JPH0519578B2 - - Google Patents
Info
- Publication number
- JPH0519578B2 JPH0519578B2 JP60020100A JP2010085A JPH0519578B2 JP H0519578 B2 JPH0519578 B2 JP H0519578B2 JP 60020100 A JP60020100 A JP 60020100A JP 2010085 A JP2010085 A JP 2010085A JP H0519578 B2 JPH0519578 B2 JP H0519578B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- film
- heat
- liquid crystals
- dianhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920006015 heat resistant resin Polymers 0.000 claims description 9
- 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 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000009719 polyimide resin Substances 0.000 claims description 3
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 claims 1
- 239000004973 liquid crystal related substance Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 11
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 150000003949 imides Chemical group 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- -1 coatings Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JFOCEBKIPCVSGU-UHFFFAOYSA-N 1h-pyrrolo[2,3-d]imidazol-2-one Chemical compound C1=CNC2=NC(=O)N=C21 JFOCEBKIPCVSGU-UHFFFAOYSA-N 0.000 description 1
- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical compound C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 description 1
- FBXGQDUVJBKEAJ-UHFFFAOYSA-N 4h-oxazin-3-one Chemical compound O=C1CC=CON1 FBXGQDUVJBKEAJ-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 102000011759 adducin Human genes 0.000 description 1
- 108010076723 adducin Proteins 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000001841 cholesterols Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical compound C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000001564 phenyl benzoates Chemical class 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 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)
Description
〔産業上の利用分野〕
本発明は、光透過率の優れた、重合体主鎖中に
ヘテロのイミド環及びフラン環を有する強靭な耐
熱性樹脂の製造方法に関するものである。その目
的とするところは、閉環処理によりイミド化した
硬化樹脂が、ポリイミド樹脂としての耐熱性、耐
摩耗性、耐薬品性、電気絶縁性、皮膜形成性、可
撓性、機械特性などが優れ、電子デバイス用材
料、電気絶縁材料、被覆剤、接着材、塗料、成形
品、積層品、繊維あるいはフイルム材料などとし
て有用な耐熱性樹脂を提供するにあるが、中で
も、特に電子デバイス用の液晶表示素子の配向膜
として有用な耐熱性樹脂を提供するにある。
〔従来技術〕
従来、重合体主鎖中にヘテロ環、例えばイミ
ド、イミダゾール、チアゾール、オキサゾール、
オキサジアゾール、トリアゾール、キノキサリ
ン、チアジアゾール、オキサジノン、キナゾリ
ン、イミダゾピロロン、イソインドロキナゾロン
などを有するものが耐熱性が優れるということは
よく知られたことである。しかしながらこれら公
知の重合体は、重合体主鎖が剛直であり、フイル
ム、皮膜あるいは塗膜とした時に柔軟性、屈曲
性、伸びなどが乏しい。その為例えば液晶用配向
膜として使用すると、ラビング作業に耐えられ
ず、液晶を十分に配向できず表示素子としての機
能をはたしえない。またこれ等の重合体は硬化に
際し加熱すると著しく着色し、褐色ないしは黒褐
色になる。その為例えば液晶用配向膜として使用
すると液晶元素子が茶色を帯び、視野が暗くな
り、コントラストが低下し表示素子としての機能
をはたさなくなる。従来もこの様な観点より、耐
熱性と可撓性と淡色性と接着性を両立させるべく
種々検討が行なわれてきたが一方が良くなると他
方が悪くなるのが通例であつた。
〔発明の目的〕
本発明は、これまでのかかる欠点を克服すべく
検討した結果、ジアミン成分として、２，８−ジ
アミノジフエニレンオキサイドと、２，４−ジア
ミノトルエンを、又、テトラカルボン酸ジ無水物
成分として３，3′，４，4′−ベンゾフエノンテト
ラカルボン酸ジ無水物をそれぞれ必須成分として
使用する事により、耐熱性と可撓性と淡色性と接
着性のバランスが良くとれた耐熱性樹脂が得られ
ることを見い出し本発明を完成するに到つたもの
である。
〔発明の構成〕
本発明は、ジアミンとテトラカルボン酸ジ無水
物とを反応させイミド環を形成させるに際し、ジ
アミン成分として２，８−ジアミノジフエニレン
オキサイドと、２，４−ジアミノトルエンとを、
又テトラカルボン酸ジ無水物として、３，3′，
４，4′−ベンゾフエノンテトラカルボン酸ジ無水
物を必須成分として使用することを特徴とする耐
熱性樹脂の製造方法である。
反応式で示すと次の様になる。
[Industrial Application Field] The present invention relates to a method for producing a tough heat-resistant resin having excellent light transmittance and having a hetero imide ring and a furan ring in the polymer main chain. The purpose is that the cured resin imidized by the ring-closing process has excellent heat resistance, abrasion resistance, chemical resistance, electrical insulation, film-forming properties, flexibility, mechanical properties, etc. as a polyimide resin. We provide heat-resistant resins that are useful as materials for electronic devices, electrical insulating materials, coatings, adhesives, paints, molded products, laminates, fibers, and film materials, but especially for liquid crystal displays for electronic devices. An object of the present invention is to provide a heat-resistant resin useful as an alignment film for an element. [Prior Art] Conventionally, heterocycles such as imide, imidazole, thiazole, oxazole,
It is well known that compounds containing oxadiazole, triazole, quinoxaline, thiadiazole, oxazinone, quinazoline, imidazopyrrolone, isoindoroquinazolone, etc. have excellent heat resistance. However, these known polymers have rigid polymer main chains, and when formed into films, coatings, or coatings, they have poor flexibility, flexibility, and elongation. Therefore, when used as an alignment film for liquid crystal, for example, it cannot withstand rubbing work and cannot fully align the liquid crystal, making it unable to function as a display element. Furthermore, when these polymers are heated during curing, they become significantly colored, becoming brown or blackish brown. Therefore, when used as an alignment film for a liquid crystal, for example, the liquid crystal element becomes brownish, the visual field becomes dark, the contrast decreases, and it no longer functions as a display element. From this point of view, various studies have been made in the past in order to achieve a balance between heat resistance, flexibility, light color property, and adhesiveness, but it has generally been the case that when one is good, the other is bad. [Object of the Invention] As a result of studies aimed at overcoming such drawbacks, the present invention has been developed by using 2,8-diaminodiphenylene oxide, 2,4-diaminotoluene, and tetracarboxylic acid as diamine components. By using 3,3',4,4'-benzophenonetetracarboxylic dianhydride as an essential dianhydride component, it has a good balance of heat resistance, flexibility, light color, and adhesiveness. The present invention was completed by discovering that a heat-resistant resin can be obtained. [Structure of the Invention] The present invention uses 2,8-diaminodiphenylene oxide and 2,4-diaminotoluene as diamine components when reacting a diamine and a tetracarboxylic dianhydride to form an imide ring. ,
Also, as tetracarboxylic dianhydride, 3,3′,
This is a method for producing a heat-resistant resin characterized by using 4,4'-benzophenonetetracarboxylic dianhydride as an essential component. The reaction formula is as follows.
本発明の方法に従い、２，８−ジアミノジフエ
ニレンオキサイドと、２，４−ジアミノトルエン
と、３，3′，４，4′−ベンゾフエノンテトラカル
ボン酸ジ無水物を必須成分として使用した重合体
は、耐熱性と柔軟性と淡色性をバランスよく備え
た優れた耐熱性樹脂である。
即ち、本発明の方法により合成した重合体は、
２，８−ジアミノジフエニレンオキサイドの使用
により、分子構造中に、芳香族環・複素環を多数
有しており、耐熱性が優れている。また、主鎖が
ラセン状をなしており、この為に、スプリング的
効果でもつて柔軟性が優れているものと考えられ
る。更に２，４−ジアミノトルエンと、３，3′，
４，4′−ベンゾフエノンテトラカルボン酸ジ無水
物の導入により主鎖が共役構造をとれなくなる為
か、着色の少ない耐熱性樹脂が得られる。
本発明が用いられる用途を具体的にあげると、
先ず各種電子機材の表面を保護するコート用塗膜
として、又その上に多層配線を行う耐熱絶縁膜と
して用いられる。
例えば半導体、トランジスター、リニアーIC、
ハイブリツトIC、発光ダイオード、LSI、超LSI
などの電子回路用配線構造体である。
次に、本発明になる耐熱性樹脂が淡色である事
より、液晶表示装置の配向膜としても使用でき
る。即ち、本発明の重合体溶液を、酸化スズや酸
化インジユウムを主成分とする透明導電膜の形成
されたガラス基板あるいはプラスチツクフイルム
基板に、浸漬法、回転塗布法、スプレー法、印刷
法などで塗布し、加熱硬化後、ラビング処理す
る。ラビング方法は、ガーゼ、バフ研磨その他慣
用の手段を用いて行うことができる。本発明の配
向膜と組合せて使用できる液晶は、シツフ塩基型
液晶、フエニルシクロヘキサン型液晶、アゾキシ
型液晶、アゾ型液晶、ビフエニル型液晶、エステ
ル型液晶、フエニル・ピリミジン型液晶等のネマ
テイク液晶、上記のネマテイク液晶に旋光性物
質、コレステロール化合物、光学活性な置換基を
有するビフエニル誘導体、フエニルベンゾエート
等の光学活性化合物を添加したコレステリツク型
液晶などがあげられる。その他高温用のコーテイ
ングワニスとして、電線被覆、マグネツトワイ
ヤ、各種電気部品の浸漬コーテイング、金属部品
の保護コーテイングなどとして用いられると共に
含浸ワニスとしても、ガラスクロス、溶融石英ク
ロス、グラフアイト繊維やボロン繊維の含浸に使
用し、レーダードーム、プリント基板、放射性廃
棄物収納容器、タービン翼、高温性能と優れた電
気特性を要する宇宙船、その他の構造部品に使わ
れ、またマイクロ波の防止用放射線の防止用とし
てコンピユータなどの導波管、原子機器、レント
ゲン機器の内装材としても使用される。
また成形材料としてもグラフアイト粉末、グラ
フアイト繊維、二硫化モリブデンやポリ四フツ化
エチレンを添加して自己潤滑性の摺動面の製作に
用い、ピストンリング、弁座、ベアリング、シー
ル用などに用いられまた、ガラス繊維、グラフア
イト繊維やボロン繊維を添加して、ジエツトエン
ジン部品、高強度の構造用成形部品などが作られ
る。
更に高温用接着剤として、電気回路部品の接着
や宇宙船の構造部品の接着用に用いられる。
〔実施例〕
以下実施例により本発明を説明する。
実施例 １
温度計、撹拌機、原料仕込口及び乾燥窒素ガス
吹込口を備えた四ツ口のセパラブルフラスコに、
精製した無水の２，８−ジアミノフエニレンオキ
サイド29.735ｇ（15モル％）と、２，４−ジアミ
ノトルエン103.845ｇ（85モル％）をとり、これ
に無水のＮ−メチル−２−ピロリドン95重量％、
キシレン５重量％の混合溶剤を、全仕込原料中の
固形分割合が15重量％になるだけの量を加えて、
溶解した。乾燥窒素ガスは、反応の準備段階よ
り、生成物取出しまでの全工程にわたり流してお
いた。
次いで精製した無水の３，3′，４，4′−ベンゾ
フエノンテトラカルボン酸ジ無水物322.23ｇ
（100モル％）を、撹拌しながら少量づつ添加する
が、発熱反応であるため、外部水槽に約15℃の冷
水を循環させてこれを冷却した。添加後内部温度
を20℃に設定し、12時間撹拌し、反応を終了し
た。
得られた生成物は黄色透明の極めて粘稠なポリ
アミツク酸溶液であり、Ｎ−メチル−２−ピロリ
ドン0.5重量％溶液の固有粘度は、0.76（30℃）で
あつた。
次に、このポリアミツク酸をＮ−ジメチルアセ
トアミドで５重量％溶液としたものを、ガラス板
上に滴下し、スピンナーで400rpm／minで10秒
間続いて2000rpm／minで20秒間回転させ、均一
に塗布した。これを減圧下で、80℃、150℃、250
℃、350℃で各30分間ずつ順次に加熱し脱水閉環
させ、厚さ1μの淡黄色透明で強靭なポリイミド
樹脂フイルムを得た。このフイルムの赤外線吸収
スペクトルを見ると、1780cm-1及び730cm-1にイ
ミド環に基ずく強い吸収と、1200cm-1にフラン環
に基ずく強い吸収がみられた。
このフイルムは極めて耐熱性が優れており、空
気中での熱分解開始温度は、示差熱天秤分析装置
での測定で、昇温速度５℃／minで510℃であつ
た。フイルム強度も大きく、200℃熱間での引張
強度は14Kg／mm2と優れたものであつた。又フイル
ムは淡色性に優れ、光透過率は400nmで90％であ
つた。
実施例 ２
実施例１と同様な装置及び方法で、２，８−ジ
アミノジフエニレンオキサイド39.646ｇ（20モル
％）と２，４−ジアミノトルエン79.411ｇ（65モ
ル％）と４，4′−ジアミノジフエニルエーテル
30.036ｇ（15モル％）とを、３，3′，４，4′−ベ
ンゾフエノンテトラカルボン酸ジ無水物193.338
ｇ（60モル％）とピロメリツト酸ジ無水物87.248
ｇ（40モル％）に反応させた。
得られた生成物は、黄色透明の極めて粘稠なポ
リアミツク酸溶液であり、固有粘度は0.82であつ
た。また得られたフイルムは淡黄色透明で強靭性
に富み、熱分解開始温度は515℃、熱間引張強度
は16Kg／mm2、光透過率は82％と優れたものであつ
た。
比較例 １
実施例１と同様な装置及び方法で、２，４−ジ
アミノトルエン122.170ｇ（100モル％）と３，
3′4，4′−ベンゾフエノンテトラカルボン酸ジ無
水物322.230ｇ（100モル％）とを反応させた。
得られたフイルムは淡黄色透明であつたが、熱
分解開始温度は320℃しかなく、引張強度も５
Kg／mm2で到底ラビング作業に耐えるものではなか
つた。
比較例 ２
実施例１と同様な装置及び方法で、２，８−ジ
アミノジフエニレンオキサイド118.938ｇ（60モ
ル％）と、４，4′−ジアミノジフエニルエーテル
80.096ｇ（40モル％）とを、ピロメリツト酸ジ無
水物218.120ｇ（100モル％）に反応させた。
得られたフイルムは耐熱性があり強靭ではあつ
たが光透過率が51％しかなく、到底液晶配向膜と
して使用できるものではなかつた。
According to the method of the present invention, 2,8-diaminodiphenylene oxide, 2,4-diaminotoluene and 3,3',4,4'-benzophenonetetracarboxylic dianhydride were used as essential components. The polymer is an excellent heat-resistant resin that has a good balance of heat resistance, flexibility, and light color. That is, the polymer synthesized by the method of the present invention is
By using 2,8-diaminodiphenylene oxide, it has a large number of aromatic rings and heterocycles in its molecular structure, and has excellent heat resistance. In addition, the main chain has a helical shape, which is thought to give it excellent flexibility with a spring-like effect. Furthermore, 2,4-diaminotoluene and 3,3′,
A heat-resistant resin with little coloring can be obtained, probably because the main chain cannot form a conjugated structure due to the introduction of 4,4'-benzophenonetetracarboxylic dianhydride. Specifically, the uses of the present invention are as follows:
First, it is used as a coating film to protect the surfaces of various electronic equipment, and as a heat-resistant insulating film for multilayer wiring on top of it. For example, semiconductors, transistors, linear ICs,
Hybrid IC, light emitting diode, LSI, super LSI
It is a wiring structure for electronic circuits such as. Next, since the heat-resistant resin of the present invention is light-colored, it can also be used as an alignment film for liquid crystal display devices. That is, the polymer solution of the present invention is applied to a glass substrate or a plastic film substrate on which a transparent conductive film containing tin oxide or indium oxide as a main component is formed by a dipping method, a spin coating method, a spray method, a printing method, etc. After heat curing, rubbing treatment is performed. The rubbing method can be performed using gauze, buffing, or other conventional means. Liquid crystals that can be used in combination with the alignment film of the present invention include nemate liquid crystals such as Schiff base type liquid crystals, phenylcyclohexane type liquid crystals, azoxy type liquid crystals, azo type liquid crystals, biphenyl type liquid crystals, ester type liquid crystals, and phenyl-pyrimidine type liquid crystals; Examples include cholesteric liquid crystals in which optically active compounds such as optically active substances, cholesterol compounds, biphenyl derivatives having optically active substituents, and phenylbenzoates are added to the above-mentioned nematic liquid crystals. Other high-temperature coating varnishes include electric wire coatings, magnet wires, dipping coatings for various electrical parts, and protective coatings for metal parts.They can also be used as impregnation varnishes for glass cloth, fused silica cloth, graphite fibers, and boron fibers. It is used for the impregnation of radar domes, printed circuit boards, radioactive waste containers, turbine blades, spacecraft and other structural parts that require high temperature performance and good electrical properties, and for the prevention of microwave radiation. It is also used as an interior material for waveguides in computers, atomic equipment, and X-ray equipment. It is also used as a molding material to create self-lubricating sliding surfaces by adding graphite powder, graphite fiber, molybdenum disulfide, and polytetrafluoroethylene, and is used for piston rings, valve seats, bearings, seals, etc. It is also used to make jet engine parts, high-strength structural molded parts, etc. by adding glass fiber, graphite fiber, or boron fiber. Furthermore, it is used as a high-temperature adhesive for bonding electrical circuit parts and structural parts of spacecraft. [Example] The present invention will be explained below with reference to Examples. Example 1 A four-necked separable flask equipped with a thermometer, a stirrer, a raw material inlet, and a dry nitrogen gas inlet was
Take 29.735 g (15 mol%) of purified anhydrous 2,8-diaminophenylene oxide and 103.845 g (85 mol%) of 2,4-diaminotoluene, and add 95% by weight of anhydrous N-methyl-2-pyrrolidone. %,
Add a mixed solvent of 5% by weight of xylene in an amount that makes the solid content ratio in the total raw materials 15% by weight,
Dissolved. Dry nitrogen gas was kept flowing throughout the entire process from the reaction preparation stage to product removal. Then, 322.23 g of purified anhydrous 3,3',4,4'-benzophenonetetracarboxylic dianhydride
(100 mol %) was added little by little while stirring, but since it was an exothermic reaction, it was cooled by circulating cold water at about 15°C in an external water tank. After the addition, the internal temperature was set at 20°C and stirred for 12 hours to complete the reaction. The obtained product was a transparent yellow and extremely viscous polyamic acid solution, and the intrinsic viscosity of the 0.5% by weight solution of N-methyl-2-pyrrolidone was 0.76 (30°C). Next, a 5% by weight solution of this polyamic acid in N-dimethylacetamide was dropped onto a glass plate and spun at 400 rpm/min for 10 seconds and then 2000 rpm/min for 20 seconds using a spinner to spread it evenly. did. This was done at 80℃, 150℃, and 250℃ under reduced pressure.
℃ and 350℃ for 30 minutes each to cause dehydration and ring closure to obtain a pale yellow, transparent and tough polyimide resin film with a thickness of 1 μm. Looking at the infrared absorption spectrum of this film, strong absorption based on the imide ring was observed at 1780 cm -1 and 730 cm -1 and strong absorption based on the furan ring was observed at 1200 cm -1 . This film has extremely excellent heat resistance, and the thermal decomposition onset temperature in air was 510°C at a heating rate of 5°C/min, as measured by a differential thermal balance analyzer. The film also had high strength, with an excellent tensile strength of 14 kg/mm 2 at 200°C. Furthermore, the film had excellent hypochromic properties and a light transmittance of 90% at 400 nm. Example 2 Using the same apparatus and method as in Example 1, 39.646 g (20 mol%) of 2,8-diaminodiphenylene oxide, 79.411 g (65 mol%) of 2,4-diaminotoluene, and 4,4'- Diaminodiphenyl ether
30.036g (15 mol%) of 3,3',4,4'-benzophenonetetracarboxylic dianhydride 193.338
g (60 mol%) and pyromellitic dianhydride 87.248
g (40 mol%). The obtained product was a transparent yellow and extremely viscous polyamic acid solution with an inherent viscosity of 0.82. The obtained film was pale yellow and transparent, and had excellent toughness, with a thermal decomposition initiation temperature of 515°C, a hot tensile strength of 16 Kg/mm 2 , and a light transmittance of 82%. Comparative Example 1 Using the same apparatus and method as in Example 1, 122.170 g (100 mol%) of 2,4-diaminotoluene and 3,
322.230 g (100 mol %) of 3'4,4'-benzophenonetetracarboxylic dianhydride was reacted. The obtained film was pale yellow and transparent, but its thermal decomposition onset temperature was only 320°C and its tensile strength was only 5.
Kg/mm 2 , it could not withstand rubbing work at all. Comparative Example 2 Using the same apparatus and method as in Example 1, 118.938 g (60 mol%) of 2,8-diaminodiphenylene oxide and 4,4'-diaminodiphenyl ether were prepared.
80.096 g (40 mol %) was reacted with 218.120 g (100 mol %) of pyromellitic dianhydride. Although the obtained film was heat resistant and tough, it had a light transmittance of only 51% and could not be used as a liquid crystal aligning film.
Claims (1)
なるポリイミド樹脂の製造方法において、テトラ
カルボン酸ジ無水物成分として、３，3′，４，
4′−ベンゾフエノンテトラカルボン酸ジ無水物を
20モル％以上含有し、ジアミン成分として、２，
８−ジアミノジフエニレンオキサイド及び２，４
−ジアミノトルエンを各々0.5〜50モル％、20モ
ル％以上含有し、テトラカルボン酸ジ無水物とジ
アミンとのモル比を100：95〜105とし、０〜100
℃の温度で反応させることを特徴とする耐熱性樹
脂の製造方法。1. In a method for producing a polyimide resin comprising a tetracarboxylic dianhydride and a diamine, as the tetracarboxylic dianhydride component, 3,3',4,
4′-benzophenonetetracarboxylic dianhydride
Contains 20 mol% or more, as a diamine component, 2,
8-diaminodiphenylene oxide and 2,4
- Contains 0.5 to 50 mol% and 20 mol% or more of diaminotoluene, respectively, and the molar ratio of tetracarboxylic dianhydride and diamine is 100:95 to 105, and 0 to 100
A method for producing a heat-resistant resin, characterized by carrying out the reaction at a temperature of °C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010085A JPS61181827A (en) | 1985-02-06 | 1985-02-06 | Production of heat-resistant resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010085A JPS61181827A (en) | 1985-02-06 | 1985-02-06 | Production of heat-resistant resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61181827A JPS61181827A (en) | 1986-08-14 |
| JPH0519578B2 true JPH0519578B2 (en) | 1993-03-17 |
Family
ID=12017694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010085A Granted JPS61181827A (en) | 1985-02-06 | 1985-02-06 | Production of heat-resistant resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61181827A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61176629A (en) * | 1985-02-01 | 1986-08-08 | Sumitomo Bakelite Co Ltd | Production of heat-resistant resin |
| JPS61181830A (en) * | 1985-02-06 | 1986-08-14 | Sumitomo Bakelite Co Ltd | Production of heat-resistant resin |
| JPS61181832A (en) * | 1985-02-06 | 1986-08-14 | Sumitomo Bakelite Co Ltd | Production of heat-resistant resin |
| JPS61181831A (en) * | 1985-02-06 | 1986-08-14 | Sumitomo Bakelite Co Ltd | Production of heat-resistant resin |
| JP2847701B2 (en) * | 1986-11-29 | 1999-01-20 | 鐘淵化学工業株式会社 | Polyamic acid excellent in thermal dimensional stability and method for producing polyimide comprising the same |
| JP2744786B2 (en) * | 1987-01-20 | 1998-04-28 | 鐘淵化学工業株式会社 | Polyimide with excellent thermal dimensional stability and polyamic acid used for it |
| JPS6416833A (en) * | 1987-07-10 | 1989-01-20 | Kanegafuchi Chemical Ind | Polyamic acid copolymer, polyimide copolymer therefrom and production thereof |
| JPS6416832A (en) * | 1987-07-10 | 1989-01-20 | Kanegafuchi Chemical Ind | Production of polyamic acid copolymer |
| JPS6416834A (en) * | 1987-07-10 | 1989-01-20 | Kanegafuchi Chemical Ind | Polyamic acid copolymer, polyimide copolymer therefrom and production thereof |
| JPH0455432A (en) * | 1990-06-25 | 1992-02-24 | Sumitomo Bakelite Co Ltd | Solvent-soluble polyimide oligomer and composition containing the same |
| JP2673630B2 (en) * | 1992-03-19 | 1997-11-05 | 鐘淵化学工業 株式会社 | TAB tape and method for producing the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61176629A (en) * | 1985-02-01 | 1986-08-08 | Sumitomo Bakelite Co Ltd | Production of heat-resistant resin |
| JPS61181831A (en) * | 1985-02-06 | 1986-08-14 | Sumitomo Bakelite Co Ltd | Production of heat-resistant resin |
| JPS61181830A (en) * | 1985-02-06 | 1986-08-14 | Sumitomo Bakelite Co Ltd | Production of heat-resistant resin |
| JPS61181832A (en) * | 1985-02-06 | 1986-08-14 | Sumitomo Bakelite Co Ltd | Production of heat-resistant resin |
| JPS6353210A (en) * | 1986-08-22 | 1988-03-07 | Sumitomo Metal Ind Ltd | Method for improving stress corrosion cracking resistance of stainless steel |
| JPS6366852A (en) * | 1986-09-09 | 1988-03-25 | Shin Kobe Electric Mach Co Ltd | Manufacture of electrode for lead acid battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2820683B2 (en) * | 1987-07-31 | 1998-11-05 | ランデス株式会社 | Compression joining device for concrete members |
-
1985
- 1985-02-06 JP JP2010085A patent/JPS61181827A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61176629A (en) * | 1985-02-01 | 1986-08-08 | Sumitomo Bakelite Co Ltd | Production of heat-resistant resin |
| JPS61181831A (en) * | 1985-02-06 | 1986-08-14 | Sumitomo Bakelite Co Ltd | Production of heat-resistant resin |
| JPS61181830A (en) * | 1985-02-06 | 1986-08-14 | Sumitomo Bakelite Co Ltd | Production of heat-resistant resin |
| JPS61181832A (en) * | 1985-02-06 | 1986-08-14 | Sumitomo Bakelite Co Ltd | Production of heat-resistant resin |
| JPS6353210A (en) * | 1986-08-22 | 1988-03-07 | Sumitomo Metal Ind Ltd | Method for improving stress corrosion cracking resistance of stainless steel |
| JPS6366852A (en) * | 1986-09-09 | 1988-03-25 | Shin Kobe Electric Mach Co Ltd | Manufacture of electrode for lead acid battery |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61181827A (en) | 1986-08-14 |
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