JP2694009B2 - Fluorine-containing polyimide and method for producing the same - Google Patents
Fluorine-containing polyimide and method for producing the sameInfo
- Publication number
- JP2694009B2 JP2694009B2 JP10238189A JP10238189A JP2694009B2 JP 2694009 B2 JP2694009 B2 JP 2694009B2 JP 10238189 A JP10238189 A JP 10238189A JP 10238189 A JP10238189 A JP 10238189A JP 2694009 B2 JP2694009 B2 JP 2694009B2
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- polyimide
- formula
- containing polyimide
- refractive index
- 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.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は、屈折率の小さい含フッ素ポリイミド及びそ
の製造方法に関する。TECHNICAL FIELD The present invention relates to a fluorine-containing polyimide having a small refractive index and a method for producing the same.
「従来の技術」 ポリイミドは、種々の有機ポリマーの中で最も耐熱性
に優れているため、航空・宇宙分野から電子産業分野ま
で幅広く使われている。特に最近では、単に耐熱性が優
れているだけでなく、各種の用途に応じて種々の性能を
併せ持つことが期待されている。そしてポリイミドの種
々の用途の一つとして光部品においては、光フアイバー
等の石英ガラス（屈折率＝1.46）部品とコンポーネント
を組み立てる際に、光損失を低減させるためにポリイミ
ドの屈折率を低減させることが望まれている。しかし、
これらの性能を十分に満足するポリイミドは現在得られ
ていない。“Conventional Technology” Polyimide has the highest heat resistance among various organic polymers, and is widely used in the fields of aerospace and electronics as well as in the electronics industry. In particular, recently, it is expected that not only the heat resistance will be excellent, but also various performances will be combined depending on various uses. And as one of various uses of polyimide, in optical parts, when assembling components such as optical fiber and quartz glass (refractive index = 1.46) parts and components, reduce the refractive index of polyimide to reduce optical loss. Is desired. But,
At present, no polyimide has been obtained that fully satisfies these performances.
これらのポリイミドを得るためには、ポリイミドに低
屈折性の置換基を導入する方法が提案されている。一つ
の例として、電子分極が小さいフッ素原子の導入が考え
られる。特開昭61−44969号公報で示されているよう
に、多フッ素置換基を導入することにより、これまでの
エポキシ樹脂の中でも最も低い屈折率を達成している。
このようにポリイミドにフッ素原子を導入することによ
り、ポリイミドの屈折率を低減することが期待できる。In order to obtain these polyimides, a method of introducing a low refractive index substituent into the polyimide has been proposed. As one example, introduction of a fluorine atom having a small electronic polarization can be considered. As shown in Japanese Patent Application Laid-Open No. 61-44969, the introduction of a polyfluorine substituent achieves the lowest refractive index of the epoxy resins so far.
Introducing fluorine atoms into the polyimide in this way can be expected to reduce the refractive index of the polyimide.
「発明が解決しようとする課題」 本発明の目的はポリイミドの屈折率を低減し、屈折率
の低いポリイミド及びその製造方法を提供することにあ
る。[Problems to be Solved by the Invention] An object of the present invention is to provide a polyimide having a low refractive index and a low refractive index, and a method for producing the same.
「課題を解決するための手段」 本発明を概説すれば、請求項１に記載した発明は、下
記一般式（Ｉ） （式中Ｘは下記の化学構造式 から選ばれる１種の基を示す。） で表される繰り返し単位からなることを特徴とする含フ
ッ素ポリイミドである。"Means for Solving the Problems" If the present invention is outlined, the invention described in claim 1 has the following general formula (I): (Where X is the following chemical structural formula 1 group selected from is shown. ) A fluorine-containing polyimide comprising a repeating unit represented by:
また、請求項２に記載した発明は、下記一般式（II） （式中Ｘは下記の化学構造式 から選ばれる１種の基を示す。） で表わされる酸無水物と、下記化学構造式（III） で表わされるジアミンと反応させて、下記一般式（Ｉ） （式中Ｘは上記一般式（II）と同一である。） で表される繰り返し単位からなる含フッ素ポリイミドを
得ることを特徴とする含フッ素ポリイミドの製造方法で
ある。Further, the invention described in claim 2 is the following general formula (II) (Where X is the following chemical structural formula 1 group selected from is shown. ) An acid anhydride represented by the following chemical formula (III) By reacting with a diamine represented by the following general formula (I) (In the formula, X is the same as the above general formula (II).) A method for producing a fluorine-containing polyimide, which comprises obtaining a fluorine-containing polyimide comprising a repeating unit represented by the following formula.
本発明者らは、フッ素化ポリイミドの分子構造につい
て種々検討した結果、側鎖にフッ素を20個含有する有機
基をエーテル基を介して導入したIII式の含フッ素ジア
ミンを用いてポリイミドを合成することにより屈折率1.
525以下（石英ガラス−ポリイミド光部品を製造する際
の低損失化の目安）を達成できることが明らかになっ
た。As a result of various studies on the molecular structure of the fluorinated polyimide, the present inventors synthesize a polyimide using a fluorine-containing diamine of the formula III in which an organic group containing 20 fluorines in the side chain is introduced via an ether group. The refractive index is 1.
It has been clarified that 525 or less (a guide for lowering loss when manufacturing a quartz glass-polyimide optical component) can be achieved.
本発明に使用できる酸無水物としては、上記のII式で
示されるもの、及びそれらの混合物は全て使用すること
ができる。As the acid anhydride that can be used in the present invention, all of those represented by the above formula II and mixtures thereof can be used.
本発明においては、まずIII式で示される含フッ素芳
香族ジアミンとII式で表される酸無水物の反応からポリ
アミック酸を製造する。この時の配合割合はジアミン１
モルに対して酸無水物１モルが最もよいが、0.9〜1.1モ
ルの範囲でもよい。反応条件は通常のポリアミック酸の
重合条件と同じでよく、一般的には、Ｎ−メチル−ピロ
リドン（NMP）、N,N−ジメチルアセトアミド、N,N−ジ
メチルホルムアミドなどの非プロトン性極性溶媒中で反
応させる。In the present invention, first, a polyamic acid is produced by reacting a fluorine-containing aromatic diamine represented by the formula III with an acid anhydride represented by the formula II. The compounding ratio at this time is diamine 1
The acid anhydride is most preferably 1 mol per mol, but may be in the range of 0.9 to 1.1 mol. The reaction conditions may be the same as those for ordinary polyamic acid polymerization, and generally, in an aprotic polar solvent such as N-methyl-pyrrolidone (NMP), N, N-dimethylacetamide, N, N-dimethylformamide. React with.
次に、得られたポリアミック酸のイミド化によるポリ
イミドの合成であるが、これも通常のポリイミドの合成
法が使用できる。例えば、得られたポリアミック酸を20
0℃以上に加熱すればよい。Next, regarding the synthesis of polyimide by imidization of the obtained polyamic acid, a usual polyimide synthesis method can be used. For example, the obtained polyamic acid is added to 20
It may be heated to 0 ° C or higher.
「実施例」 以下実施例により本発明の含フッ素ポリイミド及びそ
の製造方法について詳細に説明するが、本発明はこれら
の実施例に限定されない。"Examples" Hereinafter, the fluorine-containing polyimide of the present invention and the method for producing the same will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
（実施例１） フラスコに４−（1H,1H,11H−エイコサフルオロウン
デカノキシ）−1,3−ジアミノベンゼン13.684gをNMP79.
96g中に溶解した後、ビフェニルテトラカルボン酸二無
水物6.307gを加えた。この混合物を窒素雰囲気下、室温
で３日間かくはんし、ポリアミック酸のNMP溶液を得
た。この溶液の一部をガラス製のフラットシャーレに流
し、100℃で１時間、200℃で１時間、350℃で１時間加
熱した結果150μｍの含フッ素ポリイミドフィルムを得
た。後記第１表に示すようにこのポリイミドの20℃、58
9nmにおける屈折率は1.523であった。(Example 1) 13.684 g of 4- (1H, 1H, 11H-eicosafluoroundecanoxy) -1,3-diaminobenzene was added to a flask in a NMP79.
After dissolving in 96 g, 6.307 g of biphenyltetracarboxylic dianhydride was added. This mixture was stirred at room temperature for 3 days under a nitrogen atmosphere to obtain an NMP solution of polyamic acid. A part of this solution was poured into a flat dish made of glass and heated at 100 ° C. for 1 hour, 200 ° C. for 1 hour, and 350 ° C. for 1 hour. As a result, a 150 μm fluorine-containing polyimide film was obtained. As shown in Table 1 below, this polyimide has a temperature of
The refractive index at 9 nm was 1.523.
（比較例１） 実施例１の４−（1H,1H,11H−エイコサフルオロウン
デカノキシ）−1,3−ジアミノベンゼンの代わりにｍ−
フェニレンジアミンを用いて同様の操作を行ない、ポリ
イミドフィルムを得た。後記第１表に示すように、この
ポリイミドの20℃、589nmにおける屈折率は1.720であっ
た。Comparative Example 1 4- (1H, 1H, 11H-eicosafluoroundecanoxy) -1,3-diaminobenzene of Example 1 was replaced with m-
The same operation was performed using phenylenediamine to obtain a polyimide film. As shown in Table 1 below, the refractive index of this polyimide at 20 ° C. and 589 nm was 1.720.
これらの結果は、本発明の含フッ素ポリイミドが従来
のポリイミドに比較して、低い屈折率を有することを示
している。These results show that the fluorine-containing polyimide of the present invention has a lower refractive index than the conventional polyimide.
（実施例２〜６） 実施例１と同様の方法を用いて、種々のジアミンと酸
無水物を用いることにより、含フッ素ポリイミドフィル
ムを得た。第１表に用いたジアミン、酸無水物の化学構
造と含フッ素ポリイミドの20℃、589nmにおける屈折率
を示す。(Examples 2 to 6) Using the same method as in Example 1, various diamines and acid anhydrides were used to obtain fluorine-containing polyimide films. Table 1 shows the chemical structures of the diamine and acid anhydride used and the refractive index of the fluorine-containing polyimide at 20 ° C. and 589 nm.
これらの結果からも本発明の含フッ素ポリイミドは、
従来のポリイミドと比較して屈折率が低く、1.525以下
の値を示すことが明らかである。The fluorine-containing polyimide of the present invention also from these results,
It is clear that the refractive index is lower than that of the conventional polyimide and shows a value of 1.525 or less.
「発明の効果」 以上説明したように、本発明の含フッ素ポリイミド
は、屈折率が1.525以下であるため、光部品に適用した
場合、その性能を向上させる利点がある。 [Advantages of the Invention] As described above, since the fluorine-containing polyimide of the present invention has a refractive index of 1.525 or less, it has an advantage of improving its performance when applied to an optical component.
Claims (2)
ッ素ポリイミド。1. A compound represented by the following general formula (I) (Where X is the following chemical structural formula 1 group selected from is shown. ) A fluorine-containing polyimide comprising a repeating unit represented by:
得ることを特徴とする含フッ素ポリイミドの製造方法。2. The following general formula (II) (Where X is the following chemical structural formula 1 group selected from is shown. ) An acid anhydride represented by the following chemical structural formula (III) By reacting with a diamine represented by the following general formula (I) (In the formula, X is the same as the above general formula (II).) A method for producing a fluorine-containing polyimide, which comprises obtaining a fluorine-containing polyimide comprising a repeating unit represented by the following formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10238189A JP2694009B2 (en) | 1989-04-21 | 1989-04-21 | Fluorine-containing polyimide and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10238189A JP2694009B2 (en) | 1989-04-21 | 1989-04-21 | Fluorine-containing polyimide and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02281038A JPH02281038A (en) | 1990-11-16 |
| JP2694009B2 true JP2694009B2 (en) | 1997-12-24 |
Family
ID=14325877
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10238189A Expired - Lifetime JP2694009B2 (en) | 1989-04-21 | 1989-04-21 | Fluorine-containing polyimide and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2694009B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH047333A (en) * | 1990-04-25 | 1992-01-10 | Japan Carlit Co Ltd:The | New polyimide |
-
1989
- 1989-04-21 JP JP10238189A patent/JP2694009B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02281038A (en) | 1990-11-16 |
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