JPH0260933A - Fluorinated polyimide and its production - Google Patents
Fluorinated polyimide and its productionInfo
- Publication number
- JPH0260933A JPH0260933A JP21179988A JP21179988A JPH0260933A JP H0260933 A JPH0260933 A JP H0260933A JP 21179988 A JP21179988 A JP 21179988A JP 21179988 A JP21179988 A JP 21179988A JP H0260933 A JPH0260933 A JP H0260933A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- formula
- tables
- 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.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 47
- 239000004642 Polyimide Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000004985 diamines Chemical class 0.000 claims abstract description 8
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 10
- 125000000962 organic group Chemical group 0.000 abstract 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical class C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は、熱膨張係数が小さく、かつ誘電率、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。DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a fluorine-containing polyimide having a small coefficient of thermal expansion, a small dielectric constant, and 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ａ機ポリマーの中でも耐熱性に優
れているため、宇宙、航空分野から電子通信分野まで幅
広く使われ始めている。特に最近では、単に耐熱性に優
れているだけでなく用途に応じて種々の性能を合わせ持
つことが期待されている。例えば、プリント板やＬＳＩ
用の層間絶縁膜などとしては、熱膨張率係数、誘電率が
小さいことが期待され、光通信関係、特に先導波路のク
ラツド材には屈折率が小さいことが期待されている。し
かしながら、これらの性能を充分に満足するポリイミド
は現在のところ得られていない。``Prior Art'' Polyimide has excellent heat resistance among various aerosol polymers, and is therefore beginning to be widely used in fields ranging from space and aviation to electronic communications. Particularly recently, it is expected that they not only have excellent heat resistance but also have various performances depending on the purpose. For example, printed boards and LSI
It is expected that it will have a low coefficient of thermal expansion and dielectric constant for interlayer insulating films, etc., and it is expected that it will have a low refractive index for optical communications, especially cladding materials for guiding waveguides. However, a polyimide that fully satisfies these properties has not yet been obtained.
これらのポリイミドを得るためには、ポリイミドの主鎖
をできる限り剛直構造にして低熱膨張性を発現させ、さ
らにモノマーであるテトラカルボン酸二無水物またはジ
アミンに低誘電率性、低屈折率性を発現する置換基を導
入する方法が考えられる。例えばエポキシ樹脂において
は、ジャーナル オブ ポリマー サイエンス（Ｊ ｏ
ｕｒｎａｌ ｏｆＰ ｏｌｙｍｅｒ Ｓ ｃｉｅｎｃｅ
）のパー）（Ｐａｒｔ ）Ｃ，ポリマー レターズ（
Ｐ ｏｌｙｍｅｒ Ｌ ｅｎｔｅｒｓ ）、第２４巻
、第２４９頁（１９８６）に示されているようにエポキ
シ樹脂の硬化剤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最も低い誘電率を達成
している。また、特開昭６１−４４９６９号公報で示さ
れているように、屈折率においても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最も
低い屈折率を達成している。このようにポリイミド骨格
を剛直構造にし、フッ素置換基を導入することにより、
熱膨張係数、誘電率、屈折率の低減が期待できる。In order to obtain these polyimides, the main chain of the polyimide is made as rigid as possible to exhibit low thermal expansion, and the monomer tetracarboxylic dianhydride or diamine has low dielectric constant and low refractive index properties. One possible method is to introduce a substituent to be expressed. For example, regarding epoxy resins, the Journal of Polymer Science (J o
urnal of polymer science
) (Part ) C, Polymer Letters (
Polymer L Enters), Vol. 24, p. 249 (1986), by introducing polyfluorine substituents into the curing agent of epoxy resins, we achieved the lowest dielectric potential of any epoxy resin to date. rate has been achieved. Furthermore, as shown in Japanese Patent Application Laid-Open No. 61-44969, by introducing polyfluorine substituents, the lowest refractive index of any epoxy resin to date has been achieved. By making the polyimide skeleton into a rigid structure and introducing fluorine substituents in this way,
Reductions in thermal expansion coefficient, dielectric constant, and refractive index can be expected.
「発明が解決しようとする課題」
しかしながら、これまでに剛直構造のポリイミドにフッ
素置換基を導入して、低熱膨張係数、低誘電率、低屈折
率を達成したという報告は、ない。``Problem to be Solved by the Invention'' However, there has been no report to date of achieving a low coefficient of thermal expansion, low dielectric constant, and low refractive index by introducing a fluorine substituent into polyimide having a rigid structure.
本発明の目的は、従来のポリイミドでは有していなかっ
た低熱膨張係数、低誘電率、低屈折率などの優れた特性
を存するポリイミド及びその製造方法を提供することに
ある。An object of the present invention is to provide a polyimide that has excellent properties such as a low coefficient of thermal expansion, a low dielectric constant, and a low refractive index that conventional polyimides do not have, and a method for producing the same.
「課題を解決するための手段」
本発明における請求項１に記載した発明では、下記の化
学構造式［Ｉ１１］で表される含フッ素ポリイミドを提
供することを、また請求項２に記載した発明では、上記
−数式［Ｎで表される酸無水物と、上記−数式〔■］で
表されるジアミンとを反応させて含フッ素ポリイミドを
得ることを上記課題の解決手段とした。"Means for Solving the Problem" The invention described in claim 1 of the present invention provides a fluorine-containing polyimide represented by the following chemical structural formula [I11], and the invention described in claim 2 Now, the solution to the above problem is to obtain a fluorine-containing polyimide by reacting an acid anhydride represented by the above-mentioned formula [N] with a diamine represented by the above-mentioned formula [■].
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
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、ピロメリット酸無水物の側鎖に直鎖状のフ
ルオロアルキル基を導入した含フッ素ピロメリット酸無
水物を用い、さらに剛直構造ジアミンにフルオロアルキ
ル基を導入することにより、誘電率、屈折率、熱膨張係
数とも従来のポリイミドに比較して小さいポリイミドが
得られることを明らかにした。The present inventors conducted various studies on the molecular structure of fluorinated polyimides, and used a fluorinated pyromellitic anhydride in which a linear fluoroalkyl group was introduced into the side chain of pyromellitic anhydride, and further developed a rigid structure diamine. It was revealed that by introducing fluoroalkyl groups into polyimides, polyimides with lower dielectric constant, refractive index, and coefficient of thermal expansion than conventional polyimides can be obtained.
本発明における請求項１に記載の含フッ素ポリイミドに
おいて、式［Ｉ］１１中のＲ１におけるｍの歌は１また
は２とされ、ｎの敗は１〜１０とされる。In the fluorine-containing polyimide according to claim 1 of the present invention, the value of m in R1 in formula [I] 11 is 1 or 2, and the value of n is 1 to 10.
ずなわら、ｍが０であるとフッ素基の電子吸引性が大き
くなって［１コ式で表される酸無水物が不安定となり、
３以上ではフッ素基の効果か低減するからであり、また
、ｎか１１以上であると、撥水効果により基板への濡れ
性が低下するからである。However, if m is 0, the electron-withdrawing property of the fluorine group becomes large, and the acid anhydride represented by the formula 1 becomes unstable,
This is because if n is 3 or more, the effect of the fluorine group will be reduced, and if n is 11 or more, the wettability to the substrate will be reduced due to the water repellent effect.
本発明における請求項２に記載の製造方法においては、
まず、上記［ｒ］式で表される酸無水物と上記［Ｉ］］
式で表されるジアミンとの反応からポリアミド酸を製造
する。このときの配合割合としては酸無水物１モルに対
しジアミン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ド酸の重合条
件と同じでよく、一般的にはＮ−メチル−２−ピロリド
ン、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有機溶剤中で反応させる。In the manufacturing method according to claim 2 of the present invention,
First, the acid anhydride represented by the above [r] formula and the above [I]]
A polyamic acid is produced from the reaction with a diamine represented by the formula. The best blending ratio at this time is 1 mol of diamine per 1 mol of acid anhydride, but it 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 the reaction is generally carried out in an organic solvent such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, or N,N-dimethylformamide.
次に、得られたポリアミド酸のイミド化によるポリイミ
ドの合成であるが、これら通常のポリイミドの合成法り
（使用できる。Next, polyimide is synthesized by imidization of the obtained polyamic acid, and these ordinary polyimide synthesis methods can be used.
「実施例」
以下、実施例により本発明の含）・ソ索ポリイミド支び
その製造方法について具体的に説明する７′ｌ（、本発
明はこれら実施例に限定されるものではな０゜なお、下
記実施例において、誘電率は１ｋｌ−Ｔｚでの値てあり
、屈折率はナトリウムＤ線の波長（５８９６人）での値
である。また、熱膨張係数は、下３己の条件で熱処理し
たフィルムを執機械試験機に取り付けて５°Ｃ／分の条
件で窒素雰囲餓中室温からガラス転位温度の間の昇温を
操り返し行い、フィルムの吸湿水分、イミド化反応等に
よる残留歪みの影響を十分取り除き、再現性のある値を
求めｆ二。``Example'' Hereinafter, the present invention will be described in detail with reference to Examples. In the examples below, the dielectric constant is the value at 1kl-Tz, and the refractive index is the value at the wavelength of the sodium D line (5896 people).In addition, the thermal expansion coefficient is the value at 1 kl-Tz. The film was attached to a mechanical testing machine and the temperature was repeatedly raised from room temperature to the glass transition temperature in a nitrogen atmosphere at a rate of 5°C/min to check for residual distortion due to hygroscopic moisture in the film, imidization reaction, etc. Sufficiently remove the influence and find a reproducible value f2.
（実施例１）
三角フラスコにノ（２，２，２−トリフルオロエチル）
ピロメリット酸無水物１２．７３ｇ、２，２゜ヒス（ト
リフルオロメチル）−４，４°−ジアミノビフェニル７
．６３ｇ、Ｎ−メチル−２−ピロリドン（ＮＭＰ ）ｌ
Ｉ ５ｇを加えた。この混合物を窒素雰囲気下、室温
で３日間撹拌し、ポリアミド酸のＮＭＰ溶液（粘度・６
５ポアズ）を得た。このものをアルミ板」二に流し、ド
クターブレードで毛坦にした後、＋００°Ｃで１時間、
２００°Ｃで１時間、３５０℃で１時間、さらに４００
℃で加熱キュアした。このアルミ板を１０％ｌ−Ｉ Ｃ
Ｑ水溶液に浸し、アルミ板を溶解して強靭なポリイミド
フィルムを得た。(Example 1) Add (2,2,2-trifluoroethyl) to an Erlenmeyer flask.
12.73 g of pyromellitic anhydride, 2,2° his(trifluoromethyl)-4,4°-diaminobiphenyl 7
．． 63g, N-methyl-2-pyrrolidone (NMP)
5g of I was added. This mixture was stirred at room temperature under a nitrogen atmosphere for 3 days, and the NMP solution of polyamic acid (viscosity: 6.
5 poise) was obtained. Pour this material onto an aluminum plate, smooth it with a doctor blade, and heat it at +00°C for 1 hour.
1 hour at 200°C, 1 hour at 350°C, then 400°C
It was heated and cured at ℃. This aluminum plate is 10% l-I C
The aluminum plate was immersed in Q aqueous solution and dissolved to obtain a tough polyimide film.
得られたポリイミドフィルムの物性を調べたところ、誘
電率が２６、屈折率か１，５２４、熱膨張係数が９ Ｘ
Ｉ ０−１ｌ（’Ｃ”−’）であった。When the physical properties of the obtained polyimide film were examined, the dielectric constant was 26, the refractive index was 1,524, and the thermal expansion coefficient was 9.
I0-11 ('C''-').
（実施例２ ）
実施例１と同様の方法を用い、ノ（２，２，２トリフル
オロエチル）ピロメリット酸無水物とベラフエニルジア
ミンを等モルずつ用いることによって強靭なポリイミド
フィルムを得た。(Example 2) A tough polyimide film was obtained by using the same method as in Example 1 and using equal moles of no(2,2,2-trifluoroethyl)pyromellitic anhydride and veraphenyldiamine. .
得られたポリイミドフィルムの物性を調べたところ、誘
電率が２９、屈折率か１５９４、熱膨張係数が６ Ｘ
Ｊ Ｏ−″（’Ｃ””’）であった。When the physical properties of the obtained polyimide film were examined, the dielectric constant was 29, the refractive index was 1594, and the thermal expansion coefficient was 6X.
J O-''('C'''').
（実施例３ ）
実施例１と同様の方法を用い、２，２．２川・リフルオ
ロエチルピロメリット酸無水物と２．２°−ヒス（＋−
リフルオロメチル）−４，４’−ジアミノビフェニルを
等モルずつ用いることによって強靭なポリイミドフィル
ムを得ｆ二。(Example 3) Using the same method as in Example 1, 2,2.2 fluoroethylpyromellitic anhydride and 2.2°-His(+-
A strong polyimide film was obtained by using equimolar amounts of (4,4'-diaminobiphenyl).
得られたポリイミドフィルムの物性を凋へたところ、誘
電率が２７、屈折率力１５４８、熱膨張（糸数か６ ｘ
ｌ Ｏ−”（’Ｃ−’）てあった。When the physical properties of the obtained polyimide film decreased, the dielectric constant was 27, the refractive index power was 1548, and the thermal expansion (the number of threads was 6 x
1 O-"('C-').
（実施例・１ ）
実施例１と同様の方法を用い、ノ（Ｉ ｔｌ、ｌ Ｈパ
ーフルオロブチル）ピロメリット酸無水物と３３゛−ヒ
ス（トリフルオロメチル）−４，４−ノアミノビフェニ
ルを等モルずつ用いることによって強靭なポリイミドフ
ィルムを得た。(Example 1) Using the same method as in Example 1, no(Itl,lH perfluorobutyl)pyromellitic anhydride and 33'-his(trifluoromethyl)-4,4-noaminobiphenyl were prepared. A tough polyimide film was obtained by using equimolar amounts of .
得られたポリイミドフィルムの物性を調べたところ、誘
電率が２．５、屈折率力＜ｒ、−１７２、熱膨張係数が
１ 、７ Ｘ ｌ ０−５（’Ｃ−’）であった。When the physical properties of the obtained polyimide film were examined, the dielectric constant was 2.5, the refractive index power <r, -172, and the thermal expansion coefficient was 1.7 X l 0-5 ('C-').
（実施例５ ） 実施例１と同様の方法を用い、ノ（１１−１，１１（。(Example 5) Using the same method as in Example 1, ノ(11-1,11(.
２１−＋ ２ ｌ−１−パーフルオロオクチル）ピロ
メリット酸無水物と０−トリノンを等モルずつ用いるこ
とによって強靭なポリイミドフィルムを得た。A tough polyimide film was obtained by using equimolar amounts of 21-+2 l-1-perfluorooctyl)pyromellitic anhydride and 0-trinon.
得られたポリイミドフィルムの物性を調べたところ、誘
電率が２５、屈折率が１４６３、熱膨張係数が２ 、３
Ｘ ｌ ０−５（’Ｃ−’）であった。When the physical properties of the obtained polyimide film were investigated, the dielectric constant was 25, the refractive index was 1463, and the thermal expansion coefficient was 2.3.
It was X 1 0-5 ('C-').
（実施例６ ）
実施例１と同様の方法を用い、ｌ Ｉ−１、Ｉ ！−（
、２Ｈ２［−１−パーフルオロドデノルビロメリソト酸
無水物と４．４−ノアミノターフェニルを等モルずつ用
いることによって強靭なボリイミｌ’フィル１、を得た
。(Example 6) Using the same method as in Example 1, l I-1, I! −(
, 2H2[-1-perfluorododenorbiromellisotonic anhydride and 4,4-noaminoterphenyl were used in equal moles to obtain a tough polyimyl' fill 1.
得られたポリイミドフィルムの物性を調べたところ、誘
電率が２．９、屈折率が１４９５、熱膨張係数が３．３
Ｘ Ｉ ０−５（０Ｃ−’）であった。When the physical properties of the obtained polyimide film were examined, the dielectric constant was 2.9, the refractive index was 1495, and the thermal expansion coefficient was 3.3.
X I 0-5 (0C-').
（実施例７ ）
実施例１と同様の方法を用い、ノ（Ｉ Ｈ，ｌ Ｉ［パ
ーフルオロブチル）ピロメリット酸無水物と２゜５−ノ
アミノトルエン２．５−ンアミノヘンゾトリフルオライ
ドを等モルずつ用いることによって強靭なポリイミドフ
ィルムを得た。(Example 7) Using the same method as in Example 1, (IH,lI[perfluorobutyl)pyromellitic anhydride and 2.5-noaminotoluene-2.5-aminohenzotrifluoride were prepared. A tough polyimide film was obtained by using equimolar amounts.
得られたポリイミドフィルムの物性を調べたところ、誘
電率が２，６、屈折率が１．４９５、熱膨張係数が９
ｘ ｌ Ｏ”−’（’Ｃ−’）であった。When the physical properties of the obtained polyimide film were examined, the dielectric constant was 2.6, the refractive index was 1.495, and the thermal expansion coefficient was 9.
x l O"-'('C-').
（実施例８ ）
実施例１と同様の方法を用い、ジ（２，２，２トリフル
オロエチル）ピロメリット酸無水物と２゜５−ジアミノ
ベンシトリフルオライドを等モルずつ用いることによっ
て強靭なポリイミドフィルムを得た。(Example 8) Using the same method as in Example 1, a tough polyimide was produced by using equimolar amounts of di(2,2,2-trifluoroethyl)pyromellitic anhydride and 2°5-diaminobencytrifluoride. Got the film.
得られたポリイミドフィルムの物性を調べたところ、誘
電率が２．６、類１折率かｌ ５３６、熱膨張係数が９
Ｘ Ｊ Ｏ−１］（’Ｃ−’）であった。When the physical properties of the obtained polyimide film were examined, the dielectric constant was 2.6, the refractive index was 536, and the coefficient of thermal expansion was 9.
X J O-1] ('C-').
（比較例）
比較例として、先の実施例１と同様の方法により、ピロ
メリット酸無水物と４．４゛ノアミノジフエニルエーテ
ルを等モルずつ用いて市販ポリイミド（商品名：カブト
ン）と同等のポリイミドフィルムを得た。(Comparative example) As a comparative example, the same mole of pyromellitic anhydride and 4.4''noamino diphenyl ether was used in the same manner as in Example 1 to prepare a polyimide equivalent to that of a commercially available polyimide (trade name: Kabuton). A polyimide film was obtained.
屈折率か１７８４、熱膨張係数が４．ＩｘｌＯ−５（’
Ｃ−’）てあっｆこ。The refractive index is 1784, and the thermal expansion coefficient is 4. IxlO-5('
C-') Teaa fko.
これらの結果から、本発明の含フッ素ポリイミドは、従
来のらのと比較して低誘電率、低屈折率かつ低熱膨張係
数を有していることが明らかとなった。These results revealed that the fluorine-containing polyimide of the present invention has a lower dielectric constant, a lower refractive index, and a lower coefficient of thermal expansion than the conventional fluorine-containing polyimide.
「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、
従来のピロメリット酸無水物を用いたポリイミドに比較
して低誘電率、低屈折率かつ低熱膨弓良Ｇ名数となる１
１１点を荷しているので、プリント板、Ｉ、ｓＩ用の層
間絶縁膜、先導波路用財料等への適用か可能となる。"Effects of the Invention" As explained above, the fluorine-containing polyimide of the present invention has
Compared to conventional polyimide using pyromellitic anhydride, it has a lower dielectric constant, lower refractive index, and lower thermal expansion.
Since it has 11 points, it can be applied to printed boards, interlayer insulating films for I and sI, materials for guiding waveguides, etc.
出願人 日本電信：１話株式会社Applicant: Nippon Telegraph: Chapter 1 Co., Ltd.
Claims (2)
価の有機基であり、［ただしｍは１または２、ｎは１〜
１０の数を表す］ ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼ Ｒ＿２は以下の化学構造式からなる群より選ばれた二価
の基を表す ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、▲数式、化学式、表等があります▼ ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、▲数式、化学式、表等があります▼
） で示される繰り返し単位を有する含フッ素ポリイミド。(1) Formula ▲ Numerical formula, chemical formula, table, etc.
Represents the number 10] ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ R_2 represents a divalent group selected from the group consisting of the following chemical structural formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
) A fluorine-containing polyimide having a repeating unit represented by:
一般式［II］で表されるジアミンとを反応させて請求項
１に記載した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。 ▲数式、化学式、表等があります▼・・・［ I ］ Ｈ＿２Ｎ−Ｒ＿２−ＮＨ＿２・・・［II］ （式中のＲ＿１、Ｒ＿２はそれぞれ請求項１に記載した
Ｒ＿１、Ｒ＿２と同一とする。）(2) The fluorine-containing polyimide described in claim 1 is obtained by reacting an acid anhydride represented by the following general formula [I] with a diamine represented by the following general formula [II]. A method for producing fluorine-containing polyimide. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] H_2N-R_2-NH_2...[II] (R_1 and R_2 in the formula are the same as R_1 and R_2 described in claim 1, respectively. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21179988A JP2744969B2 (en) | 1988-08-26 | 1988-08-26 | Fluorine-containing polyimide and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21179988A JP2744969B2 (en) | 1988-08-26 | 1988-08-26 | Fluorine-containing polyimide and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0260933A true JPH0260933A (en) | 1990-03-01 |
| JP2744969B2 JP2744969B2 (en) | 1998-04-28 |
Family
ID=16611800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21179988A Expired - Lifetime JP2744969B2 (en) | 1988-08-26 | 1988-08-26 | Fluorine-containing polyimide and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2744969B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0454590A2 (en) * | 1990-04-27 | 1991-10-30 | Nippon Telegraph And Telephone Corporation | Polyimide optical waveguide |
| US5145999A (en) * | 1991-04-04 | 1992-09-08 | E. I. Du Pont De Nemours And Company | Perfluoroalkylated amines, and polymers made therefrom |
| US5177179A (en) * | 1991-04-04 | 1993-01-05 | E. I. Du Pont De Nemours And Company | Perfluoroalkylated diaminomesitylene and polyimides therefrom |
| US5260408A (en) * | 1991-10-29 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Low thermal expansion coefficient polyimides with improved elongation |
| US5324813A (en) * | 1992-07-22 | 1994-06-28 | International Business Machines Corporation | Low dielectric constant fluorinated polymers and methods of fabrication thereof |
| US5354839A (en) * | 1992-04-07 | 1994-10-11 | Mitsui Toatsu Chemicals, Incorporated | Polyimide and preparation process of same |
| US5470943A (en) * | 1994-01-07 | 1995-11-28 | Mitsui Toatsu Chemicals, Inc. | Polyimide |
| JP2003064182A (en) * | 2001-08-28 | 2003-03-05 | Hitachi Chem Co Ltd | Polyimide resin for optical part and optical part using the same |
| JPWO2007080801A1 (en) * | 2006-01-11 | 2009-06-11 | 出光興産株式会社 | Novel imide derivative, material for organic electroluminescence device and organic electroluminescence device using the same |
-
1988
- 1988-08-26 JP JP21179988A patent/JP2744969B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0454590A2 (en) * | 1990-04-27 | 1991-10-30 | Nippon Telegraph And Telephone Corporation | Polyimide optical waveguide |
| US5145999A (en) * | 1991-04-04 | 1992-09-08 | E. I. Du Pont De Nemours And Company | Perfluoroalkylated amines, and polymers made therefrom |
| US5177179A (en) * | 1991-04-04 | 1993-01-05 | E. I. Du Pont De Nemours And Company | Perfluoroalkylated diaminomesitylene and polyimides therefrom |
| US5280103A (en) * | 1991-04-04 | 1994-01-18 | E. I. Du Pont De Nemours And Company | Perfluoroalkylated amines, and polymers made therefrom |
| US5260408A (en) * | 1991-10-29 | 1993-11-09 | E. I. Du Pont De Nemours And Company | Low thermal expansion coefficient polyimides with improved elongation |
| US5354839A (en) * | 1992-04-07 | 1994-10-11 | Mitsui Toatsu Chemicals, Incorporated | Polyimide and preparation process of same |
| US5324813A (en) * | 1992-07-22 | 1994-06-28 | International Business Machines Corporation | Low dielectric constant fluorinated polymers and methods of fabrication thereof |
| US5470943A (en) * | 1994-01-07 | 1995-11-28 | Mitsui Toatsu Chemicals, Inc. | Polyimide |
| JP2003064182A (en) * | 2001-08-28 | 2003-03-05 | Hitachi Chem Co Ltd | Polyimide resin for optical part and optical part using the same |
| JPWO2007080801A1 (en) * | 2006-01-11 | 2009-06-11 | 出光興産株式会社 | Novel imide derivative, material for organic electroluminescence device and organic electroluminescence device using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2744969B2 (en) | 1998-04-28 |
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