JPH0249029A - Fluorine-containing polyimide and production thereof - Google Patents
Fluorine-containing polyimide and production thereofInfo
- Publication number
- JPH0249029A JPH0249029A JP20057988A JP20057988A JPH0249029A JP H0249029 A JPH0249029 A JP H0249029A JP 20057988 A JP20057988 A JP 20057988A JP 20057988 A JP20057988 A JP 20057988A JP H0249029 A JPH0249029 A JP H0249029A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- formula
- fluorine
- tables
- chemical
- 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 32
- 239000004642 Polyimide Substances 0.000 title claims abstract description 28
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 12
- 239000011737 fluorine Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000004985 diamines Chemical class 0.000 claims abstract description 7
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 4
- 125000000962 organic group Chemical group 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 13
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 abstract 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 abstract 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 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 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 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
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
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、種々の有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、特に光導波路のク
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 organic polymers, so it is beginning to be used in a wide range of fields from space and aviation to electronic communication fields. 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 to have a low coefficient of thermal expansion and dielectric constant for interlayer insulating films for industrial use, and it is expected to have a low refractive index for cladding materials for optical communications, especially optical 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、ざ
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 □
ｕｒｎａｌ ｏｆＰ ｏｌｙｍｅｒ Ｓ ｃｉｅｎｃｅ
）のパート（Ｐａｒｔ ）Ｃ，ポリマー レターズ（
Ｐ ｏｌｙｍｅｒ Ｌ ｅｔｔｅｒｓ ）、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 must be made as rigid as possible to exhibit low thermal expansion, and the monomer tetracarboxylic dianhydride or diamine must have low permittivity and low refractive index. One possible method is to introduce a substituent that expresses For example, for epoxy resins, the Journal of Polymer Science (J □
urnal of polymer science
) Part C, Polymer Letters (
Polymer Letters), 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
を有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 having excellent properties such as a low coefficient of thermal expansion, a low dielectric constant, and a low refractive index that conventional polyimides did 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
一般式［Ｉ］で表される酸無水物と、上記一般式［１１
］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 acid anhydride represented by the above general formula [I] and the above general formula [11]
] The solution to the above problem was to obtain a fluorine-containing polyimide by reacting with a diamine represented by the following.
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.
本発明においては、まず、上記［Ｉ］式で示される酸無
水物と上記［１１式で示されるジアミンとの反応からポ
リアミド酸を製造する。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、−船釣には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 present invention, first, a polyamic acid is produced by reacting an acid anhydride represented by the above formula [I] with a diamine represented by the above formula [11]. The reaction conditions may be the same as those for ordinary polyamic acid polymerization;
pyrrolidone, N,N-dimethylacetamide, N,N-
React in an organic solvent such as 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、これも通常のポリイミドの合成法が
使用できる。Next, polyimide is synthesized by imidizing the obtained polyamic acid, and a conventional polyimide synthesis method can also be used for this.
「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具体的に説明するが、本発明はこれ
ら実施例に限定されるものではない。"Examples" Hereinafter, the fluorine-containing polyimide of the present invention and the method for producing the same will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.
なお、下記実施例において、誘電率は１ｋＨｚでの値で
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、下記の条件で熱処理
したフィルムを熱機械試験機に取り付けて５℃／分の条
件で窒素雰囲気中室温からガラス転位温度の間の昇温を
繰り返し行い、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
求めた。In the following examples, the dielectric constant is a value at 1 kHz, and the refractive index is a value at the wavelength of the sodium D line (5896 people). The coefficient of thermal expansion was determined by attaching the film heat-treated under the following conditions to a thermomechanical testing machine and repeatedly raising the temperature from room temperature to the glass transition temperature in a nitrogen atmosphere at 5°C/min. , the effects of residual distortion due to imidization reactions, etc. were sufficiently removed to obtain reproducible values.
（実施例１）
三角フラスコに３．６−ジ（３，５−ジトリフルオロメ
チルフェノキシ）ピロメリット酸無水物１３゜４８９
（２０，０ｍｍｏｌ）、ｏ−トリジン４．２４９（２０
゜ＯＩＩｌｍｏｌ）、Ｎ−メチル−２−ピロリドン（Ｎ
ＭＰ）１００ｇ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
＝５８ポアズ）を得た。このものをアルミ板上に流し、
ドクターブレードで平坦にした後、１００℃で１時間、
２００℃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％ｔ−ｔ ｃ
ｘ水溶液に浸し、アルミ板を溶解してポリイミドフィル
ムを得た。(Example 1) 3,6-di(3,5-ditrifluoromethylphenoxy)pyromellitic anhydride 13°489 in an Erlenmeyer flask
(20,0 mmol), o-tolidine 4.249 (20
゜OIIlmol), N-methyl-2-pyrrolidone (N
MP) 100g was added. This mixture was mixed under a nitrogen atmosphere.
The mixture was stirred at room temperature for 3 days to obtain an NMP solution of polyamic acid (viscosity = 58 poise). Pour this onto an aluminum plate,
After flattening with a doctor blade, heat at 100℃ for 1 hour.
200℃ for 1 hour, 350℃ for 1 hour, then 400℃
It was heated and cured. This aluminum plate is 10%t-tc
A polyimide film was obtained by dipping the aluminum plate in x aqueous solution and dissolving the aluminum plate.
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３，１、屈折率が１．６３９、熱膨張係数が９
ｘ １０−”（’Ｃ″″′）であった。When the physical properties of the obtained polyimide film were examined, the dielectric constant was 3.1, the refractive index was 1.639, and the thermal expansion coefficient was 9.
x 10-''('C''''').
（実施例２〜６ ）
実施例１と同様の方法を用いて、異なる組成のポリイミ
ドフィルム５種類を得た。これらの誘電率、屈折率及び
熱膨張係数をそれぞれに測定し、第１表に示した。(Examples 2 to 6) Using the same method as in Example 1, five types of polyimide films with different compositions were obtained. The dielectric constant, refractive index, and coefficient of thermal expansion of these were measured and shown in Table 1.
なお、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゛ジアミノジフエニル
エーテルを等モルずつ用いて重板ポリイミド（商品名：
カプトン）と同等のポリイミドフィルムを得、このもの
の誘電率、屈折率、熱膨張係数を測定して第１表に示し
た。As a comparative example, heavy plate polyimide (trade name:
A polyimide film equivalent to Kapton) was obtained, and the dielectric constant, refractive index, and coefficient of thermal expansion of this film were measured and shown in Table 1.
以下余白
これらの結果より、本発明の含フッ素ポリイミドは、従
来のものと比較して低誘電率、低屈折率かつ低熱膨張係
数を存していることが明らかとなりノこ。From these results, it is clear that the fluorine-containing polyimide of the present invention has a lower dielectric constant, lower refractive index, and lower coefficient of thermal expansion than conventional ones.
「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張係数となる利点を
有しているので、プリント板、１．、 Ｓ Ｉ用の層間
絶縁膜、光導波路用材料等への適用が可能となる。"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 the advantages of lower dielectric constant, lower refractive index, and lower coefficient of thermal expansion, so it can be used for printed boards, 1. , it can be applied to interlayer insulating films for SI, materials for optical waveguides, etc.
Claims (2)
た四価の有機基であり、 ▲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▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is a tetravalent organic group selected from the group consisting of the following chemical structural formulas, ▲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 |
|---|---|---|---|
| JP63200579A JP2567049B2 (en) | 1988-08-11 | 1988-08-11 | Method for producing fluorine-containing polyimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63200579A JP2567049B2 (en) | 1988-08-11 | 1988-08-11 | Method for producing fluorine-containing polyimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0249029A true JPH0249029A (en) | 1990-02-19 |
| JP2567049B2 JP2567049B2 (en) | 1996-12-25 |
Family
ID=16426684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63200579A Expired - Fee Related JP2567049B2 (en) | 1988-08-11 | 1988-08-11 | Method for producing fluorine-containing polyimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2567049B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5324813A (en) * | 1992-07-22 | 1994-06-28 | International Business Machines Corporation | Low dielectric constant fluorinated polymers and methods of fabrication thereof |
| US5896090A (en) * | 1996-05-29 | 1999-04-20 | Aisin Seiki Kabushiki Kaisha | Occupant sensing apparatus |
| US5895900A (en) * | 1996-12-20 | 1999-04-20 | Aisin Seiki Kabushiki Kaisha | Pressure sensitive seat switch with air vent passages |
| US5965856A (en) * | 1996-11-28 | 1999-10-12 | Aisin Seiki Kabushiki Kaisha | Pressure sensitive switch |
| US6388556B1 (en) | 2000-09-07 | 2002-05-14 | Fujikura Ltd. | Film pressure sensitive resistor and pressure sensitive sensor |
| US7465479B2 (en) * | 2001-12-27 | 2008-12-16 | Merck Patent Gesellschaft Mit Beschraenkter Haftung | Polymerisable monocyclic compounds |
| EP2571019A1 (en) | 2011-08-30 | 2013-03-20 | Yamaha Corporation | Controller provided with touch detection device |
-
1988
- 1988-08-11 JP JP63200579A patent/JP2567049B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5324813A (en) * | 1992-07-22 | 1994-06-28 | International Business Machines Corporation | Low dielectric constant fluorinated polymers and methods of fabrication thereof |
| US5896090A (en) * | 1996-05-29 | 1999-04-20 | Aisin Seiki Kabushiki Kaisha | Occupant sensing apparatus |
| US5965856A (en) * | 1996-11-28 | 1999-10-12 | Aisin Seiki Kabushiki Kaisha | Pressure sensitive switch |
| US5895900A (en) * | 1996-12-20 | 1999-04-20 | Aisin Seiki Kabushiki Kaisha | Pressure sensitive seat switch with air vent passages |
| US6388556B1 (en) | 2000-09-07 | 2002-05-14 | Fujikura Ltd. | Film pressure sensitive resistor and pressure sensitive sensor |
| US7465479B2 (en) * | 2001-12-27 | 2008-12-16 | Merck Patent Gesellschaft Mit Beschraenkter Haftung | Polymerisable monocyclic compounds |
| EP2571019A1 (en) | 2011-08-30 | 2013-03-20 | Yamaha Corporation | Controller provided with touch detection device |
| US9130572B2 (en) | 2011-08-30 | 2015-09-08 | Yamaha Corporation | Controller provided with touch detection device including movable and fixed contact patterns |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2567049B2 (en) | 1996-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101545666B1 (en) | Diamine, polyimide, and polyimide film and utilization thereof | |
| EP0280801B1 (en) | Colorless transparent polyimide shaped articles and process for their production | |
| US5484879A (en) | Polyimides containing fluorine | |
| JP2640553B2 (en) | Fluorinated polyimide copolymer and method for producing the same | |
| JPH0249029A (en) | Fluorine-containing polyimide and production thereof | |
| JP2657700B2 (en) | Fluorine-containing polyimide optical material | |
| JP3131940B2 (en) | Polyimide copolymer and method for producing the same | |
| JP2744969B2 (en) | Fluorine-containing polyimide and method for producing the same | |
| KR19980079256A (en) | Polyimide precursor solution, preparation method thereof, film or film obtained from such solution and preparation method of film | |
| JP3425854B2 (en) | Low refractive index transparent polyimide copolymer, precursor solution thereof, and production method thereof | |
| JPH047333A (en) | New polyimide | |
| JP2519228B2 (en) | Colorless and transparent polyimide molding and method for producing the same | |
| JPH0676554B2 (en) | Fluorine-containing polyimide composition and method for producing the same | |
| JPH048733A (en) | Transparent polyimide film | |
| JP2694008B2 (en) | Fluorine-containing polyimide and method for producing the same | |
| JP3339205B2 (en) | Method for producing polyimide copolymer | |
| JP2843314B2 (en) | Fluorine-containing polyimide optical material | |
| JP2998835B2 (en) | Fluorine-containing polyimide optical material | |
| JPH01182324A (en) | Fluorine-containing polyimide and production thereof | |
| JPS63199239A (en) | Novel solvent-soluble polyimide and production thereof | |
| JP2811675B2 (en) | Heat-resistant coloring paste for color filters | |
| JP2004339363A (en) | Polyimide precursor liquid composition and polyimide coating film | |
| KR102699256B1 (en) | Polyamic Acid Composition and Polyimide Film Prepared with the same | |
| JP4620946B2 (en) | Method for producing polyimide precursor, method for producing polyimide precursor organic solvent solution, method for producing polyimide film, polyimide precursor, method for producing polyimide | |
| JPH04161437A (en) | Polyimide film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |