JPH0528726B2 - - Google Patents
Info
- Publication number
- JPH0528726B2 JPH0528726B2 JP61151997A JP15199786A JPH0528726B2 JP H0528726 B2 JPH0528726 B2 JP H0528726B2 JP 61151997 A JP61151997 A JP 61151997A JP 15199786 A JP15199786 A JP 15199786A JP H0528726 B2 JPH0528726 B2 JP H0528726B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- weight
- parts
- composition
- group
- 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.)
- Expired - Lifetime
Links
- 239000003822 epoxy resin Substances 0.000 claims description 22
- 229920000647 polyepoxide Polymers 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- -1 Maleimide compound Chemical class 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 125000005462 imide group Chemical group 0.000 claims description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 11
- 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 10
- 239000011248 coating agent Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 125000000962 organic group Chemical group 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 description 4
- 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 3
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 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 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AXJZCJSXNZZMDU-UHFFFAOYSA-N (5-methyl-1h-imidazol-4-yl)methanol Chemical compound CC=1N=CNC=1CO AXJZCJSXNZZMDU-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- FBHPRUXJQNWTEW-UHFFFAOYSA-N 1-benzyl-2-methylimidazole Chemical compound CC1=NC=CN1CC1=CC=CC=C1 FBHPRUXJQNWTEW-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 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 1
- OQTIKANCBNPBKT-UHFFFAOYSA-N 2-(2-undecyl-1h-imidazol-5-yl)propanenitrile Chemical compound CCCCCCCCCCCC1=NC(C(C)C#N)=CN1 OQTIKANCBNPBKT-UHFFFAOYSA-N 0.000 description 1
- JDNYGFMXLOAYAR-UHFFFAOYSA-N 2-(5-ethyl-1h-imidazol-2-yl)propanenitrile Chemical compound CCC1=CN=C(C(C)C#N)N1 JDNYGFMXLOAYAR-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-O 2-methyl-1h-imidazol-3-ium Chemical compound CC=1NC=C[NH+]=1 LXBGSDVWAMZHDD-UHFFFAOYSA-O 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 description 1
- BVYPJEBKDLFIDL-UHFFFAOYSA-N 3-(2-phenylimidazol-1-yl)propanenitrile Chemical compound N#CCCN1C=CN=C1C1=CC=CC=C1 BVYPJEBKDLFIDL-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 102100021617 Ankyrin repeat and SOCS box protein 4 Human genes 0.000 description 1
- 101710183425 Ankyrin repeat and SOCS box protein 4 Proteins 0.000 description 1
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 125000000623 heterocyclic group 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 group [H]* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920012287 polyphenylene sulfone Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Epoxy Resins (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
(産業上の利用分野)
本発明は、熱硬化性粉体組成物、特に耐熱性に
すぐれた硬化物を与える組成物に関する。
該組成物は、各種成形材料、積層材料製造用バ
インダー、素子封止材料等に好適とされ、なかで
も粉体塗装法を採用しての各種コイル類への含
浸、固着に有用とされる。
(従来の技術)
従来、上記のような用途に用いられる耐熱性を
有する熱硬化性粉体組成物としては、種々の組成
からなるものが知られている。
具体的には、シリコーン樹脂、シリコーン変性
エポキシ樹脂及び硬化剤からなる組成物、ポリイ
ミド樹脂、ポリイミド変性エポキシ樹脂及び硬化
剤からなる組成物、ビスマレイミド・トリアジン
樹脂、エポキシ樹脂及び硬化剤からなる組成物、
モノマレイミド化合物、ポリマレイミド化合物及
びエポキシ樹脂からなる組成物(特開昭57−
74327号)、特定の化学構造を有するモノマレイミ
ド化合物とエポキシ樹脂とからなる組成物(特開
昭57−74328号)等が公知とされている。
しかしながら、上記したような従来の組成物に
は下記の欠点がある。すなわち、耐熱性と機械的
物性とのバランスのとれた硬化物を得ることが困
難であり用途に制限がある。また、硬化物を得る
のに高温で、長時間が必要とされ、例えば前記組
成物をコイルの含浸、固着用として用いる場合に
は硬化過程において、極端な粘度低下がみられ、
組成物の漏れやタレが生じ、得られる硬化物に発
泡やボイドがみられるようになる。さらに、得ら
れる硬化物は金属類との密着性に劣り、変性樹脂
を使用する場合は、変性するための合成に煩雑な
工程が必要となる。
また、モノ−又はポリマレイミド化合物とエポ
キシ樹脂からなる系に硬化剤として、例えば3、
3′、4、4′−ベンゾフエノンテトラカルボン酸無
水物やジシクロペンタジエンと無水マレイン酸と
の反応生成物などのような酸無水物を配合してな
る組成物を硬化させて得られる塗膜は、発泡が生
じ、しかも光沢がなく、目的とする性能を有する
塗膜が得られない。
(発明が解決しようとする問題点)
本発明は、上述の如き従来の欠点を除去した新
規かつ改良された組成物を提供しようとするもの
である。
(問題点を解決するための手段)
本発明は、(A)分子中にイミド基を少なくとも1
個有するマレイミド化合物及び又はその初期縮合
物10〜90重量部、(B)エポキシ樹脂90〜10重量部、
(C)ジシアンジアミド類−イミダゾール類混合系の
少なくとも1種からなる硬化剤の有効量、並びに
(D)充てん材30〜250重量部を含む熱硬化性粉体組
成物である。
本発明において、分子中にイミド基を少なくと
も1個、好ましくは2個有するマレイミド化合物
としては、下記に示すような化合物があげること
ができる。
(i) 式
(式中、R1は1価の原子又は基、R2、R3は同
一若しくは異なりて水素原子、ハロゲン原子、
アルキル基、アリール基である。)で示される
モノマレイミド化合物
(ii) 式
(式中、R4はマレイミド基を有しない2価の
有機基、R2、R3は前記と同じものである。)で
示されるビスマレイミド化合物
(iii) 式
(式中、R5、R7は同種若しくは異種の2価の
有機基、R6は3価の有機基、R2、R3は前記3
同じものである。mは正の整数である。)で示
される多価マレイミド化合物
(iv) 式
(式中、R8、R9は同種若しくは異種の2価の
有機基、R2、R3は前記と同じものである。n
は正の整数である。)で示されるポリマレイミ
ド化合物
(v) 式
(式中、R10は3価以上の多価有機基、qは3
以上の正の整数、R2、R3は前記と同じもので
ある。)で示されるポリマレイミド化合物
前記式中のR1で示される1価の原子又は基と
しては、フエニル基、メトキシフエニル基などを
例示することができ、R2、R3で示されるハロゲ
ン原子、アルキル基、アリール基としては、塩素
原子、臭素原子、よう素原子、メチル基、エチル
基、プロピル基、フエニル基などをあげることが
できる。R4、R5、R7で示される2価の基として
は、ビフエニル、ジフエニルメタン、α,α′−ジ
メチルジフエニルメタン、ジフエニルエーテル、
ジフエニルチオエーテル、ジフエニルケトン、ジ
フエニルアミン、ジフエニルスルホキシド、ジフ
エニルスルホン、トリフエニルホスフエートなど
から誘導される基やアルキレン基、オキシアルキ
レン基、アルケニレン基、フエニレン基、シクロ
ヘキシレン基などやこれらの基の水素原子が部分
的に置換した基などが、またR6としては、上記
と同様の化合物から誘導される3価の基があげら
れる。R8、R9としては、前記R4で例示した基か
ら選択される基をあげることができる。
さらに、R10としては、芳香族炭化水素化合物
から誘導される残基、任意の原子や基を介して結
合した有機基をあげることができる。
上記したような各種マレイミド化合物は、いず
れも公知の方法により合成することができる。例
えば式
(式中R′は2価の有機基である。)で示されるポ
リマレイミドは、ジアミノジフエニルメタン1モ
ルとビスマレイミド2モルとを反応させることに
より得ることができる。
このマレイミド化合物、その初期縮合物は使用
に当つては1種類に限定されず2種若しくはそれ
以上を併用してもよい。
つぎにエポキシ樹脂としては、従来から知られ
ている種々のものを使用することができる。
これらのエポキシ樹脂を具体的に例示すると、
ビスフエノールA型、ビスフエノールB型、ビス
フエノールF型、フエノールノボラツク型、クレ
ゾールノボラツク型エポキシ樹脂、グリシジルエ
ーテル型エポキシ樹脂、グリシジルエステル型エ
ポキシ樹脂、グリシジルアミン型エポキシ樹脂、
脂環式エポキシ樹脂、線状脂肪族エポキシ樹脂、
複素環型エポキシ樹脂、ハロゲン化特に臭素化エ
ポキシ樹脂等があげられ、これらからなる群より
選ばれる1種若しくは2種以上のものが用いられ
る。
これらのうちでも本発明において好ましいエポ
キシ樹脂は、常態において固体状を呈し、エポキ
シ当量が450〜800、融点が65〜90℃の範囲にある
ビスフエノールA型エポキシ樹脂である。
具体的には、エピコート1001、同1002、同1003
(いずれも油化シエルエポキシ社製エポキシ樹脂
商品名)等をあげることができる。
上記したマレイミド化合物及び/又はその初期
縮合物とエポキシ樹脂との使用割合は、前者10〜
90重量部に対して後者90〜10重量部、好ましくは
前者50〜80重量部に対して後者50〜20重量部であ
る。
この量限定の理由は、下記のとおりである。マ
レイミド化合物類が余りに少なすぎると耐熱性に
すぐれた硬化物を得ることが困難となる等の不利
がみられ、逆に余りに多すぎると金属類への接着
性ないし固着性に劣る、無機質充填剤を混練する
際に高粘度となり十分な均一分散が困難となる、
また得られる硬化物に割れが生じ切削加工作業に
支障をきたす、さらに被塗物へのぬれ性に劣り平
滑な塗膜が得られない等の問題が発生する。
本発明で最重要点である混合系硬化剤について
は、下記のような組合せであることが必須とされ
る。
(i) ジシアンジアミド類−イミダゾール類混合系
本発明において硬化剤は、上記のような特定組
合せの混合系で使用することが必要であり、これ
以外の混合系や、単独使用では、本発明の目的を
達成することができない。
ここにジシアンジアミド類としては、例えばジ
シアンジアミドのほかに、ジシアンジアミドと芳
香族アミン化合物から合成されるグアニジン化合
物も包含される。
また、イミダゾール類としては、2−メチルイ
ミダゾール、2−ウンデシルイミダゾール、2−
ヘプタデシルイミダゾール、2−エチル−4−メ
チルイミダゾール、2−フエニルイミダゾール、
1−ベンジル−2−メチルイミダゾール、1−シ
アノエチル−2−メチルイミダゾール、1−シア
ノエチル−4−エチルイミダゾール、1−シアノ
エチル−ウンデシルイミダゾール、1−シアノエ
チル−2−フエニルイミダゾール、1−シアノエ
チル−2−ウンデシルイミダゾリウムトリメリテ
ート、2−メチルイミダゾリウムイソシアヌレー
ト、2,4−ジアミノ−6−〔2−メチルイミダ
ゾリル−(1)〕エチル−S−トリアジン、2,4−
ジアミノ−6−〔2−ウンデシルイミダゾリル−
(1)〕−エチル−S−トリアジン、2−フエニル−
4−メチル−5−ヒドロキシメチルイミダゾール
等があげられる。
これらのうちでも反応性、安定性からは1−シ
アノエチル−2−ウンデシルイミダゾリウムトリ
メリテート、2,4−ジアミノ−6−〔2−ウン
デシルイミダゾリル−(1)〕−エチル−S−トリア
ジンが特に好ましい。
上記した混合系硬化剤における各成分の使用比
については、硬化剤の種類により若干相違し、具
体的にはジシアンジアミド類とイミダゾール類の
使用比は4:1〜1:1、好ましくは3〜2:1
である。
この混合系硬化剤の使用量は、上記(A)及び(B)成
分の合計量に対して有効量、具体的には0.01〜20
重量%とされる。この使用量が少なすぎると硬化
反応が十分に進行せず、高温初期の加熱減量も大
きくなり、所望の耐熱性が得られず、しかも割
れ、クラツクが生ずるようになり、逆に多すぎる
と硬化物を高温雰囲気中にさらした場合、酸化、
熱分解が促進されるようになる。
本発明で使用される充てん剤としては、シリ
カ、アルミナ、炭酸カルシウム、ウオラストナイ
ト、マイカなどの無機質系、フエノール樹脂の半
硬化ないし硬化物やポリイミド、ポリフエニレン
スルホンあるいはポリエーテルスルホンの硬化物
などの有機質系のものがあげられる。これらは任
意の粒径の微粉末として使用に供される。
この充てん剤は、本発明では重要な成分であ
り、このものを欠如した組成物では、本発明の目
的を達成することができない。
この充てん剤は、上記(A)成分と(B)成分との合計
量100重量部に対して30〜250重量部の範囲とされ
る。該使用量が30重量部未満では、硬化物の如収
縮、硬化収縮を十分に防止することができず、割
れ、クラツクの発生が大で、また塗装、硬化過程
において、粉体材料が流れ出してタレが発生し均
一な硬化塗膜を得ることが困難となる。
また、250重量部を超えると被着体に対しての
ぬれ性が劣るようになり、平滑な塗膜が得られ
ず、さらに接着性も悪くなる。
本発明の組成物は、本質的には上記した(A)〜(D)
成分からなるが、必要に応じて任意の成分を本発
明の目的を阻害しない範囲で含むことは何ら差支
えない。任意の成分としては、例えば顔料、硬化
促進剤、耐熱性付与剤、たれ止め剤、分散助剤、
塗膜改質剤、難燃性付与剤等をあげることができ
る。
本発明の組成物は、通常の粉体組成物とほぼ同
様にして調製することができる。具体的には、上
記(A)〜(D)成分を均一に混練後(機械的に行つても
よい)、必要に応じて所望の粒径に粉砕すること
により調製することができる。
(発明の効果)
本発明の組成物から得られる硬化物は、耐熱性
と機械的強さのバランスにすぐれている。硬化の
際には従来のような高温、長時間の加熱を必要と
せず比較的低温、短時間で硬化させることができ
ることから粘度に悪影響を及ぼさず、結果として
良好な硬化物を得ることができる。硬化物は、金
属、セラミツク等種々の材料の塗装面に対する密
着性ないし固着性においてすぐれている。本発明
の組成物を用いると、構成成分として、その合成
が煩雑な変性化合物を使用しなくても所期の目的
を達成することができる。
本発明の組成物は、成形材料、積層材料(バイ
ンダーとして)、封止材料、接着材料、絶縁材料
等の用途に広く応用可能である。
(実施例と比較例)
つぎに、本発明の実施例及び比較例をあげる
が、本発明はこれらの実施例に限定されるもので
はない。
なお、例中の部はすべて重量部を示す。
実施例1〜14及び比較例1〜10
マレイミド化合物、マレイミド化合物の初期縮
合物、エポキシ樹脂、硬化剤及び充填剤を下記の
第1表に示すような量割合でニーダーを用いて均
一に混合した。
ついで、粉体塗装に適するような粒度分布とな
るように常法より粉砕した。
この粉砕物について諸物性を調べたところ、下
記の第1表に示すような結果が得られた。
各物性の測定方法、評価を下記に示す。
(1) ゲル化時間
粉体約0.1〜0.2gを150℃に加熱した金属板
の円形凹部に充てんし、該粉体がゲル化するま
での時間(秒)を測定し、これをゲル化時間と
した(JIS C2104に準じた)。
(2) クラツク発生の有無
予め180〜200℃に加熱した鉄板(20mm×150
mm×3.2mm)に粉体を塗布した。塗布量は、硬
化後の膜厚が0.3〜0.5mmとなるような量とし
た。鉄板を同温度に保持した後、冷却したとこ
ろ、硬化塗膜が得られた。この硬化塗膜につい
て、クラツクの発生の有無を調べた。
(3) 引張せん断強さ
予め脱脂したテストピース(軟鋼板100×20
×3mm)にて接着力(せん断強さ)を測定し
た。ただし引張速度は5mm/分の条件とし、高
温中測定は規定温度中に10分保持してから測定
した。また圧着時の加圧力は1Kg/15×10mm2又
は1Kg/15×10mm2相当ピンチコツクとした。
(4) 加熱撓み温度(HDT)
規定の条件でプレス成形しテストピースを成
形し200℃で1時間、220℃で1時間加熱硬化し
た。得られた硬化物についてASTM D648に
準じてHDTを測定した。
(5) 加熱重量減少率
加熱重量減少率の分数における分子
示差熱分析法により、450℃で加熱を開始
し3分から4分の間の1分間に生じた残渣か
ら減少量を計算によつて求めた。
加熱重量減少率の分数における分母
350℃で1時間、400℃で20分間加熱後の重
量減少率を計算によつて求めた。
(Industrial Application Field) The present invention relates to a thermosetting powder composition, and particularly to a composition that provides a cured product with excellent heat resistance. The composition is suitable for various molding materials, binders for producing laminated materials, element sealing materials, etc., and is particularly useful for impregnating and fixing various coils using a powder coating method. (Prior Art) Conventionally, heat-resistant thermosetting powder compositions used in the above-mentioned applications are known to have various compositions. Specifically, a composition consisting of a silicone resin, a silicone-modified epoxy resin, and a curing agent, a composition consisting of a polyimide resin, a polyimide-modified epoxy resin, and a curing agent, a composition consisting of a bismaleimide triazine resin, an epoxy resin, and a curing agent. ,
Composition consisting of a monomaleimide compound, a polymaleimide compound, and an epoxy resin
74327), a composition comprising a monomaleimide compound having a specific chemical structure and an epoxy resin (Japanese Patent Application Laid-Open No. 74328/1983), and the like are known. However, the conventional compositions as described above have the following drawbacks. That is, it is difficult to obtain a cured product with well-balanced heat resistance and mechanical properties, and its uses are limited. In addition, it takes a long time at high temperatures to obtain a cured product, and for example, when the composition is used for impregnating and fixing coils, an extreme decrease in viscosity is observed during the curing process.
Leakage and sagging of the composition occur, and foaming and voids appear in the resulting cured product. Furthermore, the obtained cured product has poor adhesion to metals, and when a modified resin is used, a complicated process is required for synthesis for modification. In addition, as a curing agent, for example, 3,
A coating obtained by curing a composition containing an acid anhydride such as 3',4,4'-benzophenonetetracarboxylic anhydride or a reaction product of dicyclopentadiene and maleic anhydride. The film is foamed and lacks gloss, making it impossible to obtain a coating film with the desired performance. (Problems to be Solved by the Invention) The present invention seeks to provide a new and improved composition that eliminates the conventional drawbacks as described above. (Means for solving the problems) The present invention provides (A) at least one imide group in the molecule.
10 to 90 parts by weight of a maleimide compound and/or its initial condensate, (B) 90 to 10 parts by weight of an epoxy resin,
(C) an effective amount of a curing agent consisting of at least one dicyandiamide-imidazole mixed system, and
(D) A thermosetting powder composition containing 30 to 250 parts by weight of a filler. In the present invention, examples of maleimide compounds having at least one, preferably two imide groups in the molecule include the compounds shown below. (i) Eq. (In the formula, R 1 is a monovalent atom or group, R 2 and R 3 are the same or different, and are a hydrogen atom, a halogen atom,
They are an alkyl group and an aryl group. ) Monomaleimide compound (ii) represented by formula (In the formula, R 4 is a divalent organic group not having a maleimide group, and R 2 and R 3 are the same as above.) Bismaleimide compound (iii) represented by the formula (In the formula, R 5 and R 7 are the same or different divalent organic groups, R 6 is a trivalent organic group, R 2 and R 3 are the above three
It's the same thing. m is a positive integer. ) Polyvalent maleimide compound (iv) represented by formula (In the formula, R 8 and R 9 are the same or different divalent organic groups, and R 2 and R 3 are the same as above.n
is a positive integer. ) Polymaleimide compound (v) represented by the formula (In the formula, R 10 is a trivalent or higher polyvalent organic group, q is 3
The above positive integers, R 2 and R 3 are the same as above. ) The monovalent atom or group represented by R 1 in the above formula includes phenyl group, methoxyphenyl group, etc., and the halogen atom represented by R 2 and R 3 Examples of the alkyl group and aryl group include a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, a propyl group, and a phenyl group. Divalent groups represented by R 4 , R 5 and R 7 include biphenyl, diphenylmethane, α,α′-dimethyldiphenylmethane, diphenyl ether,
Groups derived from diphenyl thioether, diphenyl ketone, diphenylamine, diphenyl sulfoxide, diphenyl sulfone, triphenyl phosphate, etc., alkylene groups, oxyalkylene groups, alkenylene groups, phenylene groups, cyclohexylene groups, etc., and hydrogen of these groups Examples of R 6 include groups in which atoms are partially substituted, and trivalent groups derived from the same compounds as mentioned above. Examples of R 8 and R 9 include groups selected from the groups exemplified for R 4 above. Furthermore, R 10 can include a residue derived from an aromatic hydrocarbon compound and an organic group bonded via an arbitrary atom or group. All of the various maleimide compounds described above can be synthesized by known methods. For example, the expression The polymaleimide represented by the formula (wherein R' is a divalent organic group) can be obtained by reacting 1 mole of diaminodiphenylmethane with 2 moles of bismaleimide. The maleimide compound and its initial condensate are not limited to one type, but two or more types may be used in combination. Next, as the epoxy resin, various conventionally known ones can be used. Specific examples of these epoxy resins include:
Bisphenol A type, bisphenol B type, bisphenol F type, phenol novolak type, cresol novolak type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin,
Cycloaliphatic epoxy resin, linear aliphatic epoxy resin,
Examples include heterocyclic epoxy resins, halogenated, especially brominated epoxy resins, and one or more selected from the group consisting of these resins are used. Among these, the preferred epoxy resin in the present invention is a bisphenol A type epoxy resin which is solid in normal state, has an epoxy equivalent of 450 to 800, and a melting point of 65 to 90°C. Specifically, Epicote 1001, Epicote 1002, Epicote 1003
(all are epoxy resin trade names manufactured by Yuka Ciel Epoxy Co., Ltd.). The ratio of the above-mentioned maleimide compound and/or its initial condensate to the epoxy resin is 10 to 10% for the former.
The latter is 90 to 10 parts by weight relative to 90 parts by weight, preferably 50 to 20 parts by weight to the former 50 to 80 parts by weight. The reason for this amount limitation is as follows. If the amount of maleimide compounds is too small, there will be disadvantages such as difficulty in obtaining a cured product with excellent heat resistance.On the other hand, if it is too large, the inorganic filler will have poor adhesion or fixation to metals. When kneading, the viscosity becomes high and it becomes difficult to disperse sufficiently uniformly.
In addition, cracks occur in the resulting cured product, which interferes with cutting work, and further problems arise, such as poor wettability to the object to be coated, making it impossible to obtain a smooth coating film. Regarding the mixed curing agent, which is the most important point in the present invention, it is essential that the combination is as shown below. (i) Mixed system of dicyandiamides and imidazoles In the present invention, it is necessary to use the curing agent in a mixed system in a specific combination as described above. cannot be achieved. The dicyandiamides herein include, for example, in addition to dicyandiamide, guanidine compounds synthesized from dicyandiamide and aromatic amine compounds. In addition, as imidazoles, 2-methylimidazole, 2-undecylimidazole, 2-
heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole,
1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-4-ethylimidazole, 1-cyanoethyl-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2 -Undecylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-S-triazine, 2,4-
Diamino-6-[2-undecylimidazolyl-
(1)]-Ethyl-S-triazine, 2-phenyl-
Examples include 4-methyl-5-hydroxymethylimidazole. Among these, 1-cyanoethyl-2-undecylimidazolium trimellitate, 2,4-diamino-6-[2-undecylimidazolyl-(1)]-ethyl-S-triazine, and is particularly preferred. The usage ratio of each component in the above-mentioned mixed curing agent varies slightly depending on the type of curing agent. Specifically, the usage ratio of dicyandiamides and imidazoles is 4:1 to 1:1, preferably 3 to 2. :1
It is. The amount of this mixed curing agent used is an effective amount based on the total amount of components (A) and (B) above, specifically 0.01 to 20
% by weight. If the amount used is too small, the curing reaction will not proceed sufficiently, and the heating loss at the initial high temperature will also be large, making it impossible to obtain the desired heat resistance and causing cracks. When objects are exposed to high temperature atmospheres, oxidation,
Thermal decomposition will be accelerated. The fillers used in the present invention include inorganic materials such as silica, alumina, calcium carbonate, wollastonite, and mica, semi-cured or cured products of phenolic resin, and cured products of polyimide, polyphenylene sulfone, or polyether sulfone. Organic materials such as These can be used as fine powders of any particle size. This filler is an important component in the present invention, and a composition lacking this filler cannot achieve the purpose of the present invention. The amount of this filler is in the range of 30 to 250 parts by weight based on 100 parts by weight of the total amount of components (A) and (B). If the amount used is less than 30 parts by weight, shrinkage and curing shrinkage of the cured product cannot be sufficiently prevented, and cracks and cracks are likely to occur, and the powder material may flow out during the painting and curing process. Sagging occurs, making it difficult to obtain a uniform cured coating. Moreover, if it exceeds 250 parts by weight, the wettability to the adherend will be poor, a smooth coating film will not be obtained, and the adhesion will also deteriorate. The composition of the present invention essentially comprises (A) to (D) as described above.
However, if necessary, any component may be included within the range that does not impede the object of the present invention. Examples of optional components include pigments, curing accelerators, heat resistance imparting agents, anti-sagging agents, dispersion aids,
Examples include coating film modifiers and flame retardant imparting agents. The composition of the present invention can be prepared in substantially the same manner as conventional powder compositions. Specifically, it can be prepared by uniformly kneading the above components (A) to (D) (this may be done mechanically) and then pulverizing the mixture to a desired particle size as necessary. (Effects of the Invention) The cured product obtained from the composition of the present invention has an excellent balance of heat resistance and mechanical strength. When curing, it is possible to cure at a relatively low temperature and in a short time without the need for high temperature and long-time heating as in conventional methods, so there is no negative effect on viscosity, and as a result, a good cured product can be obtained. . The cured product has excellent adhesion or adhesion to painted surfaces of various materials such as metals and ceramics. By using the composition of the present invention, the intended purpose can be achieved without using modified compounds whose synthesis is complicated as constituent components. The composition of the present invention can be widely used as a molding material, a laminated material (as a binder), a sealing material, an adhesive material, an insulating material, and the like. (Examples and Comparative Examples) Next, Examples and Comparative Examples of the present invention will be given, but the present invention is not limited to these Examples. Note that all parts in the examples indicate parts by weight. Examples 1 to 14 and Comparative Examples 1 to 10 A maleimide compound, an initial condensate of the maleimide compound, an epoxy resin, a curing agent, and a filler were uniformly mixed using a kneader in the proportions shown in Table 1 below. . Then, it was pulverized by a conventional method to obtain a particle size distribution suitable for powder coating. When various physical properties of this pulverized product were investigated, the results shown in Table 1 below were obtained. The measurement method and evaluation of each physical property are shown below. (1) Gelation time Approximately 0.1 to 0.2 g of powder is filled into a circular recess of a metal plate heated to 150°C, and the time (seconds) it takes for the powder to gel is measured, and this is calculated as the gelation time. (based on JIS C2104). (2) Presence or absence of cracks An iron plate (20 mm x 150
The powder was applied to the area (mm x 3.2 mm). The coating amount was such that the film thickness after curing would be 0.3 to 0.5 mm. When the iron plate was kept at the same temperature and then cooled, a cured coating film was obtained. This cured coating film was examined for the occurrence of cracks. (3) Tensile shear strength Pre-degreased test piece (mild steel plate 100 x 20
The adhesive strength (shear strength) was measured at 3 mm). However, the tensile speed was set to 5 mm/min, and the measurement at high temperature was performed after holding the sample at the specified temperature for 10 minutes. The pressing force during crimping was 1Kg/15×10mm 2 or a pinch pressure equivalent to 1Kg/15×10mm 2 . (4) Heat Deflection Temperature (HDT) Test pieces were press-molded under specified conditions and heat-cured at 200°C for 1 hour and at 220°C for 1 hour. HDT of the obtained cured product was measured according to ASTM D648. (5) Heating weight loss rate The numerator of the heating weight loss rate as a fraction. Using differential thermal analysis, the amount of weight loss was calculated from the residue generated during 1 minute between 3 and 4 minutes after starting heating at 450°C. Ta. Denominator of fraction of heating weight loss rate The weight loss rate after heating at 350°C for 1 hour and 400°C for 20 minutes was determined by calculation.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
ビスマレイミド初期重合体:三菱油化社製、商品
名 MB−190M
ビスフエノールA型液状エポキシ樹脂:油化シエ
ルエポキシ社製、商品名 エピコート828
ビスフエノールA型固型エポキシ樹脂*1:油化
シエルエポキシ社製:商品名 エピコート1001
ビスフエノールA型固型エポキシ樹脂*2:油化
シエルエポキシ社製:商品名 エピコート1002
クレゾールノボラツク型エポキシ樹脂:旭化成社
製、商品名 ECN−280
C11Z−AZINE:2,4−ジアミノ−6−〔2−ウ
ンデシルイミダゾリル−(1)〕−エチル−S−ト
リアジン 四国化成社製商品名
C11Z−CNS:1−シアノエチル−2−ウンデシ
ルイミダゾリウムトリメリテート、四国化成社
製商品名
2MZ−AZINE:2,4−ジアミノ−6−〔2−メ
チルイミダゾリル(1)〕−エチル−S−トリアジ
ン、四国化成社製商品名
アルミナ微粉末:太平洋ランダム社製、商品名
LA−1200
シリカ微粉末:龍森社製、商品名A−1
けい酸カルシウム微粉末*1:龍森社製、商品名
SW−400
けい酸カルシウム微粉末*2:丸和バイオケミカ
ル社製、商品名 ASB−4
ガラス粉末:日本フエロー社製、商品名 XD−
9A−M
マイカ:白石カルシウム社製、商品名 C−1000
アクリル酸エステルオリゴマー:日本カーバイド
工業社製、商品名 XK−21[Table] Bismaleimide initial polymer: manufactured by Mitsubishi Yuka Co., Ltd., trade name MB-190M Bisphenol A type liquid epoxy resin: manufactured by Yuka Ciel Epoxy Co., Ltd., trade name Epicoat 828 Bisphenol A type solid epoxy resin *1: Manufactured by Yuka Ciel Epoxy Co., Ltd.: Product name Epicoat 1001 Bisphenol A type solid epoxy resin *2: Manufactured by Yuka Ciel Epoxy Co., Ltd.: Product name Epicoat 1002 Cresol novolac type epoxy resin: Manufactured by Asahi Kasei Co., Ltd., product name ECN-280 C 11 Z-AZINE: 2,4-diamino-6-[2-undecylimidazolyl-(1)]-ethyl-S-triazine Manufactured by Shikoku Kasei Co., Ltd. Product name C 11 Z-CNS: 1-cyanoethyl-2-undecyl Imidazolium trimellitate, product name manufactured by Shikoku Kasei Co., Ltd. 2MZ-AZINE: 2,4-diamino-6-[2-methylimidazolyl(1)]-ethyl-S-triazine, product name manufactured by Shikoku Kasei Co., Ltd. Alumina fine powder: Manufactured by Pacific Random Co., Ltd., product name
LA-1200 Silica fine powder: Manufactured by Ryumori Co., Ltd., trade name A-1 Calcium silicate fine powder *1: Manufactured by Ryumori Co., Ltd., trade name
SW-400 Calcium silicate fine powder *2: Manufactured by Maruwa Biochemical Co., Ltd., product name ASB-4 Glass powder: Manufactured by Nippon Fellow Co., Ltd., product name XD-
9A-M Mica: Shiraishi Calcium Co., Ltd., product name C-1000 Acrylic acid ester oligomer: Nippon Carbide Kogyo Co., Ltd., product name XK-21
Claims (1)
マレイミド化合物及び又はその初期縮合物10〜90
重量部、(B)エポキシ樹脂90〜10重量部、(C)ジシア
ンジアミド類−イミダゾール類混合系の少なくと
も1種からなる硬化剤の有効量、並びに、(D)充て
ん材30〜250重量部を含む熱硬化性粉体。1 (A) Maleimide compound having at least one imide group in the molecule and/or its initial condensate 10-90
parts by weight, (B) 90 to 10 parts by weight of an epoxy resin, (C) an effective amount of a curing agent consisting of at least one type of dicyandiamide-imidazole mixed system, and (D) 30 to 250 parts by weight of a filler. Thermosetting powder.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15199786A JPS638414A (en) | 1986-06-28 | 1986-06-28 | Thermosetting powder composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP15199786A JPS638414A (en) | 1986-06-28 | 1986-06-28 | Thermosetting powder composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS638414A JPS638414A (en) | 1988-01-14 |
JPH0528726B2 true JPH0528726B2 (en) | 1993-04-27 |
Family
ID=15530807
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP15199786A Granted JPS638414A (en) | 1986-06-28 | 1986-06-28 | Thermosetting powder composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS638414A (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3287348B2 (en) | 1999-12-17 | 2002-06-04 | ソニーケミカル株式会社 | Polyamic acid varnish composition and flexible printed circuit board |
GB0412196D0 (en) | 2004-06-02 | 2004-07-07 | Hexcel Composites Ltd | Cure accelerators |
FR2941557B1 (en) * | 2009-01-29 | 2011-03-25 | Commissariat Energie Atomique | PROCESS FOR PREPARING AN ELECTRICITY CONDUCTING ARTICLE |
JP2011105945A (en) * | 2011-01-04 | 2011-06-02 | Hitachi Chem Co Ltd | Method for producing curing agent, and thermosetting resin composition using the same |
JP7002645B2 (en) | 2018-05-09 | 2022-01-20 | 三菱電機株式会社 | Power semiconductor devices, their manufacturing methods, and power conversion devices |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5040628A (en) * | 1973-07-19 | 1975-04-14 | ||
JPS5087125A (en) * | 1973-12-05 | 1975-07-14 | ||
JPS50134098A (en) * | 1974-04-15 | 1975-10-23 | ||
JPS52119698A (en) * | 1976-04-01 | 1977-10-07 | Hitachi Ltd | Resin compositions |
JPS6173724A (en) * | 1984-09-20 | 1986-04-15 | Mitsubishi Petrochem Co Ltd | Resin composition |
JPS61103921A (en) * | 1984-10-29 | 1986-05-22 | Mitsubishi Petrochem Co Ltd | Thermosetting resin composition |
-
1986
- 1986-06-28 JP JP15199786A patent/JPS638414A/en active Granted
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5040628A (en) * | 1973-07-19 | 1975-04-14 | ||
JPS5087125A (en) * | 1973-12-05 | 1975-07-14 | ||
JPS50134098A (en) * | 1974-04-15 | 1975-10-23 | ||
JPS52119698A (en) * | 1976-04-01 | 1977-10-07 | Hitachi Ltd | Resin compositions |
JPS6173724A (en) * | 1984-09-20 | 1986-04-15 | Mitsubishi Petrochem Co Ltd | Resin composition |
JPS61103921A (en) * | 1984-10-29 | 1986-05-22 | Mitsubishi Petrochem Co Ltd | Thermosetting resin composition |
Also Published As
Publication number | Publication date |
---|---|
JPS638414A (en) | 1988-01-14 |
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