JPS63254130A - Copolymer of aromatic polyamic acid or ester thereof - Google Patents
Copolymer of aromatic polyamic acid or ester thereofInfo
- Publication number
- JPS63254130A JPS63254130A JP8795787A JP8795787A JPS63254130A JP S63254130 A JPS63254130 A JP S63254130A JP 8795787 A JP8795787 A JP 8795787A JP 8795787 A JP8795787 A JP 8795787A JP S63254130 A JPS63254130 A JP S63254130A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- tables
- polyamic acid
- aromatic
- structural units
- 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
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 43
- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 35
- 229920001577 copolymer Polymers 0.000 title claims abstract description 19
- 150000002148 esters Chemical class 0.000 title abstract description 5
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 15
- 238000005266 casting Methods 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 229920001721 polyimide Polymers 0.000 description 13
- 239000004642 Polyimide Substances 0.000 description 8
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical class NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- -1 aromatic tetracarboxylic diesters Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 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
- 238000007605 air drying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellityc acid Natural products OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、溶液キャスティングが可能であるなど、成形
性に優れるとともに、優れた耐熱性、機械特性、熱的特
性を示すポリイミド共重合体を与える芳香族ポリアミッ
ク酸または芳香族ポリアミック酸エステル共重合体に関
するものである。[Detailed Description of the Invention] [Field of Industrial Application] The present invention provides a polyimide copolymer that is capable of solution casting and exhibits excellent moldability, as well as excellent heat resistance, mechanical properties, and thermal properties. The invention relates to an aromatic polyamic acid or an aromatic polyamic acid ester copolymer.
Ｃ従来の技術〕
高分子材料はアルミナ基板、金属板等の上に形成するプ
リント回路用絶縁基材、フレキシブルプリント回路用基
材、ＬＳＩの多層配線用の層間絶縁膜など、膜材、フィ
ルム材の分野で、また複合材料のマトリックス樹脂など
構造材料の分野で、その優れた電気絶縁性、加工性等の
面より使用されてきている。これらの分野においては従
来高性能化のため、主として耐熱性向上が検討されてき
たが、近年部品としての信頼性の面から、寸法安定性や
、セラミックなど他材料と併用される際の熱膨張率のミ
スマツチを防ぐため、高剛性、低熱膨張率といった優れ
た機械特性、および熱的特性も要求されるようになって
きている。C. Prior art] Polymer materials are used as membrane materials, such as insulating substrates for printed circuits formed on alumina substrates, metal plates, etc., substrates for flexible printed circuits, interlayer insulating films for multilayer wiring of LSIs, etc. It has been used in the field of structural materials such as matrix resins for composite materials due to its excellent electrical insulation properties and processability. In order to improve performance in these fields, improvements in heat resistance have traditionally been considered, but in recent years, from the standpoint of reliability as parts, improvements have been made in terms of dimensional stability and thermal expansion when used in combination with other materials such as ceramics. In order to prevent index mismatch, excellent mechanical and thermal properties such as high rigidity and low coefficient of thermal expansion are also required.
従来、耐熱性の優れた高分子材料として、芳香族ポリイ
ミド、特に構造単位
（Ａ）
Ｏ
（式中、Ｒ□は水素、１価の脂肪族基、またはエーテル
結合金有脂肪族基を示す。）と、構造単位を含む芳香族
ポリアミック酸または芳香族ポリアミック酸エステルの
加熱硬化によって得られる芳香族ポリイミドが良く知ら
れている（昭和６０年１１月６日、第３回次世代産業基
盤技術シンポジウム予稿集）。Conventionally, aromatic polyimides, particularly structural units (A) O (where R□ represents hydrogen, a monovalent aliphatic group, or an ether-bonded aliphatic group), have been used as polymeric materials with excellent heat resistance. ), and aromatic polyimides obtained by heat curing of aromatic polyamic acids or aromatic polyamic acid esters containing structural units are well known (November 6, 1985, 3rd Next Generation Industrial Infrastructure Technology Symposium) Proceedings).
しかしながら、これらのうち一般の芳香族ポリイミドは
可溶性の前駆体を持つため、溶液キャスティング可能な
フィルム、もしくはコーティング材料としてよく用いら
れているが、その機械特性は一般に通常の高分子材料と
同程度であり、熱膨張率も大きいなど、特に優れたもの
ではなかった。However, among these, general aromatic polyimides have soluble precursors and are often used as solutions castable films or coating materials, but their mechanical properties are generally on the same level as ordinary polymer materials. It was not particularly excellent, as it had a large coefficient of thermal expansion.
また（Ａ）式および（Ｂ）式の構造単位を含むポリアミ
ック酸またはポリアミック酸エステルの加熱硬化によっ
て得られる芳香族ポリイミドは、分子構造上高剛性が期
待できるが、実際に得られる膜は脆弱で実用的ではない
という問題点があった。Furthermore, aromatic polyimides obtained by heat curing of polyamic acids or polyamic acid esters containing structural units of formulas (A) and (B) can be expected to have high rigidity due to their molecular structure, but the films actually obtained are brittle. The problem was that it was not practical.
本発明は芳香族ポリイミドにおける上記のような欠点を
解消するためのもので、有機溶剤に可溶または安定に分
散でき、溶液キャスティング、加熱硬化等により耐熱性
、機械特性および熱的特性に優れたフィルム、塗膜など
となるポリイミドを与える芳香族ポリアミック酸または
芳香族ポリアミック酸エステル共重合体を提供すること
を目的とするものである。The present invention is aimed at solving the above-mentioned drawbacks of aromatic polyimides, and is capable of being soluble or stably dispersed in organic solvents, and has excellent heat resistance, mechanical properties, and thermal properties through solution casting, heat curing, etc. The object of the present invention is to provide an aromatic polyamic acid or aromatic polyamic acid ester copolymer that provides polyimide for use in films, coatings, etc.
本発明の芳香族ポリアミック酸または芳香族ポリアミッ
ク酸エステル共重合体は、下記の（Ａ）。The aromatic polyamic acid or aromatic polyamic acid ester copolymer of the present invention is the following (A).
（Ｂ）、（Ｃ）および（Ｄ）の式で表わされる構造単位
ｈ 貫
（式中、Ａｒ１は４価の芳香族基、Ａｒ２は２価の芳香
族基、Ｒ□ｌ Ｒ２は水素、１価の脂肪族基、またはエ
ーテル結合金有脂肪族基を示す。ただしＡｒ、が除く。Structural units h represented by the formulas (B), (C) and (D) (wherein, Ar1 is a tetravalent aromatic group, Ar2 is a divalent aromatic group, R□l R2 is hydrogen, 1 represents a valent aliphatic group or an aliphatic group with an ether bond, except for Ar.
）を含み、単位（Ａ）と単位（Ｃ）の合計量、および単
位（Ｂ）と単位（Ｄ）の合計量は実質的に等モルであっ
て、かつ単位（Ａ）と単位（Ｃ）の重量比が１０：９０
〜９０ ： １０であり、単位（Ｂ）と単位（Ｄ）の重
量比が１０ ： ９０〜９０：１０のものである。), the total amount of the unit (A) and the unit (C), and the total amount of the unit (B) and the unit (D) are substantially equimolar, and the unit (A) and the unit (C) The weight ratio of
~90:10, and the weight ratio of units (B) to units (D) is from 10:90 to 90:10.
上記一般式（Ｃ）中のＡｒ□の具体例としては、などが
挙げられ、また一般式（０）中のＡｒ２の具体例として
は、
０−ＣＨ２−〇−１−〇−８０２−〇−１などが挙げら
れるが、Ａｒ１とＡｒ２の組合せがらに、Ｒｌｔ Ｒ２
の具体例としては水素の他に、ＣＨ３−２Ｃ２Ｈ５−１
Ｃ４Ｈ，−、ＣＩ（３０ＣＨ２ＣＨ２−、Ｃ２Ｈ，０Ｃ
Ｈ２１Ｌｌ（、−１Ｃ，Ｈ，０ＣＨ２ＣＨ２−１ＣＩ（
３０Ｃ８２ＣＨ２０ＣＨ，、ＣＩ（２−などが挙げられ
る。これらはいずれも上記具体例に限定されるものでは
なく、また２種以上を混合して用いることも可能である
。Specific examples of Ar□ in the above general formula (C) include, and specific examples of Ar2 in general formula (0) include 0-CH2-〇-1-〇-802-〇- 1 etc., but the combination of Ar1 and Ar2, Rlt R2
In addition to hydrogen, specific examples include CH3-2C2H5-1
C4H,-, CI(30CH2CH2-, C2H,0C
H21Ll(, -1C,H,0CH2CH2-1CI(
Examples include 30C82CH20CH, CI(2-), etc. None of these are limited to the above specific examples, and two or more types can be used in combination.
本発明の共重合体は、本質的に前記４つの構造単位（Ａ
） 、 （Ｂ） 、 （Ｃ）および（Ｄ）を含む。構造
単位（Ａ）および（Ｃ）は芳香族テトラカルボン酸ジ無
水物、芳香族テトラカルボン酸ジエステル、もしくはそ
の誘導体１例えばテトラカルボン酸ジエステルジハライ
ドから導入される。構造単位（Ｂ）および（Ｄ）は芳香
族ジアミンもしくは芳香族ジイソシアネートから導入さ
れる。The copolymer of the present invention essentially consists of the four structural units (A
), (B), (C) and (D). Structural units (A) and (C) are introduced from aromatic tetracarboxylic dianhydrides, aromatic tetracarboxylic diesters, or derivatives thereof, such as tetracarboxylic diester dihalides. Structural units (B) and (D) are introduced from aromatic diamines or aromatic diisocyanates.
構造単位（Ａ）と構造単位（Ｃ＞の重量比は１０ ：
９０〜９０ ： １０であり、構造単位（Ｂ）と構造単
位（Ｄ）の重量比も１０ ： ９０〜９０ ： １０で
ある。これは構造単位（Ａ）。The weight ratio of the structural unit (A) and the structural unit (C> is 10:
The weight ratio of the structural unit (B) to the structural unit (D) is also 10:90 to 90:10. This is the structural unit (A).
（Ｂ）がそれぞれ９０重量％を越えると、芳香族ポリア
ミック酸または芳香族ポリアミック酸エステル共重合溶
液を加熱硬化して得られる膜が脆弱になる傾向があり、
またそれぞれ１０重量％未満では、良好な機械特性およ
び熱的特性を示さなくなる傾向があるためである。さら
に構造単位（Ａ）と構造単位（Ｃ）の合計量は、構造単
位（Ｂ）と構造単位（Ｄ）の合計量と実質的に等モルで
なければならなし為。When each of (B) exceeds 90% by weight, the film obtained by heating and curing the aromatic polyamic acid or aromatic polyamic acid ester copolymer solution tends to become brittle.
Moreover, if each content is less than 10% by weight, good mechanical properties and thermal properties tend not to be exhibited. Furthermore, the total amount of the structural unit (A) and the structural unit (C) must be substantially equimolar to the total amount of the structural unit (B) and the structural unit (D).
本発明における芳香族ポリアミック酸または芳香族ポリ
アミック酸エステル共重合体の合成方法は、通常用いら
れている重縮合であればいずれも適用可能であるが、特
に低温溶液重縮合が好ましい。すなわち、前記の構造単
位（Ａ）と（Ｂ）を含むピロメリット酸ジ無水物と、ｐ
−フェニレンジアミン、構造単位（Ｃ）と（Ｄ）を含む
芳香族テトラカルボン酸誘導体、例えばピロメリット酸
ジ無水物、ビフェニルテ１〜ラカルボン酸ジ無水物およ
びそれらエステル酸クロライドなどと、芳香族ジアミン
、例えばｐ−フェニレンジアミン、ｍ−フェニレンジア
ミン、４．４′−ジアミノジフェニルエーテル、４，４
′−ジアミノジフェニルメタン、４，４′−ジアミノジ
フェニルスルホン、 ３．３’−ジアミノジフェニルス
ルホン、４．４′−ジアミノベンゾフェノンなどを溶媒
に溶解して重縮合すると、高分子量の芳香族ポリアミッ
ク酸または芳香族ポリアミック酸エステル共重合体が得
られる。これら共重合体溶液はキャスティングし、溶媒
を風乾後、２００〜４００℃で１〜２０時間加熱反応さ
せると、ポリイミド共重合体を与える。As the method for synthesizing the aromatic polyamic acid or aromatic polyamic acid ester copolymer in the present invention, any commonly used polycondensation method can be applied, but low-temperature solution polycondensation method is particularly preferred. That is, pyromellitic dianhydride containing the structural units (A) and (B), and p
- Phenyl diamine, aromatic tetracarboxylic acid derivatives containing structural units (C) and (D), such as pyromellitic dianhydride, biphenylte-1-lacarboxylic dianhydride and their ester acid chlorides, and aromatic diamines. , such as p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4
When '-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, etc. are dissolved in a solvent and polycondensed, a high molecular weight aromatic polyamic acid or an aromatic A group polyamic acid ester copolymer is obtained. These copolymer solutions are cast, and after the solvent is air-dried, a polyimide copolymer is obtained by heating and reacting at 200 to 400° C. for 1 to 20 hours.
上記の反応時、キャスティング時の溶媒として １は、
前記の構造単位（Ａ） 、 （Ｂ） 、 （Ｃ）および
（Ｄ）を含有している反応試薬を溶解し、かつこれらと
本質的に反応しないものであって、生成する芳香族ポリ
アミック酸または芳香族ポリアミック酸エステル共重合
体を溶解するか、あるいは安定に分散させるものが望ま
しい。このような溶媒としてはＮ−メチルピロリドン、
Ｎ、Ｎ−ジメチルアセ１〜アミド、Ｎ。As a solvent during the above reaction and casting, 1 is:
Aromatic polyamic acid or It is desirable that the aromatic polyamic acid ester copolymer be dissolved or stably dispersed. Such solvents include N-methylpyrrolidone,
N, N-dimethylace1-amide, N.
Ｎ−ジメチルホルムアミド、ヘキサメチルホスホリック
トリアミドなどが挙げられ、これらの混合溶液も使用で
きる。Examples include N-dimethylformamide and hexamethylphosphoric triamide, and mixed solutions thereof can also be used.
本発明において得られる芳香族ポリアミック酸または芳
香族ポリアミック酸エステル共重合体を加熱硬化すると
、芳香族イミド共重合体を与える。When the aromatic polyamic acid or aromatic polyamic acid ester copolymer obtained in the present invention is heated and cured, an aromatic imide copolymer is obtained.
その方法としては、重縮合溶液をそのまま用い、スピナ
ーもしくはコーターでキャスティングした後、風乾、加
熱反応を行ってもよいが、一度重縮合反応液を大量のメ
タノールなどに注ぎ、ポリアミック酸またはポリアミッ
ク酸エステルを沈澱精製した後、再度溶媒に溶解させた
溶液を用いて行ってもよい。As a method, the polycondensation solution may be used as it is, cast with a spinner or coater, air-dried, and then heated. However, once the polycondensation reaction solution is poured into a large amount of methanol etc., After precipitation and purification, a solution obtained by redissolving in a solvent may be used.
本発明における芳香族ポリアミック酸または芳。Aromatic polyamic acid or aromatic acid in the present invention.
香族ポリアミック酸エステル共重合体は、上記のように
溶媒を用いてキャスティング、風乾、加熱硬化すること
によりフィルム、塗膜などが得られるが、通常のフィル
ム製造と同様に加熱反応後、もしくは加熱反応中に延伸
処理を行うことが可能であり、これにより機械特性の向
上につながる。Aromatic polyamic acid ester copolymers can be obtained into films, coatings, etc. by casting using a solvent, air drying, and heating curing as described above. It is possible to carry out a stretching treatment during the reaction, which leads to improved mechanical properties.
また種々の充填剤、強化剤と併用し、複合材料として用
いることも可能である。It can also be used in combination with various fillers and reinforcing agents to form composite materials.
以下、本発明の詳細な説明する。 The present invention will be explained in detail below.
実施例Ｉ
Ｐ−フェニレンジアミン１，６５４ｇ（０，０１５モル
）とＮ−メチルピロリドン１９０ｃｃを、攪拌機、窒素
ガス導入管および温度計を備えた四ツロフラスコに仕込
み、溶解後水冷下にピロメリット酸ジ無水物３．０８ｇ
（０，０１４モル）を加え、０〜１０℃で・１時間、つ
いで５０℃で４時間攪拌下に重合反応を行い、末端アミ
ンアミック酸を得た。ついで室温にもどし、ジアミノジ
フェニルエーテル２．３５６ ｇ （０，０１２モル）
を溶解した後再度氷冷し、ピロメリット酸ジ無水物２．
８２２ｇ（０，０１３モル）を加えて０〜１０℃で１時
間、室温で１２時間縮合反応を行った。得られた反応液
は黄色透明であった。Example I 1,654 g (0,015 mol) of P-phenylenediamine and 190 cc of N-methylpyrrolidone were charged into a four-way flask equipped with a stirrer, a nitrogen gas inlet tube, and a thermometer, and after dissolution, pyromellitic acid diamine was added under water cooling. Anhydrous 3.08g
(0,014 mol) was added thereto, and a polymerization reaction was carried out with stirring at 0 to 10°C for 1 hour and then at 50°C for 4 hours to obtain a terminal amine amic acid. Then, the temperature was returned to room temperature, and 2.356 g (0,012 mol) of diaminodiphenyl ether was added.
After dissolving 2.
822 g (0,013 mol) was added and the condensation reaction was carried out at 0 to 10° C. for 1 hour and at room temperature for 12 hours. The resulting reaction solution was yellow and transparent.
つぎに上記反応液をガラス板上に塗布し、１００℃で１
時間風乾した後、ガラス板から取りはずして鉄枠に固定
した後、２００℃で１時間、３００℃で１時間加熱硬化
した。得られたフィルムの赤外吸収スペクトルは１７８
０ｃｍ””付近にイミド基による吸収が現われ、ポリイ
ミドのフィルムが得られたことが確認された。このフィ
ルムのガラス転移温度は３９０℃以上（ＤＳＣ法）であ
り、引張弾性率は９ＧＰａ。Next, the above reaction solution was applied onto a glass plate and heated to 100°C for 1 hour.
After being air-dried for an hour, it was removed from the glass plate, fixed to an iron frame, and then heat-cured at 200° C. for 1 hour and at 300° C. for 1 hour. The infrared absorption spectrum of the obtained film was 178
Absorption due to imide groups appeared near 0 cm'', confirming that a polyimide film was obtained. The glass transition temperature of this film is 390° C. or higher (DSC method), and the tensile modulus is 9 GPa.
１００〜１５０℃の熱膨張率は７．５ Ｘ １０−’に
一’であった。The coefficient of thermal expansion from 100 to 150°C was 7.5 x 10-'.
実施例２
実施例１に準じてＰ−フェニレンジアミン２．１６２ｇ
（０，０２モル）とピロメリット酸ジ無水物４．１０６
ｇ（０，０１９モル）をＮ−メチルピロリドン１９０ｃ
ｃ中で反応させ、ついでジアミノジフェニルエーテル０
．９４２ｇ（０，００５モル）とピロメリット酸ジ無水
物１．２８２ｇ（０，００６モル）を加えてポリアミッ
ク酸溶液を得た。Example 2 2.162 g of P-phenylenediamine according to Example 1
(0.02 mol) and pyromellitic dianhydride 4.106
g (0,019 mol) of N-methylpyrrolidone 190c
reaction in c, then diaminodiphenyl ether 0
．． 942 g (0,005 mol) and 1.282 g (0,006 mol) of pyromellitic dianhydride were added to obtain a polyamic acid solution.
上記で得られた反応液を実施例１に準じて加熱硬化させ
、ポリイミドフィルムを得た。得られたフィルムの引張
弾性率は１３Ｇｐａ、熱膨張率は１．２Ｘ１０−’に一
’であった。The reaction solution obtained above was heated and cured according to Example 1 to obtain a polyimide film. The resulting film had a tensile modulus of 13 Gpa and a coefficient of thermal expansion of 1.2 x 10-'.
実施例３
Ｐ−フェニレンジアミン１．４８８ ｇ （０，０１４
モル）、ジアミノジフェニルエーテル２．７５４ ｇ
（０，０１４モル）およびＮ−メチルピロリドン１５０
ｃｃを攪拌機、窒素ガス導入管および温度計を備えた四
ツロフラスコに仕込み、溶解後水冷下にピロメリット酸
ジ無水物’−１２−
６，０００ｇ（０，０２８モル）を加え、０〜１０℃で
１時間、ついで室温で１２時間攪拌下に重縮合反応を行
った。Example 3 P-phenylenediamine 1.488 g (0,014
mol), diaminodiphenyl ether 2.754 g
(0,014 mol) and N-methylpyrrolidone 150
cc was charged into a Yotsuro flask equipped with a stirrer, a nitrogen gas inlet tube, and a thermometer, and after dissolving, 6,000 g (0,028 mol) of pyromellitic dianhydride'-12- was added while cooling with water, and the mixture was heated at 0 to 10°C. The polycondensation reaction was carried out under stirring for 1 hour and then at room temperature for 12 hours.
上記で得られた反応液を実施例１に準じて加熱硬化させ
、ポリイミドフィルムを得た。得られたフィルムの引張
弾性率は５．ＩＧｐａ、熱膨張率は１．８Ｘ １０−’
に−１であった。The reaction solution obtained above was heated and cured according to Example 1 to obtain a polyimide film. The tensile modulus of the obtained film was 5. IGpa, thermal expansion coefficient is 1.8X 10-'
It was -1.
比較例１
実施例１に準じてＰ−フェニレンジアミン５．４１ｇ
（０，０５モル）とピロメリット酸ジ無水物１０．９１
ｇ（０，０５モル）を重縮合反応させ、ポリイミドフィ
ルムを得た。そのフィルムの特性を測定しようとしたが
、膜が脆弱であったために、測定が不可能であった。Comparative Example 1 5.41 g of P-phenylenediamine according to Example 1
(0.05 mol) and pyromellitic dianhydride 10.91
g (0.05 mol) was subjected to a polycondensation reaction to obtain a polyimide film. Attempts were made to measure the properties of the film, but measurements were not possible due to the fragility of the film.
比較例２
実施例１に準じてジアミノジフェニルエーテル１０．０
１ｇ（０，０５モル）とピロメリット酸ジ無水物１０．
９１ｇ（０，０５モル）を重縮合反応させ、ポリイミド
フィルムを得た。得られたフィルムの引張弾性率は２
、８６ｐａ、熱膨張率は２．８ Ｘ １０−’に−１で
あった。Comparative Example 2 Diaminodiphenyl ether 10.0 according to Example 1
1 g (0.05 mol) and pyromellitic dianhydride 10.
91 g (0.05 mol) was subjected to a polycondensation reaction to obtain a polyimide film. The tensile modulus of the obtained film is 2
, 86 pa, and the coefficient of thermal expansion was 2.8 x 10-'-1.
以上の通り、本発明によれば、構造単位（Ａ）〜（Ｄ）
を所定の割合で含むようにしたので、成形性に優れると
ともに、優れた耐熱性、機械特性、熱的特性などを有す
る芳香族ポリアミック酸または芳香族ポリアミック酸エ
ステル共重合体が得られる。As described above, according to the present invention, structural units (A) to (D)
Since the aromatic polyamic acid or aromatic polyamic acid ester copolymer is made to contain in a predetermined proportion, it is possible to obtain an aromatic polyamic acid or aromatic polyamic acid ester copolymer that has excellent moldability as well as excellent heat resistance, mechanical properties, thermal properties, etc.
Claims (3)
で表わされる構造単位 ▲数式、化学式、表等があります▼（Ａ） ▲数式、化学式、表等があります▼（Ｂ） ▲数式、化学式、表等があります▼（Ｃ） ▲数式、化学式、表等があります▼（Ｄ） （式中、Ａｒ＿１は４価の芳香族基、Ａｒ＿２は２価の
芳香族基、Ｒ＿１、Ｒ＿２は水素、１価の脂肪族基、ま
たはエーテル結合含有脂肪族基を示す。ただしＡｒ＿１
が▲数式、化学式、表等があります▼で、Ａｒ＿２が▲
数式、化学式、表等があります▼の組合せの場合を除く
。）を含み、単位（Ａ）と単位（Ｃ）の合計量、および
単位（Ｂ）と単位（Ｄ）の合計量は実質的に等モルであ
って、かつ単位（Ａ）と単位（Ｃ）の重量比が１０：９
０〜９０：１０であり、単位（Ｂ）と単位（Ｄ）の重量
比が１０：９０〜９０：１０であることを特徴とする芳
香族ポリアミック酸または芳香族ポリアミック酸エステ
ル共重合体。(1) Structural units represented by the following formulas (A), (B), (C), and (D) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (A) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(C) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(D) (In the formula, Ar_1 is a tetravalent aromatic group and Ar_2 is a divalent aromatic group. , R_1, R_2 represent hydrogen, a monovalent aliphatic group, or an ether bond-containing aliphatic group.However, Ar_1
is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and Ar_2 is ▲
There are mathematical formulas, chemical formulas, tables, etc.Except for the combination of ▼. ), the total amount of the unit (A) and the unit (C), and the total amount of the unit (B) and the unit (D) are substantially equimolar, and the unit (A) and the unit (C) The weight ratio of
0 to 90:10, and the weight ratio of units (B) to units (D) is 10:90 to 90:10.
表等があります▼または▲数式、化学式、表等がありま
す▼ であることを特徴とする特許請求の範囲第１項記載の芳
香族ポリアミック酸または芳香族ポリアミック酸エステ
ル共重合体。(2) Ar_1 has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
The aromatic polyamic acid or aromatic polyamic acid ester copolymer according to claim 1, wherein the aromatic polyamic acid or aromatic polyamic acid ester copolymer is characterized in that there are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼.
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▼ または▲数式、化学式、表等があります▼であることを
特徴と する特許請求の範囲第１項または第２項記載の芳香族ポ
リアミック酸または芳香族ポリアミック酸エステル共重
合体。(3) Ar_2 has ▲mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical 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,
The aromatic polyamic acid or aromatic polyamic acid ester copolymer according to claim 1 or 2, characterized in that there are tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8795787A JPS63254130A (en) | 1987-04-10 | 1987-04-10 | Copolymer of aromatic polyamic acid or ester thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8795787A JPS63254130A (en) | 1987-04-10 | 1987-04-10 | Copolymer of aromatic polyamic acid or ester thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63254130A true JPS63254130A (en) | 1988-10-20 |
Family
ID=13929348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8795787A Pending JPS63254130A (en) | 1987-04-10 | 1987-04-10 | Copolymer of aromatic polyamic acid or ester thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63254130A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05263049A (en) * | 1992-03-19 | 1993-10-12 | Kanegafuchi Chem Ind Co Ltd | Tape for tab and its production |
| JPWO2005061227A1 (en) * | 2003-12-24 | 2007-12-13 | 帝人株式会社 | Laminate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60210894A (en) * | 1984-04-04 | 1985-10-23 | 日立化成工業株式会社 | Method of producing substrate for flexible printed circuit board |
| JPS60210629A (en) * | 1984-04-04 | 1985-10-23 | Hitachi Chem Co Ltd | Production of polyimide molding |
| JPS6257916A (en) * | 1985-09-09 | 1987-03-13 | Toray Ind Inc | Copolyimide yarn |
| JPS62253621A (en) * | 1986-04-28 | 1987-11-05 | Hitachi Ltd | Polyimide resin |
| JPS63175026A (en) * | 1987-01-14 | 1988-07-19 | Kanegafuchi Chem Ind Co Ltd | Novel polyamic acid copolymer |
| JPH01103626A (en) * | 1987-01-20 | 1989-04-20 | Kanegafuchi Chem Ind Co Ltd | Preparation of polyamic acid copolymer |
-
1987
- 1987-04-10 JP JP8795787A patent/JPS63254130A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60210894A (en) * | 1984-04-04 | 1985-10-23 | 日立化成工業株式会社 | Method of producing substrate for flexible printed circuit board |
| JPS60210629A (en) * | 1984-04-04 | 1985-10-23 | Hitachi Chem Co Ltd | Production of polyimide molding |
| JPS6257916A (en) * | 1985-09-09 | 1987-03-13 | Toray Ind Inc | Copolyimide yarn |
| JPS62253621A (en) * | 1986-04-28 | 1987-11-05 | Hitachi Ltd | Polyimide resin |
| JPS63175026A (en) * | 1987-01-14 | 1988-07-19 | Kanegafuchi Chem Ind Co Ltd | Novel polyamic acid copolymer |
| JPH01103626A (en) * | 1987-01-20 | 1989-04-20 | Kanegafuchi Chem Ind Co Ltd | Preparation of polyamic acid copolymer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05263049A (en) * | 1992-03-19 | 1993-10-12 | Kanegafuchi Chem Ind Co Ltd | Tape for tab and its production |
| JPWO2005061227A1 (en) * | 2003-12-24 | 2007-12-13 | 帝人株式会社 | Laminate |
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