JP5011600B2 - Polyether resin, method for producing the same, and insulating material - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、熱硬化性官能基を有するポリエーテル樹脂とその製造方法および該ポリエーテル樹脂を用いてなる絶縁材料に関する。
【０００２】
【従来の技術】
側鎖として熱硬化性官能基を有する樹脂にはこれまでにいくつかの例がある。具体的に例を挙げれば、特公平５−８９３２号公報、特公平５−８９３３号公報に、酸化重合により得られたポリエーテル樹脂にアリル基、プロパルギル基を導入した例が記載されている。また、側鎖としてビニル基を有する樹脂についても公知の例がある。具体的には、ポリエーテルスルホンあるいはポリオキシフェニレン樹脂をクロロメチル化したものを経由しビニル基が導入した例がＭａｃｒｏｍｏｌ．Ｃｈｅｍ．１８５，２３１９（１９８４）に記載されている。しかしながら、これらの方法は、それぞれ、低温での硬化反応が困難であるか、あるいは反応操作が比較的複雑であるなどの問題点を有している。
【０００３】
また、電子デバイスの絶縁膜では、配線間が微細化することによって、絶縁膜自体の誘電率が問題視されてきた。これまで絶縁膜として使用されてきたシリカ系絶縁膜では、伝達速度低下を抑制することが難しい。この解決案として、有機ポリマーがその優れた電気特性から注目されてきた。また、絶縁膜としては、電気特性のみならず、優れた耐熱性が求められることから、芳香族環を主鎖に有するポリマー、特に、耐薬品性に優れた特徴を持つ熱硬化性官能基を側鎖に有する芳香族ポリマーが期待されている。
【０００４】
【発明が解決しようとする課題】
本発明の目的は、熱硬化性官能基をもつポリエーテル樹脂およびその製造方法を提供することにある。また、これを用いて得られる耐薬品性に優れる電子絶縁材料を提供することにある。
【０００５】
【課題を解決するための手段】
本発明は、〔１〕下式（１）の繰り返し単位を有するポリエーテル樹脂に係るものである。
【０００６】
また、本発明は、〔２〕下式（２）の繰り返し単位を有するポリエーテル樹脂に係るものである。
【０００７】
また、本発明は、〔３〕下式（３）の繰り返し単位を有する熱硬化性ポリエーテル樹脂に係るものである。
【０００８】
さらに、本発明は、〔４〕ジハロゲン化アセトフェノンとビスフェノール類との縮合反応工程を含む〔１〕に記載のポリエーテル樹脂の製造方法に係るものである。
また、本発明は、〔５〕前記〔１〕に記載のポリエーテル樹脂のアセチル基を還元反応し、ＣＨ3ＣＨＯＨ基に変換する工程を含むことを特徴とする〔２〕に記載のポリエーテル樹脂の製造方法に係るものである。
また、本発明は、〔６〕前記〔２〕に記載のポリエーテル樹脂のＣＨ3ＣＨＯＨ基を脱水反応し、ビニル基に変換する工程を含む〔３〕に記載のポリエーテル樹脂の製造方法に係るものである。
【０００９】
さらに、本発明は、〔７〕前記〔１〕〜〔３〕のいずれかに記載のポリエーテル樹脂を用いてなる絶縁材料に係るものである。
また、本発明は、〔８〕（Ａ）前記〔１〕〜〔４〕のいずれかに記載のポリエーテル樹脂、（Ｂ）有機溶媒を必須成分としてなる絶縁膜形成用塗布液に係るものである。
また、本発明は、〔９〕前記〔８〕に記載の絶縁膜形成用塗布液を用いて得られる絶縁膜に係るものである。
【００１０】
【発明の実施の形態】
次に、本発明を詳細に説明する。
本発明の式（１）〜（３）において、Ｒ1〜Ｒ11はそれぞれ独立に、水素原子、置換基を有してもよい炭素数１〜１０のアルキル基、もしくは置換基を有してもよい炭素数６〜１０のシクロアルキル基、置換基を有してもよい炭素数２〜１０のアルケニル基、置換基を有してもよい炭素数２〜１０のアルキニル基、もしくは置換基を有してもよい炭素数６〜１０の芳香族環、炭素数１〜１０のアルコキシ基、カルボニル基を持つ置換基、またはアルコール基を持つ置換基のいずれかを示す。
【００１１】
炭素数１〜１０のアルキル基として、メチル基、エチル基、プロピル基等が挙げられる。
炭素数６〜１０のシクロアルキル基として、シクロヘキシル基、シクロヘプチル基等が挙げられる。
炭素数２〜１０のアルケニル基として、ビニル基、アリル基、プロペニル基等が挙げられる。
炭素数２〜１０のアルキニル基として、エチニル基、プロパルギル基等が挙げられる。
置換基を有してもよい炭素数６〜１０の芳香族環として、フェニル基、ナフチル基等が挙げられる。
炭素数１〜１０のアルコキシ基として、メトキシ基、エトキシ基等が挙げられる。
カルボニル基を持つ置換基としてアセチル基等が挙げられ、アルコール基を持つ置換基としてＣＨ3ＣＨＯＨ基が挙げられる。
また、ここで、置換基を有してもよいとされる置換基としては、アルキル基、アルケニル基、アルキニル基、芳香族環等が挙げられる。
【００１２】
また、本発明における式（１）〜（３）において、式中Ｘは、単結合、炭素数１〜２０の炭化水素基、−Ｏ−、−ＣＯ−のいずれかを示す。炭素数１〜２０の炭化水素基の具体例を示せば、−ＣＨ2−、−Ｃ（ＣＨ3）2−、−ＣＨ（ＣＨ3）−、−Ｃ（ＣＨ3）（ＣＨ2ＣＨ3）−、−Ｃ（ＣＨ3）（ＣＨ2ＣＨ（ＣＨ3）2）−、などの直鎖もしくは分岐したものが挙げられ、また、
Ｘとして、単結合、または下式（４）のいずれかが好ましい。さらにこれらは置換基を有することもできる。
Ｒ1〜Ｒ11およびＸは、該ポリエーテルに対する要求性能に応じて選択することが好ましい。例えば、誘電率を低下させたい場合には、Ｒ1〜Ｒ11およびＸは、誘電率低下に効果のある嵩高い置換基を用いることが好ましい。また、耐熱性を高めたい場合には、これらは耐熱性の高い置換基を用いることが好ましい。
【００１４】
本発明の〔１〕に記載のポリエーテル樹脂の製造方法は、ジハロゲン化アセトフェノンとビスフェノール類との縮合反応工程を含むことを特徴とする。
本発明の製造方法におけるジハロゲン化アセトフェノンは、ベンゼン環にハロゲン原子が２個以上、アセチル基が１個以上置換しているものを示す。この例を具体的に示せば、ジフルオロアセトフェノン、ジクロロアセトフェノン、ジブロモアセトフェノン、ジヨードアセトフェノン、ジフルオロメチルアセトフェノン、ジクロロメチルアセトフェノン、ジブロモメチルアセトフェノン、ジヨードメチルアセトフェノン（各々各種異性体を含む）などが挙げられるが、これらに限定されるものではない。
【００１５】
本発明におけるビスフェノール類とは１分子中に２個のフェノール性ＯＨ基をもつものであれば、特に限定されない。具体的には、ビスフェノールＡ、ビスフェノールＦ、ビフェノール、シクロヘキシリデンビスフェノール、ビス（ヒドロキシフェニル）メタノン、（１−メチル−エチリデン）ビス［２−シクロヘキシルフェノール］、シクロヘキシリデンビス［２−シクロヘキシルフェノール］等の例が挙げられる。これらビスフェノール類を２種類以上混合して用いることも可能である。
【００１６】
本発明において、ジハロゲン化アセトフェノンとビスフェノール類との縮合反応はアルカリ条件下で行うことができる。このときの溶媒は、特に限定されるものではないが、沸点および反応の進行のしやすさから、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、ベンゾフェノンなどが好適に用いられる。
【００１７】
また、該縮合反応において使用されるアルカリ物質は特に限定されないが、具体的に例示すれば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウムなどが挙げられる。これらは、固体、または水溶液などの溶液の形で用いることができる。
【００１８】
縮合反応は、窒素、アルゴンなどの不活性雰囲気下で行われることが好ましい。また、反応温度は特に限定されないが、反応速度などの点から見て、好ましくは５０℃以上３００℃未満、さらに好ましくは１００℃以上２００℃未満である。
【００１９】
また、本発明の〔２〕に記載のポリエーテル樹脂の製造方法は、前記〔１〕に記載のポリエーテル樹脂のアセチル基を還元反応し、ＣＨ3ＣＨＯＨ基に変換する工程を含むことを特徴とする。
本発明において、アセチル基の還元反応は、溶媒中で還元剤と共存せしめることによって行うことができる。この時の溶媒は、特に限定されない。
【００２０】
還元反応に用いられる還元剤は特に限定されないが、具体例を示せば、水素化ホウ素ナトリウム、水素化ホウ素リチウム、水素化ホウ素亜鉛、トリ第二ブチル水素化ホウ素リチウム、水素化アルミニウムリチウムなどが挙げられる。
【００２１】
また、本発明の〔３〕に記載のポリエーテル樹脂の製造方法は、前記〔２〕に記載のポリエーテル樹脂のＣＨ3ＣＨＯＨ基を脱水反応し、ビニル基に変換する工程を含むことを特徴とする。
本発明において、ＣＨ3ＣＨＯＨ基の脱水反応は、溶媒中で行われる。この場合の溶媒は、特に限定されない。脱水反応は、脱水剤と共存せしめることによってより効率的に行うことができる。
【００２２】
脱水反応に用いられる脱水剤の具体例を示せば、硫酸、りん酸、硫酸水素カリウム、シュウ酸、ｐ−トルエンスルホン酸、三フッ化ホウ素エーテル錯体、ヨウ素、無水硫酸銅などが挙げられる。
【００２３】
本発明における式（３）の単位構造を有するポリエーテルは、任意の方法で硬化させることができる。具体的には、加熱による方法の他に、電子線、光などによって硬化することが可能である。
【００２４】
また、本発明における式（２）の単位構造を有するポリエーテルも、加熱により脱水反応を起こし、ビニル基を含有するポリエーテルを経由して硬化させることができる。
【００２５】
本発明の絶縁材料は、前記〔１〕〜〔３〕のいずれかに記載のポリエーテル樹脂を用いてなることを特徴とする。
本発明におけるポリエーテル樹脂を用いてなる絶縁材料としては、層間絶縁膜などの半導体またはＬＣＤ用絶縁材料、銅張積層板などのプリント配線材料が挙げられる。
【００２６】
本発明の絶縁膜形成用塗布液は、（Ａ）前記〔１〕〜〔３〕のいずれかに記載のポリエーテル樹脂、（Ｂ）有機溶媒を必須成分としてなることを特徴とする。本発明の絶縁膜は、前記の絶縁膜形成用塗布液を用いて得られる。
本発明において絶縁膜形成用塗布液を構成するにあたり必須成分となる有機溶媒は、有機溶媒であれば、特に限定はされない。具体的に例示すれば、ヘキサン、ヘプタン、シクロヘキサンなどの脂肪族炭化水素系溶剤；ベンゼン、トルエン、キシレンなどの炭化水素系溶剤；メタノール、エタノール、イソプロパノール、１−ブタノール、２−エトキシメタノール、２−エトキシエタノール、３−メトキシプロパノール等のアルコール系溶剤；アセチルアセトン、メチルエチルケトン、メチルイソブチルケトン、３−ペンタノン、２−ヘプタノン等のケトン系溶剤；酢酸プロピル、酢酸ブチル、酢酸イソブチル、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル等のエステル系溶剤；ジイソプロピルエーテル、ジブチルエーテル、アニソール等のエーテル系溶剤が工業的に入手可能な溶剤として用いることができる。また、界面活性剤、シランカップリング剤等の他の添加剤を混合することもできる。
【００２７】
本発明によれば、芳香族環に直接結合した形のビニル基を含有したポリマーが得られることから、熱硬化反応を比較的低温にて行うことのできるポリエーテル樹脂を得ることができる。
【００２８】
また、本発明によれば、加熱などの方法による硬化反応を行わしめることにより、耐熱性、耐薬品性、絶縁性などの点で優れた特性を示す熱硬化性ポリエーテル樹脂を得ることができる。
【００２９】
さらに、本発明によれば、使用するビスフェノールを適当に選択することができ、この選択の自由度により、耐熱性、誘電率、熱硬化前の溶媒への溶解度などの点で要求性能に応じた形のポリエーテル樹脂を得ることができる。
【００３０】
【実施例】
本発明を更に詳細に説明するために以下に実施例を示すが、本発明はこれらによって限定されるものではない。
実施例１
窒素気流下にて、５００ｍＬ４ツ口フラスコに１，１−ビス（４−ヒドロキシ−３−シクロヘキシルフェニル）シクロヘキシリデン４３．２ｇ、炭酸カリウム４３．２ｇ、２’，４’−ジクロロアセトフェノン１８．９ｇ、ジメチルスルホキシド６００ｇ、およびトルエン１２０．０ｇを仕込み、１７０℃／８時間保温攪拌を行った。メタノール／酢酸溶液に反応生成物を加え、析出させた。析出した結晶をろ過し、大量のメタノールで洗浄し、減圧乾燥させ、５５．５ｇの製品を得た。これを樹脂Ａと呼ぶ。
【００３１】
実施例２
１，１−ビス（４−ヒドロキシ−３−シクロヘキシルフェニル）シクロヘキシリデンの代わりに４，４’−（９Ｈ−フルオレン−９−イリデン）ビスフェノール３５．０ｇを仕込んだ以外は実施例１と同様にして５５．９ｇの製品を得た。これを樹脂Ｂと呼ぶ。
【００３２】
実施例３
樹脂Ａを２１．３ｇ、Ｎ，Ｎ−ジメチルホルムアミド３００ｇを５００ｍＬ４つ口フラスコに仕込み、室温にて水素化ホウ素ナトリウム５．０ｇを加えた。８０℃／６時間保温攪拌を行った。水に反応生成物を加え、析出させた。析出した結晶をろ過し、水洗、減圧乾燥させ、１７．０ｇの製品を得た。これを樹脂Ｃと呼ぶ。
【００３３】
実施例４
樹脂Ｂを２３．３ｇ、Ｎ，Ｎ−ジメチルホルムアミド３００ｇを５００ｍＬ４つ口フラスコに仕込み、室温にて水素化ホウ素ナトリウム３．８ｇを加えた。８０℃／６時間保温攪拌を行った。メタノールに反応生成物を加え、析出させた。析出した結晶をろ過し、水洗、減圧乾燥させ、２０．２ｇの製品を得た。これを樹脂Ｄと呼ぶ。
【００３４】
実施例５
樹脂Ｃ５．１ｇ、トルエン１００ｇ、メチルヒドロキノン０．２ｇを２００ｍＬ４つ口フラスコに仕込み、１２０℃まで昇温した。りん酸１．２ｇを仕込み１２０℃／４ｈｒ保温・攪拌を行った。反応マスをメタノールに注入し、結晶を析出させた。乾燥後得量４．６ｇであった。これを樹脂Eと呼ぶ。
【００３５】
実施例６
樹脂Ｄ９．４ｇ、トルエン１００ｇ、ジメチルスルホキシド２００ｇ、メチルヒドロキノン０．６ｇを２００ｍＬ４つ口フラスコに仕込み、１２０℃まで昇温した。りん酸１．２ｇを仕込み１２０℃／４ｈｒ保温・攪拌を行った。反応マスをメタノールに注入し、結晶を析出させた。乾燥後得量４．６ｇであった。これを樹脂Ｆと呼ぶ。
【００３６】
プロトンＮＭＲ測定により、表１のような置換基を有するポリエーテル樹脂が得られたことが確認された。各樹脂の内容を下表にまとめておく。
【表１】
参考例１
５００ｍＬの４つ口フラスコに１，１−ビス（４−ヒドロキシ−シクロヘキシルフェニル）シクロヘキシリデン２１．６ｇ、苛性ソーダ４．０ｇ、ベンゾフェノン７０．０ｇおよびトルエン５０．０ｇを仕込み、還流脱水を行った。脱水が完了した後、ジブロモビフェニル１５．６ｇを添加した。さらに塩化第１銅０．０５ｇをピリジン５ｇに溶解させた溶液を添加し、内温１８５℃で６時間反応させた。室温まで冷却させた後、メタノール６００ｇに酢酸１０ｇを混合した溶液に反応溶液を加え、生成物を析出させた。析出した結晶をろ過し、大量のメタノールで洗浄し、ポリエーテル樹脂を得た。この樹脂を樹脂Ｇと呼ぶ。
【００３８】
参考例２
窒素置換した３００ｍＬの４つ口フラスコに、テトラヒドロフランを１００ｍＬ仕込み、樹脂Ｇ４ｇを溶解させた。ｎ−ブチルリチウム（１．６Ｍ、ｎ−ヘキサン溶液）を２１．５ｍＬ加え、窒素気流下１時間攪拌した後、アリルブロミド４．０ｇを加えさらに１時間攪拌を行った。反応終了後、メタノール６５０ｇ、酢酸２０ｇの混合溶媒中に反応溶液を加え、高分子量物を析出させた。ろ過後、メタノール洗浄、水洗を行い、白色粉末状の樹脂を得た。この樹脂を樹脂Ｈと呼ぶ。
【００３９】
実施例７、８、比較例１
樹脂Ｅ、Ｆをそれぞれ、固形分が２０重量％になるように２−ヘプタノンに溶解させた。樹脂Ｇを固形分が２０重量％になるようにアニソールに溶解させた。調製した各々の溶液を０．２μｍフィルターでろ過し、４インチシリコンウェハーに回転数２０００ｒｐｍでスピンコートし、１５０℃で１分間ベークした後、窒素雰囲気下、２５０℃で４０分間熱処理を行った。
各々の塗布膜を塗布液に用いた溶媒に 分間浸漬し、耐溶剤性を調べた。この結果を表２に示す。膜厚に変化がなかったものに○、膜厚の減少が見られたものに×を付した。
【表２】
【発明の効果】
本発明によれば、熱硬化性官能基を有するポリエーテル樹脂が容易な操作で提供され、該ポリエーテル樹脂を用いて、電子デバイスの絶縁材料が得られる。本発明の絶縁材料は、誘電率が低く、耐薬品性に優れる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyether resin having a thermosetting functional group, a method for producing the same, and an insulating material using the polyether resin.
[0002]
[Prior art]
There have been some examples of resins having a thermosetting functional group as a side chain. As specific examples, Japanese Patent Publication No. 5-8932 and Japanese Patent Publication No. 5-8933 describe examples in which an allyl group and a propargyl group are introduced into a polyether resin obtained by oxidative polymerization. There are also known examples of resins having a vinyl group as a side chain. Specifically, an example in which a vinyl group is introduced via a chloromethylated polyethersulfone or polyoxyphenylene resin is described in Macromol. Chem. 185, 2319 (1984). However, each of these methods has problems such as difficulty in curing reaction at low temperatures or relatively complicated reaction operation.
[0003]
Moreover, in the insulating film of an electronic device, the dielectric constant of the insulating film itself has been regarded as a problem due to the miniaturization of the wiring. In silica-based insulating films that have been used as insulating films so far, it is difficult to suppress a decrease in transmission speed. As a solution, organic polymers have attracted attention because of their excellent electrical properties. In addition, since the insulating film is required to have not only electrical characteristics but also excellent heat resistance, a polymer having an aromatic ring in the main chain, in particular, a thermosetting functional group having excellent chemical resistance characteristics. An aromatic polymer having a side chain is expected.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a polyether resin having a thermosetting functional group and a method for producing the same. Another object of the present invention is to provide an electronic insulating material having excellent chemical resistance obtained by using this.
[0005]
[Means for Solving the Problems]
The present invention relates to [1] a polyether resin having a repeating unit of the following formula (1).
[0006]
The present invention also relates to [2] a polyether resin having a repeating unit of the following formula (2).
[0007]
The present invention also relates to [3] a thermosetting polyether resin having a repeating unit of the following formula (3).
[0008]
Furthermore, the present invention relates to the method for producing a polyether resin according to [1], which includes a condensation reaction step of [4] dihalogenated acetophenone and bisphenols.
Further, the present invention includes [5] a polyether according to [2], which comprises a step of reducing the acetyl group of the polyether resin according to [1] to convert it into a CH 3 CHOH group. The present invention relates to a resin production method.
The present invention also includes [6] the method for producing a polyether resin according to [3], which comprises a step of dehydrating a CH 3 CHOH group of the polyether resin according to [2] and converting it to a vinyl group. It is concerned.
[0009]
Furthermore, the present invention relates to [7] an insulating material using the polyether resin according to any one of [1] to [3].
The present invention also relates to [8] (A) the polyether resin according to any one of [1] to [4], and (B) a coating solution for forming an insulating film comprising an organic solvent as an essential component. is there.
The present invention also relates to [9] an insulating film obtained using the insulating film forming coating solution described in [8].
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in detail.
In the formulas (1) to (3) of the present invention, R 1 to R 11 each independently have a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, or a substituent. A cycloalkyl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms which may have a substituent, an alkynyl group having 2 to 10 carbon atoms which may have a substituent, or a substituent. It may be any of an aromatic ring having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a substituent having a carbonyl group, or a substituent having an alcohol group.
[0011]
Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, and a propyl group.
Examples of the cycloalkyl group having 6 to 10 carbon atoms include a cyclohexyl group and a cycloheptyl group.
Examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, an allyl group, and a propenyl group.
Examples of the alkynyl group having 2 to 10 carbon atoms include ethynyl group and propargyl group.
Examples of the aromatic ring having 6 to 10 carbon atoms that may have a substituent include a phenyl group and a naphthyl group.
A methoxy group, an ethoxy group, etc. are mentioned as a C1-C10 alkoxy group.
Examples of the substituent having a carbonyl group include an acetyl group and the like, and examples of the substituent having an alcohol group include a CH 3 CHOH group.
Here, examples of the substituent that may have a substituent include an alkyl group, an alkenyl group, an alkynyl group, and an aromatic ring.
[0012]
In the formulas (1) to (3) in the present invention, X in the formula represents any of a single bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, and -CO-. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include —CH 2 —, —C (CH 3 ) 2 —, —CH (CH 3 ) —, —C (CH 3 ) (CH 2 CH 3 ). -, -C (CH 3 ) (CH 2 CH (CH 3 ) 2 )-, and the like, and the like,
X is preferably a single bond or the following formula (4). Furthermore, these can also have a substituent.
R 1 to R 11 and X are preferably selected according to the required performance for the polyether. For example, when it is desired to lower the dielectric constant, it is preferable to use bulky substituents that are effective for lowering the dielectric constant for R 1 to R 11 and X. Moreover, when it is desired to improve heat resistance, it is preferable to use a substituent having high heat resistance.
[0014]
The method for producing a polyether resin according to [1] of the present invention includes a condensation reaction step of a dihalogenated acetophenone and a bisphenol.
The dihalogenated acetophenone in the production method of the present invention indicates that the benzene ring is substituted with 2 or more halogen atoms and 1 or more acetyl groups. Specific examples include difluoroacetophenone, dichloroacetophenone, dibromoacetophenone, diiodoacetophenone, difluoromethylacetophenone, dichloromethylacetophenone, dibromomethylacetophenone, and diiodomethylacetophenone (each including various isomers). However, it is not limited to these.
[0015]
The bisphenols in the present invention are not particularly limited as long as they have two phenolic OH groups in one molecule. Specifically, bisphenol A, bisphenol F, biphenol, cyclohexylidene bisphenol, bis (hydroxyphenyl) methanone, (1-methyl-ethylidene) bis [2-cyclohexylphenol], cyclohexylidene bis [2-cyclohexylphenol] Examples are given. It is also possible to use a mixture of two or more of these bisphenols.
[0016]
In the present invention, the condensation reaction of dihalogenated acetophenone and bisphenols can be performed under alkaline conditions. The solvent at this time is not particularly limited, but dimethylformamide, dimethylacetamide, dimethylsulfoxide, benzophenone, and the like are preferably used because of the boiling point and ease of reaction.
[0017]
Moreover, the alkaline substance used in the condensation reaction is not particularly limited, and specific examples include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like. These can be used in the form of a solid or a solution such as an aqueous solution.
[0018]
The condensation reaction is preferably performed under an inert atmosphere such as nitrogen or argon. The reaction temperature is not particularly limited, but is preferably 50 ° C. or higher and lower than 300 ° C., more preferably 100 ° C. or higher and lower than 200 ° C., from the viewpoint of reaction rate.
[0019]
Moreover, the method for producing a polyether resin according to [2] of the present invention includes a step of reducing the acetyl group of the polyether resin according to [1] to convert it to a CH 3 CHOH group. And
In the present invention, the reduction reaction of the acetyl group can be performed by coexisting with a reducing agent in a solvent. The solvent at this time is not particularly limited.
[0020]
The reducing agent used in the reduction reaction is not particularly limited, and specific examples include sodium borohydride, lithium borohydride, zinc borohydride, lithium tributylbutyl borohydride, lithium aluminum hydride and the like. It is done.
[0021]
Moreover, the method for producing a polyether resin according to [3] of the present invention includes a step of dehydrating the CH 3 CHOH group of the polyether resin according to [2] to convert it into a vinyl group. And
In the present invention, the CH 3 CHOH group dehydration reaction is carried out in a solvent. The solvent in this case is not particularly limited. The dehydration reaction can be performed more efficiently by coexisting with a dehydrating agent.
[0022]
Specific examples of the dehydrating agent used in the dehydration reaction include sulfuric acid, phosphoric acid, potassium hydrogen sulfate, oxalic acid, p-toluenesulfonic acid, boron trifluoride ether complex, iodine, and anhydrous copper sulfate.
[0023]
The polyether having a unit structure of the formula (3) in the present invention can be cured by any method. Specifically, it can be cured by an electron beam, light or the like in addition to the method by heating.
[0024]
In addition, the polyether having a unit structure of the formula (2) in the present invention can be dehydrated by heating and cured via a polyether containing a vinyl group.
[0025]
The insulating material of the present invention is characterized by using the polyether resin according to any one of [1] to [3].
Examples of the insulating material using the polyether resin in the present invention include semiconductors such as interlayer insulating films, insulating materials for LCDs, and printed wiring materials such as copper-clad laminates.
[0026]
The coating solution for forming an insulating film of the present invention is characterized in that it comprises (A) the polyether resin according to any one of [1] to [3] and (B) an organic solvent as essential components. The insulating film of the present invention is obtained using the above-described coating liquid for forming an insulating film.
In the present invention, the organic solvent that is an essential component in constituting the coating liquid for forming an insulating film is not particularly limited as long as it is an organic solvent. Specific examples include aliphatic hydrocarbon solvents such as hexane, heptane and cyclohexane; hydrocarbon solvents such as benzene, toluene and xylene; methanol, ethanol, isopropanol, 1-butanol, 2-ethoxymethanol, 2- Alcohol solvents such as ethoxyethanol and 3-methoxypropanol; ketone solvents such as acetylacetone, methyl ethyl ketone, methyl isobutyl ketone, 3-pentanone and 2-heptanone; propyl acetate, butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, lactic acid Ester solvents such as ethyl; ether solvents such as diisopropyl ether, dibutyl ether, and anisole can be used as industrially available solvents. Moreover, other additives, such as surfactant and a silane coupling agent, can also be mixed.
[0027]
According to the present invention, since a polymer containing a vinyl group directly bonded to an aromatic ring is obtained, a polyether resin capable of performing a thermosetting reaction at a relatively low temperature can be obtained.
[0028]
In addition, according to the present invention, a thermosetting polyether resin exhibiting excellent properties such as heat resistance, chemical resistance, and insulation can be obtained by performing a curing reaction by a method such as heating. .
[0029]
Furthermore, according to the present invention, the bisphenol to be used can be appropriately selected. Depending on the degree of freedom of this selection, the required performance is met in terms of heat resistance, dielectric constant, solubility in a solvent before thermosetting, and the like. In the form of a polyether resin.
[0030]
【Example】
In order to describe the present invention in more detail, examples are shown below, but the present invention is not limited thereto.
Example 1
Under a nitrogen stream, 1,2-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexylidene 43.2 g, potassium carbonate 43.2 g, 2 ′, 4′-dichloroacetophenone 18.9 g were placed in a 500 mL four-necked flask. Then, 600 g of dimethyl sulfoxide and 120.0 g of toluene were charged, and the mixture was stirred while keeping at 170 ° C. for 8 hours. The reaction product was added to a methanol / acetic acid solution to cause precipitation. The precipitated crystals were filtered, washed with a large amount of methanol, and dried under reduced pressure to obtain 55.5 g of product. This is called Resin A.
[0031]
Example 2
Example 1 was conducted except that 35.0 g of 4,4 ′-(9H-fluorene-9-ylidene) bisphenol was used instead of 1,1-bis (4-hydroxy-3-cyclohexylphenyl) cyclohexylidene. 55.9 g of product was obtained. This is called Resin B.
[0032]
Example 3
21.3 g of Resin A and 300 g of N, N-dimethylformamide were charged into a 500 mL four-necked flask, and 5.0 g of sodium borohydride was added at room temperature. Stirring was performed at 80 ° C. for 6 hours. The reaction product was added to water and precipitated. The precipitated crystals were filtered, washed with water and dried under reduced pressure to obtain 17.0 g of product. This is called Resin C.
[0033]
Example 4
Resin B (23.3 g) and N, N-dimethylformamide (300 g) were charged into a 500 mL four-necked flask, and sodium borohydride (3.8 g) was added at room temperature. Stirring was performed at 80 ° C. for 6 hours. The reaction product was added to methanol and precipitated. The precipitated crystals were filtered, washed with water and dried under reduced pressure to obtain 20.2 g of product. This is called Resin D.
[0034]
Example 5
The resin C5.1g, toluene 100g, and methylhydroquinone 0.2g were prepared to the 200 mL four necked flask, and it heated up to 120 degreeC. Phosphoric acid (1.2 g) was added, and the mixture was heated and stirred at 120 ° C. for 4 hours. The reaction mass was poured into methanol to precipitate crystals. The amount obtained after drying was 4.6 g. This is called Resin E.
[0035]
Example 6
9.4 g of resin D, 100 g of toluene, 200 g of dimethyl sulfoxide, and 0.6 g of methylhydroquinone were charged into a 200 mL four-necked flask and heated to 120 ° C. Phosphoric acid (1.2 g) was added, and the mixture was heated and stirred at 120 ° C. for 4 hours. The reaction mass was poured into methanol to precipitate crystals. The amount obtained after drying was 4.6 g. This is called Resin F.
[0036]
It was confirmed by proton NMR measurement that a polyether resin having a substituent as shown in Table 1 was obtained. The contents of each resin are summarized in the table below.
[Table 1]
Reference example 1
In a 500 mL four-necked flask, 21.6 g of 1,1-bis (4-hydroxy-cyclohexylphenyl) cyclohexylidene, 4.0 g of caustic soda, 70.0 g of benzophenone and 50.0 g of toluene were charged, and reflux dehydration was performed. After dehydration was complete, 15.6 g of dibromobiphenyl was added. Further, a solution in which 0.05 g of cuprous chloride was dissolved in 5 g of pyridine was added and reacted at an internal temperature of 185 ° C. for 6 hours. After cooling to room temperature, the reaction solution was added to a solution in which 10 g of acetic acid was mixed with 600 g of methanol to precipitate the product. The precipitated crystals were filtered and washed with a large amount of methanol to obtain a polyether resin. This resin is called resin G.
[0038]
Reference example 2
A 300 mL four-necked flask purged with nitrogen was charged with 100 mL of tetrahydrofuran to dissolve 4 g of resin G. After adding 21.5 mL of n-butyllithium (1.6 M, n-hexane solution) and stirring for 1 hour under a nitrogen stream, 4.0 g of allyl bromide was added and further stirring was performed for 1 hour. After completion of the reaction, the reaction solution was added to a mixed solvent of 650 g of methanol and 20 g of acetic acid to precipitate a high molecular weight product. After filtration, washing with methanol and washing with water were performed to obtain a white powdery resin. This resin is referred to as Resin H.
[0039]
Examples 7 and 8, Comparative Example 1
Resins E and F were each dissolved in 2-heptanone so that the solid content was 20% by weight. Resin G was dissolved in anisole so that the solid content was 20% by weight. Each of the prepared solutions was filtered through a 0.2 μm filter, spin-coated on a 4-inch silicon wafer at a rotation speed of 2000 rpm, baked at 150 ° C. for 1 minute, and then heat-treated at 250 ° C. for 40 minutes in a nitrogen atmosphere.
Each coating film was immersed in the solvent used for the coating solution for a minute and examined for solvent resistance. The results are shown in Table 2. The case where there was no change in the film thickness was marked with ○, and the case where the film thickness was reduced was marked with ×.
[Table 2]
【Effect of the invention】
According to the present invention, a polyether resin having a thermosetting functional group is provided by an easy operation, and an insulating material for an electronic device can be obtained using the polyether resin. The insulating material of the present invention has a low dielectric constant and excellent chemical resistance.
Claims (10)
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| JP2002020482A (en) * | 2000-07-05 | 2002-01-23 | Sumitomo Chem Co Ltd | Linear aromatic polymer, its manufacturing method and coating fluid for forming insulating film |
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