JPH0459759A - Flexible bisimide compound - Google Patents
Flexible bisimide compoundInfo
- Publication number
- JPH0459759A JPH0459759A JP2171232A JP17123290A JPH0459759A JP H0459759 A JPH0459759 A JP H0459759A JP 2171232 A JP2171232 A JP 2171232A JP 17123290 A JP17123290 A JP 17123290A JP H0459759 A JPH0459759 A JP H0459759A
- Authority
- JP
- Japan
- Prior art keywords
- flexible
- bisimide compound
- compound
- flexibility
- aromatic diamine
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 30
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 23
- -1 bismaleimide compound Chemical class 0.000 claims abstract description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 8
- 239000001294 propane Substances 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 150000008065 acid anhydrides Chemical class 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 150000004820 halides Chemical class 0.000 abstract description 5
- 239000003733 fiber-reinforced composite Substances 0.000 abstract description 4
- 239000012778 molding material Substances 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract description 2
- 239000011976 maleic acid Substances 0.000 abstract description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000009102 absorption Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000004985 diamines Chemical class 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-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
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical class C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- MWAGUKZCDDRDCS-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenoxy)benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1OC1=CC=C([N+]([O-])=O)C=C1 MWAGUKZCDDRDCS-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Substances [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Pyrrole Compounds (AREA)
- Indole Compounds (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、繊維強化複合材用樹脂、プリント配線板用基
板樹脂、耐熱性成形材料用樹脂などとして有用な可撓性
ビスイミド化合物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a flexible bisimide compound useful as a resin for fiber-reinforced composite materials, a substrate resin for printed wiring boards, a resin for heat-resistant molding materials, and the like.
芳香族ジアミン類は、ポリアミド、ポリイミド、ビスイ
ミド化合物などの原材料及び銅張積層板や繊維強化用な
どのエポキシ樹脂の硬化剤として広く使用されている。Aromatic diamines are widely used as raw materials for polyamides, polyimides, and bisimide compounds, and as curing agents for epoxy resins for copper-clad laminates and fiber reinforcement.
また、熱硬化性ビスイミド化合物はその機械特性、電気
特性、耐熱性が優れているため、繊維強化複合材、プリ
ント配線基板、耐熱性成形材料などの樹脂として用いら
れている。Furthermore, thermosetting bisimide compounds have excellent mechanical properties, electrical properties, and heat resistance, and are therefore used as resins for fiber-reinforced composite materials, printed wiring boards, heat-resistant molding materials, and the like.
しかし、ジアミノフェニルメタンやジアミノジフェニル
エーテルなどの通常のジアミン類を原料として用いたビ
スイミド化合物では、耐熱性が良好なものの成形加工性
が悪く、また可撓性や耐衝撃性に乏しいという欠点があ
った。However, bisimide compounds that use ordinary diamines such as diaminophenylmethane and diaminodiphenyl ether as raw materials have good heat resistance but have poor moldability and have the disadvantages of poor flexibility and impact resistance. .
そこで、ビスイミド化合物で耐熱性と可撓性や耐衝撃性
にともに優れた樹脂を得るには主鎖にエーテル結合を持
つ芳香族ジアミンを原料とする方法が用いられる０例え
ば、特公昭６３−１７０８１号公報に示されている耐熱
性ビスイミド系樹脂組成物や特公昭６３−３７７８６号
公報に示されているエーテルイミド系化合物は、原材料
の芳香族ジアミンとして、式（ＩＩ）で表される２、２
−ビス（４−アミノフェノキシフェニル）プロパンが用
いられている。Therefore, in order to obtain a resin with excellent heat resistance, flexibility, and impact resistance using a bisimide compound, a method using an aromatic diamine having an ether bond in the main chain as a raw material is used. The heat-resistant bisimide-based resin composition shown in the above publication and the etherimide-based compound shown in Japanese Patent Publication No. 63-37786 contain, as raw material aromatic diamine, 2 represented by formula (II), 2
-bis(4-aminophenoxyphenyl)propane is used.
また、エポキシ樹脂硬化物の接着性や耐衝撃性を向上さ
せるためには、硬化物に可撓性を付与できるような類僚
のジアミンが用いられる１例えば、特開昭５８−８６３
９号公報に示されている難燃性エポキシ樹脂銅張積層板
用フェスは、耐熱性と接着性をともに改善する硬化剤と
して、上記ジアミンと＠領の式（ＩＩＩ）で表される２
、２−ビス（４−（４−アミノフェノキシ）−３，５−
ジブロモフェニル〕プロパンが用いられている。Furthermore, in order to improve the adhesion and impact resistance of cured epoxy resin products, similar diamines that can impart flexibility to the cured product are used.
The flame-retardant epoxy resin face for copper-clad laminates disclosed in Publication No. 9 uses the above-mentioned diamine and 2 represented by the formula (III) of @ryo as a curing agent that improves both heat resistance and adhesion.
, 2-bis(4-(4-aminophenoxy)-3,5-
dibromophenyl]propane is used.
また、耐熱性をあまり損なうことなく耐衝撃性を大幅に
向上させるエポキシ樹脂硬化剤用の芳香族ジアミンとし
て、特開昭６２−３６４２２号公報に示されている繊維
強化プリプレグ用のエポキシ樹脂は、式（ＩＶ）で表さ
れるエーテル結合のほかにエチレンオキシド鎖も持つ芳
香族ジアミンが用いられている。In addition, epoxy resins for fiber-reinforced prepregs disclosed in JP-A-62-36422 are aromatic diamines for epoxy resin curing agents that significantly improve impact resistance without significantly impairing heat resistance. An aromatic diamine having an ethylene oxide chain in addition to the ether bond represented by formula (IV) is used.
〔発明が解決しようとするｌ１ｌｉ）
特公昭６３−１７０８１号公報に記載の耐熱性ビスイミ
ド系樹脂組成物や特公昭６３−３７７８６号公報に記載
のエーテルイミド系化合物を用いる方法は、主鎖にエー
テル結合をもつ芳香族ジアミンを原料とするため、エー
テル基が導入されて柔軟性が付与されるものの、可撓性
がいまだ不十分なために単独では依然として強靭性のな
い脆い材料になるという問題点があった。[11li to be solved by the invention] The method using the heat-resistant bisimide resin composition described in Japanese Patent Publication No. 63-17081 and the etherimide compound described in Japanese Patent Publication No. 63-37786 has an ether in the main chain. Since the material is an aromatic diamine with bonds, ether groups are introduced to give it flexibility, but the problem is that the flexibility is still insufficient and it still becomes a brittle material with no toughness when used alone. was there.
また、特開昭５８−８６３９号公報に記載の難燃性エポ
キシ樹脂銅張積層板用フェスを用いる方法も、硬化剤に
ブロム化芳香族エーテルジアミンを用いるため、硬化物
には若干は可撓性が付与されているが、いまだ不十分で
あり、銅箔との接着性において満足できる特性が得られ
ないという問題点があった。Furthermore, the method using a flame-retardant epoxy resin copper-clad laminate face described in JP-A-58-8639 also uses brominated aromatic ether diamine as a hardening agent, so the cured product has some flexibility. However, it is still insufficient, and there is a problem in that satisfactory adhesive properties with copper foil cannot be obtained.
また、特開昭６２−３６４２２号公報に記載の繊維強化
プリプレグ用のエポキシ樹脂を用いる方法では、主鎖に
エーテル結合のほかにエチレンオキシド鎖も持つ柔軟性
に優れた芳香族ジアミンを硬化剤に用いているため、可
撓性があり、耐衝撃性も十分であるが、末端のアミノフ
ェノキシ基がエステル結合で結合しているため耐熱性が
低下し、耐薬品性も低下するという問題点があった。In addition, in the method of using an epoxy resin for fiber-reinforced prepreg described in JP-A No. 62-36422, a highly flexible aromatic diamine having an ethylene oxide chain in addition to an ether bond in the main chain is used as a curing agent. Because of this, it is flexible and has sufficient impact resistance, but there are problems in that the terminal aminophenoxy groups are bonded with ester bonds, which reduces heat resistance and chemical resistance. Ta.
本発明は、柔軟性に優れた芳香族ジアミンを原料に用い
ることにより、耐熱性とともに耐衝撃性や可撓性にも優
れる樹脂となる可撓性ビスイミド化合物を提供するもの
である。The present invention provides a flexible bisimide compound that is a resin having excellent heat resistance, impact resistance, and flexibility by using an aromatic diamine with excellent flexibility as a raw material.
すなわち、本発明は一般式（１）
（式中、Ｘ１〜Ｘ４は水素原子又は炭素数１〜３のアル
キル基を示し、互いに同じであっても異なっていてもよ
い Ｒ’及びＲ２は水素原子、メチル基、エチル基、ト
リフルオロメチル基又はトリクロロメチル基を示し、互
いに同じであっても異なっていてもよい、ｎは１〜３の
整数を示す、）で表される芳香族ジアミンの末端アミノ
基をイミド化したことを特徴とする可撓性ビスイミド化
合物を提供するものである。That is, the present invention is based on the general formula (1) (wherein, X1 to X4 represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and may be the same or different from each other; R' and R2 are hydrogen atoms) , a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, which may be the same or different, n is an integer of 1 to 3). The present invention provides a flexible bisimide compound characterized in that an amino group is imidized.
本発明のビスイミド化合物の原料となる柔軟性に優れた
芳香族ジアミンは、−殺伐（、、Ｉ）においてｎの値の
増加とともに可撓性を付与する効果が大きくなるが、４
以上になると耐熱性が損なわれてしまうので好ましくな
い。具体的には、２．２−ビス〔４−（β−ｐ−アミノ
フェノキシエトキシ）フェニル〕プロパン、ビスフェノ
ールＡ−エチレンオキシド付加物のビスアミノフェノキ
シエーテル化誘導体等が挙げられ、２．２−ビス〔４−
（β−ｐ−アミノフェノキシエトキシ）フェニル〕プロ
パンが好適に用いられる。The aromatic diamine with excellent flexibility, which is a raw material for the bisimide compound of the present invention, has a greater flexibility imparting effect as the value of n increases in -slagging (,, I), but 4
If it is more than that, heat resistance will be impaired, which is not preferable. Specifically, 2.2-bis[4-(β-p-aminophenoxyethoxy)phenyl]propane, bisaminophenoxyetherified derivatives of bisphenol A-ethylene oxide adducts, etc. 4-
(β-p-aminophenoxyethoxy)phenyl]propane is preferably used.
本発明の可撓性ビスイミド化合物の製造は、通常のジア
ミン類と酸無水物又は酸ハロゲン化物とのイミド化反応
による方法で製造することができる。すなわち前記柔軟
性に優れた芳香族ジアミンを脱水された適当な溶媒、例
えばアセトン、テトラヒドロフラン、Ｎ、Ｎ−ジメチル
ホルムアミドやＮ−メチルピロリドンなどに溶解し、常
温若しくは水浴中で酸無水物又は酸ハロゲン化物をその
まま若しくは溶液で加えることによりアミド酸を製造す
る。この際、酸無水物又は酸ハロゲン化物にジアミン類
を後から加えてもよい。The flexible bisimide compound of the present invention can be produced by a conventional method of imidization reaction between diamines and acid anhydrides or acid halides. That is, the above-mentioned highly flexible aromatic diamine is dissolved in a suitable dehydrated solvent such as acetone, tetrahydrofuran, N,N-dimethylformamide or N-methylpyrrolidone, and the acid anhydride or acid halogen is dissolved at room temperature or in a water bath. Amic acid is produced by adding the compound as it is or in solution. At this time, diamines may be added to the acid anhydride or acid halide later.
生成したアミド酸は、アミド酸が析出した場合は濾別し
た後に次の閉環工程に進み、イミド化が行われる。また
、アミド酸が溶液の状態で得られる場合はそのまま次へ
進むこともできる。閉環はいわゆる化学閉環で行うこと
ができる。閉環助剤には通常無水酢酸などの酸無水物が
用いられる。The generated amic acid, if precipitated, is filtered and then proceeds to the next ring-closing step, where imidization is performed. Alternatively, if the amic acid is obtained in the form of a solution, you can proceed to the next step as is. Ring closure can be carried out by so-called chemical ring closure. Acid anhydrides such as acetic anhydride are usually used as ring-closing aids.
閉環反応の触媒には酢酸ニッケル、無水酢酸カリウム、
酢酸コバルトなどの無機塩類やピリジンやトリエチルア
ミンなどの有機アミン類が用いられる。Catalysts for the ring-closing reaction include nickel acetate, potassium acetate anhydride,
Inorganic salts such as cobalt acetate and organic amines such as pyridine and triethylamine are used.
なお、柔軟性に優れた芳香族ジアミンの末端アミノ基を
イミド化してビスイミド化合物を製造する場合、反応に
用いられる酸無水物、酸ハロゲン化物としては、特に制
限はないが、マレイン酸、ナジック酸の酸無水物や酸ハ
ロゲン化物が好適に用いられる。In addition, when producing a bisimide compound by imidizing the terminal amino group of an aromatic diamine with excellent flexibility, there are no particular restrictions on the acid anhydride or acid halide used in the reaction, but maleic acid, nadic acid, etc. Acid anhydrides and acid halides are preferably used.
また、本発明のビスイミド化合物には、従来公知の他の
芳香族ジアミンから得られたビスイミド化合物を併用し
て使用することもできる。Moreover, the bisimide compound of the present invention can also be used in combination with a bisimide compound obtained from other conventionally known aromatic diamines.
以下、本発明を実施例に基づいて詳細に説明するが、本
発明はこれに限定されるものではない。Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto.
実施例１
本発明のビスイミド化合物の原料となる柔軟性に優れた
芳香族ジアミンの製造方法の一例を以下に示す。Example 1 An example of a method for producing an aromatic diamine with excellent flexibility, which is a raw material for the bisimide compound of the present invention, is shown below.
攪拌装置、水分定量受器とコンデンサー及び温度計を備
えた２Ｉｌの三ロフラスコに、ＤＫフレックスＢＰＥ−
２Ｐ （ビスフェノールＡのエチレンオキシド付加物、
第一工業製薬株式会社製商品名）１２６ｇを投入し、Ｎ
−メチルピロリドン１１を加えて溶解した。次いで攪拌
しながら含有置駒６０％の水素化ナトリウム３５ｇを少
しづつ加え、３０分間攪拌した。DK Flex BPE-
2P (ethylene oxide adduct of bisphenol A,
Add 126g of Daiichi Kogyo Seiyaku Co., Ltd. (product name), and
-Methylpyrrolidone 11 was added and dissolved. Next, while stirring, 35 g of sodium hydride containing 60% sodium hydride was added little by little, and the mixture was stirred for 30 minutes.
次にトルエン２５０＋ｄとＰ−二トロクロルベンゼン１
５１ｇを加えて完全に溶解した後オイルバスにて加熱し
た。還流温度で２時間反応させて水を系外に溜出させ、
次いでトルエンを留去した後１７５〜１８０℃で１時間
反応させた。Next, toluene 250+d and P-nitrochlorobenzene 1
After 51 g was added and completely dissolved, it was heated in an oil bath. React at reflux temperature for 2 hours to distill water out of the system,
Next, after distilling off toluene, the mixture was reacted at 175 to 180°C for 1 hour.
冷却後、析出した塩化ナトリウムを濾別し、梨形フラス
コに移して減圧下でＮ−メチルピロリドンを留去した（
５８℃７４ ｍ１ｇ） 、次いで得られた樹脂状物をメ
タノールで洗浄し沈澱物８０ｇを得た。After cooling, the precipitated sodium chloride was filtered off, transferred to a pear-shaped flask, and N-methylpyrrolidone was distilled off under reduced pressure (
The resulting resinous material was then washed with methanol to obtain 80 g of precipitate.
この沈澱の赤外線吸収スペクトルでは３５００ｅ１ｍ−
’付近の水酸基の吸収が消失し、新たに１３４０ｃｔ−
’にニトロ基の吸収が現れていた。The infrared absorption spectrum of this precipitate is 3500e1m-
The absorption of the hydroxyl group near ' disappeared, and a new 1340 ct-
'The absorption of nitro group appeared.
次にニトロ基の還元を行った。攪拌装置、コンデンサー
、温度計を備えた３ｊ！の三ロフラスコに、上記のビス
（ｐ−ニトロフェニルエーテル）化物８０ｇを投入し、
ベンゼン３１に溶解させた。湯浴上で攪拌しながら、予
め鉄粉１ｋｇと濃塩酸２５０１ｄを用いて作製しておい
た活性鉄を３時間かけて少しづつ加え、その後７０〜７
５℃で２時間反応させた０次いで水２５０１ｄを加え、
更に１時間反応させた。Next, the nitro group was reduced. 3j equipped with stirrer, condenser, and thermometer! Pour 80 g of the above bis(p-nitrophenyl ether) compound into a three-ring flask,
It was dissolved in benzene 31. While stirring on a hot water bath, activated iron prepared in advance using 1 kg of iron powder and 2501 d of concentrated hydrochloric acid was added little by little over 3 hours, and then
After reacting at 5°C for 2 hours, 2501d of water was added,
The reaction was further continued for 1 hour.
冷却後不溶物を濾別し、ベンゼン溶液を分液ロートに移
して２回水洗した０次いで無水硫酸ナトリウムを加えて
一昼夜乾燥した後、ベンゼンを揮散させて固形物５４ｇ
を得た。この粉末の赤外線吸収スペクトルでは１３４０
Ｃ１１−’付近のニトロ基の吸収が消失し、新たに３３
５０〜３５００Ｃ１ｌ−’に一級アミンの２本の吸収が
現れていた。After cooling, insoluble matter was filtered out, and the benzene solution was transferred to a separating funnel and washed twice with water. Then, anhydrous sodium sulfate was added and dried overnight, and the benzene was evaporated to give 54 g of solid matter.
I got it. The infrared absorption spectrum of this powder is 1340
The absorption of the nitro group near C11-' disappears, and a new 33
Two primary amine absorptions appeared between 50 and 3500 C1l-'.
上記の一級アミン吸収のほかに２９００〜３０ＱＱｃｍ
−’にイソプロペニル基のｃｔｔｓの吸収、１２４Ｑｃ
ｍ−’に芳香族エーテルの吸収、１０００−１１０００
１−’にエチレンオキシド鎖の吸収が認められた。In addition to the above primary amine absorption, 2900~30QQcm
-' is absorption of ctts of isopropenyl group, 124Qc
Absorption of aromatic ether in m-', 1000-11000
Absorption of ethylene oxide chains was observed at 1-'.
以上のことから上記芳香族ジアミン化合物は柔軟性に優
れた芳香族ジアミンである式（１）％式％
を有するビスフェノールＡエチレンオキシド付加物のビ
ス（ｐ−アミノフェニルエーテル）化物であることが確
認された。From the above, it was confirmed that the above-mentioned aromatic diamine compound is a bis(p-aminophenyl ether) compound of bisphenol A ethylene oxide adduct having the formula (1), which is an aromatic diamine with excellent flexibility. Ta.
次にこの芳香族ジアミンを原材料とするビスイミド系化
合物の製造方法とその硬化物の特性について述べる。Next, a method for producing a bisimide compound using this aromatic diamine as a raw material and the characteristics of the cured product will be described.
攪拌装置、コンデンサー及びガス導入管を備えた５００
ｄの三ロフラスコに実施例１で製造した本発明の芳香族
ジアミン５０ｇを投入し、アセトン２００ｄに溶解した
。水浴上室゛素気流下で無水マレイン酸２２ｇを溶解し
たアセトン溶液５０Ｉｄｌを１時間かけて滴下した０滴
下終了後室温で２時間攪拌した。析出したアミック酸を
濾過し、アセトンで洗浄して過剰の無水マレイン酸を除
去した後、減圧で乾燥した。500 equipped with stirring device, condenser and gas inlet pipe
50 g of the aromatic diamine of the present invention produced in Example 1 was placed in the three-hole flask (d) and dissolved in 200 g of acetone. 50 Idl of an acetone solution in which 22 g of maleic anhydride was dissolved was added dropwise over a period of 1 hour under a stream of oxygen in the upper room of a water bath. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. The precipitated amic acid was filtered, washed with acetone to remove excess maleic anhydride, and then dried under reduced pressure.
次に攪拌装置、コンデンサー及びガス導入管を備えた５
００Ｉｄの三ロフラスコに上記アミック酸５２ｇを投入
し、Ｎ−メチルピロリドン２００ａｄに溶解させた０次
いで、トリエチルアミン１４Ｈ１及び酢酸ニッケル（■
）４水塩１．２５ｇを投入し溶解させた。Next, 5 units equipped with a stirring device, condenser and gas inlet pipe
52 g of the above amic acid was put into a three-ring flask, and dissolved in 200 ad of N-methylpyrrolidone. Then, triethylamine 14H1 and nickel acetate (■
) 1.25 g of tetrahydrate was added and dissolved.
次に常温窒素気流下で無水酢酸３０ｊｄを１時間かけて
滴下し、その後常温で一昼夜攪拌反応させた。Next, 30 jd of acetic anhydride was added dropwise over 1 hour under a nitrogen stream at room temperature, and the reaction was then stirred at room temperature all day and night.
冷却後反応混合物を水中再沈させ、濾過及び炭酸水素ナ
トリウム水溶液で中和後、水で十分洗浄した。減圧で乾
燥後、本発明の可撓性ビスマレイミド化合物４６ｇを得
た。After cooling, the reaction mixture was reprecipitated in water, filtered, neutralized with an aqueous sodium bicarbonate solution, and thoroughly washed with water. After drying under reduced pressure, 46 g of the flexible bismaleimide compound of the present invention was obtained.
次にこのビスマレイミド化物の硬化物を作製し機械特性
を測定した。Next, a cured product of this bismaleimide compound was prepared and its mechanical properties were measured.
上記ビスマレイミド化物３５ｇと２−エチル−４−メチ
ルイミダゾール０．５ｇをステンレス鏡板間に挟んだ２
■厚のテフロン製スペーサ内に投入した０次に接触圧で
１７０°Ｃ３０分、続いて１０ｋｇ／ｃｊで１７０℃２
時間硬化させ、１００ｍ角×２−の硬化物を得た０次い
で乾燥器中で２００℃で１時間、最後に２８０℃で１時
間アフターキュアを行った。35 g of the above bismaleimide compound and 0.5 g of 2-ethyl-4-methylimidazole were sandwiched between stainless steel mirror plates.
■ 170°C for 30 minutes with contact pressure placed in a thick Teflon spacer, then 170°C2 with 10kg/cj
After curing for several hours, a 100 m square x 2 cured product was obtained.Next, after-curing was performed in a dryer at 200°C for 1 hour, and finally at 280°C for 1 hour.
この硬化物から輻５■長さ５０簡の試験片を切り出し、
支点間距離３０簡で曲げ試験を行った。A test piece with a diameter of 5 mm and a length of 50 strips was cut out from this cured product.
A bending test was conducted with a distance between fulcrums of 30 points.
比較例１
実施例１において、本発明の芳香族ジアミンの代わりに
、４．４’−ジアミノジフェニルメタンをジアミン成分
として用い、それ以外は実施例２と同様にしてビスマレ
イミド化物及びその硬化物を作製し、曲げ試験を行った
。Comparative Example 1 In Example 1, 4,4'-diaminodiphenylmethane was used as the diamine component instead of the aromatic diamine of the present invention, and a bismaleimide compound and a cured product thereof were produced in the same manner as in Example 2 except for that. Then, a bending test was conducted.
比較例２
比較例１と同様にジアミン成分として２．２−ビス（４
−（４−アミノフェノキシ）フェニル〕プロパンを用い
て、ビスマレイミド化物及びその硬化物を作製し、曲げ
試験を行った。Comparative Example 2 Similar to Comparative Example 1, 2.2-bis(4
A bismaleimide compound and a cured product thereof were prepared using -(4-aminophenoxy)phenyl]propane and subjected to a bending test.
第１表より、柔軟性に優れているジアミンを原料として
用いた本発明のビスマレイミド化合物は可撓化があり、
繊維強化複合材、プリント配線板用基板樹脂、耐熱性成
形材料の強靭化に有用であることが明らかである。From Table 1, the bismaleimide compound of the present invention using diamine, which has excellent flexibility, as a raw material has flexibility,
It is clear that it is useful for toughening fiber-reinforced composite materials, substrate resins for printed wiring boards, and heat-resistant molding materials.
実施例１及び比較例１．２の曲げ強度試験結果を第１表
に示す。The bending strength test results of Example 1 and Comparative Examples 1.2 are shown in Table 1.
第１表
曲げ試験結果
〔発明の効果〕
本発明により、従来に比べ柔軟性に優れた芳香族ジアミ
ンを原料として用いることにより耐熱性に優れるととも
に、強靭かつ可撓性のある有用なビスイミド化合物を得
ることができるようになった。Table 1 Bending test results [Effects of the invention] The present invention provides a useful bisimide compound that has superior heat resistance, toughness, and flexibility by using aromatic diamine, which has superior flexibility compared to conventional materials, as a raw material. Now you can get it.
Claims (1)
アルキル基を示し、互いに同じであっても異なっていて
もよい。Ｒ＾１及びＲ＾２は水素原子、メチル基、エチ
ル基、トリフルオロメチル基又はトリクロロメチル基を
示し、互いに同じであっても異なっていてもよい。ｎは
１〜３の整数を示す。）で表される芳香族ジアミンの末
端アミノ基をイミド化したことを特徴とする可撓性ビス
イミド化合物。 ２、ビスイミド化合物がビスマレイミド化合物である請
求項１に記載の可撓性ビスイミド化合物。 ３、ビスイミド化合物がナジック酸ビスイミド化合物で
ある請求項１に記載の可撓性ビスイミド化合物。 ４、一般式〔 I 〕で示される芳香族ジアミンが２，２
−ビス〔４−（β−ｐ−アミノフェノキシエトキシ）フ
ェニル〕プロパンである請求項１、２又は３に記載の可
撓性ビスイミド化合物。[Claims] 1. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, X^1 to X^4 represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R^1 and R^2 represent a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group, or a trichloromethyl group, and may be the same or different. A flexible bisimide compound characterized in that the terminal amino group of an aromatic diamine represented by (n is an integer of 1 to 3) is imidized. 2. The flexible bisimide compound according to claim 1, wherein the bisimide compound is a bismaleimide compound. 3. The flexible bisimide compound according to claim 1, wherein the bisimide compound is a nadic acid bisimide compound. 4. The aromatic diamine represented by the general formula [I] is 2,2
4. The flexible bisimide compound according to claim 1, which is -bis[4-(β-p-aminophenoxyethoxy)phenyl]propane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2171232A JP2792209B2 (en) | 1990-06-28 | 1990-06-28 | Flexible bisimide compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2171232A JP2792209B2 (en) | 1990-06-28 | 1990-06-28 | Flexible bisimide compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0459759A true JPH0459759A (en) | 1992-02-26 |
| JP2792209B2 JP2792209B2 (en) | 1998-09-03 |
Family
ID=15919497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2171232A Expired - Lifetime JP2792209B2 (en) | 1990-06-28 | 1990-06-28 | Flexible bisimide compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2792209B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017209236A1 (en) * | 2016-06-03 | 2017-12-07 | Dic株式会社 | Substituted or unsubstituted allyl group-containing maleimide compound, production method therefor, and composition and cured product using said compound |
| CN117533001A (en) * | 2023-10-25 | 2024-02-09 | 江门建滔积层板有限公司 | Impact-resistant flame-retardant copper-clad plate and preparation method thereof |
-
1990
- 1990-06-28 JP JP2171232A patent/JP2792209B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017209236A1 (en) * | 2016-06-03 | 2017-12-07 | Dic株式会社 | Substituted or unsubstituted allyl group-containing maleimide compound, production method therefor, and composition and cured product using said compound |
| JPWO2017209236A1 (en) * | 2016-06-03 | 2019-03-28 | Dic株式会社 | Substituted or unsubstituted allyl group-containing maleimide compound, production method thereof, and composition and cured product using the compound |
| CN117533001A (en) * | 2023-10-25 | 2024-02-09 | 江门建滔积层板有限公司 | Impact-resistant flame-retardant copper-clad plate and preparation method thereof |
| CN117533001B (en) * | 2023-10-25 | 2024-05-10 | 江门建滔积层板有限公司 | Impact-resistant flame-retardant copper-clad plate and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2792209B2 (en) | 1998-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5159054A (en) | Synthesis of phthalonitrile resins containing ether and imide linkages | |
| EP0107897B1 (en) | Polyamino-bis-imide resin | |
| US5689004A (en) | Diamines containing pendent phenylethynyl groups | |
| US5003078A (en) | Synthesis of phthalonitrile resins containing ether and imide linkages | |
| JPH02140232A (en) | Low elasticity polyimide and its production | |
| JPH0459759A (en) | Flexible bisimide compound | |
| CA2028312C (en) | Thermosetting resin forming composition and process for preparing same | |
| JPH04214727A (en) | Diacetylene based polyamic acid derivative and polyimide | |
| JPH04114035A (en) | Thermosetting resin composition | |
| JP2751583B2 (en) | Aromatic diamine having ethylene oxide chain and method for producing the same | |
| JPH0522699B2 (en) | ||
| JPS62185715A (en) | Colorless polyimide film | |
| JP3022933B2 (en) | Thermosetting oligomer and method for producing the same | |
| JPH02164857A (en) | New halogenated aromatic diamine and production thereof | |
| JP2005314630A (en) | Aromatic polyamic acid and polyimide | |
| JPH05301960A (en) | Thermosetting oligomer and its production | |
| JPS6140322A (en) | Production of curable polyaminobisimide resin | |
| JPH05339375A (en) | Curable imide oligomer | |
| JP3022940B2 (en) | Polyimide resin composition | |
| JP3404071B2 (en) | Novel curable resin and its composition | |
| JP2983616B2 (en) | Compound for heat-resistant laminate and method for producing laminate using the compound | |
| JPH0381327A (en) | Diacetylenic polyamic acid, derivative thereof, and polyimide | |
| JPS6395220A (en) | Epoxyimide and production thereof | |
| JP2958104B2 (en) | Thermosetting oligomer and method for producing the same | |
| JPH0481428A (en) | Thermosetting compound and production thereof |