JPH11100502A - Polyimide resin composition - Google Patents
Polyimide resin compositionInfo
- Publication number
- JPH11100502A JPH11100502A JP26337297A JP26337297A JPH11100502A JP H11100502 A JPH11100502 A JP H11100502A JP 26337297 A JP26337297 A JP 26337297A JP 26337297 A JP26337297 A JP 26337297A JP H11100502 A JPH11100502 A JP H11100502A
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- formula
- embedded image
- resin composition
- polyimide resin
- 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.)
- Pending
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 19
- 239000004642 Polyimide Substances 0.000 claims abstract description 21
- 239000011347 resin Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 43
- 238000002834 transmittance Methods 0.000 abstract description 14
- 239000004952 Polyamide Substances 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 3
- 229920002647 polyamide Polymers 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 239000011256 inorganic filler Substances 0.000 abstract description 2
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 2
- 239000003495 polar organic solvent Substances 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- 239000011342 resin composition Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 229920005575 poly(amic acid) Polymers 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- -1 3-amino-4-methylphenyl Chemical group 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- DGQOZCNCJKEVOA-UHFFFAOYSA-N 5-(2,5-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1CC(=O)OC1=O DGQOZCNCJKEVOA-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はポリイミド系樹脂の
被膜、フィルムを得る材料であり、さらに詳しくは誘電
率が極めて低く、膜厚の均一な被膜、フィルムを得るこ
とができるポリイミド樹脂組成物に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for obtaining a polyimide resin film or film, and more particularly to a polyimide resin composition capable of obtaining a film or film having a very low dielectric constant and a uniform film thickness. Things.
【０００２】[0002]
【従来の技術】ポリイミド系樹脂の被膜およびフィルム
は、高耐熱性、高純度、高耐環境性等の特徴を持ち、電
子機器を中心に各種用途に用いられている。通常、ポリ
イミド系樹脂の被膜およびフィルムは、ポリイミド前駆
体であるポリアミド酸、ポリアミド酸エステル、ポリイ
ソイミド等の溶液や溶剤可溶なポリイミド、ポリアミド
イミドの溶液を基板上に塗布し、焼成することにより得
る。2. Description of the Related Art Polyimide-based coatings and films have characteristics such as high heat resistance, high purity, and high environmental resistance, and are used for various purposes mainly in electronic equipment. Usually, a coating and a film of a polyimide resin are obtained by applying a solution of a polyimide precursor such as a polyamic acid, a polyamic acid ester, or a polyisoimide, or a solvent-soluble polyimide, or a polyamideimide solution on a substrate, and baking the applied solution. .
【０００３】焼成後の被膜は一般に濃色に着色してお
り、４００ｎｍ前後の短波長域の光の透過率に優れたも
のは少なく、高透過率を必要とされる用途、例えば、液
晶ディスプレイや光通信ケーブルなどに適用することが
できなかった。[0003] The film after baking is generally colored deep, and few of them are excellent in transmittance of light in a short wavelength region of about 400 nm, and are used in applications requiring high transmittance, such as liquid crystal displays and liquid crystal displays. It could not be applied to optical communication cables and the like.
【０００４】絶縁材料として用いた場合、従来のフッ素
を導入したポリイミド系樹脂の被膜、フィルムでは、焼
成温度を３００℃以上にしなければ、１ＭＨｚでの誘電
率が３を下回ることは非常に困難なことであり、低温プ
ロセスには不適であった。When used as an insulating material, it is very difficult for a conventional fluorine-containing polyimide resin film or film to have a dielectric constant of less than 3 at 1 MHz unless the firing temperature is set to 300 ° C. or more. This was unsuitable for the low-temperature process.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、上記のよう
なポリイミド樹脂組成物の問題点を解決し、２５０℃以
下の低い焼成温度での絶縁性に優れ、かつ、高い透過率
を有する、ポリイミド樹脂組成物である。SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the polyimide resin composition, has excellent insulation at a low firing temperature of 250 ° C. or lower, and has high transmittance. It is a polyimide resin composition.
【０００６】[0006]
【課題を解決する手段】本発明は、 （１）一般式（１）で表される繰り返し単位を有するポ
リイミド前駆体を樹脂成分とするポリイミド樹脂組成物
であり、The present invention provides (1) a polyimide resin composition containing a polyimide precursor having a repeating unit represented by the general formula (1) as a resin component,
【０００７】[0007]
【化１】 （式中、Ｘは４価の有機基を表し、ＲはＨまたはアルキ
ル基を表す。）Embedded image (In the formula, X represents a tetravalent organic group, and R represents H or an alkyl group.)
【０００８】（２）Ｘが式２，３，４，５，６，７，
８，９，１０および／または１１である（１）記載のポ
リイミド前駆体を樹脂成分とするポリイミド樹脂組成物
であり、(2) X is represented by the formulas 2, 3, 4, 5, 6, 7,
A polyimide resin composition comprising the polyimide precursor according to (1), which is 8, 9, 10, and / or 11, as a resin component,
【０００９】[0009]
【化２】 Embedded image
【００１０】[0010]
【化３】 Embedded image
【００１１】[0011]
【化４】 Embedded image
【００１２】[0012]
【化５】 Embedded image
【００１３】[0013]
【化６】 Embedded image
【００１４】[0014]
【化７】 Embedded image
【００１５】[0015]
【化８】 Embedded image
【００１６】[0016]
【化９】 Embedded image
【００１７】[0017]
【化１０】 Embedded image
【００１８】[0018]
【化１１】 Embedded image
【００１９】（３）一般式（１２）で表される繰り返し
単位を有するポリイミドを樹脂成分とするポリイミド樹
脂組成物であり、(3) A polyimide resin composition containing a polyimide having a repeating unit represented by the general formula (12) as a resin component,
【００２０】[0020]
【化１２】 （式中、Ｘは４価の有機基をを表し、ＲはＨまたはアル
キル基を表す。）Embedded image (In the formula, X represents a tetravalent organic group, and R represents H or an alkyl group.)
【００２１】（４）Ｘが式２，３，４，５，６，７，
８，９，１０および／または１１である（３）記載のポ
リイミドを樹脂成分とするポリイミド樹脂組成物であ
る。(4) X is represented by the formulas 2, 3, 4, 5, 6, 7,
A polyimide resin composition containing the polyimide according to (3), which is 8, 9, 10, and / or 11, as a resin component.
【００２２】本発明のポリイミド樹脂組成物は、一般式
（１）または（１２）と、極性有機溶媒を成分とする樹
脂組成物である。The polyimide resin composition of the present invention is a resin composition containing the general formula (1) or (12) and a polar organic solvent as a component.
【００２３】一般式（１）および（１２）の溶剤として
は、Ｎ−メチル−２−ピロリドン、γ−ブチロラクト
ン、ジメチルアセトアミド、Ｎ−ビニル−２−ピロリド
ン、ジメチルスルホキシド等が挙げられるがこれらに限
定されるものではない。Examples of the solvents of the general formulas (1) and (12) include, but are not limited to, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylacetamide, N-vinyl-2-pyrrolidone, dimethylsulfoxide and the like. It is not something to be done.
【００２４】本発明中の樹脂成分はポリイミド前駆体で
あるポリアミド酸、ポリアミド酸エステル、および溶剤
可溶なポリイミド等のポリイミド系樹脂であるが、エポ
キシ樹脂等を混合したり、無機物フィラーを添加しても
よい。The resin component in the present invention is a polyimide-based resin such as polyamide acid, polyamic acid ester, and a polyimide soluble in a solvent, which are polyimide precursors, and may be mixed with an epoxy resin or the like or added with an inorganic filler. You may.
【００２５】[0025]
【実施例】以下、実施例により詳細を説明するが、本発
明はこれらの実施例によって何等限定されるものではな
い。The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples.
【００２６】（合成例１）温度計、攪拌機、原料投入
口、乾燥窒素ガス導入管を備えた四つ口セパラブルフラ
スコ中、２，２−ビス（３−アミノ−４−メチルフェニ
ル）ヘキサフルオロプロパン３３．８g（０．１０モ
ル）をＮ−メチル−２−ピロリドン（ＮＭＰ）２５６．
９g中に溶解させる。この系に、原料投入口からブタン
テトラカルボン酸二無水物１９．８g（０．１０モル）
を投入し、系の温度を１０℃に保ちながら窒素流入下、
５時間攪拌を続けた。系の温度を室温に戻してさらに３
時間攪拌を続け、ポリアミド酸のＮＭＰ溶液を得た。Synthesis Example 1 In a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 2,2-bis (3-amino-4-methylphenyl) hexafluoro 33.8 g (0.10 mol) of propane was added to N-methyl-2-pyrrolidone (NMP).
Dissolve in 9 g. 19.8 g (0.10 mol) of butanetetracarboxylic dianhydride was added to the system from the raw material inlet.
And keeping the temperature of the system at 10 ° C under nitrogen flow,
Stirring was continued for 5 hours. Return the temperature of the system to room temperature and
Stirring was continued for an hour to obtain an NMP solution of polyamic acid.
【００２７】（合成例２）温度計、攪拌機、原料投入
口、乾燥窒素ガス導入管を備えた四つ口セパラブルフラ
スコ中、２，２−ビス（３−アミノ−４−メチルフェニ
ル）ヘキサフルオロプロパン３３．８g（０．１０モ
ル）をＮ−メチル−２−ピロリドン（ＮＭＰ）３１２．
８g中に溶解させる。この系に、原料投入口から２，２
−ビス（３，４−アンハイドロジカルボキシフェニル）
ヘキサフルオロプロパン４４．４g（０．１０モル）を
投入し、系の温度を１０℃に保ちながら窒素流入下、５
時間攪拌を続けた。系の温度を室温に戻してさらに３時
間攪拌を続け、ポリアミド酸のＮＭＰ溶液を得た。Synthesis Example 2 In a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 2,2-bis (3-amino-4-methylphenyl) hexafluoro 33.8 g (0.10 mol) of propane was added to N-methyl-2-pyrrolidone (NMP).
Dissolve in 8 g. In this system, 2, 2
-Bis (3,4-anhydrodicarboxyphenyl)
Hexafluoropropane (44.4 g, 0.10 mol) was charged, and the system temperature was maintained at 10 ° C., and nitrogen was introduced thereinto.
Stirring was continued for hours. The temperature of the system was returned to room temperature, and stirring was further continued for 3 hours to obtain an NMP solution of polyamic acid.
【００２８】（合成例３）温度計、攪拌機、原料投入
口、乾燥窒素ガス導入管を備えた四つ口セパラブルフラ
スコ中、２，２−ビス（３−アミノ−４−メチルフェニ
ル）ヘキサフルオロプロパン４４．４g（０．１０モ
ル）をＮ−メチル−２−ピロリドン（ＮＭＰ）２４０．
９g中に溶解させる。この系に、原料投入口から５−
（２，５−ジオキソテトラヒドロフリル）−３−メチル
−３−シクロヘキセン−１，２−ジカルボン酸無水物２
６．４g（０．１０モル）を投入し、系の温度を１０℃
に保ちながら窒素流入下、５時間攪拌を続けた。系の温
度を室温に戻してさらに３時間攪拌を続け、ポリアミド
酸のＮＭＰ溶液を得た。(Synthesis Example 3) In a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 2,2-bis (3-amino-4-methylphenyl) hexafluoro 44.4 g (0.10 mol) of propane was added to N-methyl-2-pyrrolidone (NMP).
Dissolve in 9 g. In this system, 5-
(2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride 2
6.4 g (0.10 mol) was charged, and the temperature of the system was set to 10 ° C.
And stirring was continued for 5 hours under nitrogen flow. The temperature of the system was returned to room temperature, and stirring was further continued for 3 hours to obtain an NMP solution of polyamic acid.
【００２９】（合成例４）温度計、攪拌機、原料投入
口、乾燥窒素ガス導入管を備えた四つ口セパラブルフラ
スコ中、２，２’−ビス（トリフルオロメチル）ベンジ
ジン３２．０g（０．１０モル）をＮ−メチル−２−ピ
ロリドン（ＮＭＰ）３０５．６g中に溶解させる。この
系に、原料投入口から２，２−ビス（３，４−アンハイ
ドロジカルボキシフェニル）ヘキサフルオロプロパン４
４．４g（０．１０モル）を投入し、系の温度を１０℃
に保ちながら窒素流入下、５時間攪拌を続けた。系の温
度を室温に戻してさらに３時間攪拌を続け、ポリアミド
酸のＮＭＰ溶液を得た。(Synthesis Example 4) In a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 32.0 g of 2,2'-bis (trifluoromethyl) benzidine (0 .10 mol) in 305.6 g of N-methyl-2-pyrrolidone (NMP). In this system, 2,2-bis (3,4-anhydrodicarboxyphenyl) hexafluoropropane 4
4.4 g (0.10 mol) was charged, and the temperature of the system was reduced to 10 ° C.
And stirring was continued for 5 hours under nitrogen flow. The temperature of the system was returned to room temperature, and stirring was further continued for 3 hours to obtain an NMP solution of polyamic acid.
【００３０】（合成例５）温度計、攪拌機、原料投入
口、乾燥窒素ガス導入管を備えた四つ口セパラブルフラ
スコ中、２，２−ビス（４−（４−アミノフェノキシ）
フェニル）プロパン４１．１g（０．１０モル）をＮ−
メチル−２−ピロリドン（ＮＭＰ）２５１．５g中に溶
解させる。この系に、原料投入口からピロメリット酸無
水物２１．８g（０．１０モル）を投入し、系の温度を
１０℃に保ちながら窒素流入下、５時間攪拌を続けた。
系の温度を室温に戻してさらに３時間攪拌を続け、ポリ
アミド酸のＮＭＰ溶液を得た。Synthesis Example 5 In a four-neck separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet tube, 2,2-bis (4- (4-aminophenoxy))
Phenyl) propane (41.1 g, 0.10 mol)
Dissolve in 251.5 g of methyl-2-pyrrolidone (NMP). To this system, 21.8 g (0.10 mol) of pyromellitic anhydride was introduced from the raw material introduction port, and stirring was continued for 5 hours under nitrogen flow while maintaining the system temperature at 10 ° C.
The temperature of the system was returned to room temperature, and stirring was further continued for 3 hours to obtain an NMP solution of polyamic acid.
【００３１】（実施例１）合成例１で得たポリアミド酸
溶液をＮＭＰ溶液に溶解し、１５％溶液とし、厚さ１０
０μmのアルミ板にスピンコートで塗布、２５０℃で焼
成し１０μmのポリイミド膜を形成した。その後このア
ルミ板を、ＪＩＳ−Ｋ６９１１に従い、誘電率の測定を
行った。結果、１MHzでの誘電率は２．９１であり、４
００nmでの透過率は９０％であった。Example 1 The polyamic acid solution obtained in Synthesis Example 1 was dissolved in an NMP solution to form a 15% solution,
It was applied on a 0 μm aluminum plate by spin coating and baked at 250 ° C. to form a 10 μm polyimide film. Thereafter, the dielectric constant of the aluminum plate was measured according to JIS-K6911. As a result, the dielectric constant at 1 MHz was 2.91 and 4
The transmittance at 00 nm was 90%.
【００３２】（実施例２）合成例２で得たポリアミド酸
溶液をＮＭＰ溶液に溶解し、１５％溶液とし、厚さ１０
０μmのアルミ板にスピンコートで塗布、２５０℃で焼
成し１０μmのポリイミド膜を形成した。その後このア
ルミ板を、ＪＩＳ−Ｋ６９１１に従い、誘電率の測定を
行った。結果、１MHzでの誘電率は２．６８であり、４
００nmでの透過率は８８％であった。(Example 2) The polyamic acid solution obtained in Synthesis Example 2 was dissolved in an NMP solution to make a 15% solution,
It was applied on a 0 μm aluminum plate by spin coating and baked at 250 ° C. to form a 10 μm polyimide film. Thereafter, the dielectric constant of the aluminum plate was measured according to JIS-K6911. As a result, the dielectric constant at 1 MHz is 2.68 and 4
The transmittance at 00 nm was 88%.
【００３３】（比較例１）合成例３で得たポリアミド酸
溶液をＮＭＰ溶液に溶解し、１５％溶液とし、厚さ１０
０μmのアルミ板にスピンコートで塗布、２５０℃で焼
成し１０μmのポリイミド膜を形成した。その後このア
ルミ板を、ＪＩＳ−Ｋ６９１１に従い、誘電率の測定を
行った。結果、１MHzでの誘電率は３．４０であり、４
００nmでの透過率は３６％であった。Comparative Example 1 The polyamic acid solution obtained in Synthesis Example 3 was dissolved in an NMP solution to make a 15% solution,
It was applied on a 0 μm aluminum plate by spin coating and baked at 250 ° C. to form a 10 μm polyimide film. Thereafter, the dielectric constant of the aluminum plate was measured according to JIS-K6911. As a result, the dielectric constant at 1 MHz was 3.40 and 4
The transmittance at 00 nm was 36%.
【００３４】（比較例２）合成例４で得たポリアミド酸
溶液をＮＭＰ溶液に溶解し、１５％溶液とし、厚さ１０
０μmのアルミ板にスピンコートで塗布、２５０℃で焼
成し１０μmのポリイミド膜を形成した。その後このア
ルミ板を、ＪＩＳ−Ｋ６９１１に従い、誘電率の測定を
行った。結果、１MHzでの誘電率は３．１０であり、４
００nmでの透過率は９５％であった。(Comparative Example 2) The polyamic acid solution obtained in Synthesis Example 4 was dissolved in an NMP solution to make a 15% solution,
It was applied on a 0 μm aluminum plate by spin coating and baked at 250 ° C. to form a 10 μm polyimide film. Thereafter, the dielectric constant of the aluminum plate was measured according to JIS-K6911. As a result, the dielectric constant at 1 MHz is 3.10 and 4
The transmittance at 00 nm was 95%.
【００３５】（比較例３）合成例５で得たポリアミド酸
溶液をＮＭＰ溶液に溶解し、１５％溶液とし、厚さ１０
０μmのアルミ板にスピンコートで塗布、２５０℃で焼
成し１０μmのポリイミド膜を形成した。その後このア
ルミ板を、ＪＩＳ−Ｋ６９１１に従い、誘電率の測定を
行った。結果、１MHzでの誘電率は３．４であり、４０
０nmでの透過率は２８．４％であった。Comparative Example 3 The polyamic acid solution obtained in Synthesis Example 5 was dissolved in an NMP solution to make a 15% solution,
It was applied on a 0 μm aluminum plate by spin coating and baked at 250 ° C. to form a 10 μm polyimide film. Thereafter, the dielectric constant of the aluminum plate was measured according to JIS-K6911. As a result, the dielectric constant at 1 MHz is 3.4 and 40
The transmittance at 0 nm was 28.4%.
【００３６】実施例１、２では、１MHzでの誘電率は低
く、４００nmでの透過率は高かった。比較例１では、酸
無水物にフッ素を導入していないため、１MHzでの誘電
率が高かった。また、焼成した膜が濃色に着色してお
り、４００nmでの透過率が低かった。比較例２では、焼
成温度が低すぎたため、１MHzでの誘電率が高かった。
比較例３では、酸無水物、ジアミンともにフッ素を導入
していないため、誘電率が高かった。また、酸無水物に
芳香族を用いたため、４００nmでの透過率が低かった。In Examples 1 and 2, the dielectric constant at 1 MHz was low, and the transmittance at 400 nm was high. In Comparative Example 1, since no fluorine was introduced into the acid anhydride, the dielectric constant at 1 MHz was high. Further, the fired film was colored dark, and the transmittance at 400 nm was low. In Comparative Example 2, since the firing temperature was too low, the dielectric constant at 1 MHz was high.
In Comparative Example 3, the dielectric constant was high because no fluorine was introduced into both the acid anhydride and the diamine. In addition, the transmittance at 400 nm was low because an aromatic was used as the acid anhydride.
【００３７】[0037]
【発明の効果】本発明のポリイミド樹脂組成物は、２５
０℃以下の低い焼成温度での絶縁性に優れ、かつ、高い
透過率を有する、ポリイミド樹脂組成物である。The polyimide resin composition of the present invention has a composition of 25
A polyimide resin composition having excellent insulation at a low firing temperature of 0 ° C. or less and having high transmittance.
Claims (4)
有するポリイミド前駆体を樹脂成分とするポリイミド樹
脂組成物。 【化１】 （式中、Ｘは４価の有機基を表し、ＲはＨまたはアルキ
ル基を表す。）1. A polyimide resin composition comprising, as a resin component, a polyimide precursor having a repeating unit represented by the general formula (1). Embedded image (In the formula, X represents a tetravalent organic group, and R represents H or an alkyl group.)
９，１０および／または１１である請求項１記載のポリ
イミド前駆体を樹脂成分とするポリイミド樹脂組成物。 【化２】 【化３】 【化４】 【化５】 【化６】 【化７】 【化８】 【化９】 【化１０】 【化１１】 2. X is represented by the formula 2, 3, 4, 5, 6, 7, 8,
2. A polyimide resin composition comprising the polyimide precursor according to claim 1 as a resin component. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image
を有するポリイミドを樹脂成分とするポリイミド樹脂組
成物。 【化１２】 （式中、Ｘは４価の有機基をを表し、ＲはＨまたはアル
キル基を表す。）3. A polyimide resin composition comprising a polyimide having a repeating unit represented by the general formula (12) as a resin component. Embedded image (In the formula, X represents a tetravalent organic group, and R represents H or an alkyl group.)
９，１０および／または１１である請求項３記載のポリ
イミドを樹脂成分とするポリイミド樹脂組成物。4. The method according to claim 1, wherein X is of the formula 2, 3, 4, 5, 6, 7, 8,
A polyimide resin composition comprising the polyimide as a resin component according to claim 3, which is 9, 10, and / or 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26337297A JPH11100502A (en) | 1997-09-29 | 1997-09-29 | Polyimide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26337297A JPH11100502A (en) | 1997-09-29 | 1997-09-29 | Polyimide resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11100502A true JPH11100502A (en) | 1999-04-13 |
Family
ID=17388584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26337297A Pending JPH11100502A (en) | 1997-09-29 | 1997-09-29 | Polyimide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11100502A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000022029A1 (en) * | 1998-10-13 | 2000-04-20 | Nissan Chemical Industries, Ltd. | Polyimide precursors and polyimides |
-
1997
- 1997-09-29 JP JP26337297A patent/JPH11100502A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000022029A1 (en) * | 1998-10-13 | 2000-04-20 | Nissan Chemical Industries, Ltd. | Polyimide precursors and polyimides |
| US6489431B1 (en) | 1998-10-13 | 2002-12-03 | Nissan Chemical Industries, Ltd. | Polyimide precursors and polyimides |
| JP4639471B2 (en) * | 1998-10-13 | 2011-02-23 | 日産化学工業株式会社 | Polyimide material |
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