JP2007039685A - Modified layered clay, novolac epoxy resin composite material containing the modified layered clay, and method for producing the same - Google Patents
Modified layered clay, novolac epoxy resin composite material containing the modified layered clay, and method for producing the same Download PDFInfo
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- 239000004927 clay Substances 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 239000004843 novolac epoxy resin Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000003822 epoxy resin Substances 0.000 claims abstract description 44
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 44
- 229920003986 novolac Polymers 0.000 claims abstract description 41
- 239000003607 modifier Substances 0.000 claims abstract description 18
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 imidazole compound Chemical class 0.000 claims abstract description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000011229 interlayer Substances 0.000 claims description 17
- 229960000686 benzalkonium chloride Drugs 0.000 claims description 14
- CADWTSSKOVRVJC-UHFFFAOYSA-N benzyl(dimethyl)azanium;chloride Chemical compound [Cl-].C[NH+](C)CC1=CC=CC=C1 CADWTSSKOVRVJC-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 229910021647 smectite Inorganic materials 0.000 claims description 4
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910000273 nontronite Inorganic materials 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 2
- NJQHZENQKNIRSY-UHFFFAOYSA-N 5-ethyl-1h-imidazole Chemical compound CCC1=CNC=N1 NJQHZENQKNIRSY-UHFFFAOYSA-N 0.000 claims description 2
- XHLKOHSAWQPOFO-UHFFFAOYSA-N 5-phenyl-1h-imidazole Chemical compound N1C=NC=C1C1=CC=CC=C1 XHLKOHSAWQPOFO-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 2
- 238000005341 cation exchange Methods 0.000 claims description 2
- 229910000271 hectorite Inorganic materials 0.000 claims description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 229910052902 vermiculite Inorganic materials 0.000 claims description 2
- 239000010455 vermiculite Substances 0.000 claims description 2
- 235000019354 vermiculite Nutrition 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 229910052570 clay Inorganic materials 0.000 description 60
- 239000000463 material Substances 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000002114 nanocomposite Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- WTFAGPBUAGFMQX-UHFFFAOYSA-N 1-[2-[2-(2-aminopropoxy)propoxy]propoxy]propan-2-amine Chemical compound CC(N)COCC(C)OCC(C)OCC(C)N WTFAGPBUAGFMQX-UHFFFAOYSA-N 0.000 description 1
- GMQVFHZSXKJCIV-UHFFFAOYSA-N 2,2,2-trifluoro-n-(2,2,2-trifluoroacetyl)acetamide Chemical compound FC(F)(F)C(=O)NC(=O)C(F)(F)F GMQVFHZSXKJCIV-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-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
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 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 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
【課題】粘土−ノボラックエポキシ樹脂複合材料を提供する。
【解決手段】本発明に係る粘土−ノボラックエポキシ樹脂複合材料は、ノボラックエポキシ樹脂と、該ノボラックエポキシ樹脂中に均一に分散する改質型層状粘土とを含む。該改質型層状粘土は、イミダゾール化合物および４級アンモニウム塩を含む２つの改質剤がインターカレートされている。また、本発明は、基板に用いられる粘土−ノボラックエポキシ樹脂複合材料の製造方法も提供する。
【選択図】なしA clay-novolac epoxy resin composite material is provided.
A clay-novolac epoxy resin composite material according to the present invention includes a novolac epoxy resin and a modified layered clay that is uniformly dispersed in the novolac epoxy resin. In the modified layered clay, two modifiers including an imidazole compound and a quaternary ammonium salt are intercalated. Moreover, this invention also provides the manufacturing method of the clay- novolak epoxy resin composite material used for a board | substrate.
[Selection figure] None
Description
本発明はナノ複合材料に関し、特に粘土−ノボラックエポキシ樹脂ナノ複合材料およびその製造方法に関するものである。 The present invention relates to a nanocomposite material, and more particularly, to a clay-novolak epoxy resin nanocomposite material and a method for producing the same.
電子パッケージとは、作製が完了した半導体集積回路を他の電子素子と共に１つの配線構造中に実装して電子製品とすることにより特定の設計・機能を実現させる全てのプロセスのことをいう。電子パッケージの主な機能は４つあり、それは、電力供給（power distribution）、信号伝送（signal distribution）、放熱（heat dissipation）、および保護と保持（protect and support）である。 An electronic package refers to all processes for realizing a specific design / function by mounting a semiconductor integrated circuit, which has been completed, together with other electronic elements in one wiring structure to form an electronic product. The electronic package has four main functions: power distribution, signal distribution, heat dissipation, and protect and support.
電子パッケージのうち、高分子材料が最も多く応用されているのはプリント回路板である。電子素子を組み合わせてなるプリント回路板は、ほとんどが複合材料の積層板からなっており、所望のプリント回路板を得るために、その外層銅箔にはさらにエッチングが施される。この複合材料は、強化繊維（例えばガラス繊維、炭素繊維または有機繊維など）と樹脂（熱硬化性樹脂または熱塑性樹脂）を結合させてなる一種の構造材料である。複合材料は優れた機械強度を持つのみならず、同時に極めて高い寸法安定性をも有している。現在、プリント回路板の材料においては、強化繊維としてガラス材料が最も一般的に用いられ、また、樹脂としては、その寸法安定性と耐熱性が熱塑性樹脂よりも優れることから、熱硬化性樹脂が主に用いられている。そして、熱硬化性樹脂の中で最も多く用いられているのはエポキシ樹脂である。 Among electronic packages, printed circuit boards have the most application of polymer materials. A printed circuit board formed by combining electronic elements is mostly composed of a laminate of composite materials, and the outer layer copper foil is further etched to obtain a desired printed circuit board. This composite material is a kind of structural material formed by bonding reinforcing fibers (such as glass fibers, carbon fibers, or organic fibers) and a resin (thermosetting resin or thermoplastic resin). Composite materials not only have excellent mechanical strength, but also have extremely high dimensional stability. Currently, in printed circuit board materials, glass materials are most commonly used as reinforcing fibers, and as resins, dimensional stability and heat resistance are superior to thermoplastic resins. Mainly used. The most frequently used thermosetting resin is an epoxy resin.
ナノ複合材料（Nanocomposite）は、分散相の粒径が１〜１００ｎｍの間にある複合材料である。かかるナノ複合材料は、その小粒径、高アスペクト比、層状強化構造、イオン結合などといった分子スケール故の構造的特性により、補強材の含量を低減させて軽量化をもたらすことができると共に、高強度、高剛性、高耐熱性、低吸水率、低通気率などの特性も備え持つ高性能材料である。 A nanocomposite is a composite material with a dispersed phase particle size between 1 and 100 nm. Such nanocomposites can reduce the amount of reinforcing material and reduce the weight due to the structural characteristics due to the molecular scale such as small particle size, high aspect ratio, layered reinforcement structure, ionic bond, etc. It is a high-performance material that has properties such as strength, high rigidity, high heat resistance, low water absorption, and low air permeability.
パッケージ材料として用いられるエポキシ樹脂には、従来より、低応力、高熱伝導性、高耐熱性、耐湿性、耐腐食性、および電気特性などの性質を備えることが要求されている。そして、これらの性質に対する要求は、今日益々厳しくなってきている。 An epoxy resin used as a package material has conventionally been required to have properties such as low stress, high thermal conductivity, high heat resistance, moisture resistance, corrosion resistance, and electrical characteristics. And the demands for these properties are becoming increasingly severe today.
特許文献１には、約２〜１３％のＤＧＥＢＡと、４０〜７０％のフェノールホルムアルデヒド樹脂を含む２種類の異なるエポキシ樹脂を用いることで、温度−６５℃〜１５０℃の範囲で熱による劣化を起こさないエポキシ樹脂を作製できることが開示されている。当該文献においては、２種類の異なる樹脂の割合を調整することを通して良好な熱安定性が実現されている。 Patent Document 1 uses two different types of epoxy resins including about 2 to 13% DGEBA and 40 to 70% phenol formaldehyde resin, thereby preventing deterioration due to heat in a temperature range of −65 ° C. to 150 ° C. It is disclosed that an epoxy resin that does not occur can be produced. In this document, good thermal stability is realized through adjusting the ratio of two different resins.
特許文献２には、２種類の異なる硬化剤、ＢＤＭＡおよびＢＴＦＡにより、同一のエポキシ樹脂（ＤＧＥＢＡ）で合成されたナノ複合材料を架橋させることが開示されており、その層間距離は１００Åよりも大きいとされている。 Patent Document 2 discloses cross-linking of nanocomposites synthesized with the same epoxy resin (DGEBA) using two different curing agents, BDMA and BTFA, and the interlayer distance is greater than 100 mm. It is said that.
特許文献３には、改質剤が粘土の層間で分散する形態には５種類あり、それら形態のうち分散が均一であるほど、剥離（exfoliated）を形成する確率が高くなるということが開示されている。さらに当該文献は、分散性が最も良いものは、引っ張り強さと引っ張り係数にも最も優れるとしている。 Patent Document 3 discloses that there are five types of forms in which the modifier is dispersed between clay layers, and the more uniformly the form is dispersed, the higher the probability of forming exfoliated. ing. Furthermore, the document states that the best dispersibility is the best in tensile strength and tensile modulus.
特許文献４には、ジファミン（JEFFAMINE）のＤ２３０、Ｄ４００、Ｄ４０００、Ｔ３０４、Ｔ３０００およびＴ５０００（分子鎖長が異なる）を含む多くの異なる硬化剤によって、各種エポキシ樹脂−粘土ナノ複合材料を作製することが開示されており、このうちＴ５０００（分子鎖が最長）で作ったものの層間距離（d-spacing）が最も大きいとされている。 In Patent Document 4, various epoxy resin-clay nanocomposites are prepared with many different curing agents including JEFFAMINE D230, D400, D4000, T304, T3000 and T5000 (different molecular chain lengths). Among them, those made of T5000 (longest molecular chain) are said to have the largest interlayer distance (d-spacing).
特許文献５には、エポキシ樹脂、硬化剤およびモンモリロナイトの比率がＤＤＰ／ＤＥＲ３３１／ＭＭＴ＝１：１：０．７５であるときに層間距離は３４．３８Åであり、比率を１：３：２．５に変えると層間距離は３２．９２Åとなり、また、長い炭素鎖の改質剤に置き換えて用いると層間距離は最も拡げられ、かつ機械特性およびガラス転移温度も改善を得るということが開示されている。 In Patent Document 5, when the ratio of epoxy resin, curing agent and montmorillonite is DDP / DER331 / MMT = 1: 1: 0.75, the interlayer distance is 34.38 mm, and the ratio is 1: 3: 2. When it is changed to 5, the interlayer distance becomes 32.92 mm, and when used in place of a long carbon chain modifier, the interlayer distance is most widened, and it is disclosed that the mechanical properties and the glass transition temperature are improved. Yes.
非特許文献１には、良好な分散性は微量の硬化剤ＭＰＤＡのみで得られ、濃度が高すぎるとインターカレートの現象が増加するという結果が提示されており、ＭＰＤＡの量が多すぎると分散性が低下することがＸＲＤ（Ｘ線回折装置）により観察されている。また、層間距離はＭＰＤＡによって３４．５〜１８０Åに制御可能であると述べられている。 Non-Patent Document 1 shows that good dispersibility can be obtained only with a small amount of the curing agent MPDA, and the intercalation phenomenon increases when the concentration is too high. If the amount of MPDA is too large, It has been observed by XRD (X-ray diffractometer) that the dispersibility decreases. Further, it is stated that the interlayer distance can be controlled to 34.5 to 180 mm by MPDA.
非特許文献２には、硬化剤ＢＤＭＡを３％および５％でそれぞれ加え、１８０℃、にて１時間硬化させたところ、粘土のピークは２〜１０°で検出されなかったとされている。一方、Ｎ-Ｎ-ジメチルベンジルアミン（N-N-dimethyl benzylamine）を触媒または促進剤として用いると（ＤＭＢＡを結合剤とする）、ＸＲＤ分析により、同一の硬化条件下における触媒の適度な添加は剥離を起こし易くするということが確認できた、と述べられている。
本発明の目的は、機械特性、および低吸湿率、高耐熱性、高寸法安定性などパッケージ材料に要求される特性を大幅に改善できる改質型層状粘土、該改質型層状粘土を含むノボラックエポキシ樹脂複合材料、およびその製造方法を提供することにある。 An object of the present invention is to provide a modified layered clay capable of greatly improving mechanical properties and properties required for a package material such as a low moisture absorption rate, high heat resistance, and high dimensional stability, and a novolak containing the modified layered clay An object of the present invention is to provide an epoxy resin composite material and a method for producing the same.
本発明者らは、上述したパッケージ材料の性質に対する要求が益々厳しいものとなってきている状況に鑑み、鋭意研究の結果、ナノ複合材料が備える優れた特性をパッケージ材料上に応用することに成功し、本発明を完成させるに至った。 The present inventors have succeeded in applying the superior characteristics of nanocomposite materials to package materials as a result of diligent research in view of the situation where the requirements for the properties of the package materials described above are becoming increasingly severe. As a result, the present invention has been completed.
本発明では、先ず、網目形成を促進する２−フェニルイミダゾール（２−ＰＩ）を粘土にインターカレートし改質させてから、無機層材料をエポキシ樹脂中に分散させ、無機層材料の層間で高分子網目の形成が起こるようにする。こうすることによって、ナノスケールのハイブリダイゼーション効果が機械特性を強化させ、かつ、パッケージ材料に求められる、例えば低吸湿率、高耐熱性、高寸法安定性などといった特性が大幅に改善されることとなる。 In the present invention, first, 2-phenylimidazole (2-PI) that promotes network formation is intercalated and modified in clay, and then the inorganic layer material is dispersed in the epoxy resin, and between the layers of the inorganic layer material. Allow the formation of a polymer network. By doing this, the nanoscale hybridization effect enhances the mechanical properties, and the properties required for the packaging material, such as low moisture absorption, high heat resistance, and high dimensional stability, are greatly improved. Become.
すなわち、本発明は、イミダゾール化合物および４級アンモニウム塩を含む２つの改質剤がインターカレートされた層状粘土を含んでなる改質型層状粘土を提供する。 That is, the present invention provides a modified layered clay comprising a layered clay in which two modifiers including an imidazole compound and a quaternary ammonium salt are intercalated.
また本発明は、ノボラックエポキシ樹脂と、該ノボラックエポキシ樹脂中に均一に分散する上記改質型層状粘土と、を含む粘土−ノボラックエポキシ樹脂複合材料を提供する。 The present invention also provides a clay-novolac epoxy resin composite material including a novolac epoxy resin and the modified layered clay dispersed uniformly in the novolac epoxy resin.
また本発明は、粘土−ノボラックエポキシ樹脂複合材料の製造方法を提供する。該方法は、上記改質型層状粘土を準備する工程、該改質型層状粘土と硬化剤を混合する工程、および、その硬化剤を含有した改質型層状粘土をノボラックエポキシ樹脂と架橋反応させて、該改質型層状粘土を該ノボラックエポキシ樹脂中に均一に分散させ、粘土−ノボラックエポキシ樹脂複合材料を形成する工程、を含む。 The present invention also provides a method for producing a clay-novolak epoxy resin composite material. The method includes a step of preparing the modified layered clay, a step of mixing the modified layered clay and a curing agent, and a crosslinking reaction of the modified layered clay containing the curing agent with a novolac epoxy resin. And the step of uniformly dispersing the modified layered clay in the novolac epoxy resin to form a clay-novolac epoxy resin composite material.
本発明の改質型層状粘土、該改質型層状粘土を含むノボラックエポキシ樹脂複合材料、およびその製造方法によれば、機械特性が強化されると共に、パッケージ材料に求められる、低吸湿率、高耐熱性、高寸法安定性などといった特性が大幅に改善される。 According to the modified layered clay of the present invention, the novolac epoxy resin composite material containing the modified layered clay, and the method for producing the same, the mechanical properties are enhanced, and the low moisture absorption rate, the high Properties such as heat resistance and high dimensional stability are greatly improved.
本発明は改質型層状粘土を提供するものである。該改質型層状粘土は、イミダゾール化合物および４級アンモニウム塩を含む２つの改質剤がインターカレートされた層状粘土を含んでいる。 The present invention provides a modified layered clay. The modified layered clay includes a layered clay in which two modifiers including an imidazole compound and a quaternary ammonium salt are intercalated.
上述の２つの改質剤は、同比率で混合されて層状粘土中にインターカレートされ、その層状粘土における重量パーセントは約１０〜４０ｗｔ％である。イミダゾール化合物には、２−メチルイミダゾール、４−メチルイミダゾール、２−エチルイミダゾール、４−エチルイミダゾール、２−フェニルイミダゾール、または４−フェニルイミダゾールが含まれる。４級アンモニア塩には塩化ベンザルコニウム（benzalkonium chloride,ＢＥＮ）が含まれる。層状粘土には、スメクタイト粘土（smectite clay）、バーミキュライト（vermiculite）、ハロイサイト（halloysite）、セリサイト（sericite）またはマイカ（mica）が含まれ、スメクタイト粘土には、モンモリロナイト（montmorillonite）、サポナイト（saponite）、バイデライト（beidellite）、ノントロナイト（nontronite）またはヘクトライト（hectorite）が含まれる。本発明における層状粘土の陽イオン交換容量（ＣＥＣ）は約５０〜２００ｍｅｑ／１００ｇである。また、改質型層状粘土の層間距離は１６Åよりも大きい。 The two modifiers described above are mixed in the same ratio and intercalated into the layered clay, with the weight percent in the layered clay being about 10-40 wt%. The imidazole compound includes 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, 4-ethylimidazole, 2-phenylimidazole, or 4-phenylimidazole. Quaternary ammonia salts include benzalkonium chloride (BEN). Layered clay includes smectite clay, vermiculite, halloysite, sericite or mica, and smectite clay includes montmorillonite and saponite. , Beidellite, nontronite or hectorite. The cation exchange capacity (CEC) of the layered clay in the present invention is about 50 to 200 meq / 100 g. The interlayer distance of the modified layered clay is greater than 16 mm.
本発明はさらに粘土−ノボラックエポキシ樹脂複合材料を提供する。該複合材料は、ノボラックエポキシ樹脂と、該ノボラックエポキシ樹脂中に均一に分散する上記改質型層状粘土と、を含む。 The present invention further provides a clay-novolak epoxy resin composite. The composite material includes a novolac epoxy resin and the modified layered clay that is uniformly dispersed in the novolac epoxy resin.
ノボラックエポキシ樹脂にはビスフェノールＡノボラックエポキシ樹脂が含まれ、その固形分は約９３〜９９．５％である。上記改質型層状粘土には、例えばフェノールノボラック（phenolic novolak）樹脂またはテトラブロモビスフェノールＡ（tetrabromo bisphenol A）樹脂である硬化剤がさらにインターカレートされており、その含量は約１５〜３０％である。複合材料中、硬化剤とノボラックエポキシ樹脂との重量比は約０．２〜０．５であり、改質型層状粘土は全複合材料の約０．５〜７重量パーセントを占める。 The novolac epoxy resin includes bisphenol A novolac epoxy resin, and its solid content is about 93-99.5%. The modified layered clay is further intercalated with a curing agent such as phenolic novolak resin or tetrabromobisphenol A resin, and the content thereof is about 15 to 30%. is there. In the composite material, the weight ratio of curing agent to novolac epoxy resin is about 0.2 to 0.5, and the modified layered clay accounts for about 0.5 to 7 weight percent of the total composite material.
本発明の複合材料の層間距離は５０Åよりも大きい。また、その吸水率は０．６％よりも低く、銅箔の剥離強度は６ｌｂ／ｉｎよりも大きく、ガラス転移温度（Ｔｇ）は摂氏１３０℃よりも高く、ガラス転移温度前の熱膨張係数（coefficient of thermal expansion,ＣＴＥ）は６０ｐｐｍ／℃よりも低い。 The interlayer distance of the composite material of the present invention is greater than 50 mm. Further, the water absorption is lower than 0.6%, the peel strength of the copper foil is higher than 6 lb / in, the glass transition temperature (Tg) is higher than 130 ° C., and the thermal expansion coefficient before the glass transition temperature ( The coefficient of thermal expansion (CTE) is lower than 60 ppm / ° C.
本発明はさらに粘土−ノボラックエポキシ樹脂複合材料の製造方法を提供する。該方法は次の工程を含む。先ず、上記改質型層状粘土を準備してから、改質型層状粘土を硬化剤と混合し、続いて、その硬化剤を含有した改質型層状粘土をノボラックエポキシ樹脂と架橋反応させて改質型層状粘土をノボラックエポキシ樹脂中に均一に分散させ、粘土−ノボラックエポキシ樹脂複合材料を形成する。 The present invention further provides a method for producing a clay-novolak epoxy resin composite. The method includes the following steps. First, after preparing the modified layered clay, the modified layered clay is mixed with a curing agent, and then the modified layered clay containing the curing agent is subjected to a crosslinking reaction with a novolac epoxy resin. The layered clay is uniformly dispersed in the novolac epoxy resin to form a clay-novolac epoxy resin composite material.
本発明に係る粘土−ノボラックエポキシ樹脂複合材料は、銅張積層板の作製に用いることもできる。銅張積層板の作製方法は次の工程を含む。先ず、粘土−ノボラックエポキシ樹脂複合材料とガラス繊維布を含浸槽中に浸す。続いて、含浸させたガラス繊維布を摂氏約１７０〜１９０℃のオーブンに入れ、約３〜５分かけてフィルムに形成する。その後、フィルムを切断、積層および加熱プレスする。最後に縁をトリミングしたら、粘土−ノボラックエポキシ樹脂複合材料を含む銅張積層板（copper clad laminate,ＣＣＬ）の作製は完了である。 The clay-novolak epoxy resin composite material according to the present invention can also be used for producing a copper-clad laminate. The method for producing a copper clad laminate includes the following steps. First, a clay-novolak epoxy resin composite material and a glass fiber cloth are immersed in an impregnation tank. Subsequently, the impregnated glass fiber cloth is placed in an oven at about 170-190 ° C. and formed into a film over about 3-5 minutes. Thereafter, the film is cut, laminated and heated. Finally, after trimming the edges, the preparation of a copper clad laminate (CCL) containing the clay-novolak epoxy resin composite is complete.
以下にいくつかの実施例を挙げて、本発明の特徴と長所をより詳細に説明する。 The features and advantages of the present invention will be described in more detail below with reference to some examples.
（実施例１）
改質型層状粘土（ＰＫ−８０５）の作製
先ず、ＰＫ−８０５粘土（ノントロナイト）３０ｇを脱イオン水２７００ｍｌ中に入れ、一晩撹拌し、膨潤処理した。同時に、同比率の２−フェニルイミダゾール（２−ＰＩ）と塩化ベンザルコニウム（ＢＥＮ）を適量の脱イオン水中に加え、完全に溶解するまで撹拌することで、適量の改質剤を作った。続いて、この改質剤を上述の粘土溶液にゆっくり加えてから、１Ｎ塩酸でｐＨ値を３〜４の間に調整し、一晩撹拌した。その後、その溶液を遠心瓶に入れて遠心分離し、遠心分離が終わったら、水溶液を捨てて下層に沈殿した粘土を回収し、さらに脱イオン水により膨潤させ、撹拌した。そして、上層の水溶液に硝酸銀を滴下しても塩化銀の白色沈殿物が生じなくなるまで、遠心分離を数回繰り返して行った。次いで、下層の粘土を冷蔵庫に放置した後、さらに冷凍乾燥機に入れ完全に乾燥させて、本発明の改質型層状粘土の作製を完了した。この改質型層状粘土の層間距離は１８．０１Åであった。改質剤を同比率で混合した２−メチルイミダゾール（２−ＭＩ）と塩化ベンザルコニウム （ＢＥＮ）に置き換えたところ、できた改質型層状粘土の層間距離は１７．６５Åとなった。
Example 1
Preparation of modified layered clay (PK-805) First, 30 g of PK-805 clay (nontronite) was placed in 2700 ml of deionized water and stirred overnight to swell. At the same time, the same amount of 2-phenylimidazole (2-PI) and benzalkonium chloride (BEN) were added to an appropriate amount of deionized water and stirred until completely dissolved to produce an appropriate amount of modifier. Subsequently, this modifier was slowly added to the above clay solution, and then the pH value was adjusted to between 3 and 4 with 1N hydrochloric acid and stirred overnight. Then, the solution was put into a centrifuge bottle and centrifuged, and when the centrifugation was completed, the aqueous solution was discarded and the clay precipitated in the lower layer was collected, further swollen with deionized water, and stirred. Centrifugation was repeated several times until no silver chloride white precipitate was formed even when silver nitrate was dropped into the upper aqueous solution. Next, after the lower layer clay was left in the refrigerator, it was further placed in a freeze dryer and completely dried to complete the production of the modified layered clay of the present invention. The interlayer distance of this modified layered clay was 18.01 mm. When the modifier was replaced with 2-methylimidazole (2-MI) and benzalkonium chloride (BEN) mixed at the same ratio, the interlayer distance of the resulting modified layered clay was 17.65 mm.
（実施例２）
改質型層状粘土（ＰＫ−８０２）の作製
先ず、ＰＫ−８０２粘土（モンモリロナイト）３０ｇを脱イオン水２７００ｍｌ中に入れ、一晩撹拌し、膨潤処理した。同時に、同比率の２−フェニルイミダゾールと塩化ベンザルコニウムを適量の脱イオン水中に加え、完全に溶解するまで撹拌することで、適量の改質剤を作った。続いて、この改質剤を上述の粘土溶液にゆっくり加えてから、１Ｎ塩酸でｐＨ値を３〜４の間に調整し、一晩撹拌した。その後、その溶液を遠心瓶に入れて遠心分離し、遠心分離が終わったら、水溶液を捨てて下層に沈殿した粘土を回収し、さらに脱イオン水により膨潤させ、撹拌した。そして、上層の水溶液に硝酸銀を滴下しても塩化銀の白色沈殿物が生じなくなるまで、遠心分離を数回繰り返して行った。次いで、下層の粘土を冷蔵庫に放置した後、さらに冷凍乾燥機に入れ完全に乾燥させて、本発明の改質型層状粘土の作製を完了した。この改質型層状粘土の層間距離は１７.１４Åであった。改質剤を同比率で混合した２−メチルイミダゾール（２−ＭＩ）と塩化ベンザルコニウム （ＢＥＮ）に置き換えたところ、できた改質型層状粘土の層間距離は１６．０５Åとなった。
(Example 2)
Production of Modified Layered Clay (PK-802) First, 30 g of PK-802 clay (montmorillonite) was placed in 2700 ml of deionized water and stirred overnight to swell. At the same time, the same amount of 2-phenylimidazole and benzalkonium chloride were added to an appropriate amount of deionized water and stirred until completely dissolved to make an appropriate amount of modifier. Subsequently, this modifier was slowly added to the above clay solution, and then the pH value was adjusted to between 3 and 4 with 1N hydrochloric acid and stirred overnight. Then, the solution was put into a centrifuge bottle and centrifuged, and when the centrifugation was completed, the aqueous solution was discarded and the clay precipitated in the lower layer was collected, further swollen with deionized water, and stirred. Centrifugation was repeated several times until no silver chloride white precipitate was formed even when silver nitrate was dropped into the upper aqueous solution. Next, after the lower layer clay was left in the refrigerator, it was further placed in a freeze dryer and completely dried to complete the production of the modified layered clay of the present invention. The interlayer distance of this modified layered clay was 17.14 mm. When the modifier was replaced with 2-methylimidazole (2-MI) and benzalkonium chloride (BEN) mixed at the same ratio, the interlayer distance of the resulting modified layered clay was 16.05 mm.
（実施例３）
改質型層状粘土（Ｋｕｎｉｐｉａ−Ｆ）の作製
先ず、Ｋｕｎｉｐｉａ−Ｆ粘土（モンモリロナイト）３０ｇを脱イオン水２７００ｍｌ中に入れ、一晩撹拌し、膨潤処理した。同時に、同比率の２−フェニルイミダゾールと塩化ベンザルコニウムを適量の脱イオン水中に加え、完全に溶解するまで撹拌することで、適量の改質剤を作った。続いて、この改質剤を上述の粘土溶液にゆっくり加えてから、１Ｎ塩酸でｐＨ値を３〜４の間に調整し、一晩撹拌した。その後、その溶液を遠心瓶に入れて遠心分離し、遠心分離が終わったら、水溶液を捨てて下層に沈殿した粘土を回収し、さらに脱イオン水により膨潤させ、撹拌した。そして、上層の水溶液に硝酸銀を滴下しても塩化銀の白色沈殿物が生じなくなるまで、遠心分離を数回繰り返して行った。次いで、下層の粘土を冷蔵庫に放置した後、さらに冷凍乾燥機に入れ完全に乾燥させて、本発明の改質型層状粘土の作製を完了した。この改質型層状粘土の層間距離は１７．４８Åであった。改質剤を同比率で混合した２−メチルイミダゾール（２−ＭＩ）と塩化ベンザルコニウム（ＢＥＮ）に置き換えたところ、できた改質型層状粘土の層間距離は１７．６６Åとなった。
(Example 3)
Production of Modified Layered Clay (Kunipia-F) First, 30 g of Kunipia-F clay (montmorillonite) was placed in 2700 ml of deionized water and stirred overnight to swell. At the same time, the same amount of 2-phenylimidazole and benzalkonium chloride were added to an appropriate amount of deionized water and stirred until completely dissolved to make an appropriate amount of modifier. Subsequently, this modifier was slowly added to the above clay solution, and then the pH value was adjusted to between 3 and 4 with 1N hydrochloric acid and stirred overnight. Then, the solution was put into a centrifuge bottle and centrifuged, and when the centrifugation was completed, the aqueous solution was discarded and the clay precipitated in the lower layer was collected, further swollen with deionized water, and stirred. Centrifugation was repeated several times until no silver chloride white precipitate was formed even when silver nitrate was dropped into the upper aqueous solution. Next, after the lower layer clay was left in the refrigerator, it was further placed in a freeze dryer and completely dried to complete the production of the modified layered clay of the present invention. The interlayer distance of this modified layered clay was 17.48 mm. When the modifier was replaced with 2-methylimidazole (2-MI) and benzalkonium chloride (BEN) mixed at the same ratio, the interlayer distance of the resulting modified layered clay was 17.66 mm.
（実施例４）
ナノ複合材料の作製
先ず、適量のＰＫ−８０５改質粘土をプロピレングリコールモノメチルエーテル（propylene glycol monomethyl ether, ＰＭ）からなる溶剤中に加え、完全に溶解するまで撹拌した。次に、その粘土溶液中に適量の硬化剤−フェノールノボラック（phenolic novolac）樹脂を加えて混合しインターカレートさせた。続いて、その粘土溶液中にノボラックエポキシ（novolak epoxy）樹脂を加え、撹拌して均一に分散させた。そして、その樹脂溶液を型に流し込み、真空オーブンに入れて溶剤を除去した後、熱風循環オーブンに入れ１９０℃で９０分硬化させてから取り出し、本発明の粘土−ノボラックエポキシ樹脂複合材料の作製を完了させた。
Example 4
Preparation of Nanocomposite Material First, an appropriate amount of PK-805 modified clay was added to a solvent composed of propylene glycol monomethyl ether (PM) and stirred until completely dissolved. Next, an appropriate amount of a curing agent-phenolic novolac resin was added to the clay solution, mixed and intercalated. Subsequently, a novolak epoxy resin was added to the clay solution, and the mixture was stirred and dispersed uniformly. Then, the resin solution is poured into a mold, and after removing the solvent by putting it in a vacuum oven, it is put into a hot air circulating oven and cured at 190 ° C. for 90 minutes, and then taken out to prepare the clay-novolak epoxy resin composite material of the present invention. Completed.
以上、好適な実施例を挙げて説明したが、これらは本発明を限定するものではない。当業者であれば、本発明の精神および範囲を逸脱しない限りにおいて、変更および修飾を加えることができる。よって本発明の範囲は、添付の特許請求の範囲によって決まる。 The preferred embodiments have been described above, but these do not limit the present invention. Those skilled in the art can make changes and modifications without departing from the spirit and scope of the present invention. Accordingly, the scope of the invention is determined by the appended claims.
Claims (34)
前記改質型層状粘土と硬化剤を混合する工程、および
前記の硬化剤を含有した改質型層状粘土をノボラックエポキシ樹脂と架橋反応させて、前記改質型層状粘土を前記ノボラックエポキシ樹脂中に均一に分散させ、粘土−ノボラックエポキシ樹脂複合材料を形成する工程、
を含む粘土−ノボラックエポキシ樹脂複合材料の製造方法。 Preparing the modified layered clay according to claim 1;
A step of mixing the modified layered clay and a curing agent; and a crosslinking reaction of the modified layered clay containing the curing agent with a novolac epoxy resin, and the modified layered clay in the novolak epoxy resin Uniformly dispersing and forming a clay-novolak epoxy resin composite material,
A method for producing a clay-novolak epoxy resin composite material comprising:
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|---|---|---|---|
| TW094125895 | 2005-07-29 | ||
| TW094125895A TWI275579B (en) | 2005-07-29 | 2005-07-29 | Modified clay, novolac epoxy composite material including the modified clay and method of fabricating the same |
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| JP4903514B2 JP4903514B2 (en) | 2012-03-28 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2461172A (en) * | 2008-06-24 | 2009-12-30 | Univ Chung Yuan Christian | A modified clay for use in a fire retardant polymer composite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04292410A (en) * | 1991-03-20 | 1992-10-16 | Toyo Dorai Le-Bu Kk | Antibacterial antimycotic silicate having excellent durability |
| JPH10120414A (en) * | 1996-10-14 | 1998-05-12 | Toagosei Co Ltd | Antimicrobial lamellar silicate |
-
2005
- 2005-07-29 TW TW094125895A patent/TWI275579B/en not_active IP Right Cessation
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- 2006-07-26 JP JP2006203803A patent/JP4903514B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04292410A (en) * | 1991-03-20 | 1992-10-16 | Toyo Dorai Le-Bu Kk | Antibacterial antimycotic silicate having excellent durability |
| JPH10120414A (en) * | 1996-10-14 | 1998-05-12 | Toagosei Co Ltd | Antimicrobial lamellar silicate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2461172A (en) * | 2008-06-24 | 2009-12-30 | Univ Chung Yuan Christian | A modified clay for use in a fire retardant polymer composite |
| JP2010006695A (en) * | 2008-06-24 | 2010-01-14 | Chung Yuan Christian Univ | Modified clay and clay-polymer composite material |
| US8871339B2 (en) | 2008-06-24 | 2014-10-28 | Chung Yuan Christian University | Modified clay and clay-polymer composite |
| DE102009030248B4 (en) | 2008-06-24 | 2020-07-09 | Chung Yuan Christian University | Modified clay and clay-polymer composite |
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| TWI275579B (en) | 2007-03-11 |
| TW200704621A (en) | 2007-02-01 |
| JP4903514B2 (en) | 2012-03-28 |
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