JP2546104B2 - Silicone modified acid anhydride and method for producing the same - Google Patents
Silicone modified acid anhydride and method for producing the sameInfo
- Publication number
- JP2546104B2 JP2546104B2 JP4174851A JP17485192A JP2546104B2 JP 2546104 B2 JP2546104 B2 JP 2546104B2 JP 4174851 A JP4174851 A JP 4174851A JP 17485192 A JP17485192 A JP 17485192A JP 2546104 B2 JP2546104 B2 JP 2546104B2
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- JP
- Japan
- Prior art keywords
- acid anhydride
- group
- silicone
- formula
- represented
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Epoxy Resins (AREA)
- Silicon Polymers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、エポキシ樹脂の硬化剤
等として有用で、半導体封止用、塗料用、接着剤用樹脂
組成物などに好適に使用される新規なシリコーン変性酸
無水物及びその製造方法に関する。FIELD OF THE INVENTION The present invention relates to a novel silicone-modified acid anhydride useful as a curing agent for epoxy resins and suitable for use in resin compositions for semiconductor encapsulation, paints, adhesives and the like. The manufacturing method is related.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来よ
り、エポキシ樹脂は、これに硬化剤及び無機充填剤など
を加えた組成物として各種成形材料、粉体塗装用材料、
電気絶縁材料などに広く利用され、特に最近においては
半導体装置封止用材料として大量に使用されている。こ
れは、エポキシ樹脂が一般に他の熱硬化性樹脂に比べて
成形性、接着性、電気特性、機械的特性、耐湿性などに
優れているという特性を有しているからである。2. Description of the Related Art Epoxy resins have hitherto been used as various molding materials, powder coating materials, and epoxy resins as compositions containing a curing agent and an inorganic filler.
It is widely used as an electric insulating material and the like, and in recent years, it has been used in large quantities as a material for sealing semiconductor devices. This is because the epoxy resin generally has characteristics such as excellent moldability, adhesiveness, electrical characteristics, mechanical characteristics, and moisture resistance as compared with other thermosetting resins.
【０００３】しかしながら、エポキシ樹脂は、一般的に
低弾性率で可撓性に乏しいため、例えば半導体素子の封
止工程や封止した半導体装置のヒートサイクル試験時に
おいてパッケージクラックが発生し易く、また、過大な
ストレスがかかって素子が変形し、この結果、素子の機
能低下や破損が生じ易いという問題がある。このため、
可撓性に優れたエポキシ樹脂組成物の開発が要望されて
いる。However, since epoxy resins generally have a low elastic modulus and poor flexibility, package cracks are likely to occur during, for example, a semiconductor element sealing process or a heat cycle test of a sealed semiconductor device. However, there is a problem that the element is deformed due to excessive stress, and as a result, the function of the element is deteriorated or damaged. For this reason,
Development of an epoxy resin composition having excellent flexibility has been demanded.
【０００４】この問題に対し、本出願人は、先に硬化性
エポキシ樹脂にオルガノポリシロキサンを配合したエポ
キシ樹脂組成物（特開昭５６−１２９２４６号公報）、
更には芳香族重合体とオルガノポリシロキサンとからな
るブロック共重合体を添加したエポキシ樹脂組成物（特
開昭５８−２１４１７号公報）を提案し、エポキシ樹脂
組成物の耐クラック性を改善した。To address this problem, the present applicant has previously proposed an epoxy resin composition in which a curable epoxy resin is mixed with an organopolysiloxane (Japanese Patent Laid-Open No. 56-129246),
Furthermore, an epoxy resin composition (Japanese Patent Laid-Open No. 58-21417) to which a block copolymer composed of an aromatic polymer and an organopolysiloxane is added has been proposed to improve the crack resistance of the epoxy resin composition.
【０００５】しかしながら、近年、益々半導体装置封止
用材料への要求特性が厳しくなり、このため更に耐クラ
ック性の向上したエポキシ樹脂組成物が望まれる。However, in recent years, the required characteristics of the semiconductor device encapsulating material have become more and more severe, and therefore, an epoxy resin composition having further improved crack resistance is desired.
【０００６】一方、半導体装置の封止方法も、従来のト
ランスファー成形から液状エポキシ樹脂組成物による封
止に変わりつつあり、このような液状エポキシ樹脂組成
物には、硬化剤として種々の酸無水物が主に使用されて
いるが、更に可撓性に優れた硬化物を与える酸無水物系
硬化剤の開発が要望されている。On the other hand, the method of encapsulating a semiconductor device is also changing from the conventional transfer molding to encapsulation by a liquid epoxy resin composition. Such a liquid epoxy resin composition contains various acid anhydrides as a curing agent. Is mainly used, but there is a demand for the development of an acid anhydride-based curing agent that gives a cured product having even more flexibility.
【０００７】本発明は、上記事情に鑑みなされたもの
で、エポキシ樹脂の硬化剤等として低応力性に優れた硬
化物を与え、半導体装置封止用、塗料用、接着剤用樹脂
組成物などに好適に使用できる新規なシリコーン変性酸
無水物及びその製造方法を提供することを目的とする。The present invention has been made in view of the above circumstances, and provides a cured product excellent in low stress as a curing agent for epoxy resin and the like, and a resin composition for encapsulating a semiconductor device, a coating material, an adhesive agent, etc. It is an object of the present invention to provide a novel silicone-modified acid anhydride that can be suitably used for the above, and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段及び作用】本発明者は、上
記目的を達成するため鋭意検討を重ねた結果、下記式
（２）で表されるアルケニル基を有する酸無水物のアル
ケニル基に、下記式（３）で表される環状有機珪素化合
物の≡ＳｉＨ結合を付加反応させることにより、下記式
（１）で表される新規なシリコーン変性酸無水物が容易
に得られること、このような付加反応を用いることによ
り、酸無水物に結合していない遊離の有機珪素化合物を
ほとんど含まないシリコーン変性酸無水物を得ることが
できることを知見した。Means for Solving the Problems The present inventor has conducted extensive studies to achieve the above object, and as a result, the alkenyl group of the acid anhydride having an alkenyl group represented by the following formula (2) is A novel silicone-modified acid anhydride represented by the following formula (1) can be easily obtained by addition reaction of the ≡SiH bond of the cyclic organosilicon compound represented by the following formula (3). It has been found that a silicone-modified acid anhydride containing almost no free organosilicon compound that is not bound to an acid anhydride can be obtained by using an addition reaction.
【０００９】[0009]
【化３】 （但し、式中Ｒ1は水素原子、置換もしくは非置換の１
価炭化水素、水酸基、アルコキシ基又はアルケニルオキ
シ基、ｎ、ｍは１≦ｎ≦１０、０≦ｍ≦９、３≦ｎ＋ｍ
≦１０を満足する整数である。）Embedded image (However, in the formula, R 1 is a hydrogen atom, substituted or unsubstituted 1
Valent hydrocarbon, hydroxyl group, alkoxy group or alkenyloxy group, n and m are 1 ≦ n ≦ 10, 0 ≦ m ≦ 9, 3 ≦ n + m
It is an integer that satisfies ≦ 10. )
【００１０】このようにして得られた上記式（１）で表
されるシリコーン変性酸無水物は、エポキシ樹脂の硬化
剤としてそれ単独で、又は公知の硬化剤、特には酸無水
物系硬化剤と併用した場合、低応力でしかも強靭なエポ
キシ樹脂硬化物を形成でき、このため優れた耐クラック
性を有し、かつガラス転移点も低下しない硬化物を与え
るエポキシ樹脂組成物を製造でき、従って、半導体封止
用エポキシ樹脂組成物の硬化剤として非常に有用で、特
に硬化物の透明性を損なわないので、透明性を要求され
る用途に有用であること、また、上記シリコーン変性酸
無水物は、有機錫化合物等のシリコーン用硬化触媒の存
在下で硬化させることができ、この硬化物はエポキシ樹
脂組成物の低応力化剤として有用であること、更にポリ
イミドの原料である酸無水物成分としても使用でき、ポ
リイミドの低弾性率化に有効に作用すること、種々の用
途に使用されることを見い出し、本発明をなすに至った
ものである。The silicone-modified acid anhydride represented by the above formula (1) thus obtained is used alone or as a curing agent for epoxy resins, or as a known curing agent, particularly an acid anhydride curing agent. When used in combination with, a low-stress and tough epoxy resin cured product can be formed, and thus an epoxy resin composition which has excellent crack resistance and gives a cured product which does not lower the glass transition point can be produced. , Which is very useful as a curing agent for epoxy resin compositions for semiconductor encapsulation, and particularly does not impair the transparency of the cured product, and thus is useful for applications requiring transparency, and the above silicone-modified acid anhydride. Can be cured in the presence of a curing catalyst for silicone such as an organic tin compound. This cured product is useful as a stress-reducing agent for epoxy resin compositions, and is a raw material for polyimide. Can also be used as an acid anhydride component, to act effectively on the low modulus of the polyimide, it found to be used for various applications, in which the present invention has been accomplished.
【００１１】以下、本発明について更に詳しく説明する
と、本発明のシリコーン変性酸無水物は、下記一般式
（１）で示されるものである。The present invention will be described in more detail below. The silicone-modified acid anhydride of the present invention is represented by the following general formula (1).
【００１２】[0012]
【化４】 Embedded image
【００１３】この式（１）中、Ｒ1は水素原子、置換も
しくは非置換の１価炭化水素基、水酸基、アルコキシ基
又はアルケニルオキシ基を示す。具体的にはメチル基、
エチル基等のアルキル基、フェニル基等のアリール基、
ベンジル基等のアラルキル基などが挙げられ、またこれ
ら炭化水素基の水素原子の一部又は全部をハロゲン原
子、シアノ基、グリシジル基などで置換したクロロプロ
ピル基、クロロメチル基、グリシジルプロピル基などを
挙げることもできる。また、具体的にアルコキシ基とし
てはメトキシ基、エトキシ基などが挙げられ、アルケニ
ルオキシ基としてはイソプロぺニルオキシ基、イソブテ
ニルオキシ基などが挙げられる。In the formula (1), R 1 represents a hydrogen atom, a substituted or unsubstituted monovalent hydrocarbon group, a hydroxyl group, an alkoxy group or an alkenyloxy group. Specifically, a methyl group,
Alkyl group such as ethyl group, aryl group such as phenyl group,
Examples thereof include aralkyl groups such as a benzyl group, and also a chloropropyl group, a chloromethyl group, a glycidylpropyl group, etc. in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom, a cyano group, a glycidyl group or the like. You can also list them. Specific examples of the alkoxy group include a methoxy group and an ethoxy group, and examples of the alkenyloxy group include an isopropenyloxy group and an isobutenyloxy group.
【００１４】また、式（１）中、ｎ、ｍは１≦ｎ≦１
０、０≦ｍ≦９、３≦ｎ＋ｍ≦１０を満足する整数であ
り、好ましくは１≦ｎ≦６、０≦ｍ≦５、３≦ｎ＋ｍ≦
６を満足する整数である。In the formula (1), n and m are 1≤n≤1.
An integer satisfying 0, 0 ≦ m ≦ 9, 3 ≦ n + m ≦ 10, preferably 1 ≦ n ≦ 6, 0 ≦ m ≦ 5, 3 ≦ n + m ≦
It is an integer that satisfies 6.
【００１５】上記式（１）のシリコーン変性酸無水物と
しては、具体的に下記のものを例示することができる。Specific examples of the silicone-modified acid anhydride of the above formula (1) include the following.
【００１６】[0016]
【化５】 Embedded image
【００１７】上記式（１）のシリコーン変性酸無水物
は、下記式（２）で表わされるアルケニル基含有酸無水
物のアルケニル基に下記一般式（３）で表わされる環状
有機珪素化合物の≡ＳｉＨ基を付加反応させることによ
り合成することができる。The silicone-modified acid anhydride of the above formula (1) is obtained by adding ≡SiH of the cyclic organic silicon compound represented by the following general formula (3) to the alkenyl group of the alkenyl group-containing acid anhydride represented by the following formula (2). It can be synthesized by subjecting a group to an addition reaction.
【００１８】ここで、本発明においては、アルケニル基
含有酸無水物として、下記式（２）で表されるものを使
用する。Here, in the present invention, as the alkenyl group-containing acid anhydride, one represented by the following formula (2) is used.
【００１９】[0019]
【化６】 [Chemical 6]
【００２０】このアルケニル基含有酸無水物に付加する
環状有機珪素化合物としては、下記式（３）で表され、
分子中に≡ＳｉＨ基を有するものを使用する。The cyclic organosilicon compound added to the alkenyl group-containing acid anhydride is represented by the following formula (3):
The one having an ≡SiH group in the molecule is used.
【００２１】[0021]
【化７】 [Chemical 7]
【００２２】この式（３）において、Ｒ1，ｎ，ｍは上
記と同様の意味を示す。なおｎ＋ｍは上述したように３
≦ｎ＋ｍ≦１０であるが、ｎ＋ｍが１０より大きいと、
このような環状有機珪素化合物は、ｎ＋ｍがこれに近い
環状有機化合物との混合物から分離するのが困難である
ため、純度が低くなるという問題がある。In the formula (3), R 1 , n and m have the same meanings as described above. Note that n + m is 3 as described above.
≦ n + m ≦ 10, but when n + m is larger than 10,
Such a cyclic organosilicon compound has a problem of low purity because it is difficult to separate n + m from a mixture with a cyclic organic compound close to n + m.
【００２３】このような式（３）で表される環状有機珪
素化合物としては、下記に示すものが例示されるが、こ
れに制限されるものではない。Examples of the cyclic organosilicon compound represented by the formula (3) are shown below, but the invention is not limited thereto.
【００２４】[0024]
【化８】 Embedded image
【００２５】上記式（２）の化合物と式（３）の化合物
の付加反応に際しては、従来公知の付加触媒、例えば塩
化白金酸のような白金系触媒を使用することができる。
また、反応し際して溶媒を使用することができるが、こ
の溶媒としてはベンゼン、トルエン、メチルイソブチル
ケトンなどの不活性溶媒を用いることができる。反応温
度は特に制限されないが、６０〜１２０℃の範囲が好ま
しく、反応時間は通常３０分〜１０時間である。In the addition reaction of the compound of formula (2) with the compound of formula (3), a conventionally known addition catalyst, for example, a platinum catalyst such as chloroplatinic acid can be used.
In addition, a solvent can be used during the reaction, and as the solvent, an inert solvent such as benzene, toluene, and methyl isobutyl ketone can be used. The reaction temperature is not particularly limited, but is preferably in the range of 60 to 120 ° C., and the reaction time is usually 30 minutes to 10 hours.
【００２６】更に、式（２）で表される酸無水物と式
（３）で表される有機珪素化合物の配合比は、式（２）
で表される酸無水物中のアルケニル基の当量をＡ、式
（３）で表される環状有機珪素化合物中の≡ＳｉＨ基の
当量をＢとした場合、０．１≦Ｂ／Ａ≦２の範囲、特に
０．８≦Ｂ／Ａ≦１．２の範囲で反応させることが好ま
しい。Ｂ／Ａの比が０．１より低いと未反応で残存する
アルケニル基含有酸無水物が多いため、反応後除去する
のに多大な労力を必要とする場合があり、一方、２より
高いと未反応の環状有機珪素化合物を除去するのが困難
である場合が生じる。Further, the compounding ratio of the acid anhydride represented by the formula (2) and the organosilicon compound represented by the formula (3) is as shown in the formula (2).
When the equivalent of the alkenyl group in the acid anhydride represented by the formula is A and the equivalent of the ≡SiH group in the cyclic organosilicon compound represented by the formula (3) is B, 0.1 ≦ B / A ≦ 2 It is preferable to carry out the reaction within the range of 0.8 ≦ B / A ≦ 1.2. If the ratio of B / A is lower than 0.1, a large amount of alkenyl group-containing acid anhydride that remains unreacted may be required, so that it may require a great deal of labor to remove it after the reaction. In some cases, it is difficult to remove the unreacted cyclic organosilicon compound.
【００２７】本発明の式（１）で表されるシリコーン変
性酸無水物は、酸無水物系硬化剤として単独で又は従来
の酸無水物系硬化剤と併用して従来公知のエポキシ樹脂
を硬化させることができ、また、場合により有機錫化合
物などのシリコーン用硬化剤の存在下で硬化させること
もでき、これにより低応力で耐クラック性に優れ、ガラ
ス転移点も低下しない強靭な硬化物を与えることができ
る。従って、本発明のシリコーン変性酸無水物は、エポ
キシ樹脂組成物の硬化剤や低応力剤として好適に使用す
ることができる。なお、本発明のシリコーン変性酸無水
物をエポキシ樹脂の硬化剤として使用する場合、エポキ
シ樹脂組成物としては従来のエポキシ樹脂と同様の配合
で良く、例えば本発明のシリコーン変性酸無水物の１種
を単独で又は２種以上を混合してそのまま単独の硬化剤
に用いても良く、又は従来の酸無水物と併用し、これに
エポキシ樹脂、硬化促進剤、充填剤、難燃剤、カップリ
ング剤などを配合してエポキシ樹脂組成物を調製するこ
とができ、塗料、接着剤、半導体封止剤、半導体表面保
護膜などの用途に好適に使用することができる。そのほ
かポリイミドの原料である酸無水物成分として使用する
こともでき、これによってポリイミドを有効に低弾性率
化することができる。The silicone-modified acid anhydride represented by the formula (1) of the present invention cures a conventionally known epoxy resin alone as an acid anhydride curing agent or in combination with a conventional acid anhydride curing agent. In addition, it can be cured in the presence of a curing agent for silicone such as an organic tin compound as the case may be, whereby a strong cured product having low stress, excellent crack resistance and a glass transition point not lowered is obtained. Can be given. Therefore, the silicone-modified acid anhydride of the present invention can be suitably used as a curing agent or a low stress agent for epoxy resin compositions. When the silicone-modified acid anhydride of the present invention is used as a curing agent for an epoxy resin, the epoxy resin composition may have the same composition as that of a conventional epoxy resin. For example, one kind of the silicone-modified acid anhydride of the present invention may be used. May be used alone or as a mixture of two or more kinds as they are as a single curing agent, or may be used in combination with a conventional acid anhydride, and an epoxy resin, a curing accelerator, a filler, a flame retardant, a coupling agent may be added thereto. The epoxy resin composition can be prepared by blending the above, and can be suitably used for applications such as paints, adhesives, semiconductor encapsulants, and semiconductor surface protective films. In addition, it can also be used as an acid anhydride component which is a raw material of polyimide, which can effectively reduce the elastic modulus of polyimide.
【００２８】[0028]
【発明の効果】本発明のシリコーン変性酸無水物は、硬
化物に低応力性を付与することができるため半導体封止
用材料などとして有用であり、また、本発明の製造方法
によれば、かかるシリコーン変性酸無水物を簡単に効率
よく製造することができる。INDUSTRIAL APPLICABILITY The silicone-modified acid anhydride of the present invention is useful as a material for semiconductor encapsulation and the like because it can impart a low stress property to a cured product, and according to the production method of the present invention, Such a silicone-modified acid anhydride can be produced easily and efficiently.
【００２９】[0029]
【実施例】以下、実施例を示し、本発明を具体的に示す
が、本発明は下記の実施例に制限されるものではない。EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
【００３０】［実施例１］リフラックスコンデンサー、
温度計、攪拌機及び滴下ロートを具備した内容積２リッ
ターの四つ口フラスコ内に、下記式（２）で表される酸
無水物１０８ｇと溶剤としてトルエン３２０ｇを入れ、
共沸脱水した後、塩化白金酸系触媒（信越化学ＰＬ−５
０Ｔ）６．５ｇを加え、攪拌機で攪拌しながら１１２℃
の温度で滴下ロートにて下記式（３−ａ）で表される環
状有機珪素化合物５１．８ｇを３０分間で滴下し、更に
同温度で９時間攪拌を継続した。こうして得られた生成
物から未反応の酸無水物と溶剤を減圧下で留去して目的
とする下記式（１−ａ）で表されるシリコーン変性酸無
水物１２３ｇを得た。[Example 1] Reflux condenser,
In a four-necked flask having an internal volume of 2 liters equipped with a thermometer, a stirrer and a dropping funnel, 108 g of an acid anhydride represented by the following formula (2) and 320 g of toluene as a solvent were put,
After azeotropic dehydration, chloroplatinic acid-based catalyst (Shin-Etsu Chemical PL-5
(0T) 6.5 g was added, with stirring with a stirrer at 112 ° C.
51.8 g of the cyclic organosilicon compound represented by the following formula (3-a) was added dropwise at the temperature of 30 minutes in the dropping funnel, and stirring was continued at the same temperature for 9 hours. From the product thus obtained, the unreacted acid anhydride and the solvent were distilled off under reduced pressure to obtain 123 g of the desired silicone-modified acid anhydride represented by the following formula (1-a).
【００３１】[0031]
【化９】 [Chemical 9]
【００３２】得られたシリコーン変性酸無水物の外観は
淡黄色透明の液体であった。このシリコーン変性酸無水
物のＩＲ分析を行った結果、≡ＳｉＨ基の存在を表す２
１５０ｃｍ-1の吸収帯が消失していた。また、ＮＭＲ分
析の結果、≡ＳｉＨ基の存在を表す４．４ｐｐｍ付近の
ピークが消失していた。更に、ＧＰＣ分析の結果、原料
よりも高分子量な化合物の存在を示すピークが出現し
た。以上の分析結果及び元素分析結果より、このシリコ
ーン変性酸無水物は上記（１−ａ）で表される構造を有
していることが確認された。なお、下記に式（１−ａ）
の化合物の特性値を示す。The appearance of the obtained silicone-modified acid anhydride was a pale yellow transparent liquid. As a result of IR analysis of this silicone-modified acid anhydride, the presence of ≡SiH group is shown.
The absorption band at 150 cm -1 had disappeared. Further, as a result of NMR analysis, the peak around 4.4 ppm indicating the presence of the ≡SiH group disappeared. Furthermore, as a result of the GPC analysis, a peak appeared indicating the presence of a compound having a higher molecular weight than the raw material. From the above analysis results and elemental analysis results, it was confirmed that this silicone-modified acid anhydride has the structure represented by the above (1-a). In addition, the following formula (1-a)
The characteristic values of the compound are shown.
【００３３】[0033]
【化１０】 [Chemical 10]
【００３４】［実施例２］実施例１と同様な四つ口フラ
スコを反応装置として使用し、このフラスコに上記式
（１）で表される酸無水物１６３ｇと溶剤としてトルエ
ン３８５ｇを入れ、共沸脱水した後、塩化白金酸系触媒
（信越化学ＰＬ−５０Ｔ）９．５ｇを加え、攪拌機で攪
拌しながら１１２℃の温度で滴下ロートにて下記平均組
成式（３−ｂ）で表される環状有機珪素化合物２９．５
ｇを３０分間で滴下し、更に同温度で１０時間攪拌を継
続した。こうして得られた生成物から未反応の酸無水物
と溶剤を減圧下で留去して目的とする下記式（１−ｂ）
で示されるシリコーン変性酸無水物１３８．５ｇを得
た。[Example 2] A four-necked flask similar to that used in Example 1 was used as a reactor, and 163 g of the acid anhydride represented by the above formula (1) and 385 g of toluene as a solvent were charged in the flask. After boiling dehydration, 9.5 g of a chloroplatinic acid catalyst (Shin-Etsu Chemical PL-50T) was added, and the mixture was represented by the following average composition formula (3-b) in a dropping funnel at a temperature of 112 ° C. while stirring with a stirrer. Cyclic Organosilicon Compound 29.5
g was added dropwise over 30 minutes, and stirring was continued at the same temperature for 10 hours. From the product thus obtained, the unreacted acid anhydride and solvent are distilled off under reduced pressure to obtain the target compound of the following formula (1-b)
138.5 g of a silicone-modified acid anhydride represented by
【００３５】[0035]
【化１１】 [Chemical 11]
【００３６】得られたシリコーン変性酸無水物の外観は
淡黄色透明の半固体であった。このシリコーン変性酸無
水物のＩＲ分析を行った結果、≡ＳｉＨ基の存在を表す
２１４０ｃｍ-1の吸収帯が消失していた。また、ＮＭＲ
分析の結果、≡ＳｉＨ基の存在を表す４．４ＰＰｍ付近
のピークが消失していた。更に、ＧＰＣ分析の結果、原
料よりも高分子量な化合物の存在を示すピークが出現し
た。以上の分析結果及び元素分析結果より、このシリコ
ーン変性酸無水物は上記式（１−ｂ）で表される構造を
有していることが確認された。なお、式（１−ｂ）の化
合物の特性値を下記に示す。The appearance of the obtained silicone-modified acid anhydride was a pale yellow transparent semi-solid. As a result of IR analysis of this silicone-modified acid anhydride, the absorption band at 2140 cm −1 indicating the presence of ≡SiH group disappeared. Also, NMR
As a result of the analysis, the peak near 4.4PPm indicating the presence of the ≡SiH group disappeared. Furthermore, as a result of the GPC analysis, a peak appeared indicating the presence of a compound having a higher molecular weight than the raw material. From the above analysis results and elemental analysis results, it was confirmed that this silicone-modified acid anhydride has a structure represented by the above formula (1-b). The characteristic values of the compound of formula (1-b) are shown below.
【００３７】[0037]
【化１２】 [Chemical 12]
【００３８】［実施例３］実施例１と同様な四つ口フラ
スコを反応装置として使用し、このフラスコに上記式
（１）で表される酸無水物６４ｇと溶剤としてトルエン
３２８ｇを入れ、共沸脱水した後、塩化白金酸系触媒
（信越化学ＰＬ−５０Ｔ）５．０ｇを加え、攪拌機で攪
拌しながら１１２℃の温度で滴下ロートにて下記平均組
成式（３−ｃ）で表される環状有機珪素化合物１００ｇ
を３０分間で滴下し、更に同温度で５時間攪拌を継続し
た。こうして得られた生成物から未反応の酸無水物と溶
剤を減圧下で留去して目的とする下記式（１−ｃ）で示
されるシリコーン変性酸無水物１４２ｇを得た。[Example 3] A four-necked flask similar to that used in Example 1 was used as a reactor, and 64 g of the acid anhydride represented by the above formula (1) and 328 g of toluene as a solvent were charged in the flask. After boiling dehydration, 5.0 g of chloroplatinic acid catalyst (Shin-Etsu Chemical PL-50T) was added, and the mixture was represented by the following average composition formula (3-c) in a dropping funnel at a temperature of 112 ° C. while stirring with a stirrer. Cyclic organosilicon compound 100g
Was added dropwise over 30 minutes, and stirring was continued at the same temperature for 5 hours. Unreacted acid anhydride and solvent were distilled off from the product thus obtained under reduced pressure to obtain 142 g of the desired silicone-modified acid anhydride represented by the following formula (1-c).
【００３９】[0039]
【化１３】 [Chemical 13]
【００４０】得られたシリコーン変性酸無水物の外観は
淡黄色透明の液状物質であった。このシリコーン変性酸
無水物のＩＲ分析を行った結果、≡ＳｉＨ基の存在を表
す２１５０ｃｍ-1の吸収帯が消失していた。また、ＮＭ
Ｒ分析の結果、≡ＳｉＨ基の存在を表す４．４ＰＰｍ付
近のピークが消失していた。更に、ＧＰＣ分析の結果、
原料よりも高分子量な化合物の存在を示すピークが出現
した。以上の分析結果及び元素分析結果より、このシリ
コーン変性酸無水物は上記式（１−ｃ）で表される構造
を有していることが確認された。なお、式（１−ｃ）の
化合物の特性値を下記に示す。The appearance of the obtained silicone-modified acid anhydride was a pale yellow transparent liquid substance. As a result of IR analysis of this silicone-modified acid anhydride, the absorption band at 2150 cm −1 indicating the presence of ≡SiH group disappeared. Also, NM
As a result of R analysis, the peak around 4.4PPm indicating the presence of ≡SiH group disappeared. Furthermore, as a result of GPC analysis,
A peak showing the presence of a compound having a higher molecular weight than the raw material appeared. From the above analysis results and elemental analysis results, it was confirmed that this silicone-modified acid anhydride has a structure represented by the above formula (1-c). The characteristic values of the compound of formula (1-c) are shown below.
【００４１】[0041]
【化１４】 Embedded image
【００４２】[0042]
【化１５】 Embedded image
【００４３】［実施例４］実施例１と同様な四つ口フラ
スコを反応装置として使用し、このフラスコに上記式
（１）で表される酸無水物７４ｇと溶剤としてトルエン
３０８ｇを入れ、共沸脱水した後、塩化白金酸系触媒
（信越化学ＰＬ−５０Ｔ）４．８ｇを加え、攪拌機で攪
拌しながら１１２℃の温度で滴下ロートにて下記平均組
成式（３−ｄ）で表される環状有機珪素化合物８０ｇを
３０分間で滴下し、更に同温度で５時間攪拌を継続し
た。こうして得られた生成物から未反応の酸無水物と溶
剤を減圧下で留去して目的とする下記式（１−ｄ）で示
されるシリコーン変性酸無水物１２９ｇを得た。[Example 4] A four-necked flask similar to that used in Example 1 was used as a reactor, and 74 g of the acid anhydride represented by the above formula (1) and 308 g of toluene as a solvent were charged in the flask. After dehydration by boiling, 4.8 g of chloroplatinic acid-based catalyst (Shin-Etsu Chemical PL-50T) was added, and the mixture was represented by the following average composition formula (3-d) in a dropping funnel at a temperature of 112 ° C. while stirring with a stirrer. 80 g of cyclic organosilicon compound was added dropwise over 30 minutes, and stirring was continued at the same temperature for 5 hours. From the product thus obtained, the unreacted acid anhydride and the solvent were distilled off under reduced pressure to obtain 129 g of the desired silicone-modified acid anhydride represented by the following formula (1-d).
【００４４】[0044]
【化１６】 Embedded image
【００４５】得られたシリコーン変性酸無水物の外観は
淡黄色透明の液状物質であった。このシリコーン変性酸
無水物のＩＲ分析を行った結果、≡ＳｉＨ基の存在を表
す２１５０ｃｍ-1の吸収帯が消失していた。また、ＮＭ
Ｒ分析の結果、≡ＳｉＨ基の存在を表す４．４ＰＰｍ付
近のピークが消失していた。更に、ＧＰＣ分析の結果、
原料よりも高分子量な化合物の存在を示すピークが出現
した。以上の分析結果及び元素分析結果より、このシリ
コーン変性酸無水物は上記式（１−ｄ）で表される構造
を有していることが確認された。なお、式（１−ｄ）の
化合物の特性値を下記に示す。The appearance of the obtained silicone-modified acid anhydride was a pale yellow transparent liquid substance. As a result of IR analysis of this silicone-modified acid anhydride, the absorption band at 2150 cm −1 indicating the presence of ≡SiH group disappeared. Also, NM
As a result of R analysis, the peak around 4.4PPm indicating the presence of ≡SiH group disappeared. Furthermore, as a result of GPC analysis,
A peak showing the presence of a compound having a higher molecular weight than the raw material appeared. From the above analysis results and elemental analysis results, it was confirmed that this silicone-modified acid anhydride has a structure represented by the above formula (1-d). The characteristic values of the compound of formula (1-d) are shown below.
【００４６】[0046]
【化１７】 [Chemical 17]
【図１】実施例１で得られた生成物のゲルパーミエーシ
ョンクロマトグラフィーのチャートである。1 is a chart of gel permeation chromatography of the product obtained in Example 1. FIG.
【図２】実施例２で得られた生成物のゲルパーミエーシ
ョンクロマトグラフィーのチャートである。FIG. 2 is a gel permeation chromatography chart of the product obtained in Example 2.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 新井 一弘 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社 シリコーン電 子材料技術研究所内 (72)発明者 井野 茂樹 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社 シリコーン電 子材料技術研究所内 (72)発明者 清水 久司 群馬県碓氷郡松井田町大字人見１番地10 信越化学工業株式会社 シリコーン電 子材料技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Kazuhiro Arai, Kazuhiro Arai 1-1 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Materials Research Laboratory (72) Inventor Shigeki Ino Matsui, Usui-gun, Gunma Prefecture Tamachi Daiji Hitomi 1-10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (72) Inventor Koji Shimizu Matsuida-cho, Usui District, Gunma Daiji Hitomi 10 Shin-Etsu Chemical Industrial Co., Ltd. Silicon Electronic Materials Research Laboratory
Claims (2)
変性酸無水物。 【化１】 （但し、式中Ｒ1は水素原子、置換もしくは非置換の１
価炭化水素基、水酸基、アルコキシ基又はアルケニルオ
キシ基、ｎ、ｍは１≦ｎ≦１０、０≦ｍ≦９、３≦ｎ＋
ｍ≦１０を満足する整数である。）1. A silicone-modified acid anhydride represented by the following general formula (1). Embedded image (However, in the formula, R 1 is a hydrogen atom, substituted or unsubstituted 1
Valent hydrocarbon group, hydroxyl group, alkoxy group or alkenyloxy group, n and m are 1 ≦ n ≦ 10, 0 ≦ m ≦ 9, 3 ≦ n +
It is an integer that satisfies m ≦ 10. )
酸無水物のアルケニル基に下記一般式（３）で表される
環状有機珪素化合物の≡ＳｉＨ基を付加反応させること
を特徴とする請求項１記載のシリコーン変性酸無水物の
製造方法。 【化２】 （但し、式中Ｒ1は水素原子、置換もしくは非置換の１
価炭化水素、水酸基、アルコキシ基又はアルケニルオキ
シ基、ｎ、ｍは１≦ｎ≦１０、０≦ｍ≦９、３≦ｎ＋ｍ
≦１０を満足する整数である。）2. An alkenyl group of an acid anhydride containing an alkenyl group represented by the following formula (2) is subjected to an addition reaction with an ≡SiH group of a cyclic organosilicon compound represented by the following general formula (3). The method for producing the silicone-modified acid anhydride according to claim 1. Embedded image (However, in the formula, R 1 is a hydrogen atom, substituted or unsubstituted 1
Valent hydrocarbon, hydroxyl group, alkoxy group or alkenyloxy group, n and m are 1 ≦ n ≦ 10, 0 ≦ m ≦ 9, 3 ≦ n + m
It is an integer that satisfies ≦ 10. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4174851A JP2546104B2 (en) | 1992-06-09 | 1992-06-09 | Silicone modified acid anhydride and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4174851A JP2546104B2 (en) | 1992-06-09 | 1992-06-09 | Silicone modified acid anhydride and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05339279A JPH05339279A (en) | 1993-12-21 |
| JP2546104B2 true JP2546104B2 (en) | 1996-10-23 |
Family
ID=15985763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4174851A Expired - Fee Related JP2546104B2 (en) | 1992-06-09 | 1992-06-09 | Silicone modified acid anhydride and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2546104B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130006331A (en) | 2011-07-06 | 2013-01-16 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Succinic anhydride group containing cyclic organosiloxane, preparation thereof, organosiloxane composition and thermosetting resin composition |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2682359B2 (en) * | 1992-11-27 | 1997-11-26 | 信越化学工業株式会社 | Silicone modified acid anhydride and method for producing the same |
| EP1809689A1 (en) * | 2004-09-10 | 2007-07-25 | Dow Corning Corporation | Anhydride-functional silsesquioxane resins |
| US7727595B2 (en) | 2004-10-25 | 2010-06-01 | Dow Corning Corporation | Coating compositions containing a carbinol functional silicone resin or an anhydride functional silicone resin |
| US7807012B2 (en) | 2004-10-25 | 2010-10-05 | Dow Corning Corporation | Moldable compositions containing carbinol functional silicone resins or anhydride functional silicone resins |
| WO2012173460A2 (en) * | 2011-06-17 | 2012-12-20 | 주식회사 엘지화학 | Curable composition |
| JP5790480B2 (en) * | 2011-12-20 | 2015-10-07 | 信越化学工業株式会社 | Acid anhydride group-containing organosiloxane and method for producing the same |
| JP6376692B2 (en) * | 2014-10-17 | 2018-08-22 | 日本化薬株式会社 | Carboxylic anhydride group-containing cyclic siloxane compound, epoxy resin composition containing the same, and cured product thereof |
| JP7290115B2 (en) * | 2020-01-10 | 2023-06-13 | 信越化学工業株式会社 | Method for preparing (meth)acrylic-functional organopolysiloxane, curable composition and inkjet ink |
-
1992
- 1992-06-09 JP JP4174851A patent/JP2546104B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130006331A (en) | 2011-07-06 | 2013-01-16 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Succinic anhydride group containing cyclic organosiloxane, preparation thereof, organosiloxane composition and thermosetting resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05339279A (en) | 1993-12-21 |
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