JPH0291153A - Aqueous dispersion of bismaleimide resin and production thereof - Google Patents
Aqueous dispersion of bismaleimide resin and production thereofInfo
- Publication number
- JPH0291153A JPH0291153A JP24355488A JP24355488A JPH0291153A JP H0291153 A JPH0291153 A JP H0291153A JP 24355488 A JP24355488 A JP 24355488A JP 24355488 A JP24355488 A JP 24355488A JP H0291153 A JPH0291153 A JP H0291153A
- Authority
- JP
- Japan
- Prior art keywords
- bismaleimide
- org
- resin
- solvent
- bismaleimide resin
- 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.)
- Pending
Links
- 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 title claims abstract description 36
- 229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 35
- 229920005989 resin Polymers 0.000 title claims abstract description 31
- 239000011347 resin Substances 0.000 title claims abstract description 31
- 239000006185 dispersion Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 4
- 229920000768 polyamine Polymers 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000000962 organic group Chemical group 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 12
- -1 polyoxyethylene nonylphenyl ether Polymers 0.000 abstract description 10
- 239000000839 emulsion Substances 0.000 abstract description 4
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- 125000002993 cycloalkylene group Chemical group 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 125000005649 substituted arylene group Chemical group 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- LGXVIGDEPROXKC-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C LGXVIGDEPROXKC-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- PYVHLZLQVWXBDZ-UHFFFAOYSA-N 1-[6-(2,5-dioxopyrrol-1-yl)hexyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CCCCCCN1C(=O)C=CC1=O PYVHLZLQVWXBDZ-UHFFFAOYSA-N 0.000 description 1
- LYCKDYZIIOVFCX-UHFFFAOYSA-N 1-[[3-[(2,5-dioxopyrrol-1-yl)methyl]phenyl]methyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC(CN2C(C=CC2=O)=O)=C1 LYCKDYZIIOVFCX-UHFFFAOYSA-N 0.000 description 1
- XFRPTDABLAIJMY-UHFFFAOYSA-N 1-[[4-[(2,5-dioxopyrrol-1-yl)methyl]phenyl]methyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC(C=C1)=CC=C1CN1C(=O)C=CC1=O XFRPTDABLAIJMY-UHFFFAOYSA-N 0.000 description 1
- FBPVUBVZRPURIU-UHFFFAOYSA-N 1-hexylpyrrole-2,5-dione Chemical compound CCCCCCN1C(=O)C=CC1=O FBPVUBVZRPURIU-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- PSFDAYXWBWRTSM-UHFFFAOYSA-N 1-prop-2-enylpyrrole-2,5-dione Chemical compound C=CCN1C(=O)C=CC1=O PSFDAYXWBWRTSM-UHFFFAOYSA-N 0.000 description 1
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 1
- HWYQOMOHBPPWSI-UHFFFAOYSA-N 3,5-diamino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC(N)=CC(N)=C1 HWYQOMOHBPPWSI-UHFFFAOYSA-N 0.000 description 1
- UDKYPBUWOIPGDY-UHFFFAOYSA-N 3-amino-n-(4-aminophenyl)benzamide Chemical compound C1=CC(N)=CC=C1NC(=O)C1=CC=CC(N)=C1 UDKYPBUWOIPGDY-UHFFFAOYSA-N 0.000 description 1
- CQJDVLNDEGRVHE-UHFFFAOYSA-N 3-ethyl-1-[4-[[4-(3-ethyl-2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C(CC)=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C(CC)=CC2=O)=O)C=C1 CQJDVLNDEGRVHE-UHFFFAOYSA-N 0.000 description 1
- NCINWBDCRVPXGK-UHFFFAOYSA-N 3-methyl-1-[4-(3-methyl-2,5-dioxopyrrol-1-yl)-6-methylidenecyclohexa-2,4-dien-1-yl]pyrrole-2,5-dione Chemical compound O=C1C(C)=CC(=O)N1C1C(=C)C=C(N2C(C(C)=CC2=O)=O)C=C1 NCINWBDCRVPXGK-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- ADUMIBSPEHFSLA-UHFFFAOYSA-N 4-[bis(4-aminophenyl)methyl]aniline Chemical compound C1=CC(N)=CC=C1C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 ADUMIBSPEHFSLA-UHFFFAOYSA-N 0.000 description 1
- CAMAADNLIGZSSD-UHFFFAOYSA-N 4-pyridin-2-ylbenzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=CC=N1 CAMAADNLIGZSSD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- RRMMQEKJTLOMLE-UHFFFAOYSA-N NC1=C(C=C(C(=C1)N)N)N.N1=C(N)N=C(N)N=C1N Chemical compound NC1=C(C=C(C(=C1)N)N)N.N1=C(N)N=C(N)N=C1N RRMMQEKJTLOMLE-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Abstract
Description
【発明の詳細な説明】
皮栗上夏■几分黙
本発明は、ビスマレイミド樹脂水性分散液及びその製造
方法に関し、詳しくは、不飽和ビスマレイミド化合物と
ポリアミノ化合物との反応によって得られる熱硬化性ビ
スマレイミドプレポリマーの微細な粒子を含む水性分散
液、及びその製造方法に関する。Detailed Description of the Invention The present invention relates to an aqueous bismaleimide resin dispersion and a method for producing the same. The present invention relates to an aqueous dispersion containing fine particles of a bismaleimide prepolymer, and a method for producing the same.
従来夏伎止
不飽和ビスマレイミド化合物とポリアミノ化合物とを反
応させて得られるプレポリマー、即ち、ビスマレイミド
樹脂は、これをＮ−メチルピロリドン、ジメチルホルム
アミド等の溶剤に硬化剤と共に溶解してフェスとし、こ
のフェスをガラスクロス等の基布に含浸した後、加熱硬
化させることによって、プリント配線基板の製造に用い
ることは、よ（知られている。Conventionally, a prepolymer obtained by reacting an unsaturated bismaleimide compound and a polyamino compound, that is, a bismaleimide resin, is prepared by dissolving it in a solvent such as N-methylpyrrolidone or dimethylformamide together with a curing agent to form a face. It is well known that this fabric is impregnated into a base fabric such as glass cloth and then heated and cured to be used in the production of printed wiring boards.
しかし、上記のように、従来のビスマレイミド樹脂フェ
スは、溶剤を含むために、その用途において自ずから制
限があるし、また、使用する際に溶剤回収等の付帯設備
が必要となる。However, as mentioned above, the conventional bismaleimide resin face contains a solvent, so there are inherent limitations in its use, and additional equipment such as solvent recovery is required when using it.
主所■課舅
本発明は、ビスマレイミド樹脂の用途の拡大及びより経
済的な使用方法を可能とするビスマレイミドプレポリマ
ーの微細な粒子を含む水性分散液、及びその製造方法を
提供することを目的とする。The present invention aims to provide an aqueous dispersion containing fine particles of a bismaleimide prepolymer and a method for producing the same, which enables expansion of the applications of bismaleimide resin and a more economical method of use. purpose.
ｉ ′ るための
本発明によるビスマレイミド樹脂水性分散液は、−投銭
（式中、Ａは炭素数２以上のｎ価の有機基を示し、Ｂは
炭素−炭素間二重結合を有する２価の有機基を示し、ｎ
は１以上の整数を示す。）
で表わされる不飽和ビスマレイミド化合物と、投銭
％式％）
（式中、Ｒはｍ価の有機基を示し、ｍは２以上の整数を
示す。）
で表わされるポリアミン化合物とから得られるビスマレ
イミド樹脂を含有することを特徴とする。The aqueous bismaleimide resin dispersion according to the present invention for the purpose of represents an organic group of n
indicates an integer greater than or equal to 1. ) and a polyamine compound represented by the following formula: It is characterized by containing maleimide resin.
かかるビスマレイミド樹脂水性分散液は、本発明に従っ
て、上記ビスマレイミド樹脂を疎水性有機溶剤に溶解さ
せ、界面活性剤の存在下に水と混合撹拌し、乳化させた
後、上記有機溶剤を除去することによって得ることがで
きる。According to the present invention, such a bismaleimide resin aqueous dispersion is prepared by dissolving the bismaleimide resin in a hydrophobic organic solvent, mixing and stirring with water in the presence of a surfactant to emulsify, and then removing the organic solvent. You can get it by doing this.
本発明において用いる不飽和ビスマレイミド化合物は、
−投銭
（式中、Ａは炭素数２以上のｎ価の有機基を示し、Ｂは
炭素−炭素間二重結合を有する２価の有機基を示し、ｎ
は１以上の整数を示す。）
で表わされ、ここに、Ａは、好ましくは、アルキル基、
シクロアルキル基若しくはアリール基、又はこれらに対
応する２価以上の炭化水素基である。The unsaturated bismaleimide compound used in the present invention is
- Nice coin (in the formula, A represents an n-valent organic group having 2 or more carbon atoms, B represents a divalent organic group having a carbon-carbon double bond, and n
indicates an integer greater than or equal to 1. ), where A is preferably an alkyl group,
It is a cycloalkyl group, an aryl group, or a divalent or higher hydrocarbon group corresponding thereto.
本発明においては、特に、ｎは２であることが好ましく
、従って、かかる場合、Ａは、好ましくは、アルキレン
基、シクロアルキレン基又はアリーレン基である。In the present invention, n is particularly preferably 2, and therefore, in such a case, A is preferably an alkylene group, a cycloalkylene group, or an arylene group.
Ｂは、好ましくは、−投銭
（式中、Ｒ１及びＲ２は、それぞれ独立に水素、ハロゲ
ン、アルキル基、アリール基又は置換アリール基を示す
。）
で表わされるエチレン性二重結合を有する基である。B is preferably a group having an ethylenic double bond represented by -Isen (in the formula, R1 and R2 each independently represent hydrogen, halogen, an alkyl group, an aryl group, or a substituted aryl group). .
従って、本発明において用いる好ましい不飽和ビスマレ
イミド化合物の具体例として、例えば、Ｎ、Ｎ’−フェ
ニレンビスマレイミド、Ｎ、Ｎ’−ヘキサメチレンビス
マレイミド、Ｎ、Ｎ″−メチレン−ジ−ｐ−フェニレン
ビスマレイミド、Ｎ、Ｎ″−オキシ−ジ−ｐ−フェニレ
ンビスマレイミド、Ｎ、Ｎ’−４，４’ −ベンゾフェ
ノンビスマレイミド、Ｎ、Ｎ”−ｐ−ジフェニルスルホ
ンマレイミド、 Ｎ、Ｎ’−（３，３’−ジメチル）−
メチレン−ｐ−フェニレンビスマレイミド、Ｎ、Ｎ’−
４，４’−ジシクロヘキシルメタンビスマレイミド、Ｎ
、Ｎ’−ｍ−キシリレンビスマレイミド、Ｎ、Ｎ’ −
ｐ−キシリレンビスマレイミド、Ｎ、Ｎ’−（３，３’
−ジエチル）−メチレン−ジ−ｐ−フェニレンビスマレ
イミド、Ｎ、Ｎ’−ｍ−トルイレンビスマレイミド、ア
ニリン−ホルマリン反応物と無水マレイン酸との反応生
成物等を挙げることができる。Therefore, as specific examples of preferable unsaturated bismaleimide compounds used in the present invention, for example, N,N'-phenylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N''-methylene-di-p-phenylene Bismaleimide, N,N''-oxy-di-p-phenylenebismaleimide, N,N'-4,4'-benzophenone bismaleimide, N,N''-p-diphenylsulfonemaleimide, N,N'-(3 ,3'-dimethyl)-
Methylene-p-phenylene bismaleimide, N, N'-
4,4'-dicyclohexylmethane bismaleimide, N
, N'-m-xylylene bismaleimide, N, N' -
p-xylylene bismaleimide, N, N'-(3,3'
-diethyl)-methylene-di-p-phenylenebismaleimide, N,N'-m-toluylenebismaleimide, a reaction product of an aniline-formalin reaction product and maleic anhydride, and the like.
これらの不飽和ビスマレイミド化合物は、その約６０重
量％までを、例えば、Ｎ−アリルマレイミド、Ｎ−プロ
ピルマレイミド、Ｎ−へキシルマレイミド、Ｎ−フェニ
ルマレイミド等のモノマレイミド化合物に置換すること
ができる。These unsaturated bismaleimide compounds can be substituted up to about 60% by weight with monomaleimide compounds such as N-allylmaleimide, N-propylmaleimide, N-hexylmaleimide, N-phenylmaleimide, etc. .
また、本発明において用いるポリアミノ化合物は、−投
銭
％式％））
（式中、Ｒはｍ価の有機基を示し、ｍは２以上の整数を
示す。）
で表わされ、ここに、Ｒは、好ましくは、アルキレン基
、シクロアルキレン基、アリーレン基、置換アリーレン
基若しくはそれらの２以上の結合からなる有機基、又は
これらに対応するｍ価の有機基である。本発明において
は、ｍは２又は３であることが好ましく、従って、例え
ば、ｍが２であるとき、Ｒは好ましくはアルキレン基、
シクロアルキレン基、アリーレン基、置換アリーレン基
又はそれらの２以上の結合からなる２価の有機基である
。Furthermore, the polyamino compound used in the present invention is represented by the following formula: is preferably an alkylene group, a cycloalkylene group, an arylene group, a substituted arylene group, an organic group consisting of a bond of two or more thereof, or an m-valent organic group corresponding thereto. In the present invention, m is preferably 2 or 3, and therefore, for example, when m is 2, R is preferably an alkylene group,
It is a cycloalkylene group, an arylene group, a substituted arylene group, or a divalent organic group consisting of two or more bonds thereof.
従って、本発明において好ましく用いるポリアミノ化合
物の具体例として、例えば、４，４°−ジアミノジシク
ロヘキシルメタン、４．４゛−ジアミノジフェニル−ｍ
−ジイソプロペニルベンゼン、１．４−ジアミノシクロ
ヘキサン、２．６−リアミノピリジン、ｍ−フェニレン
ジアミン、ｐ−フェニレンジアミン、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
ーテル、２．２−ビス（４−アミノフェニル）プロパン
、ベンチジン、４．４″−ジアミノジフェニルスルフィ
ド、４，４°−ジアミノジフェニルスルホン、ビス（４
−アミノフェニル）メチルホスフィン、ビス（４−アミ
ノフェニル）−ｐ−ジイソプロペニルベンゼン、１．５
−ジアミノナフタレン、ｐ−キシリレンジアミン、ヘキ
サメチレンジアミン、１．４”−ジアミノベンゾフェノ
ン、２．５−ビス（ｍ−アミノフェニル）−１，３，４
−オキサジチアゾール、２，５−ビス（ｐアミノフェニ
ル） −１，３，４−オキサジチアゾール、４．４°−
ビス（ｐ−アミノフェニル） −２，２’−ジチアゾー
ル、３．４’−ジアミノベンツアニリド、２，２゛−ヒ
ス（ｍ−アミノフェニル） −５，５’−ジベンツイミ
ダゾール、Ｎ、Ｎ″−ビス（ｐ−アミノベンゾイル）
−４，４’−ジアミノジフェニルメタン等のジアミノ化
合物を挙げることができる。Therefore, specific examples of polyamino compounds preferably used in the present invention include 4,4°-diaminodicyclohexylmethane, 4,4°-diaminodiphenyl-m
-diisopropenylbenzene, 1,4-diaminocyclohexane, 2,6-riaminopyridine, m-phenylenediamine, p-phenylenediamine, 4,4°-diaminodiphenylmethane, 4゜4゛-diaminodiphenyl ether, 2.2 -Bis(4-aminophenyl)propane, benzidine, 4.4″-diaminodiphenylsulfide, 4,4°-diaminodiphenylsulfone, bis(4-aminophenyl)propane,
-aminophenyl)methylphosphine, bis(4-aminophenyl)-p-diisopropenylbenzene, 1.5
-diaminonaphthalene, p-xylylene diamine, hexamethylene diamine, 1.4”-diaminobenzophenone, 2.5-bis(m-aminophenyl)-1,3,4
-Oxadithiazole, 2,5-bis(p-aminophenyl) -1,3,4-oxadithiazole, 4.4°-
Bis(p-aminophenyl)-2,2'-dithiazole, 3,4'-diaminobenzanilide, 2,2'-his(m-aminophenyl)-5,5'-dibenzimidazole, N, N'' -bis(p-aminobenzoyl)
Diamino compounds such as -4,4'-diaminodiphenylmethane can be mentioned.
また、１．２．４− ）リアミノベンゼン、１．３．５
−トリアミノベンゼン、２，４．６−ドリアミノトルエ
ン、２，４．６− ）リアミノ−１，３，５−１−リア
ミノベンゼン、１，３．７− ）リアミノナフタレン、
２．４．４”−トリアミノジフェニル、２，４．６−
）リアミノピリジン、２，４．４°−トリアミノジフェ
ニルメタン、ｐ−アミノフェニル−４，４′−ジフェニ
ルメタン、トリ（４−アミノフェニル）メタン、２．４
．４’−トリアミノベンゾフェノン、３，５．４’ −
トリアミノベンズアニリド、メラミン−１，２，４，５
−テトラアミノベンゼン、２．３．６．７−テトラアミ
ノナフタレン、３．３’、４．４’−テトラアミノジフ
ェニルエーテル、３．３’ 、４．４°−テトラアミノ
ジフェニルメタン、３．５−ヒス（３，４’−ジアミノ
フェニル）ピリジン、投銭
（式中、Ｒは炭素数１〜８の有機基、Ｘは０．１〜２の
数を示す。）
で表わされる分子内に３個以上のアミノ基を有する化合
物を挙げることができる。Also, 1.2.4-) riaminobenzene, 1.3.5
-triaminobenzene, 2,4.6-diaminotoluene, 2,4.6-)riamino-1,3,5-1-riaminobenzene, 1,3.7-)riaminonaphthalene,
2.4.4”-triaminodiphenyl, 2,4.6-
) riaminopyridine, 2,4.4°-triaminodiphenylmethane, p-aminophenyl-4,4'-diphenylmethane, tri(4-aminophenyl)methane, 2.4
．． 4'-triaminobenzophenone, 3,5.4'-
Triaminobenzanilide, melamine-1,2,4,5
-tetraaminobenzene, 2.3.6.7-tetraaminonaphthalene, 3.3', 4.4'-tetraaminodiphenyl ether, 3.3', 4.4°-tetraaminodiphenylmethane, 3.5-his (3,4'-diaminophenyl)pyridine, 3 or more in the molecule represented by pyridine (in the formula, R is an organic group having 1 to 8 carbon atoms, and X is a number of 0.1 to 2). Compounds having an amino group can be mentioned.
上記ポリアミノ化合物は単独にて、又は２種以上の混合
物として用いられる。The above polyamino compounds may be used alone or as a mixture of two or more.
本発明において用いる不飽和ビスマレイミド化合物とポ
リアミン化合物とから得られるビスマレイミド樹脂は、
通常、ポリアミノ化合物１当量に対して、不飽和マレイ
ミド化合物的０．１〜ｌＯ当量、好ましくは約０．５〜
５当量を加え、ロール等を用いて、約７０〜１７０°Ｃ
の温度に加熱しつつ、混練することによって、プレポリ
マー（ビスマレイミド樹脂）として得ることができる。The bismaleimide resin obtained from the unsaturated bismaleimide compound and the polyamine compound used in the present invention is
Usually, 0.1 to 1 O equivalent of the unsaturated maleimide compound, preferably about 0.5 to 1 O equivalent, per 1 equivalent of the polyamino compound.
Add 5 equivalents and heat to about 70-170°C using a roll etc.
It can be obtained as a prepolymer (bismaleimide resin) by kneading while heating to a temperature of .
このプレポリマーは、不飽和ビスマレイミド化合物の不
飽和二重結合に主にポリアミノ化合物のアミノ基がマイ
ケル付加してなる熱硬化性のポリアミノビスマレイミド
である。このプレポリマーの軟化点は、４０〜１８０°
Ｃ１特に、８０〜１２０°Ｃのものが好ましい。This prepolymer is a thermosetting polyamino bismaleimide formed by Michael addition of amino groups of a polyamino compound to unsaturated double bonds of an unsaturated bismaleimide compound. The softening point of this prepolymer is 40-180°
C1 is particularly preferably 80 to 120°C.
本発明によるビスマレイミド樹脂水性分散液は、このよ
うにして得られるビスマレイミド樹脂を疎水性有機溶剤
に溶解させ、界面活性剤の存在下に水と混合撹拌し、乳
化させた後、上記有機溶剤を除去することによって得る
ことができる。The bismaleimide resin aqueous dispersion according to the present invention can be obtained by dissolving the bismaleimide resin obtained in this way in a hydrophobic organic solvent, mixing and stirring with water in the presence of a surfactant to emulsify it, and then dissolving the bismaleimide resin obtained in this way in a hydrophobic organic solvent. can be obtained by removing .
上記有機溶剤としては、ビスマレイミド樹脂を溶解させ
る疎水性溶剤が用いられ、好ましくは、塩化メチレン、
ジクロロエチレン、クロロベンゼン等ノハロゲン化炭化
水素、ベンゼン、トルエン等の芳香族炭化水素、酢酸メ
チル、酢酸エチル等の脂肪族低級カルボン酸の低級アル
キルエステル、アセトフェノン、シクロヘキサノン等の
ケトン等が好ましく用いられる。特に限定されるもので
はないが、溶剤は、通常、ビスマレイミド樹脂に対して
、約５０〜１０００重量％の範囲で用いられる。このよ
うにして得られる樹脂溶液の粘度は、約１００ボイズ以
下、好ましくは約１ポイズ以下とするのがよい。As the organic solvent, a hydrophobic solvent that dissolves the bismaleimide resin is used, preferably methylene chloride,
Preferably used are halogenated hydrocarbons such as dichloroethylene and chlorobenzene, aromatic hydrocarbons such as benzene and toluene, lower alkyl esters of aliphatic lower carboxylic acids such as methyl acetate and ethyl acetate, and ketones such as acetophenone and cyclohexanone. Although not particularly limited, the solvent is usually used in an amount of about 50 to 1000% by weight based on the bismaleimide resin. The viscosity of the resin solution thus obtained is preferably about 100 poise or less, preferably about 1 poise or less.
次いで、予め界面活性剤を溶解させた水に上記樹脂溶液
を加え、ホモミキサー、ホモジナイザー等の強撹拌可能
な分散機にて、溶剤が気化しない条件下、好ましくは、
常圧下、溶剤の沸点より低い温度にて、混合物を強攪拌
して、乳化させる。Next, the above resin solution is added to water in which a surfactant has been dissolved in advance, and the mixture is mixed with a disperser capable of strong stirring such as a homomixer or homogenizer under conditions that the solvent does not vaporize, preferably.
The mixture is vigorously stirred and emulsified at a temperature lower than the boiling point of the solvent under normal pressure.
上記水の量は、前記樹脂溶液に対して、２０〜１０００
重量％、好ましくは５０〜２００重量％の範囲であるが
、しかし、これに限定されるものではない。The amount of water is 20 to 1,000 with respect to the resin solution.
% by weight, preferably in the range from 50 to 200% by weight, but without limitation.
上記界面活性剤としては、例えば、ポリオキシエチレン
ノニルフェニルエーテル、ポリオキシエチレンポリオキ
シプロピレンブロック共重合体、ポリオキシエチレンソ
ルビタンエステル等のノニオン系界面活性剤、オレイン
酸カリウム、ラウリル硫酸ナトリウム、ドデシルベンゼ
ンスルホン酸ナトリウム等のアニオン系界面活性剤、塩
化ラウリルトリメチルアンモニウム等のカチオン系界面
活性剤のいずれの界面活性剤も用いることができる。か
かる界面活性剤は、通常、ビスマレイミドプレポリマー
に対して、０゜１ＮｌＯ重量％、好ましくは、１〜５重
量％の範囲で用いられる。Examples of the surfactant include nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene sorbitan ester, potassium oleate, sodium lauryl sulfate, and dodecylbenzene. Any of anionic surfactants such as sodium sulfonate and cationic surfactants such as lauryltrimethylammonium chloride can be used. Such surfactants are generally used in an amount of 0.1 NIO, preferably 1 to 5% by weight, based on the bismaleimide prepolymer.
このようにして得られた乳化液から有機溶剤を除去し、
例えばエバポレータにて脱溶剤し、この後、必要に応じ
て、濃縮すれば、本発明によるビスマレイミド樹脂水性
分散液を得ることができる。The organic solvent is removed from the emulsion thus obtained,
For example, the aqueous bismaleimide resin dispersion according to the present invention can be obtained by removing the solvent using an evaporator and then concentrating if necessary.
本発明による水性分散液は、そのままの状態で、例えば
、被着体上、型枠内等で加熱乾燥し、更に、１５０°Ｃ
で１〜４時間程度加熱することによって、硬化させるこ
とができる。The aqueous dispersion according to the present invention is dried as it is by heating, for example, on an adherend or in a mold, and further dried at 150°C.
It can be cured by heating for about 1 to 4 hours.
また、本発明による水性分散液は、これにラジカル触媒
、イミダゾール触媒等の硬化促進剤を加えて、実用に供
することもでき・る。Further, the aqueous dispersion according to the present invention can be put to practical use by adding a curing accelerator such as a radical catalyst or an imidazole catalyst.
光皿皇分来
本発明によれば、熱硬化性ビスマレイミドプレポリマー
を含む水性分散液が提供され、樹脂粒子の平均粒子径が
ｌａｍ以下である場合に、特に、製膜性にすぐれる。従
って、かかる水性分散液は、例えば、ガラス繊維収束剤
、電子電気機器における熱絶縁性コーティング剤、テー
プ、フィルム等の耐熱性及び摺動向上のためのコーティ
ング剤として有用である。According to the present invention, an aqueous dispersion containing a thermosetting bismaleimide prepolymer is provided, and particularly when the average particle diameter of the resin particles is lam or less, film forming properties are excellent. Therefore, such aqueous dispersions are useful as, for example, glass fiber sizing agents, thermally insulating coatings for electronic and electrical equipment, and coatings for improving the heat resistance and sliding properties of tapes, films, and the like.
災施透
以下に実施例及び参考例を挙げて本発明を説明するが、
本発明はこれら実施例により何ら限定されるものではな
い。The present invention will be explained below with reference to Examples and Reference Examples.
The present invention is not limited in any way by these Examples.
参考例
Ｎ、Ｎ’−４，４”−ジフェニルメタンビスマレイミド
７１．２重量部、４．４゛−ジアミノフェニル−ｍ−ジ
イソプロペニルベンゼン２８．７重１ 部及ヒ５− シ
アノ−２−エチル−４−メチルイミダゾール０．１重量
部をガラス製フラスコ中にて１３０°Ｃで１５分間加熱
して、ビスマレイミドプレポリマーを得た。このプレポ
リマーは、軟化点１０６℃、４５％Ｎ−メチルピロリド
ン溶液として、温度２５°Ｃにて２７０センチポイズの
粘度を有するものであった。Reference Example N, 71.2 parts by weight of N'-4,4''-diphenylmethane bismaleimide, 28.7 parts by weight of 4.4'-diaminophenyl-m-diisopropenylbenzene, and 5-cyano-2-ethyl. -0.1 part by weight of 4-methylimidazole was heated in a glass flask at 130°C for 15 minutes to obtain a bismaleimide prepolymer.This prepolymer had a softening point of 106°C and 45% N-methyl As a pyrrolidone solution, it had a viscosity of 270 centipoise at a temperature of 25°C.
実施例１
上記参考例にて得たビスマレイミドプレポリマーを常温
にて塩化メチレンに溶解させ、１４．３重量％溶液を調
製した。この溶液の粘度は２５°Ｃで１０センチポイズ
であった。Example 1 The bismaleimide prepolymer obtained in the above reference example was dissolved in methylene chloride at room temperature to prepare a 14.3% by weight solution. The viscosity of this solution was 10 centipoise at 25°C.
ドデシルベンゼンスルホン酸ナトリウムの１．４３重量
％水溶液に上記ビスマレイミドプレポリマー溶液の２重
量倍量を加え、得られた混合物を１２°Ｃ１常圧下にホ
モミキサーにて１０００Ｏｒｐｍにて強攪拌し、乳化さ
せた。次いで、ロータリー・エバポレーターを用いて、
この乳化液から塩化メチレンを脱溶剤させた後、更に、
６５°Ｃ，１１０ｍｍ１１ｇの条件下に濃縮して、ビス
マレイミド樹脂水性分散液を得た。Two times the weight of the above bismaleimide prepolymer solution was added to a 1.43% by weight aqueous solution of sodium dodecylbenzenesulfonate, and the resulting mixture was strongly stirred at 1000 rpm with a homomixer at 12°C and normal pressure to emulsify. I let it happen. Then, using a rotary evaporator,
After removing the methylene chloride from this emulsion,
It was concentrated under conditions of 65°C, 110 mm, and 11 g to obtain an aqueous bismaleimide resin dispersion.
この分散液は、固形分濃度４０重量％、Ｂ型粘度計で測
定した温度２５°Ｃでの粘度９センチポイズ、マイクロ
トラック粒度分布計による平均粒子径は０．３５μｍで
あった。This dispersion had a solid content concentration of 40% by weight, a viscosity of 9 centipoise at a temperature of 25° C. as measured by a B-type viscometer, and an average particle diameter of 0.35 μm as measured by a Microtrac particle size distribution meter.
Claims (2)
炭素−炭素間二重結合を有する２価の有機基を示し、ｎ
は１以上の整数を示す。）で表わされる不飽和ビスマレ
イミド化合物と、一般式 Ｒ−（−ＮＨ＿２）ｍ （式中、Ｒはｍ価の有機基を示し、ｍは２以上の整数を
示す。） で表わされるポリアミノ化合物とから得られるビスマレ
イミド樹脂を含有することを特徴とするビスマレイミド
樹脂水性分散液。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A represents an n-valent organic group having 2 or more carbon atoms, and B represents a divalent organic group having a carbon-carbon double bond. and n
indicates an integer greater than or equal to 1. ), and a polyamino compound represented by the general formula R-(-NH_2)m (wherein, R represents an m-valent organic group, and m represents an integer of 2 or more). An aqueous bismaleimide resin dispersion comprising a bismaleimide resin obtained from.
炭素−炭素間二重結合を有する２価の有機基を示し、ｎ
は１以上の整数を示す。）で表わされる不飽和ビスマレ
イミド化合物と、一般式 Ｒ−（−ＮＨ＿２）ｍ （式中、Ｒはｍ価の有機基を示し、ｍは２以上の整数を
示す。） で表わされるポリアミン化合物とから得られるビスマレ
イミド樹脂を疎水性有機溶剤に溶解させ、界面活性剤の
存在下に水と混合攪拌し、乳化させた後、上記有機溶剤
を除去することを特徴とするビスマレイミド樹脂水性分
散液の製造方法。(2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A represents an n-valent organic group having 2 or more carbon atoms, and B represents a divalent organic group having a carbon-carbon double bond. and n
indicates an integer greater than or equal to 1. ), and a polyamine compound represented by the general formula R-(-NH_2)m (wherein, R represents an m-valent organic group, and m represents an integer of 2 or more). An aqueous dispersion of a bismaleimide resin obtained by dissolving the bismaleimide resin obtained from the above in a hydrophobic organic solvent, mixing and stirring with water in the presence of a surfactant to emulsify, and then removing the organic solvent. manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24355488A JPH0291153A (en) | 1988-09-27 | 1988-09-27 | Aqueous dispersion of bismaleimide resin and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24355488A JPH0291153A (en) | 1988-09-27 | 1988-09-27 | Aqueous dispersion of bismaleimide resin and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0291153A true JPH0291153A (en) | 1990-03-30 |
Family
ID=17105586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24355488A Pending JPH0291153A (en) | 1988-09-27 | 1988-09-27 | Aqueous dispersion of bismaleimide resin and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0291153A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE36102E (en) * | 1991-09-17 | 1999-02-16 | Globe-Union Inc. | Dual lug battery plate construction |
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| JPS6426669A (en) * | 1988-07-06 | 1989-01-27 | Mitsubishi Gas Chemical Co | Production of curable polymer colloidal solution |
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1988
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4853063A (en) * | 1971-10-20 | 1973-07-25 | ||
| JPS5486597A (en) * | 1977-12-23 | 1979-07-10 | Nitto Electric Ind Co Ltd | Slurry composition |
| JPS6426669A (en) * | 1988-07-06 | 1989-01-27 | Mitsubishi Gas Chemical Co | Production of curable polymer colloidal solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USRE36102E (en) * | 1991-09-17 | 1999-02-16 | Globe-Union Inc. | Dual lug battery plate construction |
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