JPS62185715A - Colorless polyimide film - Google Patents
Colorless polyimide filmInfo
- Publication number
- JPS62185715A JPS62185715A JP2782986A JP2782986A JPS62185715A JP S62185715 A JPS62185715 A JP S62185715A JP 2782986 A JP2782986 A JP 2782986A JP 2782986 A JP2782986 A JP 2782986A JP S62185715 A JPS62185715 A JP S62185715A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyimide film
- bis
- aminophenoxy
- polyamic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 41
- -1 tetracarboxylic acid dianhydride Chemical class 0.000 claims abstract description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 4
- 125000004149 thio group Chemical group *S* 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 125000005462 imide group Chemical group 0.000 claims abstract 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 229920005575 poly(amic acid) Polymers 0.000 abstract description 21
- 239000004642 Polyimide Substances 0.000 abstract description 10
- 238000002834 transmittance Methods 0.000 abstract description 8
- 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 abstract description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- UCQABCHSIIXVOY-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]phenoxy]aniline Chemical group NC1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 UCQABCHSIIXVOY-UHFFFAOYSA-N 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DZLUPKIRNOCKJB-UHFFFAOYSA-N 2-methoxy-n,n-dimethylacetamide Chemical compound COCC(=O)N(C)C DZLUPKIRNOCKJB-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- YJQRLTCXYNGNSE-UHFFFAOYSA-N 3-(4-phenylphenoxy)aniline Chemical group NC1=CC=CC(OC=2C=CC(=CC=2)C=2C=CC=CC=2)=C1 YJQRLTCXYNGNSE-UHFFFAOYSA-N 0.000 description 1
- MFTFTIALAXXIMU-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MFTFTIALAXXIMU-UHFFFAOYSA-N 0.000 description 1
- HHLMWQDRYZAENA-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)C=C1 HHLMWQDRYZAENA-UHFFFAOYSA-N 0.000 description 1
- ZWXPDGCFMMFNRW-UHFFFAOYSA-N N-methylcaprolactam Chemical compound CN1CCCCCC1=O ZWXPDGCFMMFNRW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 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
- 238000007429 general method Methods 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
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- 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〕 本発明は新規なポリイミドフィルムに関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a novel polyimide film.
さらに詳しくは、著るしく光線透過率が高く、殆ど無色
のポリイミドフィルムに関する。More specifically, the present invention relates to an almost colorless polyimide film that has extremely high light transmittance.
従来からテトラカルボン酸二無水物とジアミンとの反応
により得られるポリイミド樹脂はその高耐熱性に加え、
力学的強度、寸法安定性、軟燃性、電気絶縁性などを併
せ持っており、電気電子機器、宇宙航空用機器、輸送機
器などの分野で、素材として、あるいは耐熱性接着剤と
して使用されている。そのポリイミド樹脂の製品形態の
一つとして、ボ°リイミドフィルムは、その優れた物性
により今后も耐熱性が要求される分野に広く用いられる
ことが期待されている。Traditionally, polyimide resins obtained by the reaction of tetracarboxylic dianhydrides and diamines have high heat resistance,
It has mechanical strength, dimensional stability, soft combustibility, and electrical insulation properties, and is used as a material or as a heat-resistant adhesive in fields such as electrical and electronic equipment, aerospace equipment, and transportation equipment. . As one of the product forms of polyimide resin, polyimide film is expected to be widely used in fields where heat resistance is required due to its excellent physical properties.
ところが従来開発されたポリイミドフィルムには優れた
特性を示すものが多いが、一般的に光線透過率が低く、
：Ｉａ黄色あるいは茶褐色のものが多い。However, although many of the polyimide films developed so far have excellent properties, they generally have low light transmittance.
:Ia Most of them are yellow or brownish.
選ばれた基を表し、アミノ基の結合位置はエーテル結合
に対しメタまたはパラ位置である。）で表されるエーテ
ルジアミンの１種以上とを重縮合させて得られる下記式
（ＩＩＩ）
（Ｉ［［）
（式中、Ｘは直結、炭素数１ないし１ｏの２価の鎖式炭
化水素基、ペルフルオロ（１−メチルエチリデン）基、
カルボニル基、チオ基からなる群より選ばれた哉を表し
、アミドの窒素原子の結合位置はエーテル結合に対しメ
タまたはパラ位置である。）で表される繰り返し単位を
有するポリアミド酸を、さらに塩水環化して得られる新
規なポリイミドである。It represents a selected group, and the bonding position of the amino group is meta or para to the ether bond. ) The following formula (III) obtained by polycondensation with one or more ether diamines represented by group, perfluoro(1-methylethylidene) group,
It represents a group selected from the group consisting of a carbonyl group and a thio group, and the bonding position of the nitrogen atom of the amide is meta or para to the ether bond. ) is a novel polyimide obtained by further cyclizing a polyamic acid with a salt water cyclization.
この方法で使用されるジアミンとしては、ビス（４−（
３−アミノフェノキシ）フェニルコメタン、ビス（４−
（４−アミノフェノキシ）フェニルコメタン、１．１−
ビス（４−（３−アミノフェノキシ）フェニル〕エタン
、１．１−ビス（４−（４−アミノフェノ“キシ）フェ
ニル〕エタン、１．２−ビス（４−（３−アミノフェノ
キシ）フェニル〕エタン、１．２−ビス（４−（４−ア
ミノフェノキシ）フェニル〕エタン、２．２−ビス（４
−（３−アミノフェノキシ）フェニル〕プロパン、２．
２−ビス（４−（４−アミノフェノキシ）フェニル〕プ
ロパン、２．２−ビス（４−（３−アミノフェノキシ）
フェニルコブタン、２，２−ビス（４−（４−アミノフ
ェノキシ）フェニルコブタン、２，２−ビス（４−（３
−アミノフェノキシ）フェニル） −１，１，１，３，
３，３−へキサフルオロプロパン、２．２−ビス（４−
（４−アミノフェノキシ）フェニル） −１，１，１，
３，３，３−へキサフルオロプロパン、４．４’−ビス
（３−アミノフェノキシ）ビフェニル、４，４′−ビス
（４−アミノフェノキシ）ビフェニル、ビス（４−（３
−アミノフェノキシ）フェニルコケトン、ビス（４−（
４−アミノフェノキシ）フェニルコケトン、ビス（４−
（３−アミノフェノキシ）フェニル〕スルフィド、ビス
（４−（４−アミノフェノキシ）フェニルフスルフィド
などがあげられ、これらは単独あるいは２種以上混合し
て用いられる。Diamines used in this method include bis(4-(
3-aminophenoxy)phenylcomethane, bis(4-
(4-aminophenoxy)phenylcomethane, 1.1-
Bis(4-(3-aminophenoxy)phenyl)ethane, 1.1-bis(4-(4-aminophenoxy)phenyl)ethane, 1.2-bis(4-(3-aminophenoxy)phenyl)ethane , 1.2-bis(4-(4-aminophenoxy)phenyl)ethane, 2.2-bis(4
-(3-aminophenoxy)phenyl]propane, 2.
2-bis(4-(4-aminophenoxy)phenyl)propane, 2.2-bis(4-(3-aminophenoxy)
Phenylcobutane, 2,2-bis(4-(4-aminophenoxy)phenylcobutane, 2,2-bis(4-(3
-aminophenoxy)phenyl) -1,1,1,3,
3,3-hexafluoropropane, 2,2-bis(4-
(4-aminophenoxy)phenyl) -1,1,1,
3,3,3-hexafluoropropane, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(3-aminophenoxy)biphenyl,
-aminophenoxy)phenylkoketone, bis(4-(
4-aminophenoxy)phenylkoketone, bis(4-
Examples include (3-aminophenoxy) phenyl] sulfide and bis(4-(4-aminophenoxy) phenyl sulfide), which may be used alone or in combination of two or more.
このようなエーテル結合と芳香族アミノ基を同一分子中
に有するエーテルジアミン類と、３，３）４゜４′−ジ
フェニルエーテルテトラカルボン酸二無水物とを使用し
て著しく光線透過率の高いポリイミドフィルムを作るこ
とは全く知られていない。A polyimide film with extremely high light transmittance is produced by using ether diamines having such an ether bond and an aromatic amino group in the same molecule and 3,3) 4゜4'-diphenyl ether tetracarboxylic dianhydride. is completely unknown to make.
これらの重合体を得るためには通常、先ずエーテルジア
ミンと、３．３（４，４’−ジフェニルエーテルテトラ
カルボン酸二無水物を有機溶媒中で反応させる。この反
応に用いる有機溶媒としては、例えばＮ、Ｎ−ジメチル
ホルムアミド、Ｎ、Ｎ−ジメチルアセトアミド、Ｎ、Ｎ
−ジエチルアセトアミド、Ｎ、Ｎ−ジメチルメトキシア
セトアミド、Ｎ−メチル−２−ピロリドン、１．３−ジ
メチル−２−イミダゾリジノン、Ｎ−メチルカプロラク
タム、１．２−ジメトキシエタン、ビス（２−メトキシ
エチル）エーテル、１．２−ビス（２−メトキシエトキ
シ）エタン、ビス（２−（２−メトキシエトキシ）エチ
ル）エーテル、テトラヒドロフラン、１，３−ジオキサ
ン、１．４−ジオキサン、ピリジン、ピコリン、ジメチ
ルスルホキシド、ジメチルスルホン、テトラメチル尿素
、ヘキサメチルホスホルアミドなどが挙げられる。また
これらの有機溶剤は単独でも或いは２種以上混合して用
いても差し支えない。In order to obtain these polymers, ether diamine and 3.3(4,4'-diphenyl ether tetracarboxylic dianhydride) are usually reacted in an organic solvent. Examples of the organic solvent used in this reaction include, for example. N,N-dimethylformamide, N,N-dimethylacetamide, N,N
-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis(2-methoxyethyl ) ether, 1,2-bis(2-methoxyethoxy)ethane, bis(2-(2-methoxyethoxy)ethyl)ether, tetrahydrofuran, 1,3-dioxane, 1,4-dioxane, pyridine, picoline, dimethyl sulfoxide , dimethylsulfone, tetramethylurea, hexamethylphosphoramide, and the like. Further, these organic solvents may be used alone or in combination of two or more.
反応温度は通常６０ ’Ｃ以下、好ましくは５０°Ｃ以
下である。The reaction temperature is usually below 60'C, preferably below 50°C.
反応圧力は特に限定されず、常圧で十分実施できる。The reaction pressure is not particularly limited, and the reaction can be carried out at normal pressure.
反応時間は、使用するジアミン、溶剤の種類および反応
温度により異なり、通常、下記式（ＩＩ［）で表わされ
るポリアミド酸の生成が完了するに十分な時間反応させ
る。通常４〜２４時間で十分である。The reaction time varies depending on the diamine used, the type of solvent, and the reaction temperature, and is usually carried out for a sufficient time to complete the production of the polyamic acid represented by the following formula (II[). Usually 4 to 24 hours is sufficient.
このような反応により、下記式（ＩＩＩ）の繰り返し単
位を有するポリアミド酸が得られる。Through such a reaction, a polyamic acid having a repeating unit of the following formula (III) is obtained.
（Ｉｔ）
（式中、Ｘは直結、炭素数１ないしｌＯの２価の鎖式炭
化水素基、ペルフルオロ（１−メチルエチリデン）基、
カルボニル基、チオ基からなる群より選ばれた基を表し
、アミドの窒素原子の結合位置はエーテル結合に対しメ
タまたはパラ位置である。）次いで得られたポリアミド
酸を１００〜４００℃に加熱してイミド化するか、また
は通常用いられるイミド化剤を用いて化学的にイミド化
することにより、下記式（Ｉ）の繰り返し単位を有する
対応するポリイミドが得られる。(It) (wherein, X is a direct bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms, a perfluoro(1-methylethylidene) group,
It represents a group selected from the group consisting of a carbonyl group and a thio group, and the bonding position of the nitrogen atom of the amide is meta or para to the ether bond. ) Then, the obtained polyamic acid is imidized by heating to 100 to 400°C, or chemically imidized using a commonly used imidizing agent to produce a polyamic acid having a repeating unit of the following formula (I). The corresponding polyimide is obtained.
（式中、Ｘ、およびイミド環の窒素原子の結合位置は前
記と同様である。）
従来のポリイミド樹脂は一般に有機溶剤には不溶の為、
その使用上に制限があったが、本発明のポリイミドの中
のあるものは有機溶剤に可溶であり、またあるものは熱
可塑性であってこの点も本発明の大きな特徴である。(In the formula, the bonding positions of X and the nitrogen atom of the imide ring are the same as above.) Since conventional polyimide resins are generally insoluble in organic solvents,
Although there are restrictions on their use, some of the polyimides of the present invention are soluble in organic solvents, and some are thermoplastic, which are also major features of the present invention.
本発明の重縮合体のポリイミドフィルムを得るためには
その前駆体であるポリアミド酸を用いることも、またポ
リイミドを用いることもできる。In order to obtain the polyimide film of the polycondensate of the present invention, polyamic acid, which is a precursor thereof, can be used, or polyimide can also be used.
また、ポリイミドフィルムを得るための成膜方法として
は、流延法、熔融押出し法などの一般の方法が用いられ
る。Moreover, as a film forming method for obtaining a polyimide film, general methods such as a casting method and a melt extrusion method are used.
例えば、ポリアミド酸を用いる場合は、その有機溶媒溶
液をドクターナイフ、コーターなどを用いて金属板また
はガラス板上に流延し、加熱してイミド化するとポリイ
ミドフィルムが得られる。For example, when using polyamic acid, a polyimide film is obtained by casting the organic solvent solution onto a metal plate or glass plate using a doctor knife, coater, etc., and imidizing it by heating.
またポリアミド酸の有機溶媒溶液に無水酢酸などのイミ
ド化剤を加えて速やかにガラス板などの上に流延し、加
熱乾燥して残存溶媒やイミド化剤を除いて成膜すること
もできる。It is also possible to form a film by adding an imidizing agent such as acetic anhydride to an organic solvent solution of polyamic acid, immediately casting the solution onto a glass plate, etc., and heating and drying to remove the remaining solvent and imidizing agent.
またこのポリアミド酸
は、その有機溶媒溶液を用いて流延、加熱脱溶媒してポ
リイミドフィルムを得ることができる。Further, this polyamic acid can be cast using an organic solvent solution thereof, and a polyimide film can be obtained by heating and removing the solvent.
さらにまたポリイミドが熱可塑性を示すときは溶融押出
し法で成膜することもできる。Furthermore, when the polyimide exhibits thermoplasticity, it can also be formed into a film by melt extrusion.
本発明を実施例および比較例により具体的に説明する。 The present invention will be specifically explained with reference to Examples and Comparative Examples.
実施例−１
かきまぜ機、連流冷却器および窒素導入管を備えた容器
に、４．４′−ビス（３−アミノフェノキシ）ビフェニ
ル３６．８ ｇ （０，１モル）とＮ、Ｎ−ジメチルア
セトアミド２０２ｇを装入し、室温で窒素雰囲気下に３
．３； ４．４’−ジフェニルエーテルテトラカルポン
酸二無水物３０．５ ｇ （０，０９９モル）を溶液温
度の上昇に注意しながら分割して加え、室温で約２０時
間かきまぜた。かくして得られたポリアミド酸の対数粘
度は１．７ｄｌ／ｇであった。ここに対数粘度はＮ、Ｎ
−ジメチルアセトアミドを溶媒として用い、ポリアミド
酸０．５ｇを１００ ｍｌの溶媒に溶解し、３５℃で測
定した値である。Example-1 36.8 g (0.1 mol) of 4,4'-bis(3-aminophenoxy)biphenyl and N,N-dimethyl were placed in a container equipped with a stirrer, continuous flow cooler, and nitrogen inlet pipe. Charge 202 g of acetamide and heat under nitrogen atmosphere at room temperature for 30 minutes.
．． 3; 30.5 g (0,099 mol) of 4.4'-diphenylethertetracarboxylic acid dianhydride was added in portions while being careful not to increase the solution temperature, and the mixture was stirred at room temperature for about 20 hours. The logarithmic viscosity of the polyamic acid thus obtained was 1.7 dl/g. Here, the logarithmic viscosity is N, N
- Using dimethylacetamide as a solvent, 0.5 g of polyamic acid was dissolved in 100 ml of solvent, and the value was measured at 35°C.
上記ポリアミド酸溶液の一部を取り、ガラス板上にキャ
ストした後、 １００℃、 ２００℃、３００℃で各々
１時間加熱して無色透明、厚み４０μのポリイミドフィ
ルムを得た。このポリイミドフィルムの引っ張り強さは
１３．８ｋｇ ／ ｃｔ、引張り伸び率は１５％であっ
た。（測定方法は、ともにＡＳＴｌ’ｌ Ｄ−８８２に
拠る。以下同様。）またこのポリイミドフィルムのガラ
ス転位温度は２０８℃（ＴＭＡ針人法で測定。以下同様
。）、空気中での５％重量減少温度は５１５’Ｃ（ＤＴ
Ａ−ＴＧで測定。以下同様。）であった。A portion of the polyamic acid solution was taken and cast onto a glass plate, and heated at 100°C, 200°C, and 300°C for 1 hour each to obtain a colorless and transparent polyimide film with a thickness of 40 μm. The tensile strength of this polyimide film was 13.8 kg/ct, and the tensile elongation rate was 15%. (Measurement methods are based on ASTl'l D-882. The same applies hereinafter.) The glass transition temperature of this polyimide film is 208°C (measured by the TMA needle method. The same applies hereinafter), 5% weight in air. The decreasing temperature is 515'C (DT
Measured with A-TG. Same below. )Met.
このポリイミドフィルムの光線透過率は８８％、ヘイズ
は０．５２％であった。（測定方法は、ともに＾ＳＴＭ
Ｄ−１００３に拠る。以下同様。）図１に、このフィ
ルムの可視、紫外領域の吸収スペクトルを示す。The light transmittance of this polyimide film was 88%, and the haze was 0.52%. (Measurement methods are both ^STM
Based on D-1003. Same below. ) Figure 1 shows the absorption spectrum of this film in the visible and ultraviolet regions.
また、上記ポリアミド酸溶液を電解銅箔上にキャストし
た後、 １００℃、 ２００℃、 ３００℃で各々１時
間加熱して、フレキシブル銅張回路基板を得た。Further, the polyamic acid solution was cast onto an electrolytic copper foil, and then heated at 100°C, 200°C, and 300°C for 1 hour each to obtain a flexible copper-clad circuit board.
コーテイング膜の膜厚は約３５μであった。この銅張回
路基板の銅箔引き剥し強さは９０°ビ一ル強度試験で２
．８ ｋｇ ／ ｃｍであった。また３００℃で１８０
秒はんだ浴に浸漬しても膨れなどは全く生じなかった。The thickness of the coating film was approximately 35μ. The copper foil peeling strength of this copper-clad circuit board was 2 in a 90° building strength test.
．． It was 8 kg/cm. Also, 180 at 300℃
Even when immersed in a solder bath for a second, no blistering occurred.
実施例−２
実施例−１において４，４′−ビス（３−アミノフェノ
キシ）ビフェニルのかわりに４，４′−ビス（４−アミ
ノフェノキシ）ビフェニルを用いた以外は実施例−１と
同様に重合を行った。かくして得られたポリアミド酸の
対数粘度は１．３５ｄｌ／ ｇであった。Example-2 Same as Example-1 except that 4,4'-bis(4-aminophenoxy)biphenyl was used instead of 4,4'-bis(3-aminophenoxy)biphenyl in Example-1. Polymerization was performed. The logarithmic viscosity of the polyamic acid thus obtained was 1.35 dl/g.
゛このポリアミド酸溶液の一部を取り、ガラス板上にキ
ャストした後、 １００℃、２００℃、３００℃で各々
１時間加熱して厚み４０μの無色透明のポリイミドフィ
ルムを得た。このポリイミドフィルムの引張強度は１２
．５ｋｇ ／ ｃ＋！、引張伸び率は２２％であった。A portion of this polyamic acid solution was taken and cast onto a glass plate, and heated at 100°C, 200°C, and 300°C for 1 hour each to obtain a colorless and transparent polyimide film with a thickness of 40 μm. The tensile strength of this polyimide film is 12
．． 5kg/c+! , the tensile elongation rate was 22%.
またこのポリイミドフィルムのガラス転移温度は２４３
℃、空気中での５％重量減少温度は５３０℃であった。In addition, the glass transition temperature of this polyimide film is 243
The 5% weight loss temperature in air was 530°C.
このポリイミドフィルムの光線透過率は８９．５％、ヘ
イズは０．３８％であった。The light transmittance of this polyimide film was 89.5%, and the haze was 0.38%.
実施例−３
実施例−１における４、４′−ビス（３−アミノフェノ
キシ）ビフェニル３６．８ｇ （０，１モル）を４．４
’ −ビス（３−アミノフェノキシ）ジフェニルスルフ
ィド４０ｇ （０，１モル）に、Ｎ、Ｎ−ジメチルアセ
トアミド２０２ｇを２１２ ｇに代えた他は、全て実施
例−１と同様にｍ縮合を行った。かくして得られたポリ
アミド酸の対数粘度は１．１ｄｌ／ ｇであった。Example-3 36.8 g (0.1 mol) of 4,4'-bis(3-aminophenoxy)biphenyl in Example-1 was added to 4.4
m-condensation was carried out in the same manner as in Example 1, except that 40 g (0.1 mol) of -bis(3-aminophenoxy)diphenyl sulfide and 212 g of N,N-dimethylacetamide were used instead of 202 g. The logarithmic viscosity of the polyamic acid thus obtained was 1.1 dl/g.
このポリアミド酸溶液１７０ｇにＮ、Ｎ−ジメチルアセ
トアミド２５４ｇを装入し、かきまぜながら窒素雰囲気
下に、室温で２４．８ｇ （０，２４モル）の無水酢酸
および９．０５ｇ （０，０９モル）のトリエチルアミ
ンを滴下し、５時間かきまぜた。この溶液を水４００ｇ
に排出し、析出物をろ別し、メタノールで洗浄し、１５
０℃で８時間減圧乾燥して、３８．７ｇの無色粉末を得
た。（収率９６．４％）
ここに得られたポリイミド粉の赤外吸収スペクトル図を
第２図に示す。254 g of N,N-dimethylacetamide was charged to 170 g of this polyamic acid solution, and 24.8 g (0.24 mol) of acetic anhydride and 9.05 g (0.09 mol) of acetic anhydride and 9.05 g (0.09 mol) of Triethylamine was added dropwise and stirred for 5 hours. Add this solution to 400g of water.
The precipitate was filtered, washed with methanol, and
It was dried under reduced pressure at 0° C. for 8 hours to obtain 38.7 g of colorless powder. (Yield: 96.4%) The infrared absorption spectrum of the polyimide powder thus obtained is shown in FIG.
このスペクトル図では、イミドの特性吸収帯である１７
８０ｃｆｆｌ−１付近および１７２０ｃｎ＋−’付近の
吸収が顕著に認められた。In this spectrum diagram, 17 is the characteristic absorption band of imide.
Absorption near 80 cffl-1 and near 1720 cn+-' was observed significantly.
上記ポリイミド粉２０ｇを６０ｇのＮ、Ｎ−ジメチルア
セトアミドに熔解し、ガラス板上にキャストし、１００
℃、２００℃で各々１時間加熱し、溶媒を揮散させ、無
色透明、厚み５０μのポリイミドフィルムを得た。20g of the above polyimide powder was dissolved in 60g of N,N-dimethylacetamide, cast on a glass plate,
C. and 200.degree. C. for 1 hour to volatilize the solvent to obtain a colorless and transparent polyimide film with a thickness of 50 .mu.m.
このポリイミドフィルムの引張り強さは１３．５ｋｇ／
ｅｒａ、引張り伸び率は１５％であった。またこのフ
ィルムのガラス転移温度は１７４℃、空気中での５％重
１減少温度は、５２３℃であった。The tensile strength of this polyimide film is 13.5 kg/
era and tensile elongation were 15%. Further, the glass transition temperature of this film was 174°C, and the 5% weight loss temperature in air was 523°C.
またこのポリイミドフィルムの光線透過率は８８％、ヘ
イズは０．６９％であった。Moreover, the light transmittance of this polyimide film was 88%, and the haze was 0.69%.
実施例−４〜８
実施例−１における４、４′−ビス（３−アミノフェノ
キシ）ビフェニルに代えて各種ジアミンを用い、ジアミ
ン、Ｎ、Ｎ−ジメチルアセトアミドの量を変えて反応を
行った他は全て実施例−１と同様に行って、ポリアミド
酸およびポリイミドフィルムを得た。表１に結果を示す
。Examples-4 to 8 Various diamines were used in place of 4,4'-bis(3-aminophenoxy)biphenyl in Example-1, and the reactions were carried out by changing the amounts of diamine and N,N-dimethylacetamide. All procedures were carried out in the same manner as in Example-1 to obtain polyamic acid and polyimide films. Table 1 shows the results.
比較例＝１〜２
実施例−１における４、４′−ビス（３−アミノフェノ
キシ）ビフェニルに代えて４，４′−ビス（４−アミノ
フェノキシ）ビフェニルまたはビス（４−（３−アミノ
フェノキシ）フェニル〕スルフィドを用い、Ｎ、Ｎ−ジ
メチルアセトアミドの量をかえ、テトラカルボン酸二無
水物として、本発明の３．３’、４．４′−ジフェニル
エーテルテトラカルボン酸二無水物の代りに３．３’、
４．４’−へンゾフェノンテトラヵルボン酸二無水物ま
たは無水ピロメリット酸を用いた他は全て、実施例−１
と同様に行ってポリアミド酸及びポリイミドフィルムを
得た。結果を表−１に併せて示す。尚、表＝１には実施
例−１〜３の結果も併せて表示する。Comparative Examples = 1 to 2 4,4'-bis(4-aminophenoxy)biphenyl or bis(4-(3-aminophenoxy) ) phenyl] sulfide, the amount of N,N-dimethylacetamide was changed, and as the tetracarboxylic dianhydride, 3. .3',
4. All examples were Example-1 except that 4'-henzophenone tetracarboxylic dianhydride or pyromellitic anhydride was used.
Polyamic acid and polyimide films were obtained in the same manner as above. The results are also shown in Table-1. Note that Table 1 also shows the results of Examples 1 to 3.
本発明のポリイミドフィルムはポリイミドが本来有する
優れた耐熱性に加えて、著るしく光線透過率が高く、耐
熱性耐光性を備えた無色透明性フィルムである。The polyimide film of the present invention is a colorless and transparent film that not only has the excellent heat resistance inherent to polyimide but also has a significantly high light transmittance and has heat resistance and light resistance.
第１図は本発明のポリイミドフィルムの可視・紫外領域
の吸収スペクトル図の一例であり、第２図は本発明に用
いられるポリイミドの粉末の赤外線吸収スペクトル図の
一例である。FIG. 1 is an example of an absorption spectrum in the visible and ultraviolet regions of the polyimide film of the present invention, and FIG. 2 is an example of an infrared absorption spectrum of the polyimide powder used in the present invention.
Claims (1)
化水素基、ペルフルオロ（１−メチルエチリデン）基、
カルボニル基、チオ基からなる群より選ばれた基を表し
、イミド環の窒素原子の結合位置はエーテル結合に対し
メタまたはパラ位置である。） で表される繰り返し単位を有する重縮合体よりなるポリ
イミドフィルム。[Claims] Formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, X is a direct bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms, perfluoro (1- methylethylidene) group,
It represents a group selected from the group consisting of a carbonyl group and a thio group, and the bonding position of the nitrogen atom of the imide ring is meta or para to the ether bond. ) A polyimide film made of a polycondensate having a repeating unit represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61027829A JP2567375B2 (en) | 1986-02-13 | 1986-02-13 | Colorless polyimide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61027829A JP2567375B2 (en) | 1986-02-13 | 1986-02-13 | Colorless polyimide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62185715A true JPS62185715A (en) | 1987-08-14 |
| JP2567375B2 JP2567375B2 (en) | 1996-12-25 |
Family
ID=12231835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61027829A Expired - Lifetime JP2567375B2 (en) | 1986-02-13 | 1986-02-13 | Colorless polyimide film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2567375B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62197426A (en) * | 1986-02-25 | 1987-09-01 | Mitsui Toatsu Chem Inc | Heat-resistant adhesive |
| JPH01118527A (en) * | 1987-07-15 | 1989-05-11 | Usa Government | Production of low dielectric polyimide |
| JPH01188555A (en) * | 1988-01-22 | 1989-07-27 | Mitsui Toatsu Chem Inc | Resin composition |
| EP0409465A2 (en) * | 1989-07-17 | 1991-01-23 | MITSUI TOATSU CHEMICALS, Inc. | Preparation process of polyimide film |
| JPH03166517A (en) * | 1989-11-27 | 1991-07-18 | Mitsui Toatsu Chem Inc | Orientational agent for liquid crystal panel |
| JPH069936A (en) * | 1993-04-30 | 1994-01-18 | Mitsui Toatsu Chem Inc | Heat-resistant adhesive |
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| JPS58157190A (en) * | 1982-03-12 | 1983-09-19 | 日立化成工業株式会社 | Method of producing substrate for flexible printed circuit |
| JPS5950691A (en) * | 1982-09-16 | 1984-03-23 | Yamatake Honeywell Co Ltd | Motor driven actuator |
| JPS5976451A (en) * | 1982-10-26 | 1984-05-01 | Hitachi Ltd | Semiconductor device |
| JPS59168030A (en) * | 1983-03-15 | 1984-09-21 | Hitachi Chem Co Ltd | Production of thermoplastic polyether-imide |
| JPS6097647A (en) * | 1983-11-02 | 1985-05-31 | Hitachi Ltd | Semiconductor device |
| JPS60186610A (en) * | 1984-03-06 | 1985-09-24 | Matsushita Electric Ind Co Ltd | Liquid fuel combustion device |
| JPS60205283A (en) * | 1984-03-30 | 1985-10-16 | 株式会社日立製作所 | Fast breeder reactor |
| JPS60224812A (en) * | 1984-04-17 | 1985-11-09 | Kanebo Ltd | Electrically conductive composite fiber |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62197426A (en) * | 1986-02-25 | 1987-09-01 | Mitsui Toatsu Chem Inc | Heat-resistant adhesive |
| JPH01118527A (en) * | 1987-07-15 | 1989-05-11 | Usa Government | Production of low dielectric polyimide |
| JPH01188555A (en) * | 1988-01-22 | 1989-07-27 | Mitsui Toatsu Chem Inc | Resin composition |
| EP0409465A2 (en) * | 1989-07-17 | 1991-01-23 | MITSUI TOATSU CHEMICALS, Inc. | Preparation process of polyimide film |
| JPH03166517A (en) * | 1989-11-27 | 1991-07-18 | Mitsui Toatsu Chem Inc | Orientational agent for liquid crystal panel |
| JPH069936A (en) * | 1993-04-30 | 1994-01-18 | Mitsui Toatsu Chem Inc | Heat-resistant adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2567375B2 (en) | 1996-12-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |