JPH0245529A - Modified polyimide copolymer and polyamic acid copolymer - Google Patents
Modified polyimide copolymer and polyamic acid copolymerInfo
- Publication number
- JPH0245529A JPH0245529A JP19545688A JP19545688A JPH0245529A JP H0245529 A JPH0245529 A JP H0245529A JP 19545688 A JP19545688 A JP 19545688A JP 19545688 A JP19545688 A JP 19545688A JP H0245529 A JPH0245529 A JP H0245529A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine atom
- bis
- acid
- dianhydride
- copolymer
- 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
- 229920005575 poly(amic acid) Polymers 0.000 title claims abstract description 15
- 229920001721 polyimide Polymers 0.000 title claims description 39
- 239000004642 Polyimide Substances 0.000 title claims description 30
- 239000002253 acid Substances 0.000 claims abstract description 37
- 150000004985 diamines Chemical class 0.000 claims abstract description 28
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 27
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 26
- 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 abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000004580 weight loss Effects 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 abstract description 9
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 abstract description 7
- 229920001577 copolymer Polymers 0.000 abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 6
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002798 polar solvent Substances 0.000 abstract description 3
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 abstract 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 abstract 1
- 239000011737 fluorine Substances 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 23
- 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 14
- -1 monofluoroisopropyl anhydride Chemical class 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- 235000002597 Solanum melongena Nutrition 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 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 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000012024 dehydrating agents Substances 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- XYKZEZPREAUXDQ-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethylbenzene Chemical compound FC(F)(F)C(F)(F)C1=CC=CC=C1 XYKZEZPREAUXDQ-UHFFFAOYSA-N 0.000 description 1
- LERDAFCBKALCKT-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(2,3,4-trifluorophenyl)benzene Chemical group FC1=C(F)C(F)=CC=C1C1=C(F)C(F)=C(F)C(F)=C1F LERDAFCBKALCKT-UHFFFAOYSA-N 0.000 description 1
- SOZFIIXUNAKEJP-UHFFFAOYSA-N 1,2,3,4-tetrafluorobenzene Chemical compound FC1=CC=C(F)C(F)=C1F SOZFIIXUNAKEJP-UHFFFAOYSA-N 0.000 description 1
- IOHPPIBXAKZWGA-UHFFFAOYSA-N 2-[2-(2-aminophenoxy)-3,4,5,6-tetrakis(trifluoromethyl)phenoxy]aniline Chemical compound NC1=CC=CC=C1OC(C(=C(C(=C1C(F)(F)F)C(F)(F)F)C(F)(F)F)C(F)(F)F)=C1OC1=CC=CC=C1N IOHPPIBXAKZWGA-UHFFFAOYSA-N 0.000 description 1
- WCSNAIRUIYSGOP-UHFFFAOYSA-N 2-amino-5-[2-(4-amino-3-carbamoylphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]benzamide Chemical compound C1=C(N)C(C(=O)N)=CC(C(C=2C=C(C(N)=CC=2)C(N)=O)(C(F)(F)F)C(F)(F)F)=C1 WCSNAIRUIYSGOP-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- PWTKZYBDXDXRMR-UHFFFAOYSA-N 3,4,5,6-tetrakis(trifluoromethyl)benzene-1,2-diamine Chemical compound NC1=C(N)C(C(F)(F)F)=C(C(F)(F)F)C(C(F)(F)F)=C1C(F)(F)F PWTKZYBDXDXRMR-UHFFFAOYSA-N 0.000 description 1
- JAUWPCNIJHYPGO-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenoxy)-3,4,5,6-tetrakis(trifluoromethyl)phenoxy]phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C(=C(C(=C(C=2OC=2C(=C(C(O)=O)C=CC=2)C(O)=O)C(F)(F)F)C(F)(F)F)C(F)(F)F)C(F)(F)F)=C1C(O)=O JAUWPCNIJHYPGO-UHFFFAOYSA-N 0.000 description 1
- GIDZGEJVGCDPLV-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenoxy)-3,4-bis(trifluoromethyl)phenoxy]phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C(=C(C(=CC=2)C(F)(F)F)C(F)(F)F)OC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GIDZGEJVGCDPLV-UHFFFAOYSA-N 0.000 description 1
- QBQWCUVAROAAQA-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenoxy)-3-(trifluoromethyl)phenoxy]phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C(=C(C=CC=2)C(F)(F)F)OC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O QBQWCUVAROAAQA-UHFFFAOYSA-N 0.000 description 1
- AASJYPLKPXYUJL-UHFFFAOYSA-N 3-[2-(2,3-dicarboxyphenoxy)phenoxy]phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C(=CC=CC=2)OC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O AASJYPLKPXYUJL-UHFFFAOYSA-N 0.000 description 1
- FWOLORXQTIGHFX-UHFFFAOYSA-N 4-(4-amino-2,3,5,6-tetrafluorophenyl)-2,3,5,6-tetrafluoroaniline Chemical group FC1=C(F)C(N)=C(F)C(F)=C1C1=C(F)C(F)=C(N)C(F)=C1F FWOLORXQTIGHFX-UHFFFAOYSA-N 0.000 description 1
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 1
- PJWQLRKRVISYPL-UHFFFAOYSA-N 4-[4-amino-3-(trifluoromethyl)phenyl]-2-(trifluoromethyl)aniline Chemical compound C1=C(C(F)(F)F)C(N)=CC=C1C1=CC=C(N)C(C(F)(F)F)=C1 PJWQLRKRVISYPL-UHFFFAOYSA-N 0.000 description 1
- 101100272588 Escherichia coli (strain K12) bisC gene Proteins 0.000 description 1
- ZEGLXFHIJNPVNE-UHFFFAOYSA-N FC(F)(F)NC1=C(C=CC=C1)NC(F)(F)F Chemical compound FC(F)(F)NC1=C(C=CC=C1)NC(F)(F)F ZEGLXFHIJNPVNE-UHFFFAOYSA-N 0.000 description 1
- 101100099970 Haemophilus influenzae (strain ATCC 51907 / DSM 11121 / KW20 / Rd) torZ gene Proteins 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は耐熱性樹脂として知られるポリイミドに関する
。詳しくは、優れた熱的寸法安定性を有するポリイミド
共重合体の改質に関する。さらに詳しくは、フッ素原子
含有モノマーを共重合させることにより耐アルカリ加水
分解性が改良されたポリイミド共重合体に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to polyimide, which is known as a heat-resistant resin. Specifically, the present invention relates to modification of polyimide copolymers having excellent thermal dimensional stability. More specifically, the present invention relates to a polyimide copolymer with improved alkali hydrolysis resistance by copolymerizing a fluorine atom-containing monomer.
（従来の技術〕
ポリイミドはすぐれた耐熱性を有するポリマーとして良
く知られている。このポリマーはさらにすぐれた耐薬品
性、電気的特性、機械的特性を有している。代表的なポ
リイミドはよく知られているように４，４′−ジアミノ
ジフェニルエーテルとピロメリット酸二無水物から得ら
れるポリマーで商業的に大規模に生産されている。この
ポリマーはフレキシブルプリント基板など耐熱性を要す
る電気材料として用いられている。このポリマーは引張
特性などすぐれた機械的特性を有しているが熱的寸法安
定性が劣る（ ３ Ｘ １０−５℃−１程度の大きい線
膨張係数）という欠点を有している。(Prior Art) Polyimide is well known as a polymer with excellent heat resistance.This polymer also has excellent chemical resistance, electrical properties, and mechanical properties.A typical polyimide is As is known, it is a polymer obtained from 4,4'-diaminodiphenyl ether and pyromellitic dianhydride and is produced commercially on a large scale.This polymer is used for electrical materials that require heat resistance such as flexible printed circuit boards. Although this polymer has excellent mechanical properties such as tensile properties, it has the disadvantage of poor thermal dimensional stability (large coefficient of linear expansion on the order of 3 x 10-5°C-1). ing.
ポリイミドは耐熱性を有しているので大きな温度変化を
うけることが多い。従ってすぐれた熱的寸法安定性を有
するポリイミドが望まれている。Since polyimide has heat resistance, it is often subject to large temperature changes. Therefore, polyimides with excellent thermal dimensional stability are desired.
特に最近のエレクトロニクスの発達と共にこのような要
望が増大している。In particular, such demands are increasing with the recent development of electronics.
これに伴い、熱的寸法安定性に優れた４リイミドの開発
がさかんに行なわれている。In line with this trend, 4-limides with excellent thermal dimensional stability are being actively developed.
酸成分として
ジアミン成分として
を用い、これから得られる一般式（Ａ）（式中、ｍ、ｎ
は正の整数）
で示されるポリイミド９共重合体は優れた熱的寸法安定
性を有するポリイミド共重合体である。General formula (A) obtained from the diamine component is used as the acid component (in the formula, m, n
is a positive integer) The polyimide 9 copolymer represented by is a polyimide copolymer having excellent thermal dimensional stability.
しかしながらこのようにして得られたポリイミド共重合
体は代表的なポリイミドであるピロメリット酸二無水物
と４，４′−ジアミノジフェニルエーテルとから得られ
るポリマーと比べて、耐アルカリ加水分解性に劣ってい
るという欠点を有する。However, the polyimide copolymer obtained in this way has inferior alkali hydrolysis resistance compared to a polymer obtained from pyromellitic dianhydride and 4,4'-diaminodiphenyl ether, which are typical polyimides. It has the disadvantage of being
ポリイミドフィルムがフレキシブルプリント基板材料等
に用いられる際には、アルカリ処理工程が含まれるため
、耐アルカリ加水分解性に優れたポリイミドフィルムが
望まれている。When a polyimide film is used as a material for a flexible printed circuit board or the like, an alkali treatment step is involved, so a polyimide film with excellent alkali hydrolysis resistance is desired.
尚、ここでいう耐アルカリ加水分解性は、５重ｆｆｉ％
のＮａＯＨ水溶液に５０℃にてポリイミドフィルムを５
分間浸漬したときの重量減少率のことを言うＯ
（発明が解決しようとする問題点）
本発明の目的は、優れた熱的寸法安定性を有する一般式
（Ａ）で表わされるポリイミド共重合体の改質にある。In addition, the alkali hydrolysis resistance referred to here is 5 times ffi%.
Polyimide film was added to NaOH aqueous solution at 50℃ for 5 minutes.
O refers to the weight loss rate when immersed for minutes (Problem to be solved by the invention) The object of the present invention is to provide a polyimide copolymer represented by the general formula (A) having excellent thermal dimensional stability. It lies in the reformation of
詳しくはこのポリイミド共重合体の優れた熱的寸法安定
性、機械的性質を損なうととなく、耐アルカリ加水分解
性を改良することにある。Specifically, the objective is to improve the alkali hydrolysis resistance of this polyimide copolymer without impairing its excellent thermal dimensional stability and mechanical properties.
（問題点を解決するための手段）
本発明は、酸成分として
ジアミン成分として
を主に使用し、さらにフッ素原子含有酸二無水物および
／またはフッ素原子含有ジアミンを一部使用して得られ
るポリアミド酸共重合体を脱水閉環イミド化してなるこ
とを特徴とするポリイミド共重合体に関する。(Means for Solving the Problems) The present invention provides a polyamide obtained by mainly using a diamine component as an acid component and further using a fluorine atom-containing acid dianhydride and/or a fluorine atom-containing diamine in part. The present invention relates to a polyimide copolymer obtained by dehydrating and ring-closing an acid copolymer.
はじめに本発明の一すイミド酸共重合体の製造方法につ
いて説明する。First, the method for producing the monoimide acid copolymer of the present invention will be explained.
酸成分としてぎロメリット酸二無水物、ジアミン成分と
して４，４′−ノアミノノフェニルエーテル（以下ＯＤ
Ａという）およびｐ−７エニレンジアミン（以下ｐ −
ＰＤＡという）を主として用い、さらにフッ素原子含有
酸二無水物および／またはフッ素原子含有ジアミンを用
いて全酸成分を全ジアミン成分とを実質上等モル使用し
、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−
メチル−２−ピロリドン等の有機極性溶媒中、１００℃
以下、好ましくは８０℃以下、さらに好ましくは５０℃
以下、特に好ましくは１０℃以下の温度で反応させて本
発明のｙＪ？ ＩＪイミド共重合体前駆体であるポリア
ミド酸共重合体を得る。Gyromellitic dianhydride is used as the acid component, and 4,4'-noaminonophenyl ether (hereinafter referred to as OD) is used as the diamine component.
A) and p-7 enylenediamine (hereinafter referred to as p-
(referred to as PDA), and furthermore, using a fluorine atom-containing acid dianhydride and/or a fluorine atom-containing diamine, the total acid component and the total diamine component are used in substantially equimolar amounts, and dimethylformamide, dimethylacetamide, N-
In an organic polar solvent such as methyl-2-pyrrolidone at 100°C
Below, preferably 80°C or less, more preferably 50°C
Hereinafter, the yJ? of the present invention is preferably reacted at a temperature of 10°C or lower. A polyamic acid copolymer which is an IJ imide copolymer precursor is obtained.
このポリアミド酸共重合体を得るに際しては、ジアミン
主成分であるｐ −ＰＤＡとＯＤＡの使用割合は、モル
比で１）−ＰＤＡｌｏＤＡ −１／９〜９／１、好まし
くは１／７〜７／１、さらに好ましくは１／４〜４／１
である。When obtaining this polyamic acid copolymer, the molar ratio of p-PDA and ODA, which are diamine main components, is 1)-PDAloDA-1/9 to 9/1, preferably 1/7 to 7/1. 1, more preferably 1/4 to 4/1
It is.
まだ共重合方法には何ら制約を受けるものでなくランダ
ム共重合等公知の方法、あるいは特願昭６２−１７４１
２６、同６２−１７４１２８あるいは同６２−１９９２
２３明細書に記載されている反復単位のシーケンスをコ
ントロールするような重合方法等どのような方法によっ
ても本発明の効果を発現できる。反復単位のシーケンス
をコントロールすることによシ最終的に得られるポリイ
ミド共重合体の物性、特に引張物性がすぐれたものにす
ることができる。反復単位のシーケンスをコントロール
するには酸無水物あるいはジアミンのどちらか一方を過
剰に用い酸無水物基末端あるいはアミン基末端を有する
ブレポリマーをまず合成し、このブレポリマーを酸無水
物あるいはジアミンとして用いることによシ行なうこと
ができる。特に酸無水物基末端を有するブレポリマーを
用いる場合には最終的に得られるポリイミド共重合体の
物性がすぐれたものになる。There are no restrictions on the copolymerization method yet, and known methods such as random copolymerization or patent application No. 1741/1986
26, 62-174128 or 62-1992
The effects of the present invention can be achieved by any method, such as the polymerization method that controls the sequence of repeating units described in the 23 specification. By controlling the sequence of repeating units, the physical properties of the polyimide copolymer finally obtained can be made to have excellent properties, especially tensile properties. To control the sequence of repeating units, first synthesize a brepolymer with an acid anhydride group or amine group end using an excess of either the acid anhydride or diamine, and then synthesize this brepolymer as the acid anhydride or diamine. This can be done by using In particular, when a brepolymer having an acid anhydride group terminal is used, the physical properties of the polyimide copolymer finally obtained are excellent.
本発明のポリアミド酸共重合体は前記の有機極性溶媒中
、５〜４０１１Ｌ量チ、好ましくは５〜３０重量％、さ
らに好ましくは５〜２５重量％溶解されているのが取扱
いの面からも望ましい。From the viewpoint of handling, the polyamic acid copolymer of the present invention is preferably dissolved in the organic polar solvent in an amount of 5 to 4011 L, preferably 5 to 30% by weight, and more preferably 5 to 25% by weight. .
フッ素原子含有酸二無水物の使用量は酸成分全量に対し
て３０ｍｏｌ％以下、好ましくは２５ ｍｏｌ％以下、
さらに好ましくは２０ ｍｏｌ％、特に好ましくは１５
ｍｏｌチ以下である。The amount of the fluorine atom-containing acid dianhydride used is 30 mol% or less, preferably 25 mol% or less, based on the total amount of acid components.
More preferably 20 mol%, particularly preferably 15
It is less than mol.
また、フッ素原子含有ジアミンの使用量は、ジアミン成
分全量に対して３０ｍｏｌ％以下、好ましくは２５ ｍ
ｏｌ％以下、さらに好ましくは２０ ｍｏｌ％以下、特
に好ましくは１５ ｍｏｌ％以下である。ただし、これ
らフッ素原子含有酸二無水物とフッ素原子含有ジアミン
の合計使用量は、酸成分全量とジアミン成分全量の合計
量に対して３０ｍｏｌ％以下、好ましくは２５ｍｏｌチ
以下、さらに好ましくは２０ｍｏｌ％以下、特に好まし
くは１５ ｍｏｌ％以下である。伺故ならば、これより
も過剰量の使用はポリイミド共重合体（Ａ）が有する優
れた特性（熱的寸法安定性、機械的性質、耐熱性等）を
損なうからである。これらフッ素原子含有酸二無水物と
フッ素原子含有ジアミンは、そのどちらか一方、または
その両方、いずれでも使用することができ、また、その
各々は２種以上の異なるフッ素原子含有酸二無水物およ
び／またはフッ素原子含有ジアミンであってもよい。Further, the amount of the fluorine atom-containing diamine used is 30 mol% or less, preferably 25 m
ol% or less, more preferably 20 mol% or less, particularly preferably 15 mol% or less. However, the total usage amount of these fluorine atom-containing acid dianhydride and fluorine atom-containing diamine is 30 mol% or less, preferably 25 mol% or less, more preferably 20 mol% or less based on the total amount of the acid component and the diamine component. , particularly preferably 15 mol% or less. This is because using an amount in excess of this will impair the excellent properties (thermal dimensional stability, mechanical properties, heat resistance, etc.) possessed by the polyimide copolymer (A). Either or both of these fluorine atom-containing acid dianhydrides and fluorine atom-containing diamines can be used, and each of them can be used with two or more different fluorine atom-containing acid dianhydrides and /Or it may be a fluorine atom-containing diamine.
次に本発明に使用することができるフッ素原子含有のモ
ノマーを具体的に例示する。Next, specific examples of fluorine atom-containing monomers that can be used in the present invention will be given.
フッ素原子含有の酸二無水物としては２，２−ビス（３
，４−ジカルデキシフェニル）へキサフルオロプロパン
ニ無水物、２，２−ビス（４−（３，４−ジカル〆キシ
フェノキシ）フェニル）へキサフルオロプロパンニ無水
物などのノや一フルオロイソプロぎル残基を有する酸二
無水物を挙げることができるが、さらには芳香環にフッ
素化アルキル基が直接結合したテトラカルボン酸二無水
物、例えば（トリフルオロメチル）ピロメリット酸二無
水物、ビス（トリフルオロメチル）ピロメリット酸二無
水物、５，５′−ビス（トリフルオロメチル） −３，
３’。As the acid dianhydride containing a fluorine atom, 2,2-bis(3
, 4-dicardexyphenyl) hexafluoropropanihydride, 2,2-bis(4-(3,4-dicardoxyphenoxy)phenyl)hexafluoropropanihydride, and monofluoroisopropyl anhydride. In addition, tetracarboxylic dianhydrides with a fluorinated alkyl group directly bonded to the aromatic ring, such as (trifluoromethyl)pyromellitic dianhydride, bis (trifluoromethyl)pyromellitic dianhydride, 5,5'-bis(trifluoromethyl)-3,
3'.
４．４′−ビフェニルテトラカルデン酸二無水物、２
、２’、 ５ 、５’−テトラキス（トリフルオロメチ
ル）−３、３’、 ４ 、４’−ビフェニルテトラカル
デン酸二無水物、５．５′−ビス（トリフルオロメチル
） −３，３’、４．４’ −ジフェニルエーテルテト
ラカルがン酸二無水物、５．５′−ビス（トリフルオロ
メチル） −３，３’、４．４’−ベンゾフェノンテト
ラカルボン酸二無水物、ビス（（）リフルオロメチル）
ジカルボキシフェノキシ）ベンゼン二無水物、ビス（（
）リフルオロメチル）ジカルボキシフェノキシ）ビフェ
ニルニ無水物、ビス（（トリフルオロメチル）ジカルボ
キシフェノキシ）（）リフルオロメチル）ベンゼン二無
水物、ビス（（）リフルオロメチル）ジカルボキシフェ
ノキシ）ビス（トリフルオロメチル）ビフェニルニ無水
物、ビス（（）リフルオロメチル）ジカルボキシフェノ
キシ）ジフェニルエーテルニ無水物、ビス（ジカルボキ
シフェノキシ）（トリフルオロメチル）ベンゼン二無水
物、ビス（ジカルボキシフェノキシ）ビス（トリフルオ
ロメチル）ベンゼン二無水物、ビス（ジカルボキシフェ
ノキシ）テトラキス（トリフルオロメチル）ベンゼン二
無水物、ビス（ジカルボキシフェノキンンヒス（トリフ
ルオロメチル）ビフェニルニ無水物、ビス（ジカルボキ
シフェノキシ）テトラキス（トリフルオロメチル）ビフ
ェニルニ無水物などを挙げることができる。4.4'-biphenyltetracaldic acid dianhydride, 2
, 2', 5, 5'-tetrakis(trifluoromethyl)-3,3', 4,4'-biphenyltetracaldic acid dianhydride, 5,5'-bis(trifluoromethyl)-3,3 ',4,4'-diphenyl ethertetracarboxylic dianhydride, 5,5'-bis(trifluoromethyl)-3,3',4,4'-benzophenonetetracarboxylic dianhydride, bis(( ) refluoromethyl)
dicarboxyphenoxy)benzene dianhydride, bis((
)lifluoromethyl)dicarboxyphenoxy)biphenyl dianhydride, bis((trifluoromethyl)dicarboxyphenoxy)()lifluoromethyl)benzene dianhydride, bis(()lifluoromethyl)dicarboxyphenoxy)bis( trifluoromethyl)biphenyl dianhydride, bis(()lifluoromethyl)dicarboxyphenoxy)diphenyl ether dianhydride, bis(dicarboxyphenoxy)(trifluoromethyl)benzene dianhydride, bis(dicarboxyphenoxy)bis( trifluoromethyl)benzene dianhydride, bis(dicarboxyphenoxy)tetrakis(trifluoromethyl)benzene dianhydride, bis(dicarboxyphenoxy)benzene dianhydride, bis(dicarboxyphenoxy)tetrakis(trifluoromethyl)biphenyl dianhydride, bis(dicarboxyphenoxy)tetrakis Examples include (trifluoromethyl)biphenyl dianhydride.
フッ素原子含有のジアミンとしては、２．２−ビス（４
−アミノフェニル）へキサフルオログロノクン、２．２
−ビス（４−（２−アミノフェノキシ）フェニル）へキ
サフルオログロノクン、 ２．２−ビス（４−（３−ア
ミノフェノキシ）フェニル）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
）へキサフルオロプロパン、２，２−ビス（３−カルバ
モイル−４−アミノフェニル）へキサフルオロプロパン
、２，２−ビス（４−（３−カルバモイル−４−アミノ
フェノキシ）フェニル）へキサフルオログロノクン、２
．２−ビス（３−スルファモイル−４−アミノフェニル
）へキサフルオロプロパン、２．２−ビス（４−（３−
スルファモイル）−４−アミノフェノキシ）フェニル）
ヘキサフルオログロノぐン、２．２−ビス（３−カルブ
キシ−４−アミノフェニル）へキサフルオログロノ９ン
、２．２−ビス（４−（３−カルブキシ−４−アミノフ
ェノキシ）フェニル）へキサフルオロゾロ／やン、１，
３−ビス［２−（４−（４−アミノフェノキシ）フェニ
ル）へキ丈フルオロイソプロピル〕ベンゼンなどのパー
フルオロイソゾロピル残基を有するジアミンを挙げるこ
とができるが、さらにはｐ−ビス（３−カル？午シー４
−アミノフェノキシ）テトラフルオロベンゼン、４，４
′−ビス（３−カルデ、キシー４−アミノフェノキシ）
オクタフルオロビフェニル、４．４’−ジアミノオクタ
フルオロビフェニル、１．２−ビス（３〜カルデキシー
４−アミノフェニル）テトラフルオロエタン、１，３−
ビス（３−カル？キシ４−アミノフェニル）ヘキサフル
オログロノクン、１．５−ビス（３−カルボキシ−４−
アミノフェニル）ｆカフルオロベンタン、ジアミノペン
シトリフルオライド、ビス（トリフルオロメチル）フェ
ニレンジアミン、ジアミノテトラ（トリフルオロメチル
）ベンゼン、ノアミノ（ペンタフルオロエチル）ベンゼ
ン、２．２’−ビス（トリフルオロメチル）ベンジノン
、３．３’−ビス（トリフルオロメチル）ベンジジン、
２．２’−ビス（） ＩＪ フルオロメチル）−４，４
′−ジアミノジフェニルエーテル、３，３′−ビス（ト
リフルオロメチル）−４，４’−ジアミノジフェニルエ
ーテル、３ 、３’、 ５ 、５’−テトラキス（トリ
フルオロメチル）−４，４’−ジアミノジフェニルエー
テル、３．３’−ビス（トリフルオロメチル）−４，４
′−ジアミノベンゾフェノン、ビス（アミノフェノキシ
））（ト’）フルオロメチルウベンゼン、ビス（アミノ
フェノキシ）テトラキス（トリフルオロメチル）ベンゼ
ン、ビス〔〔トリフルオロメチル）アミノフェノキシ〕
ベンゼン、ビスＣ（）リフルオロメチル）アミノフェノ
キシフビフェニル、ビス（［（）リフルオロメチル）ア
ミノフェノキシ〕フェニル）へキサフルオログロノやン
ナトのフッ素原子含有ジアミンの使用も可能である。As the fluorine atom-containing diamine, 2.2-bis(4
-aminophenyl)hexafluoroglonocune, 2.2
-bis(4-(2-aminophenoxy)phenyl)hexafluoroglonocune, 2.2-bis(4-(3-aminophenoxy)phenyl)hexafluoropropane,
2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(3-carbamoyl-4-aminophenyl)hexafluoropropane, 2,2-bis(4-( 3-Carbamoyl-4-aminophenoxy)phenyl)hexafluoroglonocune, 2
．． 2-bis(3-sulfamoyl-4-aminophenyl)hexafluoropropane, 2.2-bis(4-(3-
sulfamoyl)-4-aminophenoxy)phenyl)
Hexafluorogulon, 2,2-bis(3-carboxy-4-aminophenyl)hexafluorogulon, 2,2-bis(4-(3-carboxy-4-aminophenoxy)phenyl) Hexafluorozoro/yan, 1,
Examples include diamines having perfluoroisozolopyl residues such as 3-bis[2-(4-(4-aminophenoxy)phenyl)hexylfluoroisopropyl]benzene; -Kal?Go Sea 4
-aminophenoxy)tetrafluorobenzene, 4,4
'-bis(3-calde, xy-4-aminophenoxy)
Octafluorobiphenyl, 4,4'-diaminooctafluorobiphenyl, 1,2-bis(3-caldexy4-aminophenyl)tetrafluoroethane, 1,3-
Bis(3-carboxy-4-aminophenyl)hexafluoroglonocune, 1,5-bis(3-carboxy-4-
(aminophenyl)f-cafluorobentane, diaminopencitrifluoride, bis(trifluoromethyl)phenylenediamine, diaminotetra(trifluoromethyl)benzene, noamino(pentafluoroethyl)benzene, 2,2'-bis(trifluoromethyl) benzinone, 3,3'-bis(trifluoromethyl)benzidine,
2.2'-bis() IJ fluoromethyl)-4,4
'-diaminodiphenyl ether, 3,3'-bis(trifluoromethyl)-4,4'-diaminodiphenyl ether, 3,3',5,5'-tetrakis(trifluoromethyl)-4,4'-diaminodiphenyl ether, 3.3'-bis(trifluoromethyl)-4,4
'-Diaminobenzophenone, bis(aminophenoxy))(t')fluoromethylubenzene, bis(aminophenoxy)tetrakis(trifluoromethyl)benzene, bis[[trifluoromethyl)aminophenoxy]
It is also possible to use fluorine atom-containing diamines such as benzene, bisC()lifluoromethyl)aminophenoxyfubiphenyl, bis([()lifluoromethyl)aminophenoxy]phenyl)hexafluoroglono and annato.
次にかくして得られた本発明のポリアミド酸共重合体か
らポリイミド共重合体を製造する方法について説明する
。本発明の２リイミド共重合体を製造する方法としては
、ポリイミド酸溶液からポリイミドフィルムを製造する
、一般に公知の方法をそのまま用いることができる。即
ち、０）熱的に脱水閉環（イミド化）する方法（ロ）化
学的に脱水閉環（イミド化）する方法がある。詳しく説
明するとＣ）では例えばコポリアミド酸溶液を加熱ドラ
ムあるいはエンドレスベルト上に流延または塗布して膜
状とし、その膜を１５０℃以下の温度で約３０〜９０分
間乾燥した後、自己支持性の膜を得る。次いでこれをド
ラムあるいはエンドレスベルト上から引き剥し、端部を
固定し、さらに約１００〜５００℃の温度に徐保に加温
し、冷却後これよシ取外しコポリイミドフィルムを得る
。Next, a method for producing a polyimide copolymer from the thus obtained polyamic acid copolymer of the present invention will be explained. As a method for producing the 2-imide copolymer of the present invention, a generally known method for producing a polyimide film from a polyimide acid solution can be used as is. That is, there are 0) a method of thermally dehydrating and ring-closing (imidization); and (2) a method of chemically dehydrating and ring-closing (imidization). To explain in detail, in C), for example, a copolyamic acid solution is cast or coated onto a heated drum or endless belt to form a film, and after drying the film at a temperature of 150°C or less for about 30 to 90 minutes, self-supporting obtain a film of Next, the film is peeled off from the drum or endless belt, the ends are fixed, and the film is slowly heated to a temperature of about 100 to 500°C, and after cooling, it can be removed to obtain a copolyimide film.
（ロ）では例えばコポリアミド酸溶液に化学量論量以上
の脱水剤と触媒量の第３級アミン類を混合後、加熱ドラ
ムあるいはエンドレスベルト上に流延または塗布して膜
状とし、その膜を１５０℃以下の温度で約５〜３０分間
乾燥した後、自己支持性の膜を得る。次いでこれをドラ
ムあるいはエンドレスベルト上から引き剥し、端部を固
定し、さらに約１００〜５００℃の温度に徐々に加温し
、冷却後これより取外しコポリイミドフィルムを得る。In (b), for example, a copolyamic acid solution is mixed with a stoichiometric amount or more of a dehydrating agent and a catalytic amount of tertiary amines, and then cast or coated onto a heated drum or endless belt to form a film. After drying at a temperature below 150° C. for about 5 to 30 minutes, a self-supporting membrane is obtained. Next, this is peeled off from the drum or endless belt, the ends are fixed, and the film is gradually heated to a temperature of about 100 to 500°C, and after cooling, it is removed to obtain a copolyimide film.
このとき用いる脱水剤としては、例えば脂肪族酸無水物
、芳香族酸無水物等が挙げられる。また触媒としては、
例えばトリエチルアミン等の脂肪族第３級アミン類、ジ
メチルアニリン等の芳香族第３級アミン類、ピリジン、
ピコリン、イソキノリン等の複素環式第３級アミン類等
が挙げられる。Examples of the dehydrating agent used at this time include aliphatic acid anhydrides and aromatic acid anhydrides. Also, as a catalyst,
For example, aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, pyridine,
Examples include heterocyclic tertiary amines such as picoline and isoquinoline.
（実施例）
以下、実施例によシ本発明を具体的に説明するが、本発
明はこれら実施例のみに限定されるものではない。(Examples) Hereinafter, the present invention will be specifically explained using Examples, but the present invention is not limited only to these Examples.
尚、ここで言う耐アルカリ加水分解性は該ポリイミド共
重合体を５重量％のＮａＯＨ水溶液に５０℃にて５分間
浸漬したときの重量減少率のことである。結果はまとめ
て表１に示す。Note that the alkali hydrolysis resistance referred to herein refers to the weight loss rate when the polyimide copolymer is immersed in a 5% by weight NaOH aqueous solution at 50° C. for 5 minutes. The results are summarized in Table 1.
実施例１
５００−四ツ目フラスコにＯＤＡ （４，４’−ジアミ
ノジフェニルエーテル）１０．８５ｊ？および２，２−
ビス（４−（４−アミノフェノキシ）フェニル）へキサ
フルオロプロパン１．９８ ｙ−を採取し、１４５．０
ＯｉＰのＮ、Ｎ−ジメチルアセトアミドを加え溶解した
。他方、５０ｍＪナスフラスコにピロメリット酸二無水
物（以下ＰＭＤＡという）１６．９０ノを採取し、前記
ジアミン溶液中に固形状で添加した。更にこの５Ｑｒｎ
ｌナスフラスコ中の壁面に残存付着するＰＭＤＡを１０
．ＯＯＰのＮ、Ｎジメチルアセトアミドで反応系（四ツ
目フラスコ）へ流し入れ、更に１時間攪拌を続は酸無水
物基末端アミド酸グレポリマーを得た。一方、５０ｍ／
三角フラスコにｐ−ＰＤＡ （パラフェニレンジアミン
）２．０９ｉＰを採ＭＬ、１５．ＯＯＰのＮ、Ｎ−ツメ
チルアセトアミドを加え溶解した。この溶液を反応系（
四ツ目フラスコ）内へ添加し、共重合ポリアミド酸溶液
を得た。Example 1 10.85j of ODA (4,4'-diaminodiphenyl ether) was added to a 500-four-eye flask. and 2,2-
Bis(4-(4-aminophenoxy)phenyl)hexafluoropropane 1.98 y- was collected and 145.0
OiP N,N-dimethylacetamide was added and dissolved. On the other hand, 16.90 g of pyromellitic dianhydride (hereinafter referred to as PMDA) was collected in a 50 mJ eggplant flask and added in solid form to the diamine solution. Furthermore, this 5Qrn
10% of PMDA remaining on the wall of the eggplant flask
．． The mixture was poured into the reaction system (four-eye flask) with OOP N,N dimethylacetamide, and stirred for an additional hour to obtain an acid anhydride group-terminated amic acid grepolymer. On the other hand, 50m/
15. Take 2.09 iP of p-PDA (paraphenylenediamine) into an Erlenmeyer flask; 15. OOP N,N-trimethylacetamide was added and dissolved. This solution is added to the reaction system (
A copolymerized polyamic acid solution was obtained.
以上の反応操作に於て、反応温度は５〜１０℃に、また
ＰＭＤＡとｐ−ＰＤＡの取シ扱い及び反応系内は乾燥窒
素気流下にて行った。In the above reaction operation, the reaction temperature was 5 to 10°C, and the handling of PMDA and p-PDA and the inside of the reaction system were carried out under a stream of dry nitrogen.
次にこの溶液をガラス板状に流延塗布し約１００℃にて
約６０分間乾燥後、塗膜をガラス板より剥し、その塗膜
を支持枠に固定し、その後約１００℃で約３０分間、約
２００℃で約６０分間、約３００℃で約６０分間加熱し
、脱水閉環乾燥後２５ミクロンのポリイミドフィルムを
得た。Next, this solution was cast onto a glass plate and dried at about 100°C for about 60 minutes, then the coating was peeled off from the glass plate, fixed on a support frame, and then heated at about 100°C for about 30 minutes. The mixture was heated at about 200°C for about 60 minutes and at about 300°C for about 60 minutes to obtain a polyimide film of 25 microns after dehydration and ring closure drying.
実施例２
５００−四ソロフラスコにｐ−ＰＤＡ ４．３５ ｙ−
を採取し、１１０．００ｉ！−のＮ、Ｎ−ツメチルアセ
トアミドを加え溶解した。他方、５ＯＮナスフラスコに
ＰＭＤＡを１７．５７！？を採取し、前記ｐ−ＰＤＡ溶
液中に固形状で添加した。更にこの５０ｍ１ナスフラス
コ中の壁面に残存付着するＰＭＤＡを１０．００？のＮ
、Ｎ−ツメチルアセトアミドで反応系（四ツ目フラスコ
）へ流し入れ、更に１時間攪拌を続は酸無水物基末端ア
ミド酸プレポリマーを得た。一方、１００−三角フラス
コにＯＤＡ ６．７８ ？および２，２−ビス（４−ア
ミノフェニル）へキサフルオロプロパン２、１５ ｙ−
を採取し、５０．００ｙ−のＮ、Ｎ−ジメチルアセトア
ミドを加え溶解した。この溶液を反応系（四ツ目フラス
コ）内へ添加し、ポリアミド酸共重合体溶液を得た。Example 2 p-PDA 4.35 y- in a 500-tetra solo flask
Collected 110.00i! -N,N-trimethylacetamide was added and dissolved. On the other hand, add 17.57 PMDA to a 5ON eggplant flask! ? was collected and added in solid form to the p-PDA solution. Furthermore, the amount of PMDA remaining on the wall of this 50m1 eggplant flask was 10.00? N of
, N-trimethylacetamide was poured into the reaction system (four-eye flask), and the mixture was further stirred for 1 hour to obtain an acid anhydride group-terminated amic acid prepolymer. On the other hand, ODA 6.78 in a 100-erlenmeyer flask? and 2,2-bis(4-aminophenyl)hexafluoropropane 2,15 y-
was collected and dissolved by adding 50.00y of N,N-dimethylacetamide. This solution was added into the reaction system (four-eye flask) to obtain a polyamic acid copolymer solution.
以上の反応操作に於て、反応温度は５〜１０℃に、また
ＰＭＤＡとＯＤＡおよび２，２−ビス（４−アミノフェ
ニル）ヘキサフルオログロノヤンの取扱い及び反応系内
は乾燥窒素気流下にて行った。次に、実施例１の方法に
従い、ポリイミドフィルムを得た。In the above reaction operation, the reaction temperature was kept at 5 to 10°C, and PMDA, ODA, and 2,2-bis(4-aminophenyl)hexafluoroglonoyan were handled and the reaction system was kept under a stream of dry nitrogen. went. Next, according to the method of Example 1, a polyimide film was obtained.
実施例３
５００ｍｌ四ツロフラｘ＝＋にＯＤＡ １８．０３ ？
を採取し、１３５．００ｉＰのＮ、Ｎ−ジメチルアセト
アミドを加え溶解した。他方、１００７ｄナスフラスコ
にＰＭＤＡ １６．９７ ｉＰおよび２，２−ビス（３
，４−ジカルボキシフェニル）へキサフルオロプロノ臂
ンニ無水物１．４４ ｙ−を採取し、前記ＯＤＡ溶液中
に固形状で添加し、そのまま１時間攪拌を続はアミノ基
末端アミド酸プレポリマー溶液を得た。次いで、５０ｄ
ナスフラスコにｐ−ＰＤＡ ３．２４ ｔを採取し、こ
のアミノ基末端アミド酸プレポリマー溶液に固形状で添
加し、添加したｐ−ＰＤＡが完全に溶解するまで十分に
攪拌した後、別途に１ｏｏｕｚナスフラスコに不足分の
ＰＭＤＡ ８．５０ ？を採取し、反応系（四ツ目フラ
スコ）内へ固形状で添加した。反応温度は５〜１０℃に
保った。但し以上の操作でＰＭＤＡおよヒ２．２−ビス
（３，４−）力ルデキシフェニル）へキサフルオロプロ
パンニ無水物の取シ扱い及び反応系内は乾燥窒素気流下
に置いた。Example 3 ODA 18.03 to 500ml Yotsurofura x=+?
was collected and dissolved by adding 135.00 iP of N,N-dimethylacetamide. On the other hand, PMDA 16.97 iP and 2,2-bis(3
, 4-Dicarboxyphenyl) hexafluoroproxyanhydride (1.44 y) was collected and added to the above ODA solution in solid form, and stirred for 1 hour. Subsequently, the amino group-terminated amic acid prepolymer solution was added. I got it. Then 50d
Collect 3.24 t of p-PDA in an eggplant flask, add it in solid form to this amino group-terminated amic acid prepolymer solution, stir thoroughly until the added p-PDA is completely dissolved, and then add 1 oz separately. PMDA 8.50 missing in the eggplant flask? was collected and added in solid form into the reaction system (four-eye flask). The reaction temperature was kept at 5-10°C. However, in the above operations, PMDA and 2,2-bis(3,4-)dyrodexyphenyl)hexafluoropropanihydride were handled and the inside of the reaction system was placed under a stream of dry nitrogen.
次に実施例１の方法に従い、この溶液よシポリイミドフ
ィルムヲ得り。Next, according to the method of Example 1, a polyimide film was obtained from this solution.
実施例４
５００１７！四ツロフラスコにＯＤＡ １１．１６７−
およヒ２，２−ビス（４−（４−アミノフェノキシ）フ
ェニル）へキザフルオログロ／４’ン１．１ｃ＋ｙヲ採
取し、１４５．００．ＰのＮ、Ｎ−ジメチルアセトアミ
ドを加え溶解した。他方、５ＱｍｌナスフラスコにＰＭ
ＤＡ１６．３９ｙ−および２，２−ビス（３，４−）力
ルデキシフェニル）へキサフルオロプロノ！ンニ無水物
１．０３ｙ−を採取し、前記ＯＤＡ溶液中に固形状で添
加した。更にこの５０ｍ１ナスフラスコ中の壁面に残存
付着する酸二無水物を１０．ＯＯＰのＮ、Ｎツメチルア
セトアミドで反応系（四ツ目フラスコ）へ流し入れ、更
に１時間攪拌を続は酸無水物基末端アミド酸グレポリマ
ーを得た。一方、５． Ｏａｔ三角フラスコにｐ−ＰＤ
Ａ ２．０９ 、Ｓ’を採取し７．１５．ＯＣ１’のＮ
、Ｎ−ジメチルアセトアミドを加え溶解した。Example 4 50017! ODA in Yotsuro flask 11.167-
and 2,2-bis(4-(4-aminophenoxy)phenyl)hekizafluoroglobin/4'n 1.1c+y were collected, and 145.00. N,N-dimethylacetamide of P was added and dissolved. On the other hand, add PM to a 5Qml eggplant flask.
DA16.39y- and 2,2-bis(3,4-)rudexyphenyl)hexafluoroprono! 1.03y of anhydride was collected and added in solid form to the ODA solution. Furthermore, the acid dianhydride remaining on the wall of this 50 ml eggplant flask was removed by 10. The mixture was poured into the reaction system (four-eye flask) with OOP N,N-methylacetamide, and stirred for an additional hour to obtain an acid anhydride group-terminated amic acid grepolymer. On the other hand, 5. p-PD in Oat Erlenmeyer flask
A 2.09, S' was collected and 7.15. N of OC1'
, N-dimethylacetamide was added and dissolved.
この溶液を反応系（四ツ目フラスコ）内へ添加し、共重
合ポリアミド酸溶液を得た。This solution was added into the reaction system (four-eye flask) to obtain a copolymerized polyamic acid solution.
以上の反応操作に於て、反応温度は５〜１０℃に、まだ
ＰＭＤＡおよび２，２−ビス（３，４−ジカルボキシフ
ェニル）ヘキサフルオログロノ９ンニ無水物とｐ−ＰＤ
Ａの取り扱い及び反応系内は乾燥窒素気流下にて行った
。In the above reaction operation, the reaction temperature was 5 to 10°C, while PMDA and 2,2-bis(3,4-dicarboxyphenyl)hexafluoroglobin anhydride and p-PD
Handling of A and the inside of the reaction system were carried out under a stream of dry nitrogen.
次に実施例１の方法に従い、この溶液よりポリイミドフ
ィルムを得た。Next, according to the method of Example 1, a polyimide film was obtained from this solution.
比較例１
５００ｍｌ四ツロフラスコにＯＤＡ ２１．５４ Ｐを
採取し、２４５．００ノのＮ、Ｎ−ツメチルアセトアミ
ドを加え溶解した。他方、１００ｍ１ナスフラスコにｐ
ＭＤＡ ２３．４６ ｉＩ−を採取し、ＯＤＡ溶液中に
固形状で添加した。さらに、この１００ｍ／ナスフラス
コ中の壁面に付着残存するＰＭＤＡを１０．００ｙ−の
Ｎ、Ｎ −ジメチルアセトアミドで反応系（四ツ目フラ
スコ）内へ流し入れた。更に引き続き１時間攪拌を続け
、１５重量％のポリアミド酸溶液を得た。反応温度は５
〜１０℃に保った。但し以上の操作でＰＭＤＡの取シ扱
い及び反応系内は乾燥窒素気流下に置いた。Comparative Example 1 21.54 P of ODA was collected in a 500 ml four-piece flask, and 245.00 g of N,N-methylacetamide was added thereto to dissolve it. On the other hand, add p to a 100 m eggplant flask.
23.46 iI- of MDA was collected and added in solid form into the ODA solution. Furthermore, the PMDA remaining attached to the wall of this 100 m round bottom flask was poured into the reaction system (four-eye flask) with 10.00 y of N,N-dimethylacetamide. Stirring was further continued for 1 hour to obtain a 15% by weight polyamic acid solution. The reaction temperature is 5
It was kept at ~10°C. However, in the above operations, PMDA was handled and the inside of the reaction system was placed under a stream of dry nitrogen.
次に実施例１の方法に従い、このホリアミド酸溶液よシ
ポリイミドフィルムを得た。Next, according to the method of Example 1, a polyimide film was obtained from this polyamic acid solution.
比較例２
５００ ｍｌ四ツロフラスコに４．４′−ジアミノジフ
ェニルエーテル（以下ＯＤＡという）１１．６３？を採
取シ、１４５．００？のＮ、Ｎ−ジメチルアセトアミド
を加え溶解した。他方、５０ｍ１ナスフラスコにピロメ
リット酸二無水物（以下ＰＭＤＡという）１６．９０ｊ
？を採取し、前記ＯＤＡ溶液中に固形状で添加した。更
にこの５０ｒｎｌナスフラスコ中の壁面に残存付着する
ＰＭＤＡを１０．００ｙ−のＮ、Ｎジメチルアセトアミ
ドで反応系（四ツ目フラスコ）へ流し入れ、更に１時間
攪拌を続は酸無水物基末端アミド酸ゾレポリマーを得た
。一方、５Ｑｍｌ三角フラスコニパラフェニレンジアミ
ン（以下Ｔｌ−ＰＤＡ トイう）２．０９７を採取し、
１５．００／−のＮ、Ｎ−ジメチルアセトアミドを加え
溶解した。この溶液を反応系（四ツ目フラスコ）内へ添
加し、共重合ポリアミド酸溶液を得た。Comparative Example 2 4.4'-diaminodiphenyl ether (hereinafter referred to as ODA) 11.63? I collected it for 145.00? of N,N-dimethylacetamide was added and dissolved. On the other hand, 16.90j of pyromellitic dianhydride (hereinafter referred to as PMDA) was placed in a 50ml eggplant flask.
? was collected and added in solid form to the ODA solution. Furthermore, the PMDA remaining on the wall of this 50rnl eggplant flask was poured into the reaction system (four-eye flask) with 10.00y- of N,N dimethylacetamide, and stirred for an additional hour. Solrepolymer was obtained. On the other hand, 2.097 mL of 5Qml Erlenmeyer flask was collected,
15.00/- of N,N-dimethylacetamide was added and dissolved. This solution was added into the reaction system (four-eye flask) to obtain a copolymerized polyamic acid solution.
次いで、 実施例１の方法に従いこのポリアミ ド 酸溶液よシボリイ ドフィ ルムを得た。Then, This polyamide was prepared according to the method of Example 1. de Acid solution, Shiborii Doffy Got Lum.
（発明の効果）
本発明のポリイミド共重合体は、ポリイミド共重合体（
Ａ）が有する優れた特性（熱的寸法安定性、機械的性質
等）を損なうことなく耐アルカリ加水分解性が改良され
る。具体的には本発明のポリイミド共重合体を５ｘ量チ
のＮａＯＨ水溶液に５０℃にて５分間浸漬した時の重量
減少率が３％以下にまで改善される。そのためフレキシ
ブルプリント基板等に非常に有用である。(Effect of the invention) The polyimide copolymer of the present invention is a polyimide copolymer (
Alkaline hydrolysis resistance is improved without impairing the excellent properties (thermal dimensional stability, mechanical properties, etc.) possessed by A). Specifically, when the polyimide copolymer of the present invention is immersed in a 5x amount of NaOH aqueous solution at 50° C. for 5 minutes, the weight loss rate is improved to 3% or less. Therefore, it is very useful for flexible printed circuit boards and the like.
出願人代理人 弁理士 鈴 江 武 彦手続補正書 昭和 年 特許庁長官 吉 １）文 毅 殿 ６３、Ｕ、Ｉ４ 月 日 １、事件の表示 特願昭６３−１９５４５６号 ２、発明の名称 改質されたポリイミド共重合体および ポリアミド酸共重合体 ３、補正をする者 事件との関係 特許出願人 鐘淵化学工業株式会社 ４゜Applicant's agent Patent attorney Takehiko Suzue Procedural amendment Showa year Yoshi, Commissioner of the Patent Office 1) Takeshi Moon 63, U, I4 time 1.Display of the incident Patent Application No. 1984-195456 2. Name of the invention Modified polyimide copolymer and Polyamic acid copolymer 3. Person who makes corrections Relationship to the case Patent applicant Kanebuchi Chemical Industry Co., Ltd. 4゜
Claims (5)
／またはフッ素原子含有ジアミンを一部使用して得られ
るポリアミド酸共重合体を脱水閉環イミド化してなるこ
とを特徴とするポリイミド共重合体。(1) As acid components, there are ▲mathematical formulas, chemical formulas, tables, etc.▼As for diamine components, there are ▲mathematical formulas, chemical formulas, tables, etc.▼ and ▲mathematical formulas, chemical formulas, tables, etc.▼ are mainly used, and in addition, fluorine atom-containing acids are used. A polyimide copolymer obtained by dehydrating and ring-closing imidization of a polyamic acid copolymer obtained by partially using a dianhydride and/or a fluorine atom-containing diamine.
量に対して３０ｍｏｌ％以下である請求項１記載のポリ
イミド共重合体。(2) The polyimide copolymer according to claim 1, wherein the amount of the fluorine atom-containing acid dianhydride used is 30 mol% or less based on the total amount of acid components.
分全量に対して３０ｍｏｌ％以下である請求項１記載の
ポリイミド共重合体。(3) The polyimide copolymer according to claim 1, wherein the amount of the fluorine atom-containing diamine used is 30 mol% or less based on the total amount of the diamine component.
ミンの合計使用量が酸成分全量とジアミン成分全量の合
計量に対して３０ｍｏｌ％以下である請求項１〜３記載
のポリイミド共重合体。(4) The polyimide copolymer according to any one of claims 1 to 3, wherein the total amount of the fluorine atom-containing acid dianhydride and the fluorine atom-containing diamine used is 30 mol% or less based on the total amount of the total amount of the acid component and the total amount of the diamine component.
漬した時の重量減少率が３％以下である請求項１〜４記
載のポリイミド共重合体。(5) The polyimide copolymer according to any one of claims 1 to 4, which has a weight loss rate of 3% or less when immersed in a 5% by weight NaOH aqueous solution at 50°C for 5 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63195456A JP2835052B2 (en) | 1988-08-05 | 1988-08-05 | Modified polyimide copolymer and polyamic acid copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63195456A JP2835052B2 (en) | 1988-08-05 | 1988-08-05 | Modified polyimide copolymer and polyamic acid copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0245529A true JPH0245529A (en) | 1990-02-15 |
| JP2835052B2 JP2835052B2 (en) | 1998-12-14 |
Family
ID=16341371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63195456A Expired - Lifetime JP2835052B2 (en) | 1988-08-05 | 1988-08-05 | Modified polyimide copolymer and polyamic acid copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2835052B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0641305A (en) * | 1991-10-25 | 1994-02-15 | Internatl Business Mach Corp <Ibm> | Polyamic acid and polyimide from fluorinated reactant |
| CN105601923A (en) * | 2016-02-14 | 2016-05-25 | 中国科学院化学研究所 | Fluorine-containing flexible-rigid polyimide film, and preparation method and application thereof |
| CN111808284A (en) * | 2020-07-03 | 2020-10-23 | 株洲时代新材料科技股份有限公司 | Polyamide acid, polyamide acid resin, heat-resistant transparent polyimide and preparation method |
| CN117210004A (en) * | 2023-10-13 | 2023-12-12 | 苏州沃尔峰新能源有限公司 | Acid and alkali resistant polyimide film for new energy battery and preparation process thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4945152A (en) * | 1972-07-20 | 1974-04-30 | ||
| JPS62127827A (en) * | 1985-11-29 | 1987-06-10 | Hitachi Chem Co Ltd | Composition for oriented film for liquid crystal |
-
1988
- 1988-08-05 JP JP63195456A patent/JP2835052B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4945152A (en) * | 1972-07-20 | 1974-04-30 | ||
| JPS62127827A (en) * | 1985-11-29 | 1987-06-10 | Hitachi Chem Co Ltd | Composition for oriented film for liquid crystal |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0641305A (en) * | 1991-10-25 | 1994-02-15 | Internatl Business Mach Corp <Ibm> | Polyamic acid and polyimide from fluorinated reactant |
| JPH07233325A (en) * | 1991-10-25 | 1995-09-05 | Internatl Business Mach Corp <Ibm> | Radiation-reactive composition |
| US5780199A (en) * | 1991-10-25 | 1998-07-14 | International Business Machines Corporation | Polyamic acid and polyimide from fluorinated reactant |
| CN105601923A (en) * | 2016-02-14 | 2016-05-25 | 中国科学院化学研究所 | Fluorine-containing flexible-rigid polyimide film, and preparation method and application thereof |
| CN111808284A (en) * | 2020-07-03 | 2020-10-23 | 株洲时代新材料科技股份有限公司 | Polyamide acid, polyamide acid resin, heat-resistant transparent polyimide and preparation method |
| CN111808284B (en) * | 2020-07-03 | 2022-06-03 | 株洲时代新材料科技股份有限公司 | Polyamide acid, polyamide acid resin, heat-resistant transparent polyimide and preparation method |
| CN117210004A (en) * | 2023-10-13 | 2023-12-12 | 苏州沃尔峰新能源有限公司 | Acid and alkali resistant polyimide film for new energy battery and preparation process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2835052B2 (en) | 1998-12-14 |
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