JPH03290414A - Curable resin composition - Google Patents
Curable resin compositionInfo
- Publication number
- JPH03290414A JPH03290414A JP9234690A JP9234690A JPH03290414A JP H03290414 A JPH03290414 A JP H03290414A JP 9234690 A JP9234690 A JP 9234690A JP 9234690 A JP9234690 A JP 9234690A JP H03290414 A JPH03290414 A JP H03290414A
- Authority
- JP
- Japan
- Prior art keywords
- curable resin
- resin composition
- compound
- aromatic amine
- molecule
- 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
- 239000011342 resin composition Substances 0.000 title claims description 15
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 9
- UFFVWIGGYXLXPC-UHFFFAOYSA-N 1-[2-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1N1C(=O)C=CC1=O UFFVWIGGYXLXPC-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003277 amino group Chemical group 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 2
- -1 alkenyl ether Chemical compound 0.000 description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000001723 curing Methods 0.000 description 8
- 229920003192 poly(bis maleimide) Polymers 0.000 description 8
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- BVWUEIUNONATML-UHFFFAOYSA-N n-benzylethenamine Chemical compound C=CNCC1=CC=CC=C1 BVWUEIUNONATML-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- NQSIARGGPGHMCG-UHFFFAOYSA-N 1-ethyl-1-phenylhydrazine Chemical compound CCN(N)C1=CC=CC=C1 NQSIARGGPGHMCG-UHFFFAOYSA-N 0.000 description 2
- BMIPMKQAAJKBKP-UHFFFAOYSA-N 2,4,5-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C=C1C BMIPMKQAAJKBKP-UHFFFAOYSA-N 0.000 description 2
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 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
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000013035 low temperature curing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PVRZMTHMPKVOBP-UHFFFAOYSA-N 1-n,4-n-dimethylbenzene-1,4-diamine Chemical compound CNC1=CC=C(NC)C=C1 PVRZMTHMPKVOBP-UHFFFAOYSA-N 0.000 description 1
- VOSLIUIVGWBSOK-UHFFFAOYSA-N 1-n-phenylbenzene-1,2,4-triamine Chemical compound NC1=CC(N)=CC=C1NC1=CC=CC=C1 VOSLIUIVGWBSOK-UHFFFAOYSA-N 0.000 description 1
- 229940075142 2,5-diaminotoluene Drugs 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 description 1
- OBCSAIDCZQSFQH-UHFFFAOYSA-N 2-methyl-1,4-phenylenediamine Chemical compound CC1=CC(N)=CC=C1N OBCSAIDCZQSFQH-UHFFFAOYSA-N 0.000 description 1
- WKURVXXDGMYSDP-UHFFFAOYSA-N 2-propyl-aniline Chemical compound CCCC1=CC=CC=C1N WKURVXXDGMYSDP-UHFFFAOYSA-N 0.000 description 1
- GBGUCQDUXGOLSO-UHFFFAOYSA-N 3,4-dimethylpyrrole-2,5-dione;phenoxybenzene Chemical compound CC1=C(C)C(=O)NC1=O.C=1C=CC=CC=1OC1=CC=CC=C1 GBGUCQDUXGOLSO-UHFFFAOYSA-N 0.000 description 1
- ZYMOKRVQKMAIBA-UHFFFAOYSA-N 3-(3-phenylpenta-1,4-dien-3-yloxy)penta-1,4-dien-3-ylbenzene Chemical compound C=1C=CC=CC=1C(C=C)(C=C)OC(C=C)(C=C)C1=CC=CC=C1 ZYMOKRVQKMAIBA-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- UIZDKHDPZRCOBN-UHFFFAOYSA-N 3-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCC1=CC(=O)NC1=O UIZDKHDPZRCOBN-UHFFFAOYSA-N 0.000 description 1
- AXNUJYHFQHQZBE-UHFFFAOYSA-N 3-methylbenzene-1,2-diamine Chemical compound CC1=CC=CC(N)=C1N AXNUJYHFQHQZBE-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-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
- HSBOCPVKJMBWTF-UHFFFAOYSA-N 4-[1-(4-aminophenyl)ethyl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)C1=CC=C(N)C=C1 HSBOCPVKJMBWTF-UHFFFAOYSA-N 0.000 description 1
- UXKQNCDDHDBAPD-UHFFFAOYSA-N 4-n,4-n-diphenylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UXKQNCDDHDBAPD-UHFFFAOYSA-N 0.000 description 1
- VVYWUQOTMZEJRJ-UHFFFAOYSA-N 4-n-methylbenzene-1,4-diamine Chemical compound CNC1=CC=C(N)C=C1 VVYWUQOTMZEJRJ-UHFFFAOYSA-N 0.000 description 1
- OAPDPORYXWQVJE-UHFFFAOYSA-N 4-propylaniline Chemical compound CCCC1=CC=C(N)C=C1 OAPDPORYXWQVJE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007688 edging Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- PGXWDLGWMQIXDT-UHFFFAOYSA-N methylsulfinylmethane;hydrate Chemical compound O.CS(C)=O PGXWDLGWMQIXDT-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- CHMBIJAOCISYEW-UHFFFAOYSA-N n-(4-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(N)C=C1 CHMBIJAOCISYEW-UHFFFAOYSA-N 0.000 description 1
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 description 1
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、硬化性ポリマレイミド樹脂組成物に間するも
のである。特に本発明は低温硬化に優れ、耐熱性、機械
的物性に優れた硬化性樹脂組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to curable polymaleimide resin compositions. In particular, the present invention relates to a curable resin composition that is excellent in low-temperature curing, heat resistance, and mechanical properties.
［従来の技術］
硬化性組成物は、接着、注形、コーティング、含浸、積
層、成形コンパウンド等として塗料、地縁材料、複合構
造材料等に幅広く利用されている。[Prior Art] Curable compositions are widely used as adhesives, castings, coatings, impregnations, laminations, molding compounds, etc. in paints, edging materials, composite structural materials, and the like.
その中で、ポリイミド系樹脂は最も優れた材料の一つで
あり、種々開発がすすめられている。例えばポリマレイ
ミド化合物と分子の末端にアルケニルエーテルを有する
反応性オリゴマーとの組成物が特開昭６２−５３３１９
号により知られている。Among them, polyimide resin is one of the most excellent materials, and various developments are being promoted. For example, a composition of a polymaleimide compound and a reactive oligomer having an alkenyl ether at the end of the molecule is disclosed in JP-A-62-53319.
Known by the number.
［発明が解決しようとする課題］
しかしながら、上述の樹脂組成物は、硬化温度が高く、
硬化時間も長く、これらを含めた作業性という点では、
未だ既存の汎用硬化製樹脂に較べて有利とはいえない。[Problems to be Solved by the Invention] However, the above-mentioned resin composition has a high curing temperature,
The curing time is long, and in terms of workability including this,
It still cannot be said to be advantageous compared to existing general-purpose hardened resins.
また、近年硬化性樹脂の使用用途は多岐にわたっている
ために、従来から利用されている硬化性樹脂組成物は、
様々な使用環境または使用条件においてすべて満足でき
るものではない。特に、使用温度が高温の場合における
耐熱性、！！！、間強度が充分ではなく、従来から知ら
れているビスマレイミド、芳香族アミンおよびエポキシ
樹脂の組み合わせといった、最も代表的な組＃：物にお
いても、未だ充分な材料は提供されていなかった。In addition, in recent years, curable resins have been used for a wide variety of purposes, so the curable resin compositions that have been used traditionally are
It is not possible to be completely satisfied under various usage environments or usage conditions. Especially heat resistance when the operating temperature is high! ! ! However, even in the most representative group, such as the conventionally known combination of bismaleimide, aromatic amine and epoxy resin, a sufficient material had not yet been provided.
従って本発明は、従来の硬化性樹脂組成物がもつ以上の
ような課題を解決し、硬化温度が低く、硬化時間も短く
、且つ耐熱性 熱安定性に優れ、さらに機械的物性の優
れたポリイミド系樹脂組成を提供することを目的とする
。Therefore, the present invention solves the above-mentioned problems of conventional curable resin compositions, and provides a polyimide that has a low curing temperature, short curing time, excellent heat resistance and thermal stability, and has excellent mechanical properties. The purpose is to provide a system resin composition.
［課題を解決するための手段］
本発明者らは、マレイミド系化合物と芳香族残基と結合
したビニルベンジルエーテル化合物とからなる硬化性樹
脂組成物が有効であることを見いだし、既に特開昭６４
−６５１１０号として提案したが、さらに研究を重ね、
熱間強度などの耐熱性が優れた硬化性樹脂組成物を見い
だした。[Means for Solving the Problems] The present inventors have found that a curable resin composition comprising a maleimide compound and a vinylbenzyl ether compound bonded to an aromatic residue is effective, and has already been published in JP-A-Sho. 64
-65110, but after further research,
We have discovered a curable resin composition that has excellent heat resistance such as hot strength.
すなわち本発明組成物は、（Ａ）分子中にマレイミド基
をもつ化合物、および（Ｂ）分子中にＮ−ビニルベンジ
ル基を２つ以上もつ芳香族アミンからなる硬化性樹脂組
成物であり、特開昭６４−６５１１０号の発明に較べ同
様な低温で硬化でき、硬化時間も短く、且つさらに優れ
た熱安定性、機械的物性、特に熱間強度が優れているこ
とを特徴とする硬化性樹脂組成物を提供するものである
。That is, the composition of the present invention is a curable resin composition comprising (A) a compound having a maleimide group in the molecule and (B) an aromatic amine having two or more N-vinylbenzyl groups in the molecule. A curable resin that can be cured at a similar low temperature as the invention of JP-A-64-65110, has a shorter curing time, and has even better thermal stability and mechanical properties, especially hot strength. A composition is provided.
以下に本発明をさらに詳細に説明する。The present invention will be explained in more detail below.
本発明の組成物の成分である（Ａ）分子中にマレイミド
基を有する化合物は、例えばＮ、Ｎ′−フェニレンビス
マレイミド、Ｎ、Ｎ’−キシレンビスマレイミド、Ｎ、
Ｎ’−）リレンビスマレイミド、Ｎ、Ｎ’−ジフェニル
メタンビスマレイミド、Ｎ、Ｎ”−ジフェニルエーテル
ビスマレイミド、Ｎ、Ｎ”−ジフェニルスルホンビスマ
レイミド、Ｎ、Ｎ’−ジフェニルメタンビスメチルマレ
イミド、Ｎ、Ｎ’−ジフェニルエーテルビスメチルマレ
イミド等のビスマレイミド、または上述のビスマレイミ
ドをジアミノジフェニルメタン、ジアミノジフェニルス
ルホン、およびジアミノジフェニルエーテルのようなア
ミノ化合物またはエポキシ樹脂で変性したアミン化合物
との付加物で未だ分子中に２個のマレイミド基を有する
化合物を代表的に例示することができる。また、芳香族
マレイミド例えばフェニルマレイミドや脂環式マレイミ
ド例えばシクロヘキシルマレイミド、アルキルマレイミ
ド例えばラウリルマレイミド等の単官能マレイミド化合
物も使用可能であるが、ビスマレイミド化合物の一部に
代えて好適に使用することができる。Examples of the compound (A) having a maleimide group in the molecule, which is a component of the composition of the present invention, include N,N'-phenylene bismaleimide, N,N'-xylene bismaleimide, N,
N'-) rylene bismaleimide, N,N'-diphenylmethane bismaleimide, N,N"-diphenyl ether bismaleimide, N,N"-diphenylsulfone bismaleimide, N,N'-diphenylmethane bismethylmaleimide, N,N' - Bismaleimide such as diphenyl ether bismethylmaleimide, or an adduct of the above-mentioned bismaleimide with an amine compound modified with an amino compound or epoxy resin such as diaminodiphenylmethane, diaminodiphenyl sulfone, and diaminodiphenyl ether, which still has two molecules in the molecule. Compounds having a maleimide group can be typically exemplified. Furthermore, monofunctional maleimide compounds such as aromatic maleimides such as phenylmaleimide, alicyclic maleimides such as cyclohexylmaleimide, and alkylmaleimides such as laurylmaleimide can also be used, but they may be preferably used in place of a part of the bismaleimide compound. can.
また本発明の組成物の成分である、（Ｂ）分子中にＮ−
ビニルベンジル基を２つ以上もっＮ−置換芳香族アミン
は、一般式（Ｉ）
（式中、Ｘは芳香族アミンのアミノ基中の水素原子をｙ
個除いた残基を表し、ｙは２〜６の値をもつ）
で表すことができる。In addition, N-
N-substituted aromatic amines having two or more vinylbenzyl groups have the general formula (I) (wherein, X represents the hydrogen atom in the amino group of the aromatic amine, y
y has a value of 2 to 6).
一般式（Ｉ）の原料となる代表的な芳香族アミン類は、
アニリン、０−）ルイジン、輪−トルイジン、ｐ−）ル
イジン、０−エチルアニリン、…−エチルアニリン、ｐ
−エチルアニリン、ｏ−ｎ−プロピルアニリン、ｐ−ｎ
−プロピルアニリン、０−イソプロピルアニリン、ｐ−
イソプロピルアニリン、ｏ−３−キシリジン、ｏ−４−
キシリジン、ｍ−２−キシリジン、「４−キシリジン、
＠−５−キシリジン、ｐ−ｚ−キシリジン、プソイドク
ミジン（２，４，５−トリメチルアニリン）、メジジン
（２，４゜６−トリメチルアニリン）等のモノアミン類
、０−フェニレンジアミン、箱−フェニレンジアミン、
ｐ−フェニレンジアミン、ｐ−アミノアセトアニリド、
Ｎ−メチル−ｐ−フェニレンジアミン、Ｎ−フェニル−
ｐ−フェニレンジアミン、Ｎ、Ｎ−ジメチル−ｐ−フェ
ニレンジアミン、Ｎ、Ｎ′−ジメチル−ｐ−フェニレン
ジアミン、４−アミノジフェニルアミン、Ｎ′−ジフェ
ニル−ｐ〜フェニレンジアミン、２．３−ジアミノトル
エン、２．４−ジアミノトルエン、３．４−ジアミノト
ルエン、２．６−ジアミノトルエン、３．５−ジアミノ
トルエン、２，５−ジアミノトルエン等のジアミン類、
１，２．３−）リアミノベンゼン、１，２．４−）リア
ミノベンゼン、１．３５トリアミノベンゼン等の多価ア
ミン類、α−メチルヒドラジン、β−メチルフェニルヒ
ドラジン、α−エチルフェニルヒドラジン、β−エチル
フェニルヒドラジン、２．４−ジアミノジフェニルアミ
ン、４．４′−ジアミノジフェニルメタン、４，４′−
ジアミノジフェニルエタン、４，４′−ジアミノジフェ
ニルケトン、４，４′−ジアミノジフェニルエーテル、
４４′ジアミノジフエニルスルホン等の芳香族ビスアミ
ン類等が挙げられる。Typical aromatic amines that serve as raw materials for general formula (I) are:
Aniline, 0-) luidine, ring-toluidine, p-) luidine, 0-ethylaniline, ...-ethylaniline, p
-ethylaniline, o-n-propylaniline, p-n
-propylaniline, 0-isopropylaniline, p-
Isopropylaniline, o-3-xylidine, o-4-
xylidine, m-2-xylidine, “4-xylidine,
Monoamines such as @-5-xylidine, p-z-xylidine, pseudocumidine (2,4,5-trimethylaniline), mezidine (2,4゜6-trimethylaniline), 0-phenylenediamine, box-phenylenediamine,
p-phenylenediamine, p-aminoacetanilide,
N-methyl-p-phenylenediamine, N-phenyl-
p-phenylenediamine, N,N-dimethyl-p-phenylenediamine, N,N'-dimethyl-p-phenylenediamine, 4-aminodiphenylamine, N'-diphenyl-p-phenylenediamine, 2,3-diaminotoluene, Diamines such as 2.4-diaminotoluene, 3.4-diaminotoluene, 2.6-diaminotoluene, 3.5-diaminotoluene, 2,5-diaminotoluene,
Polyvalent amines such as 1,2.3-) riaminobenzene, 1,2.4-)riaminobenzene, 1.35triaminobenzene, α-methylhydrazine, β-methylphenylhydrazine, α-ethylphenyl Hydrazine, β-ethylphenylhydrazine, 2,4-diaminodiphenylamine, 4,4'-diaminodiphenylmethane, 4,4'-
Diaminodiphenylethane, 4,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ether,
Examples include aromatic bisamines such as 44'diaminodiphenyl sulfone.
一般式（Ｉ）で表されるＮ−置換芳香族アミン＜Ｂ）は
、例えば市販のクロルメチルスチレンモノマーを上記芳
香族アミンに対し、ビニルベンジル基が２個〜６個にな
る割合で加え、例えばジメチルスルホキシドを溶媒に用
いて無機アルカリによる脱塩化水素することによって容
易に合成することができる。 本発明におけるマレイミ
ド化合物（Ａ）とＮ−ビニルベンジル芳香族アミン（Ｂ
）の組成比は使用目的に応じて幅広く変化させることが
できる。The N-substituted aromatic amine <B) represented by the general formula (I) can be obtained by adding, for example, a commercially available chloromethylstyrene monomer to the aromatic amine in a proportion of 2 to 6 vinylbenzyl groups. For example, it can be easily synthesized by dehydrochlorination with an inorganic alkali using dimethyl sulfoxide as a solvent. Maleimide compound (A) and N-vinylbenzyl aromatic amine (B) in the present invention
) can be varied widely depending on the purpose of use.
それぞれの不飽和基当量比で示すと、Ａ／Ｂ＝１００／
３０〜１／１００、好ましくは、１００１５０〜１／３
０がよい。この範囲内では、硬化に必要なラジカル開始
剤を意図して加えなくても、容易に熱硬化し、それぞれ
単独の熱硬化に比べてはるかに低温且つ短時間で反応が
進行し、また、空気中での熱分解開始温度が高く且つ分
解減量が小さい。When expressed as the equivalent ratio of each unsaturated group, A/B=100/
30 to 1/100, preferably 100150 to 1/3
0 is good. Within this range, thermal curing is easy without intentionally adding a radical initiator necessary for curing, and the reaction proceeds at a much lower temperature and in a shorter time than in thermal curing alone. The temperature at which thermal decomposition starts is high and the decomposition loss is small.
本発明の硬化性樹脂組成物は、成分（Ａ）および（Ｂ）
に、既知の単量体例えばスチレン、ビニルトルエン、ア
リルフェノール、アリルオキシベンゼン、ジアリルフタ
レート、アクリル酸エステル、メタクリル酸エステル、
またはエポキシ樹脂と（メタ）クリル酸の反応物で代表
されるようなビニルエステル樹脂、ビニルピロリドン等
を配合することができる。硬化の調製のために、ハイド
ロキノン、ベンゾキノン、銅塩、Ｎ−ニトロソフェニル
ヒドロキシルアミンのアンモニウム塩やアルミニウム塩
等を配合してもよく、さらに硬化の促進のために、公知
公用のラジカル開始剤例えば有機過酸化物類または有機
過酸化物とその分解促進剤（ＲＥＤＯＸ）も配合できる
。The curable resin composition of the present invention comprises components (A) and (B).
In addition, known monomers such as styrene, vinyltoluene, allylphenol, allyloxybenzene, diallyl phthalate, acrylic ester, methacrylic ester,
Alternatively, vinyl ester resin, vinyl pyrrolidone, etc., typified by a reaction product of epoxy resin and (meth)acrylic acid, can be blended. To prepare for curing, hydroquinone, benzoquinone, copper salt, ammonium salt or aluminum salt of N-nitrosophenylhydroxylamine, etc. may be added, and in order to accelerate curing, known and publicly available radical initiators such as organic Peroxides or organic peroxides and their decomposition accelerators (REDOX) can also be blended.
また本発明の硬化性樹脂組成物は、公知公用の光開始剤
を配合することによって、活性エネルギー線例えば紫外
線、レーザー光線で硬化でき、さらに電子線によっても
容易に硬化することができる。Furthermore, the curable resin composition of the present invention can be cured with active energy rays, such as ultraviolet rays and laser beams, and can also be easily cured with electron beams by incorporating a publicly known photoinitiator.
本発明の硬化性樹脂組成物は、ニーダ−、ブレンダー、
ロール等により、他の種々の充填剤や強化繊維を調配合
して成形材料や複合材料、および溶剤に溶かしてワニス
、塗料、接着剤、および強化繊維であるガラス繊維、カ
ーボン繊維、芳香族ポリアミド繊維、炭化珪素繊維、ア
ルミナ繊維に含浸させ、ハンドレーアツブ成形や、プリ
プレグ、またフィラメントワインデングとして、有益な
成形材料および構造材料となり得る。The curable resin composition of the present invention can be used in kneaders, blenders,
Using rolls, etc., various other fillers and reinforcing fibers are blended into molding materials and composite materials, and dissolved in solvents to produce varnishes, paints, adhesives, and reinforcing fibers such as glass fibers, carbon fibers, and aromatic polyamides. It can be impregnated into fibers, silicon carbide fibers, and alumina fibers to become useful molding and structural materials in handlay assemblies, prepregs, and filament windings.
［実施例］ 以下、実施例により本発明をさらに説明する。[Example] The present invention will be further explained below with reference to Examples.
尚、特に断らない限り、実施例中の部は重量部である。In addition, unless otherwise specified, parts in the examples are parts by weight.
１フ工ニレンジアミン２７部（１，０当量）をジメチル
スルホキシド１２０部に溶解したものに水酸化カリウム
水溶液［水酸化カリウム５６．１部（１，０当量）、水
３５部］を加え、ハイドロキノン５００ ｐｐｍを添加
した市販のクロルスチルメチレン１５２．５部（１，０
当量〉を７０〜８０℃で１時間かけて滴下し、さらに８
０℃で４時間反応を続けた。To a solution of 27 parts (1.0 equivalents) of 1-functional nylenediamine dissolved in 120 parts of dimethyl sulfoxide, an aqueous potassium hydroxide solution [56.1 parts (1.0 equivalents) of potassium hydroxide, 35 parts of water] was added, and 500 parts of hydroquinone was added. 152.5 parts of commercially available chlorstilmethylene (1,0
equivalent amount> was added dropwise over 1 hour at 70 to 80°C, and then
The reaction was continued for 4 hours at 0°C.
次に系内に大過剰の水を加え、撹拌後、水−ジメチルス
ルホキシドを取り除き、ベンゼンで油状物を抽出した。Next, a large excess of water was added to the system, and after stirring, water-dimethyl sulfoxide was removed, and an oily substance was extracted with benzene.
ベンゼン層は水層のｐＨが７になるまで水洗を繰り返し
、ベンゼンを減圧除去して油状物としてＮ、Ｎ、Ｎ′、
Ｎ’−テトラビニルベンジル−ｍフェニレンジアミン（
以下Ｎ−ＴＶＢｍ−ＰＤ＾とする）を含む生成物を収率
９７％で得た。またここで用いたジメチルスルホキシド
の代わりにジオキサンまたはＮ、Ｎ′−ジメチルホルム
アミドを使用しても同様に合成可能である。The benzene layer was washed repeatedly with water until the pH of the aqueous layer reached 7, and the benzene was removed under reduced pressure to produce N, N, N',
N'-tetravinylbenzyl-m-phenylenediamine (
A product containing (hereinafter referred to as N-TVBm-PD^) was obtained in a yield of 97%. Furthermore, the same synthesis can be performed by using dioxane or N,N'-dimethylformamide instead of the dimethyl sulfoxide used here.
同様の方法で置−フェニレンジアミンに代えてアニリン
を使用して（以下、Ｎ−ＤＶＢ＾とする〉、ジアミノフ
ェニルメタンを使用して（以下、Ｎ−ＴＶＢＤＤＭとす
る）、ジアミノジフェニルエーテルを使用して（以下、
Ｎ−ＴＶＢＤＤＥとする）およびジアミノジフェニルス
ルホン（以下、Ｎ−ＴＶＢＤＯＳとする）を使用してＮ
−ビニルベンジルアミン類を合成した。In the same manner, using aniline (hereinafter referred to as N-DVB^) in place of substituted-phenylenediamine, using diaminophenylmethane (hereinafter referred to as N-TVBDDM), and using diaminodiphenyl ether. (below,
N-TVBDDE) and diaminodiphenylsulfone (hereinafter N-TVBDOS).
-Vinylbenzylamines were synthesized.
表−１に各Ｎ−ビニルベンジルアミン類の性状を示した
。各Ｎ−ビニルベンジルアミン類は、ベンゼン、トルエ
ン、アセトン、ＭＥＫなど種々の有機溶媒に可溶であっ
た。Table 1 shows the properties of each N-vinylbenzylamine. Each N-vinylbenzylamine was soluble in various organic solvents such as benzene, toluene, acetone, and MEK.
表−ま た、（以下、ＤＤＮ変性８８１とする）。Table-ma (hereinafter referred to as DDN degeneration 881).
丈羞ＪＬＬ
参考例１で合成したＮ−ＤＶＢＡ、Ｎ−ＴＶＢ＋ｍ−Ｐ
ＤＡ、Ｎ−ＴＶＢＤＤＭ、Ｎ−ＴＶＢ［ｌＤｌ 、Ｊ−
ヒＮ−ＴＶＢＤＤＳそれぞれの１当量に対して三井東圧
製ジフェニルメタンビスマレイミド（以下、８８１とす
る）１当量を混合して試料を調製し、これらを１２０℃
のホットプレート上に置きゲル化を調べた。比較のため
それぞれのＮ−ビニルベンジルアミン、ＢＭＩについて
も同様に試験を行った。その結果を表−２に示した。JLL N-DVBA, N-TVB+m-P synthesized in Reference Example 1
DA, N-TVBDDM, N-TVB[lDl, J-
A sample was prepared by mixing 1 equivalent of diphenylmethane bismaleimide (hereinafter referred to as 881) manufactured by Mitsui Toatsu with 1 equivalent of each of HiN-TVBDDS, and the mixture was heated to 120°C.
gelation was examined by placing it on a hot plate. For comparison, the same tests were conducted for each N-vinylbenzylamine and BMI. The results are shown in Table-2.
Ｎ、Ｎ”−ジフェニルメタンビスマレイミド３５８部（
１，０モル）およびジアミノジフェニルメタン９９部（
０，５モル）をボールミールで充分に粉砕混合したもの
を１７０℃の容器中で１ｏ分間溶融撹拌を行い直ちに容
器を水冷して固形物を得た。358 parts of N,N''-diphenylmethane bismaleimide (
1.0 mol) and 99 parts of diaminodiphenylmethane (
(0.5 mol) was thoroughly ground and mixed with a ball meal, melted and stirred for 10 minutes in a container at 170°C, and the container was immediately cooled with water to obtain a solid.
この反応物はＮ−メチルピロリドン、ジメチルホルムア
ミド等の溶媒に可溶であり、さらにアセトン、メチルエ
チルケトン等の低沸点溶媒にも可溶であっ大遣Ｎ２
Ｎ−ＤＶＢＡ、Ｎ−ＴＶＢｍ＋−ＰＤＡ）＋よびＮ−Ｔ
ＶＢ［ｌ［１Ｍ（７）−すれぞれ１．０当量に対してＢ
ＭＩを１．０当量配合した試料と参考例２で合成したＤ
ＤＭ変性８ＭＩとを理論当量で１．０当量配合し、１２
０℃で３０分成形した。This reactant is soluble in solvents such as N-methylpyrrolidone and dimethylformamide, and is further soluble in low-boiling point solvents such as acetone and methyl ethyl ketone. N-T
VB[l[1M(7)-B for each 1.0 equivalent
Sample containing 1.0 equivalent of MI and D synthesized in Reference Example 2
The theoretical equivalent of 1.0 equivalent of DM-modified 8MI was blended, and 12
It was molded at 0°C for 30 minutes.
脱型後引き続き２５０℃で５時間後硬化したものについ
て、空気中での熱分解開始温度、ＪＩＳ Ｋ６９１１に
よる常温および熱間時の曲げ強度ならびに曲げ弾性率を
測定した。その結果を表−３および表−４に示す。After demolding, the product was subsequently post-cured at 250° C. for 5 hours, and its thermal decomposition start temperature in air, bending strength at room temperature and hot condition according to JIS K6911, and bending elastic modulus were measured. The results are shown in Tables 3 and 4.
表−３
ベンジルエーテル化合物からなる硬化性組成物（特開昭
６４−６５１１０号）の例として、ビスフェノールＡジ
ビニルベンジルエーテルＣＢＡＤＶＢＥ）の１当量に対
して、実施例１で使用したＢＭｒまたは参考例２で合成
した００Ｍ変性８８１とを、それぞれ理論当量で１０当
量配合し、１８０℃で３０分間成形した。Table 3 As an example of a curable composition consisting of a benzyl ether compound (JP-A No. 64-65110), BMr used in Example 1 or Reference Example 2 was added to 1 equivalent of bisphenol A divinylbenzyl ether CBADVBE). 00M modified 881 synthesized in 1 was mixed in an amount of 10 theoretical equivalents, and molded at 180° C. for 30 minutes.
引き続き２５０℃で５時間後硬化したものについて、Ｊ
ＩＳ Ｋ ６９１１による常温および熱間時の曲げ強度
、曲げ弾性率を測定した。その結果も併せて表−４に示
した。For those that were subsequently post-cured at 250°C for 5 hours, J
Bending strength and flexural modulus at room temperature and hot were measured according to IS K 6911. The results are also shown in Table 4.
の温度
思上」−一
比較として、さきに本発明者らが提案したマレイミド系
化合物と芳香族残基とを結合したビニル［発明の効果］
本発明による硬化性樹脂組成物は、前述のような構成の
ために、非結晶で低粘度であるため、作業性に優れ、ま
た優れた低温硬化性、耐熟性および機械的強度を示すの
で、接着、注形、コーティング、含浸、積層成形コンパ
ウンドとして、あるいは塗料、絶縁材料または複合構造
材料として、産業界で広範に利用することができる。As a comparison, the curable resin composition according to the present invention has a structure in which a maleimide compound and an aromatic residue are bonded together as previously proposed by the present inventors. Because of its structure, it is amorphous and has a low viscosity, which makes it easy to work with.It also exhibits excellent low-temperature curing, aging resistance, and mechanical strength, making it suitable for adhesive, casting, coating, impregnation, and lamination molding compounds. They can be widely used in industry as paints, insulating materials or composite structural materials.
Claims (1)
）分子中にＮ−ビニルベンジル基を２つ以上もつＮ−置
換芳香族アミンからなる、硬化性樹脂組成物。(A) A compound having a maleimide group in the molecule, and (B
) A curable resin composition comprising an N-substituted aromatic amine having two or more N-vinylbenzyl groups in the molecule.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9234690A JPH0617423B2 (en) | 1990-04-09 | 1990-04-09 | Curable composition |
| US07/680,364 US5128428A (en) | 1990-04-09 | 1991-04-04 | Curable resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9234690A JPH0617423B2 (en) | 1990-04-09 | 1990-04-09 | Curable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03290414A true JPH03290414A (en) | 1991-12-20 |
| JPH0617423B2 JPH0617423B2 (en) | 1994-03-09 |
Family
ID=14051843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9234690A Expired - Lifetime JPH0617423B2 (en) | 1990-04-09 | 1990-04-09 | Curable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0617423B2 (en) |
-
1990
- 1990-04-09 JP JP9234690A patent/JPH0617423B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0617423B2 (en) | 1994-03-09 |
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