとしてはさみこんで作製したセルに流し込み、60℃で6時間、続いて70℃で1時間、80℃で1時間、120℃で1時間、150℃で1時間、さらに180℃で30分間、空気中で加熱を行い、硬化させた。
別途、前記混合液10gにフィラーとしてシリカ4gを加え、攪拌、脱泡した。このフィラー入り組成物9.2gを66.5mmφの軟膏缶に注ぎ込み、前記条件で硬化させた。また、このフィラー入り組成物は、シリコンチップの装着された4mm□のセラミックパッケージにもディスペンスし、前記条件で硬化させた。
次に、上記によって得られた硬化物の物性測定を実施例1記載の方法によって行い、結果を表1に示した。
(比較例2)
2,2−ビス(4−アリルオキシシクロヘキシル)プロパン4.347g、ジアリルモノグリシジルイソシアヌレート3.598g、ビニル両末端(ジフェニルシロキサン/ジメチルシロキサン共重合体)(GELEST製PDV−2331)18.196g((A)成分と(E)成分の合計100重量部に対して70重量部)、ホウ酸トリメチル0.169g、白金−ジビニルテトラメチルジシロキサン錯体のキシレン溶液(白金3重量%含有)0.040g、イルガノックス1010(チバ・スペシャルティ・ケミカルズ製酸化防止剤)0.675gを混合し、攪拌溶解した。次に、合成例1で調製した変性体(1)7.609g、1−エチニル−1−シクロヘキサノール0.101g、3−グリシドキシプロピルトリメトキシシラン(日本ユニカー製A−187)0.844gを混合し、攪拌溶解した。この混合液20gを、2枚のガラス板に3mm厚みのシリコーンゴムシートをスペーサーとしてはさみこんで作製したセルに流し込み、60℃で6時間、続いて70℃で1時間、80℃で1時間、120℃で1時間、150℃で1時間、さらに180℃で30分間、空気中で加熱を行い、硬化させた。
別途、前記混合液10gにフィラーとしてシリカ4gを加え、攪拌、脱泡した。このフィラー入り組成物9.2gを66.5mmφの軟膏缶に注ぎ込み、前記条件で硬化させた。また、このフィラー入り組成物は、シリコンチップの装着された4mm□のセラミックパッケージにもディスペンスし、前記条件で硬化させた。
フィラー入り硬化物を目視観察した結果、PDV−2331の一部が表面に浮いた状態で硬化しており、硬化不良であった。
(実施例5)
セラミックパッケージ内に、発光素子が配される開口部を設け、銀メッキした銅板を外部電極として配置させる。別途作製した発光素子をパッケージ内部でエポキシ樹脂を用いてダイボンドして固定する。導電性ワイヤーであるAu線を発光素子の各電極とパッケージに設けられた各外部電極とにそれぞれワイヤーボンディングし、電気的に接続させる。パッケージ開口部内にモールド部材として実施例2で用いた硬化性組成物を充填する。この状態で、60℃で6時間、続いて70℃で1時間、80℃で1時間、120℃で1時間、150℃で1時間、さらに180℃で30分間、硬化させる。このようにして、チップタイプ発光ダイオード(LED)を作製することができる。
(Synthesis Example 1) Synthesis of 1,3,5,7-tetramethylcyclotetrasiloxane modified product (1) using triallyl isocyanurate 288 g of 1,3,5,7-tetramethylcyclotetrasiloxane produced was added and dissolved by adding 360 g of toluene, and then kept at 110 ° C. Separately, 40 g of triallyl isocyanurate was dissolved in 40 g of toluene, and a solution in which 0.3 g of a xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) was added was prepared. After dripping into the solution over 10 minutes, the mixture was reacted for 6 hours with stirring. After the reaction, 0.6 g of 1-ethynyl-1-cyclohexanol was added and dissolved, and then allowed to cool to 25 ° C. Thereafter, the reaction solution was transferred to a 1 L eggplant flask, and volatile matter was distilled off at 60 ° C. under reduced pressure to obtain 130 g of a modified product (1). As a result of proton NMR analysis, the hydrosilyl group content of the modified product (1) was 8.04 mmol / g. Further, as a result of the same analysis, the allyl group residual amount was 0.10 mmol / g. The hydrosilyl group content and the allyl group residual amount were determined using 1,2-dibromoethane as an internal standard, and the proton chemical shift (3.65 ppm) area of this standard substance and the hydrosilyl group proton chemical shift (4.7 ppm). ) Determined by comparing the area or chemical shift (4.5 ppm) area of the proton of the allyl group.
(Example 1)
9.396 g of 2,2-bis (4-allyloxycyclohexyl) propane, 7.777 g of diallyl monoglycidyl isocyanurate, divinylsiloxane / dimethylsiloxane copolymer (PDEL-2331 manufactured by GELEST) 0.903 g ( 5 parts by weight per 100 parts by weight of component (A) and component (E)), 0.169 g of trimethyl borate, 0.040 g of xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) Irganox 1010 (Antioxidant manufactured by Ciba Specialty Chemicals) was mixed and dissolved by stirring. Next, 15.673 g of the modified product (1) prepared in Synthesis Example 1, 0.101 g of 1-ethynyl-1-cyclohexanol, 0.844 g of 3-glycidoxypropyltrimethoxysilane (Nihon Unicar A-187) Were mixed and dissolved by stirring. Pour 20 g of this mixed solution into a cell prepared by sandwiching a 3 mm thick silicone rubber sheet as a spacer between two glass plates, 60 ° C. for 6 hours, then 70 ° C. for 1 hour, 80 ° C. for 1 hour, It was cured by heating in air at 120 ° C. for 1 hour, 150 ° C. for 1 hour, and further at 180 ° C. for 30 minutes.
Separately, 4 g of silica as a filler was added to 10 g of the mixed solution, and the mixture was stirred and degassed. 9.2 g of this filled composition was poured into a 66.5 mmφ ointment can and cured under the above conditions. The filler-containing composition was also dispensed into a 4 mm square ceramic package with a silicon chip attached, and cured under the above conditions.
Next, the physical properties of the cured product obtained above were measured by the following method, and the results are shown in Table 1.
(1) Measurement of tensile storage elastic modulus A sample having a width of 5 mm and a length of 3 cm was cut out from a cured product prepared from an ointment can of 66.5 mmφ, and a dynamic viscoelasticity measuring device DVA-200 manufactured by IT Measurement Control Co., Ltd. was used. Was measured at a heating rate of 5 ° C./min and a frequency of 10 Hz.
(2) High-temperature colorability test A sample having a width of 1.5 cm and a length of 3 cm was cut out from a cured product produced in a glass cell and heated in air at 200 ° C for 24 hours. Then, after cooling to 25 degreeC, the transmittance | permeability in 470 nm was measured, and what hold | maintained 50% or more of the transmittance | permeability before a heating was set as the pass.
(3) Solder crack resistance test After immersing the ceramic package sealed as described above in a solder bath at 250 ° C. for 10 seconds, immediately immerse it in pure water at 25 ° C. for 3 seconds and observe the presence or absence of cracks in the sealing resin. did. The thing which does not generate | occur | produce a crack was set as the pass.
(Example 2)
7.863 g of 2,2-bis (4-allyloxycyclohexyl) propane, 6.508 g of diallyl monoglycidyl isocyanurate, 6.153 g of vinyl both ends (diphenylsiloxane / dimethylsiloxane copolymer) (PDV-2331 manufactured by GELEST) 30 parts by weight based on 100 parts by weight of component (A) and component (E)), 0.169 g of trimethyl borate, 0.040 g of xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) Irganox 1010 (Antioxidant manufactured by Ciba Specialty Chemicals) was mixed and dissolved by stirring. Next, 13.225 g of the modified product (1) prepared in Synthesis Example 1, 0.101 g of 1-ethynyl-1-cyclohexanol, 0.844 g of 3-glycidoxypropyltrimethoxysilane (Nihon Unicar A-187) Were mixed and dissolved by stirring. Pour 20 g of this mixed solution into a cell prepared by sandwiching a 3 mm thick silicone rubber sheet as a spacer between two glass plates, 60 ° C. for 6 hours, then 70 ° C. for 1 hour, 80 ° C. for 1 hour, It was cured by heating in air at 120 ° C. for 1 hour, 150 ° C. for 1 hour, and further at 180 ° C. for 30 minutes.
Separately, 4 g of silica as a filler was added to 10 g of the mixed solution, and the mixture was stirred and degassed. 9.2 g of this filled composition was poured into a 66.5 mmφ ointment can and cured under the above conditions. The filler-containing composition was also dispensed into a 4 mm square ceramic package with a silicon chip attached, and cured under the above conditions.
Next, the physical properties of the cured product obtained above were measured by the method described in Example 1, and the results are shown in Table 1.
(Example 3)
4.849 g of 2,2-bis (4-allyloxycyclohexyl) propane, 4.014 g of diallyl monoglycidyl isocyanurate, vinyl both ends (diphenylsiloxane / dimethylsiloxane copolymer) (GELEST PDV-2331) 16.475 g ( 65 parts by weight based on 100 parts by weight of component (A) and component (E)), 0.169 g of trimethyl borate, 0.040 g of a xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) Irganox 1010 (Antioxidant manufactured by Ciba Specialty Chemicals) was mixed and dissolved by stirring. Next, 8.411 g of the modified product (1) prepared in Synthesis Example 1, 0.101 g of 1-ethynyl-1-cyclohexanol, 0.844 g of 3-glycidoxypropyltrimethoxysilane (Nihon Unicar A-187) Were mixed and dissolved by stirring. Pour 20 g of this mixed solution into a cell prepared by sandwiching a 3 mm thick silicone rubber sheet as a spacer between two glass plates, 60 ° C. for 6 hours, then 70 ° C. for 1 hour, 80 ° C. for 1 hour, It was cured by heating in air at 120 ° C. for 1 hour, 150 ° C. for 1 hour, and further at 180 ° C. for 30 minutes.
Separately, 4 g of silica as a filler was added to 10 g of the mixed solution, and the mixture was stirred and degassed. 9.2 g of this filled composition was poured into a 66.5 mmφ ointment can and cured under the above conditions. The filler-containing composition was also dispensed into a 4 mm square ceramic package with a silicon chip attached, and cured under the above conditions.
Next, the physical properties of the cured product obtained above were measured by the method described in Example 1, and the results are shown in Table 1.
Example 4
6.146 g of 2,2-bis (4-allyloxyphenyl) propane, 5.286 g of diallyl monoglycidyl isocyanurate, 11.447 g of vinyl terminal (diphenylsiloxane / dimethylsiloxane copolymer) (PDV-2331 manufactured by GELEST) 50 parts by weight based on 100 parts by weight of component (A) and component (E)), 0.169 g of trimethyl borate, 0.040 g of xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) Irganox 1010 (Antioxidant manufactured by Ciba Specialty Chemicals) was mixed and dissolved by stirring. Next, 10.871 g of modified product (1) prepared in Synthesis Example 1, 0.101 g of 1-ethynyl-1-cyclohexanol, 0.844 g of 3-glycidoxypropyltrimethoxysilane (Nihon Unicar A-187) Were mixed and dissolved by stirring. Pour 20 g of this mixed solution into a cell prepared by sandwiching a 3 mm thick silicone rubber sheet as a spacer between two glass plates, 60 ° C. for 6 hours, then 70 ° C. for 1 hour, 80 ° C. for 1 hour, It was cured by heating in air at 120 ° C. for 1 hour, 150 ° C. for 1 hour, and further at 180 ° C. for 30 minutes.
Separately, 4 g of silica as a filler was added to 10 g of the mixed solution, and the mixture was stirred and degassed. 9.2 g of this filled composition was poured into a 66.5 mmφ ointment can and cured under the above conditions. The filler-containing composition was also dispensed into a 4 mm square ceramic package with a silicon chip attached, and cured under the above conditions.
Next, the physical properties of the cured product obtained above were measured by the method described in Example 1, and the results are shown in Table 1.
(Comparative Example 1)
9.397 g of 2,2-bis (4-allyloxyphenyl) propane, 8.083 g of diallyl monoglycidyl isocyanurate, 0.169 g of trimethyl borate, xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) ) 0.040 g and Irganox 1010 (Ciba Specialty Chemicals antioxidant) 0.675 g were mixed and dissolved by stirring. Next, 16.270 g of the modified product (1) prepared in Synthesis Example 1, 0.101 g of 1-ethynyl-1-cyclohexanol, 0.844 g of 3-glycidoxypropyltrimethoxysilane (Nihon Unicar A-187) Were mixed and dissolved by stirring. Pour 20 g of this mixed solution into a cell prepared by sandwiching a 3 mm thick silicone rubber sheet as a spacer between two glass plates, 60 ° C. for 6 hours, then 70 ° C. for 1 hour, 80 ° C. for 1 hour, It was cured by heating in air at 120 ° C. for 1 hour, 150 ° C. for 1 hour, and further at 180 ° C. for 30 minutes.
Separately, 4 g of silica as a filler was added to 10 g of the mixed solution, and the mixture was stirred and degassed. 9.2 g of this filled composition was poured into a 66.5 mmφ ointment can and cured under the above conditions. The filler-containing composition was also dispensed into a 4 mm square ceramic package with a silicon chip attached, and cured under the above conditions.
Next, the physical properties of the cured product obtained above were measured by the method described in Example 1, and the results are shown in Table 1.
(Comparative Example 2)
2.347 g of 2,2-bis (4-allyloxycyclohexyl) propane, 3.598 g of diallyl monoglycidyl isocyanurate, vinyl both ends (diphenylsiloxane / dimethylsiloxane copolymer) (PDEL-2331 manufactured by GELEST) 18.196 g ( 70 parts by weight based on 100 parts by weight of component (A) and component (E)), 0.169 g of trimethyl borate, 0.040 g of xylene solution of platinum-divinyltetramethyldisiloxane complex (containing 3% by weight of platinum) Irganox 1010 (Antioxidant manufactured by Ciba Specialty Chemicals) was mixed and dissolved by stirring. Next, 7.609 g of the modified product (1) prepared in Synthesis Example 1, 0.101 g of 1-ethynyl-1-cyclohexanol, 0.844 g of 3-glycidoxypropyltrimethoxysilane (Nihon Unicar A-187) Were mixed and dissolved by stirring. Pour 20 g of this mixed solution into a cell prepared by sandwiching a 3 mm-thick silicone rubber sheet as a spacer between two glass plates, 60 ° C. for 6 hours, then 70 ° C. for 1 hour, 80 ° C. for 1 hour, It was cured by heating in air at 120 ° C. for 1 hour, 150 ° C. for 1 hour, and further at 180 ° C. for 30 minutes.
Separately, 4 g of silica as a filler was added to 10 g of the mixed solution, and the mixture was stirred and degassed. 9.2 g of this filled composition was poured into a 66.5 mmφ ointment can and cured under the above conditions. The filler-containing composition was also dispensed into a 4 mm square ceramic package with a silicon chip attached, and cured under the above conditions.
As a result of visual observation of the cured product with filler, a portion of PDV-2331 was cured in a state where it floated on the surface, and the curing was poor.
(Example 5)
An opening in which the light emitting element is disposed is provided in the ceramic package, and a silver-plated copper plate is disposed as an external electrode. A separately manufactured light-emitting element is die-bonded and fixed inside the package using an epoxy resin. An Au wire as a conductive wire is wire-bonded to each electrode of the light emitting element and each external electrode provided in the package, and is electrically connected. The package opening is filled with the curable composition used in Example 2 as a mold member. In this state, curing is performed at 60 ° C. for 6 hours, followed by 70 ° C. for 1 hour, 80 ° C. for 1 hour, 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 30 minutes. In this manner, a chip type light emitting diode (LED) can be manufactured.
Claims (5)
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