TW201317301A - 低介電樹脂配方、預聚合物、組成物及其複合材料與低介電樹脂預聚合物溶液的製備方法 - Google Patents
低介電樹脂配方、預聚合物、組成物及其複合材料與低介電樹脂預聚合物溶液的製備方法 Download PDFInfo
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- low dielectric
- dielectric resin
- diisocyanate
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- 239000011347 resin Substances 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 238000009472 formulation Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 12
- -1 prepolymer Substances 0.000 title claims description 16
- 239000002131 composite material Substances 0.000 title abstract description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 108
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000004744 fabric Substances 0.000 claims description 17
- 239000003365 glass fiber Substances 0.000 claims description 17
- 239000000805 composite resin Substances 0.000 claims description 14
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000011342 resin composition Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- 239000002243 precursor Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 22
- 239000003292 glue Substances 0.000 description 17
- 239000003989 dielectric material Substances 0.000 description 15
- 239000011521 glass Substances 0.000 description 15
- 239000002966 varnish Substances 0.000 description 15
- FWHUTKPMCKSUCV-UHFFFAOYSA-N 1,3-dioxo-3a,4,5,6,7,7a-hexahydro-2-benzofuran-5-carboxylic acid Chemical compound C1C(C(=O)O)CCC2C(=O)OC(=O)C12 FWHUTKPMCKSUCV-UHFFFAOYSA-N 0.000 description 12
- JIABEENURMZTTI-UHFFFAOYSA-N 1-isocyanato-2-[(2-isocyanatophenyl)methyl]benzene Chemical compound O=C=NC1=CC=CC=C1CC1=CC=CC=C1N=C=O JIABEENURMZTTI-UHFFFAOYSA-N 0.000 description 11
- 229920003023 plastic Polymers 0.000 description 11
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 11
- 239000005058 Isophorone diisocyanate Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 229920002852 poly(2,6-dimethyl-1,4-phenylene oxide) polymer Polymers 0.000 description 6
- 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 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- MMABHMIOCAINNH-UHFFFAOYSA-N pyrrole-2,5-dione;triazine Chemical compound C1=CN=NN=C1.O=C1NC(=O)C=C1.O=C1NC(=O)C=C1 MMABHMIOCAINNH-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/343—Polycarboxylic acids having at least three carboxylic acid groups
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
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- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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Abstract
本發明提供一種低介電樹脂配方,包括:20~150重量份之二異氰酸酯(diisocyanate);20~400重量份之聚(2,6-二烷基-1,4-苯醚)(Poly(2,6-dialkyl-1,4-phenylene oxide));以及200~650重量份之溶劑。本發明尚提供一種由上述低介電樹脂配方所形成之預聚合物、組成物及其複合材料與低介電樹脂預聚合物溶液的製備方法。
Description
本發明係關於一種環保樹脂,尤其是關於一種環保型高耐熱低介電樹脂配方及其應用。
在現今無鹵材料配方組成中,一般選擇磷化物當作耐燃劑以取代現有鹵素化合物,甚至因含磷量不可偏高,影響耐熱性不足,而選擇適當含磷量配方,搭配氫氧化鋁來達成UL-94 V0耐燃需求。即使無鹵無磷型配方組成,亦使用氫氧化鋁來達成UL-94 V0耐燃需求,如美國專利公開號US 2006/0084787A1”Novel cyanate ester compound,flame-retardant resin composition,and cured product thereof “,及US2008/02621397A1“Flame retardant crosslink agent and epoxy resin compositions free of halogen and phosphorous”。
在有機基板的材料選擇上,除了雙馬來亞醯胺三嗪(Bismaleimide Triazine,BT)樹脂外,目前以環氧樹脂(epoxy resin)為主的耐熱性材料,以熱機械分析儀(Thermal Mechanical Analyzer,TMA)測量所得到的Tg皆在180℃左右,因而會有耐燃不足的問題,需搭配耐燃無機粉體或耐燃樹脂,如世界專利公開號WO 03/048251”Prepreg and composition of epoxy resin(s),SMA copolymers(s) and bis-maleimide triazine resin(s)”、日本專利公開號JP 2003138241”Heat-resistant adhesive and laminate using the same adhesive-applied heatsink and adhesive-applied metallic foil”、日本專利公開號JP 2004217861”Heat-resistant adhesive and laminate using this adhesive,heat sink with adhesive,and metal foil with adhesive”。
因此,業界亟需一種能兼具環保、高耐熱性(Tg超過180℃)、以及低介電性之樹脂,以因應高頻元件的需求。
本發明提供一種低介電樹脂配方,包括:20~150重量份之二異氰酸酯(diisocyanate);20~400重量份之聚(2,6-二烷基-1,4-苯醚)(Poly(2,6-dialkyl-1,4-phenylene oxide));以及200~650重量份之溶劑。
本發明尚提供一種低介電樹脂預聚合物溶液的製備方法,包括:混合20~150重量份之二異氰酸酯(diisocyanate);20~400重量份之聚(2,6-二烷基-1,4-苯醚)(Poly(2,6-dialkyl-1,4-phenylene oxide));以及200~650重量份之溶劑以形成一低介電樹脂配方;以及加熱該低介電樹脂配方進行一預聚合反應以形成一低介電樹脂預聚合物溶液。
本發明尚提供一種低介電樹脂預聚合物,具有下列化學式I或具有下列化學式II及式III所示之重複單元:
其中,A為苯環或環己烷;X為-H、-CH3、-NCO或-CH2-NCO;Y為-NH-、-NHCO-、或-NHCOO-;Q為-CH2-、-C(CH3)2-、-O-、-S-、-SO2-或不存在;n為20~230;R3為-H、-CH3或-COOH;R1及R2為C1~C5烷基;m為0~8;y為20~230;z為1~20000;V為-NH-,-NHCO-或-NHCOO-。
本發明另提供一種低介電樹脂組成物,係由上述之低介電樹脂預聚合物溶液加熱固化而成。
本發明還提供一種低介電樹脂複合材料,包括:纖維;以及上述之低介電樹脂組成物。
本發明又提供一種低介電樹脂複合材料,包括:一金屬薄片;以及上述之低介電樹脂組成物,設於該金屬薄片上。
為讓本發明之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉出實施例,作詳細說明如下:
本發明提供一種低介電樹脂配方、預聚合物、組成物及其複合材料與低介電樹脂預聚合物溶液的製備方法。上述低介電樹脂配方主要由二異氰酸酯(diisocyanate)、聚(2,6-二烷基-1,4-苯醚)(Poly(2,6-dialkyl-1,4-phenylene oxide))、以及溶劑所組成,其中更可視需要包括羧酸酐(carboxy anhydride)衍生物,由上述成分進行反應後所得之低介電樹脂配方能兼具環保及高耐熱性,不需添加難燃劑即可達UL94-V0難燃要求,且其低介電特性使其成為良好的高頻應用材料。
上述低介電樹脂配方,包括:20~150重量份,例如30~120重量份之二異氰酸酯(diisocyanate);20~400重量份,例如50~300重量份之聚(2,6-二烷基-1,4-苯醚)(Poly(2,6-dialkyl-1,4-phenylene oxide));以及200~650重量份,例如350~600重量份之溶劑。
在一實施例中,低介電樹脂配方中的二異氰酸酯可使用具有苯環結構的衍生物,包括但不限於:例如,二異氰酸二苯甲烷(methylene diphenyl diisocyanate,MDI)、二異氰酸甲苯(toluene diisocyanate,TDI)、二異氰酸異佛爾酮(isophorone diisocyanate,IPDI)、1,6-己二異氰酸酯(hexamethylene diisocyanate)或前述之組合。
在一實施例中,低介電樹脂配方中的溶劑可依照所使用之二異氰酸酯(diisocyanate)與聚(2,6-二烷基-1,4-苯醚)(Poly(2,6-dialkyl-1,4-phenylene oxide))作適當的選擇,包括但不限於甲苯(toluene)、二甲苯(xylene)、二甲基甲醯胺(dimethyl formamide,DMF)、甲基咯烷酮(N-methyl-2-pyrrolidone,NMP)或二甲基亞碸(dimethyl sulfoxide,DMSO)、或前述之組合。
在一實施例中,上述由二異氰酸酯(diisocyanate)與聚(2,6-二烷基-1,4-苯醚)(Poly(2,6-dialkyl-1,4-phenylene oxide))所形成的預聚合物具有下列化學式I:
其中,A為苯環或環己烷;X為-H、-CH3、-NCO或-CH2-NCO;Y為-NH-、-NHCO-、或-NHCOO-;R1及R2為C1~C5烷基;Q為-CH2-、-C(CH3)2-、-O-、-S-、-SO2-或不存在;n為20~230。此低介電樹脂預聚合物另經加熱固化後可得上述之低介電樹脂組成物。
在一實施例中,上述由二異氰酸酯(diisocyanate)、以及聚(2,6-二烷基-1,4-苯醚)(Poly(2,6-dialkyl-1,4-phenylene oxide))所進行的預聚合反應,其預聚合反應的溫度約80℃至140℃,例如約110℃至130℃;預聚合反應的時間約0.5~5小時,例如約1~3小時。
在一實施例中,本發明之前述溶液中,更可包括6~100重量份,例如10~85重量份之羧酸酐(carboxy anhydride)衍生物以進行共聚合反應,上述羧酸酐可使用具有三官能基的衍生物,其可具有下列化學式IV:
其中,A為苯環或環己烷,R為-H、-CH3或-COOH,q為0~8。三官能基羧酸酐的實例包括:苯三甲酸酐(trimellitic anhydride,TMA)、c-TMA(Cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride)、或前述之組合。
在一實施例中,上述由二異氰酸酯(diisocyanate)、聚(2,6-二烷基-1,4-苯醚)(Poly(2,6-dialkyl-1,4-phenylene oxide))、以及羧酸酐(carboxy anhydride)衍生物所進行的預聚合反應,其預聚合反應的溫度約80℃至140℃,例如約110℃至130℃;預聚合反應的時間約0.5~6小時,例如約1~3.5小時。
在一實施例中,由二異氰酸酯(diisocyanate)、聚(2,6-二烷基-1,4-苯醚)(Poly(2,6-dialkyl-1,4-phenylene oxide))、以及羧酸酐(carboxy anhydride)衍生物進行的預聚合反應所得之預聚合物具有下列化學式II及式III重複單元:
其中,A為苯環或環己烷;R3為-H、-CH3或-COOH;R1及R2為C1~C5烷基;Q為-CH2-、-C(CH3)2-、-O-、-S-、-SO2-或不存在;m為0~8;y為20~230;z為1~20000或10~1500;V為-NH-,-NHCO-或-NHCOO-。此低介電樹脂預聚合物另經加熱固化後可得上述之低介電樹脂組成物。
本發明之低介電樹脂預聚合物溶液可依實際需要做各種應用。在一實施例中,可利用上述低介電樹脂預聚合物溶液來製備低介電樹脂複合材料,其方法包括:將本發明之低介電樹脂預聚合物溶液,塗佈於金屬薄片,例如銅箔後,於175~225℃下,例如185~215℃下,加熱加壓1~4.5小時,例如1.5~3.5小時,以得到一低介電樹脂複合材料,其可作高頻基板材料。
在另一實施例中,可利用上述低介電樹脂預聚合物溶液搭配纖維來製備低介電樹脂複合材料,其方法包括:將一纖維含浸於本發明之低介電樹脂預聚合物溶液,經疊層後加熱加壓。在一實施例中,本發明之低介電樹脂複合材料中的纖維,包括:玻璃纖維布、或聚醯胺纖維。上述加熱硬化步驟在約攝氏175~225度,例如約攝氏185~215度,進行約1~4.5小時,例如約1.5~3.5小時,以得到一低介電樹脂複合材料。
經上述製備方法所得之樹脂複合材料不含鹵系、磷系耐燃劑,且不需添加氫氧化鋁等無機難燃粉體即可通過UL94V-0耐燃測試,其介電常數(Dk)範圍介於約3.0~4.0,例如介於約3.2~3.9,且其玻璃轉移溫度(Tg)大於約攝氏180度,例如介於約攝氏180~230度。
本發明所提供之樹脂複合材料兼具環保、高耐熱、以及低介電之特性,其Tg超過180℃,且其訊號傳遞過程的損失程度較低(dissipation factor,Df值較小),可對於未來之高頻材料的需求提供助益,其化學組成及物理性質,與電子元件系統結合且相配合,以形成具有環保綠色材料的機械性質,及極佳的低介電複合材料。
實施例1.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入100g MDI(methylene diphenyl isocyanate,Fu-Pao Chemical Co.)、100g PPO(Poly(2,6-dimethyl-1,4-phenylene oxide),Chang Chun Plastics Co.)、200g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌60分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時,則可得到低介電材料。
實施例2.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入50g TMA(trimellitic anhydride,Fu-Pao Chemical Co.)、115.8g PPO(Poly(2,6-dimethyl-1,4-phenylene oxide),Chang Chun Plastics Co.)、65.8g MDI(methylene diphenyl isocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時,則可得到低介電材料。
實施例3.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入50g TMA(trimellitic anhydride,Fu-Pao Chemical Co.)、115.8g PPO(Poly(2,6-dimethyl-1,4-phenylene oxide),Chang Chun Plastics Co.)、41.9g MDI(methylene diphenyl isocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時,則可得到低介電材料。
實施例4.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入50g TMA(trimellitic anhydride,Fu-Pao Chemical Co.)、115.8g PPO(Poly(2,6-dimethyl-1,4-phenylene oxide),Chang Chun Plastics Co.)、109.5g MDI(methylene diphenyl isocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時,則可得到低介電材料。
實施例5.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入50g TMA(trimellitic anhydride,Fu-Pao Chemical Co.)、115.8g PPO(Poly(2,6-dimethyl-1,4-phenylene oxide),Chang Chun Plastics Co.)、68.7g IPDI(isophorone diisocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時,則可得到低介電材料。
實施例6.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入50g TMA(trimellitic anhydride,Fu-Pao Chemical Co.)、57.9g PPO(Poly(2,6-dimethyl-1,4-phenylene oxide),Chang Chun Plastics Co.)、65.8g MDI(methylene diphenyl isocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時,則可得到低介電材料。
實施例7.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入50g TMA(trimellitic anhydride,Fu-Pao Chemical Co.)、270.1g PPO(Poly(2,6-dimethyl-1,4-phenylene oxide),Chang Chun Plastics Co.)、65.8g MDI(methylene diphenyl isocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時,則可得到低介電材料。
實施例8.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入53g c-TMA(Cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride,Fu-Pao Chemical Co.)、115.8g PPO(Poly(2,6-dimethyl-1,4-phenylene oxide),Chang Chun Plastics Co.)、65.8g MDI(methylene diphenyl isocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時,則可得到低介電材料。
實施例9.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入53g c-TMA(Cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride,Fu-Pao Chemical Co.)、115.8g PPO(Poly(2,6-dimethyl-1,4-phenylene oxide),Chang Chun Plastics Co.)、68.7g IPDI(isophorone diisocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時,則可得到低介電材料。
實施例10.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入14.9g TMA(trimellitic anhydride,Fu-Pao Chemical Co.)、115.8g PPO(Poly(2,6-dimethyl-1,4-phenylene oxide),Chang Chun Plastics Co.)、65.8g MDI(methylene diphenyl isocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時,則可得到低介電材料。
實施例11.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入77g TMA(trimellitic anhydride,Fu-Pao Chemical Co.)、115.8g PPO(Poly(2,6-dimethyl-1,4-phenylene oxide),Chang Chun Plastics Co.)、65.8g MDI(methylene diphenyl isocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時,則可得到低介電材料。
比較例1.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入50g TMA(trimellitic anhydride,Fu-Pao Chemical Co.)、65.8g MDI(methylene diphenyl isocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時得到一介電材料。
比較例2.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入50g TMA(trimellitic anhydride,Fu-Pao Chemical Co.)、68.7g IPDI(isophorone diisocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時得到一介電材料。
比較例3.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入53g c-TMA(Cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride,Fu-Pao Chemical Co.)、65.8g MDI(methylene diphenyl isocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時得到一介電材料。
比較例4.
使用500毫升,3口之玻璃反應器,2片葉輪的攪拌棒,加入53g c-TMA(Cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride,Fu-Pao Chemical Co.)、68.7g IPDI(isophorone diisocyanate,Fu-Pao Chemical Co.)、444.5g甲苯(C-ECHO Co.)、及111.1g DMF(dimethylformamide,C-ECHO Co.),於125℃下攪拌180分鐘,反應結束後待溫度降至室溫,即得到無鹵無磷低介電配方膠水(varnish)。最後將配方膠水,含浸於玻璃纖維布後,經疊層於200℃下加熱加壓3小時得到一介電材料。
註:
1. TMA:苯三甲酸酐(trimellitic anhydride)
2. c-TMA:環己烷-1,2,4-三羧酸-1,2-酐(cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride)
3. PPO:聚(2,6-二甲基-1,4-苯醚)(Poly(2,6-dimethyl-1,4-phenylene oxide))
4. MDI:二異氰酸二苯甲烷(methylene diphenyl diisocyanate)
5. IPDI:二異氰酸異佛爾酮(isophorone diisocyanate)
6. Dk:介電常數(dielectric constant)
7. Df:耗散因素(dissipation factor)
8. Tg:玻璃轉化溫度(glass transition temperature)
9. Td5%: 5%被熱分解時的溫度(decomposition temperature)
由表1可知本發明實施例明顯優於比較例,實施例之樹脂複合材料的介電常數(Dk)明顯低於比較例,且其玻璃轉移溫度(Tg)皆高於180℃,以及其訊號傳遞過程的損失程度較低(dissipation factor,Df值較小),因此本發明所提供之樹脂複合材料兼具環保、高耐熱、以及低介電之特性,可對於未來之高頻材料的需求提供助益,為極佳的低介電複合材料。
雖然本發明已以數個實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作任意之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
Claims (17)
- 一種低介電樹脂配方,包括:20~150重量份之二異氰酸酯(diisocyanate);20~400重量份之聚2,6-二烷基-1,4-苯醚(Poly(2,6-dialkyl-1,4-phenylene oxide));以及200~650重量份之溶劑。
- 如申請專利範圍第1項所述之低介電樹脂配方,其中該二異氰酸酯包括二異氰酸二苯甲烷(methylene diphenyl diisocyanate,MDI)、二異氰酸甲苯(toluene diisocyanate,TDI)、二異氰酸異佛爾酮(isophorone diisocyanate,IPDI)、1,6-己二異氰酸酯(hexamethylene diisocyanate)或前述之組合。
- 如申請專利範圍第1項所述之低介電樹脂配方,其中該溶劑包括甲苯(toluene)、二甲苯(xylene)、二甲基甲醯胺(dimethyl formamide,DMF)、甲基咯烷酮(N-methyl-2-pyrrolidone,NMP)或二甲基亞碸(dimethyl sulfoxide,DMSO)、或前述之組合。
- 如申請專利範圍第1項所述之低介電樹脂配方,其中該前驅物溶液更包括6~100重量份之羧酸酐(carboxy anhydride)衍生物。
- 如申請專利範圍第4項所述之低介電樹脂配方,其中該羧酸酐衍生物具有下列化學式:
其中,A為苯環或環己烷,R為-H、-CH3或-COOH,q為0~8。 - 一種低介電樹脂預聚合物溶液的製備方法,包括:混合20~150重量份之二異氰酸酯(diisocyanate);20~400重量份之聚(2,6-二烷基-1,4-苯醚)(Poly(2,6-dialkyl-1,4-phenylene oxide));以及200~650重量份之溶劑以形成一低介電樹脂配方;以及加熱該低介電樹脂配方進行一預聚合反應以形成一低介電樹脂預聚合物溶液。
- 如申請專利範圍第6項所述之低介電樹脂預聚合物溶液的製備方法,其中該二異氰酸酯包括二異氰酸二苯甲烷(methylene diphenyl diisocyanate,MDI)、二異氰酸甲苯(toluene diisocyanate,TDI)、二異氰酸異佛爾酮(isophorone diisocyanate,IPDI)、1,6-己二異氰酸酯(hexamethylene diisocyanate)或前述之組合。
- 如申請專利範圍第6項所述之低介電樹脂預聚合物溶液的製備方法,其中該溶劑包括甲苯(toluene)、二甲苯(xylene)、二甲基甲醯胺(dimethyl formamide,DMF)、甲基咯烷酮(N-methyl-2-pyrrolidone,NMP)或二甲基亞碸(dimethyl sulfoxide,DMSO)、或前述之組合。
- 如申請專利範圍第6項所述之低介電樹脂預聚合物溶液的製備方法,其中該低介電樹脂配方更包括6~100重量份之羧酸酐(carboxy anhydride)衍生物。
- 如申請專利範圍第9項所述之低介電樹脂預聚合物溶液的製備方法,其中該羧酸酐衍生物具有下列化學式:
其中,A為苯環或環己烷,R為-H、-CH3或-COOH,q為0~8。 - 如申請專利範圍第6項所述之低介電樹脂預聚合物溶液的製備方法,其中該預聚合反應溫度約80℃至140℃。
- 如申請專利範圍第6項所述之低介電樹脂預聚合物溶液的製備方法,其中該預聚合反應溫度約110℃至130℃。
- 一種低介電樹脂預聚合物,具有下列化學式I或具有下列化學式II及式III所示之重複單元:
其中,A為苯環或環己烷;X為-H、-CH3、-NCO或-CH2-NCO;Y為-NH-、-NHCO-、或-NHCOO-;Q為-CH2-、-C(CH3)2-、-O-、-S-、-SO2-或不存在;n為20~230;R3為-H、-CH3或-COOH;R1及R2為C1~C5烷基;m為0~8;y為20~230;z為1~20000;V為-NH-,-NHCO-或-NHCOO-。 - 一種低介電樹脂組成物,係由申請專利範圍第6~12項任一項所述之低介電樹脂預聚合物溶液加熱固化而成。
- 一種低介電樹脂複合材料,包括:纖維;以及如申請專利範圍第14項所述之低介電樹脂組成物。
- 如申請專利範圍第15項所述之低介電樹脂複合材料,其中該纖維包括玻璃纖維布、或聚醯胺纖維。
- 一種低介電樹脂複合材料,包括:一金屬薄片;以及如申請專利範圍第14項所述之低介電樹脂組成物,設於該金屬薄片上。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100138225A TWI428390B (zh) | 2011-10-21 | 2011-10-21 | 低介電樹脂配方、預聚合物、組成物及其複合材料與低介電樹脂預聚合物溶液的製備方法 |
| CN201110416454.3A CN103059241B (zh) | 2011-10-21 | 2011-12-14 | 低介电树脂配制物、预聚物、组合物及其复合材料与低介电树脂预聚物溶液的制备方法 |
| US13/458,583 US8889789B2 (en) | 2011-10-21 | 2012-04-27 | Low dielectric constant resin formulation, prepolymer, composition, and composite thereof |
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| TW100138225A TWI428390B (zh) | 2011-10-21 | 2011-10-21 | 低介電樹脂配方、預聚合物、組成物及其複合材料與低介電樹脂預聚合物溶液的製備方法 |
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| TWI480329B (zh) * | 2013-05-30 | 2015-04-11 | Ind Tech Res Inst | 樹脂配方、樹脂聚合物及包含該聚合物之複合材料 |
| TWI614285B (zh) * | 2016-11-11 | 2018-02-11 | 財團法人工業技術研究院 | 聚合物及包含該聚合物之樹脂組成物 |
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| TWI480329B (zh) * | 2013-05-30 | 2015-04-11 | Ind Tech Res Inst | 樹脂配方、樹脂聚合物及包含該聚合物之複合材料 |
| TWI614285B (zh) * | 2016-11-11 | 2018-02-11 | 財團法人工業技術研究院 | 聚合物及包含該聚合物之樹脂組成物 |
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Also Published As
| Publication number | Publication date |
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| US20130101858A1 (en) | 2013-04-25 |
| US8889789B2 (en) | 2014-11-18 |
| TWI428390B (zh) | 2014-03-01 |
| CN103059241A (zh) | 2013-04-24 |
| CN103059241B (zh) | 2014-11-05 |
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