JPH0315931B2 - - Google Patents
Info
- Publication number
- JPH0315931B2 JPH0315931B2 JP12384184A JP12384184A JPH0315931B2 JP H0315931 B2 JPH0315931 B2 JP H0315931B2 JP 12384184 A JP12384184 A JP 12384184A JP 12384184 A JP12384184 A JP 12384184A JP H0315931 B2 JPH0315931 B2 JP H0315931B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide compound
- mol
- dianhydride
- polyamic acid
- film
- 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
Links
- 239000004642 Polyimide Substances 0.000 claims description 57
- 229920001721 polyimide Polymers 0.000 claims description 57
- 150000001875 compounds Chemical class 0.000 claims description 55
- 229920005575 poly(amic acid) Polymers 0.000 claims description 22
- 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 18
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 7
- -1 2,3,5-tricarboxycyclopentyl Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 18
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 239000002798 polar solvent Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 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 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- RHRNYXVSZLSRRP-UHFFFAOYSA-N 3-(carboxymethyl)cyclopentane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CC1C(C(O)=O)CC(C(O)=O)C1C(O)=O RHRNYXVSZLSRRP-UHFFFAOYSA-N 0.000 description 2
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-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
- 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 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 2
- 125000005462 imide group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002250 progressing effect Effects 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- UDKYPBUWOIPGDY-UHFFFAOYSA-N 3-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=CC(N)=C1 UDKYPBUWOIPGDY-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- HSBOCPVKJMBWTF-UHFFFAOYSA-N 4-[1-(4-aminophenyl)ethyl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)C1=CC=C(N)C=C1 HSBOCPVKJMBWTF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- IREPGQRTQFRMQR-UHFFFAOYSA-N furantetracarboxylic acid Chemical compound OC(=O)C=1OC(C(O)=O)=C(C(O)=O)C=1C(O)=O IREPGQRTQFRMQR-UHFFFAOYSA-N 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
- 239000007789 gas Substances 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
〔技術分野〕
本発明は、ポリイミド化合物の製法に関し、特
に耐熱性、抗吸水性および光透過性が改良された
有機溶媒可溶性のポリイミド化合物の製法に関す
る。
〔従来技術〕
一般にポリイミド化合物は優れた耐熱性を有し
ているため、高温下で使用するフイルム、電線被
覆剤、接着剤、塗料等の原料として非常に有用で
ある。
従来のポリイミド化合物として無水ピロメリツ
ト酸等の芳香族テトラカルボン酸二無水物と芳香
族アミンとを、極性溶媒中で重合反応させて芳香
族ポリアミツク酸を得、次にこれの溶液を基材に
塗布し、フイルム状にした後、加熱等の方法によ
り脱水閉環して得られるフイルム状芳香族ポリイ
ミド化合物が知られている。しかし、従来の芳香
族ポリイミド化合物は、その前駆体である芳香族
ポリアミツク酸の安定性が悪く、室温で放置する
と、ポリアミツク酸溶液の粘度が低下し、さらに
長期間放置すると一部が脱水閉環してポリイミド
となり、不溶化して白濁を生じるなどの欠点を有
している。このため、従来の芳香族ポリアミツク
酸の溶液は低温で保存する必要があり、その取扱
いには注意を要するという欠点があつた。
また上記のポリイミド化合物の製法では、基材
に塗布したポリアミツク酸をイミド化する際に通
常400℃以上の高温で長時間加熱する必要がある
ため省エネルギーの見地から不利であり、またイ
ミド化には脱水反応が伴なうために得られるフイ
ルムにボイド、ピンホール等の欠陥が生じ、平滑
で均質なポリイミド化合物のフイルムを得ること
は困難であるという欠点もあつた。さらに、この
ようにして製造される芳香族ポリイミド化合物
は、一般に着色が著しくて光透過性が低い上、抗
吸水性が低いため吸水率が高いという欠点を有し
ていた。
本発明者らは先に２，３，５−トリカルボキシ
シクロペンチル酢酸または無水物とから得られる
ポリイミド化合物が一定の有機溶媒に可溶で保存
安定性が高いことを見い出し特許出願を行つた
（特願昭58−73884号）、このポリイミド化合物は
一定の有機溶媒に可溶であるのでその溶液を平滑
な表面に流延することによつてポリイミド化合物
のフイルムを製造することができる。この場合、
フイルム作製の際に脱水反応等を伴なわないので
滑らかで均質なフイルムを得ることができるが、
得られたポリイミド化合物は耐熱性および抗吸水
性の点で一層の改良が望まれた。
〔発明の目的〕
本発明の目的は、前記特願昭58−73884号に開
示したポリイミド化合物の製造法を改良し、耐熱
性、抗吸水性および光透過性がさらに向上した有
機溶媒可溶性ポリイミド化合物の製法を提供する
ことである。
〔発明の構成〕
(A)２，３，５−トリカルボキシシクロペンチル
酢酸二無水物（以下、「TCH・AH」と称する）
25モル％以上と芳香族テトラカルボン酸二無水物
３モル％以上からなる混合物と、(B)有機ジアミン
とから得られるポリアミツク酸をイミド化するこ
とからなる有機溶媒可溶性ポリイミド化合物の製
法が提供される。
本発明に用いられる(A)成分の２種のテトラカル
ボン酸二無水物（以下、これらを「テトラカルボ
ン酸無水物類」と総称する）のうち、TCH・
AHは、例えばジシクロペンタジエンをオゾン分
解し、過酸化水素で酸化する方法（英国特許第
872355号、J.Org.Chem.，282537（1963）、または
ジシクロペンタジエンを水和して得られるヒドロ
キシジシクロペンタジエンを硝酸酸化する方法
（***特許第1078120号）などによつて得られるテ
トラカルボン酸を脱水することにより製造するこ
とができる。
(A)成分のうちの芳香族テトラカルボン酸二無水
物の具体例としては、ピロメリツト酸二無水物、
３，3′，４，4′−ベンゾフエノンテトラカルボン
酸二無水物、３，3′，４，4′−ビフエニルスルホ
ンテトラカルボン酸二無水物、１，２，５，６−
ナフタレンテトラカルボン酸二無水物、１，４，
５，８−ナフタレンテトラカルボン酸二無水物、
２，３，６，７−ナフタレンテトラカルボン酸二
無水物、フランテトラカルボン酸二無水物、３，
3′，４，4′−ビフエニルエーテルテトラカルボン
酸二無水物、３，3′，４，4′−ジメチルジフエニ
ルシランテトラカルボン酸二無水物、３，3′，
４，4′−テトラフエニルシランテトラカルボン酸
二無水物、３，3′，４，4′−パーフルオロイソプ
ロピリデンテトラカルボン酸二無水物等を挙げる
ことができ、好ましくはピロメリツト酸二無水
物、３，3′，４，4′−ベンゾフエノンテトラカル
ボン酸二無水物、３，3′，４，4′−ビフエニルス
ルホンテトラカルボン酸二無水物を用いることが
できる。上記の芳香族テトラカルボン酸二無水物
は１種単独でも２種以上の組合せでも使用するこ
とができる。
２種以上の芳香族テトラカルボン酸二無水物を
組合せる場合、得られるポリイミド化合物が可溶
性および耐熱性の点で一層優れることならびに入
手もしくは合成が容易であることから、
ピロメリツト酸二無水物と３，3′，４，4′−ベ
ンゾフエノンテトラカルボン酸二無水物；
３，3′，４，4′−ベンゾフエノンテトラカルボ
ン酸二無水物と３，3′，４，4′−ビフエニルスル
ホンテトラカルボン酸二無水物；
ピロメリツト酸二無水物と３，3′，４，4′−ベ
ンゾフエノンテトラカルボン酸二無水物と３，
3′，４，4′−ビフエニルスルホンテトラカルボン
酸二無水物等の組合せが好ましい。
本発明の製法において、(A)成分のテトラカルボ
ン酸無水物類の配合は、TCA・AHが25モル％
以上で、芳香族テトラカルボン酸二無水物が３モ
ル％以上の割合となるように行われる。好ましく
は、芳香族テトラカルボン酸二無水物が、５〜65
モル％、さらに好ましくは10〜60モル％となるよ
うに配合される。芳香族テトラカルボン酸二無水
物の量が３モル％未満であると耐熱性および抗吸
水性の向上は望めず、75モル％を超えると得られ
るポリイミド化合物の光透過性が悪化し、またい
ずれの有機溶媒にも不溶性のものとなる。
また、本発明に用いられる(B)成分の有機ジアミ
ンとしては、一般式：H2N−Ｒ−NH2…（）
で示される化合物（Ｒは２価の芳香族基、脂肪族
基、脂環式基またはオルガノシロキサン基を示
す）が挙げられる。上記一般式（）における好
ましいＲとしては、例えば、
[Technical Field] The present invention relates to a method for producing a polyimide compound, and particularly to a method for producing an organic solvent-soluble polyimide compound with improved heat resistance, water absorption resistance, and light transmittance. [Prior Art] Polyimide compounds generally have excellent heat resistance and are therefore very useful as raw materials for films, wire coatings, adhesives, paints, etc. that are used at high temperatures. As a conventional polyimide compound, an aromatic tetracarboxylic dianhydride such as pyromellitic anhydride and an aromatic amine are polymerized in a polar solvent to obtain an aromatic polyamic acid, and then a solution of this is applied to a substrate. A film-like aromatic polyimide compound obtained by forming the compound into a film and then dehydrating and ring-closing it by a method such as heating is known. However, in conventional aromatic polyimide compounds, the stability of aromatic polyamic acid, which is the precursor thereof, is poor, and if left at room temperature, the viscosity of the polyamic acid solution decreases, and if left for a long period of time, part of the polyamic acid solution undergoes dehydration and ring closure. It has the disadvantage that it becomes polyimide, becomes insolubilized, and becomes cloudy. For this reason, conventional solutions of aromatic polyamic acid have to be stored at low temperatures and have the drawback of requiring care in handling. In addition, the above method for producing polyimide compounds requires heating at a high temperature of 400°C or higher for a long time when imidizing the polyamic acid applied to the base material, which is disadvantageous from an energy saving perspective. Due to the accompanying dehydration reaction, defects such as voids and pinholes occur in the film obtained, and it is difficult to obtain a smooth and homogeneous polyimide compound film. Furthermore, the aromatic polyimide compounds produced in this manner generally have the drawbacks of being significantly colored and having low light transmittance, as well as having a high water absorption rate due to low water absorption resistance. The present inventors previously discovered that a polyimide compound obtained from 2,3,5-tricarboxycyclopentyl acetic acid or anhydride is soluble in certain organic solvents and has high storage stability, and filed a patent application. Since this polyimide compound is soluble in certain organic solvents, a film of the polyimide compound can be produced by casting the solution onto a smooth surface. in this case,
Since no dehydration reaction is involved during film production, smooth and homogeneous films can be obtained.
It was desired that the obtained polyimide compound would be further improved in terms of heat resistance and water absorption resistance. [Object of the Invention] The object of the present invention is to improve the method for producing a polyimide compound disclosed in the above-mentioned Japanese Patent Application No. 58-73884, and to produce an organic solvent-soluble polyimide compound with further improved heat resistance, water absorption resistance, and light transmittance. The objective is to provide a manufacturing method for [Structure of the invention] (A) 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (hereinafter referred to as "TCH・AH")
Provided is a method for producing an organic solvent-soluble polyimide compound, which comprises imidizing polyamic acid obtained from a mixture of 25 mol% or more and an aromatic tetracarboxylic dianhydride and 3 mol% or more, and (B) an organic diamine. Ru. Among the two types of tetracarboxylic dianhydrides (hereinafter collectively referred to as "tetracarboxylic anhydrides") as component (A) used in the present invention, TCH.
AH can be obtained by, for example, ozonolyzing dicyclopentadiene and oxidizing it with hydrogen peroxide (British patent no.
872355, J.Org.Chem., 28 2537 (1963), or a method of oxidizing hydroxydicyclopentadiene obtained by hydrating dicyclopentadiene with nitric acid (West German Patent No. 1078120). It can be produced by dehydrating carboxylic acid. Specific examples of the aromatic tetracarboxylic dianhydride of component (A) include pyromellitic dianhydride,
3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,2,5,6-
naphthalenetetracarboxylic dianhydride, 1,4,
5,8-naphthalenetetracarboxylic dianhydride,
2,3,6,7-naphthalenetetracarboxylic dianhydride, furantetracarboxylic dianhydride, 3,
3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',
Examples include 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-perfluoroisopropylidene tetracarboxylic dianhydride, and preferably pyromellitic dianhydride. , 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride can be used. The above aromatic tetracarboxylic dianhydrides can be used alone or in combination of two or more. When two or more aromatic tetracarboxylic dianhydrides are combined, the resulting polyimide compound has better solubility and heat resistance, and is easy to obtain or synthesize. ,3',4,4'-benzophenonetetracarboxylic dianhydride; 3,3',4,4'-benzophenone tetracarboxylic dianhydride and 3,3',4,4'-biphenate enylsulfonetetracarboxylic dianhydride; pyromellitic dianhydride and 3,3',4,4'-benzophenonetetracarboxylic dianhydride;
Combinations such as 3',4,4'-biphenylsulfone tetracarboxylic dianhydride are preferred. In the production method of the present invention, the tetracarboxylic acid anhydride as component (A) is blended with 25 mol% TCA/AH.
The above steps are carried out so that the proportion of the aromatic tetracarboxylic dianhydride is 3 mol % or more. Preferably, the aromatic tetracarboxylic dianhydride has 5 to 65
The amount is preferably 10 to 60 mol%. If the amount of aromatic tetracarboxylic dianhydride is less than 3 mol%, no improvement in heat resistance and water absorption resistance can be expected, and if it exceeds 75 mol%, the light transmittance of the resulting polyimide compound will deteriorate, and It is also insoluble in organic solvents. In addition, the organic diamine as the component (B) used in the present invention has the general formula: H 2 NR-NH 2 ... ()
Examples include compounds represented by (R represents a divalent aromatic group, aliphatic group, alicyclic group, or organosiloxane group). Preferred R in the above general formula () is, for example,
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
（式中X1，X2，X3およびX4は、同一でも異なつ
てもよく、−Ｈ、−CH3または−OCH3を示し、Ｙ
は−CH2−、−C2H4−、−Ｏ−、−Ｓ−、[Formula] (In the formula, X 1 , X 2 , X 3 and X 4 may be the same or different and represent -H, -CH 3 or -OCH 3 ,
-CH 2 -, -C 2 H 4 -, -O-, -S-,
【式】
−SO2−または−CONH−を示し、ｎは０または
１を示す）で示される芳香族基；
−（CH2）ｎ−（ｎ＝２〜20）、
[Formula] An aromatic group represented by -SO 2 - or -CONH-, where n is 0 or 1); -(CH 2 )n- (n = 2 to 20),
【式】または[expression] or
【式】
で示される炭素原子数２〜20の脂肪族基または脂
環式基；
式
〔式中、R′は[Formula] An aliphatic group or alicyclic group having 2 to 20 carbon atoms; [In the formula, R′ is
【式】 （−CH2）−l（ｌ＝１〜50）、[Formula] (-CH 2 ) -l (l=1-50),
【式】
等２価の脂肪族、脂環式または芳香族の炭化水素
基を示しR″は[Formula] Represents a divalent aliphatic, alicyclic or aromatic hydrocarbon group, and R″ is
【式】
CnH2o+1−（ｎ＝１〜20）
等の１価の脂肪族、脂環式または芳香族の炭化水
素基を示し、ｍは１〜100の整数である］
で示されるオルガノシロキサン基を挙げることが
できる。
上記一般式（）の有機ジアミンの具体例とし
ては、パラフエニレンジアミン、メタフエニレン
ジアミン、４，4′−ジアミノジフエニルメタン、
４，4′−ジアミノジフエニルエタン、ベンジジ
ン、４，4′ジアミノジフエニルスルフイド、４，
4′−ジアミノジフエニルスルホン、４，4′−ジア
ミノジフエニルエーテル、３，3′−ジアミノベン
ゾフエノン、４，4′−ジアミノベンゾフエノン、
１，５−ジアミノナフタレン、３，3′−ジメチル
−４，4′−ジアミノビフエニル、３，4′−ジアミ
ノベンズアニリド、３，4′−ジアミノジフエニル
エーテル、メタキシリレンジアミン、パラキシリ
レンジアミン、エチレンジアミン、１，３−プロ
パンジアミン、テトラメチレンジアミン、ペンタ
メチレンジアミン、ヘキサメチレンジアミン、ヘ
プタメチレンジアミン、オクタメチレンジアミ
ン、ノナメチレンジアミン、４，4′−ジメチルヘ
プタメチレンジアミン、１，４−ジアミノシクロ
ヘキサン、テトラヒドロジシクロペンタジエニレ
ンジアミン、ヘキサヒドロ−４，７−メタノイン
ダニレンジメチレンジアミン、トリシクロ〔６，
２，１，02.7〕−ウンデシレンジメチルジアミン
等、および、
等で示されるジアミノオルガノシロキサンを挙げ
ることができる。これらの有機ジアミンは、１種
単独でも２種以上の組合わせでも使用することが
できる。
これらの有機ジアミンの中でも、前記一般式
（）におけるＲが芳香族基であるものが得られ
るポリイミド化合物がより高い耐熱性を有するこ
とから好ましく、特にＲが
[Formula] Represents a monovalent aliphatic, alicyclic, or aromatic hydrocarbon group such as CnH 2o+1 − (n = 1 to 20), where m is an integer of 1 to 100] Mention may be made of siloxane groups. Specific examples of the organic diamine of the above general formula () include paraphenylenediamine, metaphenylenediamine, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylethane, benzidine, 4,4'diaminodiphenyl sulfide, 4,
4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone,
1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, metaxylylene diamine, paraxylylene diamine Amine, ethylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4'-dimethylheptamethylenediamine, 1,4-diamino Cyclohexane, tetrahydrodicyclopentadienyl diamine, hexahydro-4,7-methanoindani dimethylene diamine, tricyclo[6,
2,1,0 2.7 ]-undecylenedimethyldiamine, etc., and Examples include diaminoorganosiloxanes shown in the following. These organic diamines can be used alone or in combination of two or more. Among these organic diamines, polyimide compounds in which R in the general formula () is an aromatic group are preferable because they have higher heat resistance, and in particular, those in which R is an aromatic group are preferable because they have higher heat resistance.
【式】または[expression] or
【式】
で表わされる芳香族ジアミン、例えば４，4′−ジ
アミノフエニルエーテル、４，4′−ジアミノジフ
エニルメタン、４，4′−ジアミノジフエニルスル
ホンが好ましい。さらにＲが
Aromatic diamines represented by the formula, such as 4,4'-diaminophenyl ether, 4,4'-diaminodiphenylmethane, and 4,4'-diaminodiphenyl sulfone, are preferred. Furthermore, R
本発明の製法により得られるポリイミド化合物
は前記の一定の有機溶媒に容易に溶解し、しかも
溶液状態で非常に安定であるため長期にわたつて
保存可能である。また、このポリイミド化合物
は、耐熱性、機械的特性、電気特性、耐薬品特性
等に優れた特性を示し、特に抗吸水性、耐熱性お
よび光透過性に優れているという特徴を有するの
で、例えば高温用フイルム、接着剤、塗料等に有
用であり、具体的にはプリント配線基板、フレキ
シブル配線基板、半導体集積回路素子の表面保護
膜または層間絶縁膜、液晶配向膜、エナメル電線
用被覆材、種積層板、ガスケツト等に有用であ
る。
〔実施例〕
以下、本発明を実施例によつてさらに詳細に説
明するが、本発明はこれらの実施例によつて制限
されるものではない。
実施例 １
１フラスコ内で、窒素気流下、ジメチルホル
ムアミド（DMF）200mlに、４，４−ジアミノジ
フエニルエーテル（DDE）20.00ｇ（0.100モル）
を溶解し、得られた溶液に撹拌下、25℃でピロメ
リツト酸二無水物5.45ｇ（0.025モル）とTCH・
AH16.81ｇ（0.075モル）を粉末のまま加え、こ
の混合物を25℃で18時間反応させてポリアミツク
酸を得た。
得られたポリアミツク酸溶液にDMF200mlを加
えて希釈した後、ピリジン55.4ｇと無水酢酸51.0
ｇを加え、90℃で３時間反応させてポリイミド化
合物を合成した。得られたポリイミド化合物溶液
を大量のエタノールに注ぎ、凝固した。凝固した
ポリイミド化合物を100℃で18時間真空乾燥した。
得られたポリイミド化合物は、DMF、Ｎ−メチ
ル−２−ピロリドン等の非プロトン系極性溶媒お
よびｍ−クレゾール等のフエノール系溶媒に可溶
であつた。
得られたポリイミド化合物の赤外線吸収スペク
トルを測定すると図１に示すスペクトルが得られ
た。1780cm-1、1730cm-1にイミド基に基づくＣ
＝０伸縮振動が現われ、ポリアミツク酸のアミド
基に基づく1650cm-1のＣ＝０伸縮振動が消失し
ていることから、得られたポリイミド化合物は少
なくとも95％以上のイミド化が進行していること
がわかつた。
このポリイミド化合物に15重量％の濃度になる
ように所定量のDMFを加えて溶解し、溶液をガ
ラス板の平滑な表面上に流延し、80℃×30分、
120℃×10分、150℃×10分さらに200℃×１時間
の加熱により乾燥し、完全に溶媒を除き、厚み
25μmの均一な黄色透明フイルムを得た。得られ
たポリイミド化合物フイルムの引張強度を求め
た。また、熱重量分析（窒化気流下、昇温速度：
10℃／min）から10％熱分解の温度を測定した。
さらに、このポリイミド化合物フイルムの波長
400nmの光についての光透過率を求め、10μmの
膜厚に換算した。またこのポリイミド化合物フイ
ルムの吸水率をJIS C6481に規定の方法（浸漬温
度25℃×24時間）によつて求めた。これらの結果
を表１に示す。
実施例 ２
実施例１において、ピロメリツト酸二無水物の
代りに３，3′，４，4′−ベンゾフエノンテトラカ
ルボン酸二無水物（以下、BTDAと略す）8.06ｇ
（0.025モル）を用い、TCH・AHを16.81ｇ
（0.075モル）用い、表１に示すイミド化条件のほ
かは実施例１と同様にしてポリイミド化合物を製
造し、厚さ28μmのフイルムを作製した。実施例
１と同様に試験を行なつた結果を表１に示す。な
お、得られたポリイミド化合物は、DMF、Ｎ−
メチル−２−ピロリドン等の非プロトン系極性溶
媒およびｍ−クレゾール等のフエノール系溶媒に
可溶であつた。
実施例 ３
実施例１において、ピロメリツト酸二無水物の
代りにBTDA16.12ｇ（0.050モル）を使用し、
TCH・AHを8.41ｇ（0.050モル）使用し、表１
に示すイミド化条件を採用した以外は実施例１と
同様にしてポリイミド化合物を製造した。得られ
たポリイミドはｍ−クレゾール等のフエノール系
溶媒に可溶であつた。このポリイミド化合物か
ら、溶媒としてｍ−クレゾールを用いた以外は実
施例１と同様にして厚さ25μmのフイルムを作製
した。実施例１と同様に試験を行つた結果を表１
に示す。
実施例 ４
実施例１において、ピロメリツト酸二無水物の
代りにBTDA24.18ｇ（0.075モル）を使用し、
TCH・AHを4.21ｇ（0.025モル）使用し、表１
に示すイミド化条件を採用した以外は実施例１と
同様にしてポリイミド化合物を製造した。得られ
たポリイミドはｍ−クレゾール等のフエノール系
溶媒に可溶であつた。このポリイミド化合物か
ら、溶媒としてｍ−クレゾールを用いた以外は実
施例１と同様にして厚さ25μmのフイルムを作製
した。実施例１と同様に試験を行つた結果を表１
に示す。
実施例 ５
実施例１において、ピロメリツト酸二無水物と
TCH・AHの使用量をそれぞれ5.45ｇ（0.25モ
ル）と8.41ｇ（0.50モル）に変え、さらに
BTDA8.06ｇ（0.025モル）を使用し、表１に示
すイミド化条件を採用した以外は実施例１と同様
にしてポリイミド化合物を製造し、厚さ30μmの
フイルムを作製した。実施例１と同様に試験を行
つた結果を表１に示す。
なお、得られたポリイミドは、DMF、Ｎ−メ
チル−２−ピロリドン等の非プロトン系極性溶媒
およびｍ−クレゾール等のフエノール系溶媒に可
溶であつた。
実施例 ６
１フラスコ内で、窒素気流下、Ｎ−メチルピ
ロリドン（NMP）200mlに２，５−（４−アミノ
フエニル）−３，４−ジフエニルチオフエン12.54
ｇ（0.030モル）を溶解し、得られた溶液に撹拌
下、25℃でBTDA4.83ｇ（0.015モル）および
TCH・AH3.36ｇ（0.015モル）を粉末のまま加
え、この混合物を50℃で３時間反応させてポリア
ミツク酸を得た。
得られたポリアミツク酸溶液に無水酢酸9.18ｇ
とピリジン11.73ｇを加え、130℃で３時間反応さ
せてポリイミド化合物を合成した。得られたポリ
イミド化合物溶液を大量のエタノールに注ぎ、凝
固させた。凝固したポリイミド化合物を120℃で
18時間真空乾燥し、19.8ｇの生成物を得た。生成
ポリマーの赤外線吸収スペクトルを測定すると
1780cm-1、1730cm-1にイミド基に基づくＣ＝０
伸縮振動が現われ、ポリアミツク酸のアミド基に
基づく1650cm-1のＣ＝０伸縮振動が消失してい
ることから、得られたポリイミド化合物は少なく
とも95％以上のイミド化が進行していることがわ
かつた。このポリイミド化合物の固有粘度は
0.39dl／ｇ（NMP中）であつた。このポリイミ
ド化合物は、DMF、NMP、ｒ−ブチロラクト
ン、シクロヘキサノン等の極性溶媒およびｍ−ク
レゾール等のフエノール系溶媒に可溶であつた。
実施例 ７
実施例６において、BTDAの代りにピロメリ
ツト酸二無水物3.27ｇ（0.015モル）を加えたほ
かは、実施例６と同様にしてポリイミド化合物を
製造した。得られたポリイミド化合物の収量は
17.0ｇで、その固有粘度は0.54dl／ｇ（NMP中）
であつた。このポリイミド化合物は、DMF、
NMP、ｒ−ブチロラクトン等の非プロトン系極
性溶媒およびｍ−クレゾール等のフエノール系溶
媒に可溶であつた。
比較例 １
実施例１において、ピロメリツト酸二無水物は
用いず、TCH・AH使用量を16.82ｇ（0.100モ
ル）に変え、表１に示すイミド化条件を採用した
以外は実施例１と同様にしてポリイミド化合物を
製造した。このポリイミド化合物はDMF、Ｎ−
メチル−２−ロリドン等の非プロトン系極性溶媒
に可溶であつた。得られたポリイミド化合物か
ら、実施例１と同様にして厚さ20μmのフイルム
を作製した。実施例１と同様に試験を行つた結果
を表１に示す。
比較例 ２
実施例１において、ピロメリツト酸二無水物お
よびTCH・AHの代りにBTDA32.24ｇ（0.100モ
ル）を使用した以外は実施例１と同様にしてポリ
アミツク酸を合成し、その後このポリアミツク酸
を実施例１と同様にしてイミド化反応に供した
が、反応始直後にポリマーが析出した。生成した
ポリマーの赤外線吸収スペクトルを測定したとこ
ろ、ポリアミツク酸のイミド化が進行していた
が、このポリマーはいずれの有機溶媒にも不溶で
溶液の流延によりフイルム化することは不可能で
あつた。
比較例 ３
実施例１において、TCH・AHは使用せず、
ピロメリツト酸二無水物の使用量を21.80ｇ
（0.100モル）とした以外は実施例１と同様にして
ポリアミツク酸を合成し、その後このポリアミツ
ク酸を実施例１と同様にしてイミド化反応に供し
たが、反応開始直後にポリマーが析出した。生成
したポリマーの赤外線吸収スペクトルを測定した
ところ、ポリアミツク酸のイミド化が進行してい
たが、このポリマーはいずれの有機溶媒にも不溶
で溶液の流延によりフイルム化することは不可能
であつた。
比較例 ４
比較例３と同様にしてポリアミツク酸を合成
し、得られたポリアミツク酸溶媒をガラス板の平
滑な表面上に流延した後300℃で30分間加熱する
ことにより厚さ25μmのポリイミド化合物のフイ
ルムを得た。このフイルムの特性値を実施例１と
同様にして測定した結果を表１に示す。
The polyimide compound obtained by the production method of the present invention is easily dissolved in the above-mentioned certain organic solvent and is very stable in a solution state, so that it can be stored for a long period of time. In addition, this polyimide compound exhibits excellent properties such as heat resistance, mechanical properties, electrical properties, and chemical resistance properties, and is particularly characterized by excellent water absorption resistance, heat resistance, and light transmittance. It is useful for high-temperature films, adhesives, paints, etc., and specifically for printed wiring boards, flexible wiring boards, surface protection films or interlayer insulation films for semiconductor integrated circuit elements, liquid crystal alignment films, coating materials for enameled electric wires, and seeds. Useful for laminated plates, gaskets, etc. [Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 In a flask, 20.00 g (0.100 mol) of 4,4-diaminodiphenyl ether (DDE) was added to 200 ml of dimethylformamide (DMF) under a nitrogen stream.
5.45 g (0.025 mol) of pyromellitic dianhydride and TCH.
16.81 g (0.075 mol) of AH was added as a powder, and the mixture was reacted at 25° C. for 18 hours to obtain polyamic acid. After diluting the obtained polyamic acid solution by adding 200 ml of DMF, 55.4 g of pyridine and 51.0 g of acetic anhydride were added.
g was added thereto and reacted at 90°C for 3 hours to synthesize a polyimide compound. The obtained polyimide compound solution was poured into a large amount of ethanol and coagulated. The solidified polyimide compound was vacuum dried at 100°C for 18 hours.
The obtained polyimide compound was soluble in aprotic polar solvents such as DMF and N-methyl-2-pyrrolidone, and phenolic solvents such as m-cresol. When the infrared absorption spectrum of the obtained polyimide compound was measured, the spectrum shown in FIG. 1 was obtained. C based on imide group at 1780cm -1 and 1730cm -1
=0 stretching vibration appears and the C=0 stretching vibration at 1650 cm -1 based on the amide group of polyamic acid disappears, indicating that at least 95% or more imidization has progressed in the obtained polyimide compound. I understood. A predetermined amount of DMF was added to dissolve this polyimide compound to a concentration of 15% by weight, and the solution was cast onto the smooth surface of a glass plate and heated at 80°C for 30 minutes.
Dry by heating at 120℃ x 10 minutes, 150℃ x 10 minutes, and 200℃ x 1 hour to completely remove the solvent and reduce the thickness.
A uniform yellow transparent film of 25 μm was obtained. The tensile strength of the obtained polyimide compound film was determined. In addition, thermogravimetric analysis (under nitriding gas flow, heating rate:
The temperature of 10% thermal decomposition was measured from 10°C/min).
Furthermore, the wavelength of this polyimide compound film
The light transmittance for 400 nm light was determined and converted to a film thickness of 10 μm. In addition, the water absorption rate of this polyimide compound film was determined by the method specified in JIS C6481 (immersion temperature 25°C x 24 hours). These results are shown in Table 1. Example 2 In Example 1, 8.06 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (hereinafter abbreviated as BTDA) was used instead of pyromellitic dianhydride.
(0.025 mol), 16.81 g of TCH・AH
(0.075 mol), a polyimide compound was produced in the same manner as in Example 1 except for the imidization conditions shown in Table 1, and a film with a thickness of 28 μm was produced. Table 1 shows the results of a test conducted in the same manner as in Example 1. In addition, the obtained polyimide compound is DMF, N-
It was soluble in aprotic polar solvents such as methyl-2-pyrrolidone and phenolic solvents such as m-cresol. Example 3 In Example 1, 16.12 g (0.050 mol) of BTDA was used instead of pyromellitic dianhydride,
Using 8.41g (0.050mol) of TCH・AH, Table 1
A polyimide compound was produced in the same manner as in Example 1, except that the imidization conditions shown in . The obtained polyimide was soluble in phenolic solvents such as m-cresol. A 25 μm thick film was prepared from this polyimide compound in the same manner as in Example 1 except that m-cresol was used as the solvent. Table 1 shows the results of the test conducted in the same manner as in Example 1.
Shown below. Example 4 In Example 1, 24.18 g (0.075 mol) of BTDA was used instead of pyromellitic dianhydride,
Using 4.21g (0.025mol) of TCH・AH, Table 1
A polyimide compound was produced in the same manner as in Example 1, except that the imidization conditions shown in . The obtained polyimide was soluble in phenolic solvents such as m-cresol. A 25 μm thick film was prepared from this polyimide compound in the same manner as in Example 1 except that m-cresol was used as the solvent. Table 1 shows the results of the test conducted in the same manner as in Example 1.
Shown below. Example 5 In Example 1, pyromellitic dianhydride and
The amounts of TCH and AH used were changed to 5.45g (0.25mol) and 8.41g (0.50mol), respectively, and
A polyimide compound was produced in the same manner as in Example 1, except that 8.06 g (0.025 mol) of BTDA was used and the imidization conditions shown in Table 1 were adopted, and a film with a thickness of 30 μm was produced. Table 1 shows the results of a test conducted in the same manner as in Example 1. The obtained polyimide was soluble in aprotic polar solvents such as DMF and N-methyl-2-pyrrolidone, and phenolic solvents such as m-cresol. Example 6 In a flask, 12.54 ml of 2,5-(4-aminophenyl)-3,4-diphenylthiophene was added to 200 ml of N-methylpyrrolidone (NMP) under a nitrogen stream.
BTDA4.83g (0.015mol) and
3.36 g (0.015 mol) of TCH.AH was added as a powder, and the mixture was reacted at 50° C. for 3 hours to obtain polyamic acid. Add 9.18 g of acetic anhydride to the obtained polyamic acid solution.
and 11.73 g of pyridine were added and reacted at 130°C for 3 hours to synthesize a polyimide compound. The obtained polyimide compound solution was poured into a large amount of ethanol and coagulated. Solidified polyimide compound at 120℃
After vacuum drying for 18 hours, 19.8 g of product was obtained. When measuring the infrared absorption spectrum of the produced polymer,
C=0 based on imide group at 1780cm -1 and 1730cm -1
Since stretching vibrations appeared and C=0 stretching vibrations at 1650 cm -1 based on the amide group of polyamic acid disappeared, it was found that at least 95% or more imidization had progressed in the obtained polyimide compound. Ta. The intrinsic viscosity of this polyimide compound is
It was 0.39 dl/g (in NMP). This polyimide compound was soluble in polar solvents such as DMF, NMP, r-butyrolactone, and cyclohexanone, and phenolic solvents such as m-cresol. Example 7 A polyimide compound was produced in the same manner as in Example 6, except that 3.27 g (0.015 mol) of pyromellitic dianhydride was added instead of BTDA. The yield of the obtained polyimide compound is
17.0g, its intrinsic viscosity is 0.54dl/g (in NMP)
It was hot. This polyimide compound is composed of DMF,
It was soluble in aprotic polar solvents such as NMP and r-butyrolactone, and phenolic solvents such as m-cresol. Comparative Example 1 The same procedure as in Example 1 was carried out except that pyromellitic dianhydride was not used, the amount of TCH/AH used was changed to 16.82 g (0.100 mol), and the imidization conditions shown in Table 1 were adopted. A polyimide compound was produced. This polyimide compound is DMF, N-
It was soluble in aprotic polar solvents such as methyl-2-lolidone. A film with a thickness of 20 μm was produced from the obtained polyimide compound in the same manner as in Example 1. Table 1 shows the results of a test conducted in the same manner as in Example 1. Comparative Example 2 Polyamic acid was synthesized in the same manner as in Example 1 except that 32.24 g (0.100 mol) of BTDA was used instead of pyromellitic dianhydride and TCH・AH, and then this polyamic acid was An imidization reaction was carried out in the same manner as in Example 1, but the polymer precipitated immediately after the start of the reaction. When the infrared absorption spectrum of the produced polymer was measured, imidization of polyamic acid was progressing, but this polymer was insoluble in any organic solvent and it was impossible to form it into a film by casting the solution. . Comparative Example 3 In Example 1, TCH・AH was not used,
The amount of pyromellitic dianhydride used is 21.80g.
(0.100 mol) Polyamic acid was synthesized in the same manner as in Example 1, and then this polyamic acid was subjected to an imidization reaction in the same manner as in Example 1, but the polymer precipitated immediately after the start of the reaction. When the infrared absorption spectrum of the produced polymer was measured, imidization of polyamic acid was progressing, but this polymer was insoluble in any organic solvent and it was impossible to form it into a film by casting the solution. . Comparative Example 4 Polyamic acid was synthesized in the same manner as in Comparative Example 3, and the resulting polyamic acid solvent was cast onto the smooth surface of a glass plate and heated at 300°C for 30 minutes to produce a 25 μm thick polyimide compound. I got the film. The characteristic values of this film were measured in the same manner as in Example 1, and the results are shown in Table 1.
【表】【table】
図１は、実施例１で製造された本発明のポリイ
ミド化合物のフイルムの赤外線吸収スペクトルを
表わす。
FIG. 1 shows the infrared absorption spectrum of the film of the polyimide compound of the present invention produced in Example 1.
Claims (1)
ル酢酸二無水物25モル％以上と芳香族テトラカル
ボン酸二無水物３モル％以上からなる混合物と、
(B)有機ジアミンとから得られるポリアミツク酸を
イミド化することからなる有機溶媒可溶性ポリイ
ミド化合物の製法。1 (A) A mixture consisting of 25 mol% or more of 2,3,5-tricarboxycyclopentyl acetic dianhydride and 3 mol% or more of aromatic tetracarboxylic dianhydride;
(B) A method for producing an organic solvent-soluble polyimide compound, which comprises imidizing polyamic acid obtained from an organic diamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12384184A JPS614730A (en) | 1984-06-18 | 1984-06-18 | Production of organic solvent-soluble polyimide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12384184A JPS614730A (en) | 1984-06-18 | 1984-06-18 | Production of organic solvent-soluble polyimide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS614730A JPS614730A (en) | 1986-01-10 |
| JPH0315931B2 true JPH0315931B2 (en) | 1991-03-04 |
Family
ID=14870709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12384184A Granted JPS614730A (en) | 1984-06-18 | 1984-06-18 | Production of organic solvent-soluble polyimide compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS614730A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0631337B2 (en) * | 1985-03-13 | 1994-04-27 | 株式会社日立製作所 | Coal gasification power generator |
| JPS62163016A (en) * | 1986-01-14 | 1987-07-18 | Japan Synthetic Rubber Co Ltd | Color filter |
| JPH01247461A (en) * | 1988-03-30 | 1989-10-03 | Japan Synthetic Rubber Co Ltd | Colored resin composition |
| JPH0435708U (en) * | 1990-07-18 | 1992-03-25 | ||
| JPWO2003074587A1 (en) * | 2002-03-05 | 2005-06-30 | 鈴鹿富士ゼロックス株式会社 | Polyimide precursor solution, transfer / fixing member, and polyimide seamless belt manufacturing method |
| JP2010150379A (en) * | 2008-12-25 | 2010-07-08 | Jsr Corp | Polyimide-based material, film and composition, and method for producing the same |
| JP2010235859A (en) * | 2009-03-31 | 2010-10-21 | Jsr Corp | Polyimide material, film and composition, and method for producing the same |
| JP5606257B2 (en) * | 2010-09-30 | 2014-10-15 | 株式会社カネカ | Polyimide resin film and manufacturing method thereof |
| US20200140615A1 (en) * | 2017-05-10 | 2020-05-07 | Dupont Electronics, Inc. | Low-color polymers for flexible substrates in electronic devices |
| KR20200135980A (en) * | 2018-03-28 | 2020-12-04 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element |
-
1984
- 1984-06-18 JP JP12384184A patent/JPS614730A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS614730A (en) | 1986-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3010187B2 (en) | New polyamide-polyimide and polybenzoxazole-polyimide polymers | |
| JPS624409B2 (en) | ||
| JPS6042817B2 (en) | Method for manufacturing polyimide molded products | |
| JP2008239820A (en) | Polyamic acid's imidized polymer electrical insulation film and film-forming composition and method for producing the composition | |
| JPH0284434A (en) | Polyimide polymer and copolymer which are made by using 3,5-diaminobenzotrifluoride | |
| JPH0315931B2 (en) | ||
| JP2624724B2 (en) | Polyimide siloxane composition | |
| JP6789186B2 (en) | Polyamic acid, polyimide, electronic substrate, high frequency substrate and coverlay film | |
| JP6789185B2 (en) | Polyamic acid, polyimide, high frequency substrate and coverlay film | |
| JPH03243625A (en) | Polyimide precursor composition and production of polyimide | |
| KR920007760B1 (en) | Process for producing polyamide acid having siloxane bonds and polyamide having siloxane bonds and isoindoloquinazolinedione rings | |
| JPS62263228A (en) | Polyimide tubular body | |
| JP2730652B2 (en) | Protective coating-coated wiring member and its manufacturing method | |
| JPH0436321A (en) | Polyimidesiloxane and composition containing the same | |
| JP3989650B2 (en) | Polyimide film | |
| JP3386502B2 (en) | Method for producing polyimide and polyimide film | |
| JPS61151237A (en) | Transparent aromatic polyimide and its composition | |
| JPH0315660B2 (en) | ||
| JPS63199239A (en) | Novel solvent-soluble polyimide and production thereof | |
| KR20090089002A (en) | Polyimide film | |
| JP2603927B2 (en) | Manufacturing method of new polyimide resin | |
| JP3022625B2 (en) | Polyamic acid copolymer, polyimide copolymer comprising the same, polyimide film, and methods for producing them | |
| JPH1149857A (en) | Production of polyimide excellent in thermal dimensional stability | |
| JP3676073B2 (en) | Polyimide film and manufacturing method thereof | |
| TWI836691B (en) | Polyimide film, flexible metal foil laminate and electronic part including the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |