CN103304998B - For preparing the compositions of thermosetting resin, its cured article and containing the prepreg of this product, laminated material and printed circuit board (PCB) - Google Patents
For preparing the compositions of thermosetting resin, its cured article and containing the prepreg of this product, laminated material and printed circuit board (PCB) Download PDFInfo
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- CN103304998B CN103304998B CN201310073298.4A CN201310073298A CN103304998B CN 103304998 B CN103304998 B CN 103304998B CN 201310073298 A CN201310073298 A CN 201310073298A CN 103304998 B CN103304998 B CN 103304998B
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- prepreg
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- thermosetting resin
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- 229920005989 resin Polymers 0.000 title claims abstract description 99
- 239000011347 resin Substances 0.000 title claims abstract description 99
- 239000000203 mixture Substances 0.000 title claims abstract description 90
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 66
- 239000002648 laminated material Substances 0.000 title description 16
- 125000003118 aryl group Chemical group 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 57
- 239000003822 epoxy resin Substances 0.000 claims abstract description 45
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 45
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 238000003475 lamination Methods 0.000 claims abstract description 30
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 20
- 230000003252 repetitive effect Effects 0.000 claims description 72
- 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 34
- 150000001875 compounds Chemical class 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- -1 bisphenol-ap Chemical compound 0.000 claims description 21
- 229930185605 Bisphenol Natural products 0.000 claims description 20
- 239000011256 inorganic filler Substances 0.000 claims description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- 239000012766 organic filler Substances 0.000 claims description 8
- 150000004982 aromatic amines Chemical class 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 150000004984 aromatic diamines Chemical class 0.000 claims description 6
- 229940106691 bisphenol a Drugs 0.000 claims description 6
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000003205 fragrance Substances 0.000 claims description 3
- 239000000123 paper Substances 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 claims description 2
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 claims description 2
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 claims description 2
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 claims description 2
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 claims description 2
- JOYPPFDDTPSWCV-UHFFFAOYSA-N 3-aminonaphthalene-2-carbaldehyde Chemical compound C1=CC=C2C=C(C=O)C(N)=CC2=C1 JOYPPFDDTPSWCV-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- UMPGNGRIGSEMTC-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexyl]phenol Chemical compound C1C(C)CC(C)(C)CC1(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UMPGNGRIGSEMTC-UHFFFAOYSA-N 0.000 claims description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 2
- ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 5-aminonaphthalen-1-ol Chemical class C1=CC=C2C(N)=CC=CC2=C1O ZBIBQNVRTVLOHQ-UHFFFAOYSA-N 0.000 claims description 2
- NZTPZUIIYNYZKT-UHFFFAOYSA-N 6-aminonaphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(N)=CC=C21 NZTPZUIIYNYZKT-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- ZSFKODANZQVHCK-UHFFFAOYSA-N 4-(4-aminophenyl)benzoic acid Chemical compound C1=CC(N)=CC=C1C1=CC=C(C(O)=O)C=C1 ZSFKODANZQVHCK-UHFFFAOYSA-N 0.000 claims 1
- BETZWIKAOZRDPJ-UHFFFAOYSA-N 8-aminonaphthalene-2-carbaldehyde Chemical compound C1=C(C=O)C=C2C(N)=CC=CC2=C1 BETZWIKAOZRDPJ-UHFFFAOYSA-N 0.000 claims 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 1
- 239000005711 Benzoic acid Substances 0.000 claims 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 235000010233 benzoic acid Nutrition 0.000 claims 1
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 claims 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 30
- 229920006026 co-polymeric resin Polymers 0.000 description 29
- 239000002904 solvent Substances 0.000 description 28
- 239000007787 solid Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000002367 halogens Chemical class 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 150000008064 anhydrides Chemical class 0.000 description 9
- 238000007711 solidification Methods 0.000 description 9
- 230000008023 solidification Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 125000003368 amide group Chemical group 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 238000005917 acylation reaction Methods 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical class ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical class ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical class ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 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
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-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
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical class ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- VKJLWXGJGDEGSO-UHFFFAOYSA-N barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ba+2] VKJLWXGJGDEGSO-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-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
- 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 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- 229940044174 4-phenylenediamine Drugs 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BDKZHNJTLHOSDW-UHFFFAOYSA-N [Na].CC(O)=O Chemical compound [Na].CC(O)=O BDKZHNJTLHOSDW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
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- 238000005553 drilling Methods 0.000 description 1
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- 229920001971 elastomer Polymers 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- RPHYLOMQFAGWCD-UHFFFAOYSA-N ethane;phenol Chemical compound CC.OC1=CC=CC=C1 RPHYLOMQFAGWCD-UHFFFAOYSA-N 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- LSACYLWPPQLVSM-UHFFFAOYSA-N isobutyric acid anhydride Chemical compound CC(C)C(=O)OC(=O)C(C)C LSACYLWPPQLVSM-UHFFFAOYSA-N 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- XTBLDMQMUSHDEN-UHFFFAOYSA-N naphthalene-2,3-diamine Chemical compound C1=CC=C2C=C(N)C(N)=CC2=C1 XTBLDMQMUSHDEN-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000000807 solvent casting Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/12—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/12—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2469/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
Abstract
The present invention is provided to prepare the compositions of thermosetting resin, the cured article of said composition, the prepreg comprising this cured article and the metal-coating lamination material comprising this prepreg and printed circuit board (PCB).The described compositions for preparing thermosetting resin includes aromatic polyester amide copolymer and the epoxy resin containing at least one in amino end group and hydroxyl end groups and having excellent hot expansibility.
Description
The cross reference of related application
This application claims Korean Patent Application No. 10-2012-submitted on March 7th, 2012 in Korean Intellectual Property Office
The priority of 0023624, and disclosure of which is fully incorporated the application as reference.
Background of invention
1. technical field
The present invention relates to for preparing the compositions of thermosetting resin, the cured article of said composition, comprising this solidification product
The prepreg of product and comprise metal-coating lamination material and the printed circuit board (PCB) of this prepreg, more particularly it relates to use
In preparing the compositions of thermosetting resin, described compositions comprises at least one in amino end group, hydroxyl end groups and has excellent
The aromatic polyester amide copolymer resin of different fire resistance and epoxy resin；The cured article of said composition；Comprise this solid
Change the prepreg of product；And comprise metal-coating lamination material and the printed circuit board (PCB) of this prepreg.
2. background technology
Miniaturization according to nearest electronic equipment and multifunction trend, carry out printed circuit board (PCB) the most energetically
Densification and Miniaturization Research.Copper-clad laminate is due to punch process, Drilling processability and the low one-tenth of its excellence
This, be widely used as the printed circuit board base board of electronic equipment.
For copper-clad laminate so as printed circuit prepreg require have excellence thermostability, dimensional stability,
Chemical resistance and electric property are to obtain excellent semiconducting behavior and meeting semiconductor packages manufacturing condition.
Prepreg is to carry out impregnated glass fabric, then by the resin derivative with epoxy resin or Bismaleimide Triazine
It is dried and is prepared by this resin of semi-solid preparation.Then, copper foil layer is pressed on prepreg, and be fully cured this resin with preparation cover copper
Laminated material.This copper-clad laminate is formed thin layer, and it is carried out high-temperature process, such as reflux at 260 DEG C
Welding.When carrying out high-temperature process, the copper-clad laminate of thin layer form is it may happen that thermal deformation, thus causes copper clad layers pressure
Material productivity reduces.In addition, it is necessary to reduce epoxy resin or the high-hygroscopicity of bismaleimide-triazine resin.Particularly, exist
In the high-frequency range of more than 1GHz, the dielectric properties of resin are poor, therefore, it is difficult to be applied to carry out high frequency and High-speed machining by this resin
Semiconductor packages printed substrate on.Accordingly, it would be desirable to develop a kind of prepreg with low-k.
Recently, by using aromatic polyester resins to replace epoxy resin or bismaleimide-triazine resin system
Standby prepreg.Described prepreg is prepared by using aromatic polyester resins to impregnate organic or inorganic fabric.Especially,
Aromatic polyester resins and aromatic polyester fabric can be used to prepare aromatic polyester prepreg.In detail, fragrance adoption
Ester is dissolved in the solvent containing halogen such as chlorine to prepare composition solution, impregnates aromatic polyester fabric with described composition solution,
Then it is dried obtained product and prepares aromatic polyester prepreg.However, it is difficult to fully remove the solvent containing halogen, and
Halogen can corrode Copper Foil.Accordingly, it would be desirable to use halogen-free solvent.
It addition, Electrical and Electronic product such as copper-clad laminate needs to have meets the excellent fire-retardant of UL-94V-0 grade
Performance.Therefore, the resin for Copper Foil laminated material needs have fire resistance.To this end, use various fire retardant in resin.
Fire retardant is categorized as halogen-based flame retardants and the combustion agent of non-halogen base.Have excellence fire resistance the halogen-based flame retardants past by
Extensively application.But, halogen-based flame retardants sends the gas of severe toxicity during their burning, such as HBr or HCl, thus gives people
Body and environment bring adverse effect.Therefore, strengthen it is regulated and controled.
In order to overcome these problems, need to develop the pre-of a kind of performance such as fire resistance for having hypotoxicity and excellence
The resin of leaching material.
Summary of the invention
The present invention is provided to prepare the compositions of thermosetting resin, described compositions comprises and has amino end group, hydroxyl
At least one in end group and the aromatic polyester amide copolymer resin with excellent fire resistance；And epoxy resin.
The present invention also provides for thermosetting resin film, and described thermosetting resin film comprises described for preparing thermosetting resin
The cured article of compositions.
The present invention also provides for prepreg, and described prepreg comprises described for preparing the solidification of the compositions of thermosetting resin
Product.
The present invention also provides for comprising the metal-coating lamination material of described prepreg and printed circuit board (PCB).
According to an aspect of the present invention, it is provided that a kind of compositions for preparing thermosetting resin, described compositions bag
Contain: the aromatic polyester amide copolymer of at least one having in amino end group and hydroxyl end groups of 100 weight portions, described virtue
Fragrant adoption esteramide copolymers comprises: the repetitive A derived from aromatic hydroxy-carboxylic of 10-35 molar part；5-20 mole
Part derived from have phenolic hydroxyl group aromatic amine repetitive B and derived from aromatic diamine repetitive B' at least
A kind of；The repetitive C derived from aromatic diol of 10-25 molar part；5-15 molar part derived from aromatic series aminocarboxylic
The repetitive D of acid；With the repetitive E derived from aromatic dicarboxylic acid of 20-40 molar part, and 10-300 weight portion
Epoxy resin, wherein, the repetitive C derived from aromatic diol comprises the repetition derived from the compound represented by following formula 1
Cells D OPO-HQ and the repetitive BP derived from bis-phenol based compound:
Formula 1
The amount of described repetitive DOPO-HQ and repetitive BP can meet following condition:
0.2≤n(DOPO-HQ)/[n(DOPO-HQ)+n(BP)]≤0.7
100 weight portions based on the described compositions for preparing thermosetting resin, for preparing the group of thermosetting resin
Compound can comprise further at least one in the organic filler of 5-200 weight portion and inorganic filler (that is: 100 weight portions
Compositions there is no inorganic filler and organic filler).
According to a further aspect in the invention, it is provided that a kind of thermosetting resin film, described thermosetting resin film comprises above-mentioned
For preparing the cured article of the compositions of thermosetting resin.
According to a further aspect in the invention, it is provided that a kind of prepreg, described prepreg includes base material；Be contained in this base material
In the cured article of the described compositions for preparing thermosetting resin.
Consolidating of described compositions for preparing thermosetting resin that unit are base material is comprised and described compositions
The amount changing product can be at 0.1g/m2-1000g/m2In the range of.
It is contained in dielectric constant and the dielectric loss of the described prepreg measured after the cured article of prepreg is fully cured
The factor is less than less than 4.0 and 0.01 respectively.
Described cured article can have the glass transition temperature in the range of 200-270 DEG C.
According to a further aspect in the invention, it is provided that a kind of metal-coating lamination material, described metal-coating lamination material comprises
The prepreg stated and at least one of which metal forming being arranged at least one surface of described prepreg.
In described metal-coating lamination material, the thermal coefficient of expansion (β m) of the single direction of described metal forming and described preimpregnation
Thermal coefficient of expansion (the β of the single direction of materialpDifference (β between)m-βp) it is below 7ppm/K.
According to a further aspect in the invention, it is provided that a kind of printed circuit board (PCB), described printed circuit board (PCB) is above-mentioned by etching
Prepared by the metal forming of metal-coating lamination material.
According to a further aspect in the invention, it is provided that a kind of printed circuit board (PCB), described printed circuit board (PCB) is by above-mentioned thermosetting
On at least one surface of property resin molding prepared by type metal circuit pattern.
The detailed description of invention
Hereinafter, describe in detail according to the embodiment of the present invention a kind of compositions for preparing thermosetting resin, its
Cured article, and comprise the prepreg of this cured article.The term " for the compositions of thermosetting resin " being used herein
Refer to the mixture not having the solid constituent of solvent.
According to the embodiment of the present invention, what the compositions for preparing thermosetting resin comprised 100 weight portions has ammonia
The aromatic polyester amide copolymer resin of at least one in cardinal extremity base and hydroxyl end groups and the epoxy of 10-300 weight portion
Resin.The term " amino " being used herein refers to amino (-NH2), or by with other substituent groups substituted-amino (-NH2In)
One or two hydrogen atom and the substituted amino that formed, and term " amino end group " refers to be positioned at aromatic polyester amide
The amino of the end of copolymer resin.
Other substituent groups described it may be that such as, nitro, cyano group, substituted or unsubstituted C1-C20Alkyl, replacement
Or unsubstituted C1-C20Alkoxyl, substituted or unsubstituted C2-C20Thiazolinyl, substituted or unsubstituted C2-C20
Alkynyl, substituted or unsubstituted C1-C20Miscellaneous alkyl, substituted or unsubstituted C6-C30Aryl, substituted or do not taken
The C in generation7-C30Aralkyl, substituted or unsubstituted C5-C30Heteroaryl, substituted or unsubstituted C5-C30Cycloalkyl,
Substituted or unsubstituted C3-C30Heterocyclylalkyl is substituted or unsubstituted C3-C30Heteroarylalkyl.
If the amount of aromatic polyester amide copolymer resin and epoxy resin is in above-mentioned scope, then cross-link due to height
The high crosslink density that degree causes, the cured article being used in the compositions preparing thermosetting resin (resin i.e. cross-linked) has low
Hot expansibility, low-dielectric energy and agent of low hygroscopicity energy.
Described aromatic polyester amide copolymer resin comprises: 10-35 molar part derived from aromatic hydroxy-carboxylic
Repetitive A；5-20 molar part derived from have phenolic hydroxyl group aromatic amine repetitive B and derived from aromatic diamine
At least one of repetitive B'；The repetitive C derived from aromatic diol of 10-25 molar part；5-15 molar part
Repetitive D derived from aromatic amine yl carboxylic acid；With the repetitive E derived from aromatic dicarboxylic acid of 20-40 molar part,
Wherein, the repetitive C derived from aromatic diol includes the repetitive DOPO-derived from the compound represented by formula 1
HQ and repetitive BP (the i.e. repetitive C=repetitive DOPO-HQ+ repetitive BP derived from bis-phenol based compound
+ other repetitives):
Formula 1
If the amount of repetitive A is in above-mentioned scope, the most described aromatic polyester amide copolymer resin has height
Mechanical strength and excellent hot property.If the total amount of repetitive B and repetitive B' is in above-mentioned scope, then described
Aromatic polyester amide copolymer resin has high-dissolvability in a solvent and suitable melt temperature.If repetitive C
Amount in above-mentioned scope, the most described aromatic polyester amide copolymer resin has high-dissolvability in a solvent and suitably
Melt temperature.If the amount of repetitive D is in above-mentioned scope, the most described aromatic polyester amide copolymer resin has
High mechanical strength and high-dissolvability in a solvent.If the amount of repetitive E is in above-mentioned scope, the most described aromatic series
Polyester-amide copolymer resin has high-dissolvability in a solvent, low-thermal-expansion performance and low-dielectric energy.
It addition, described repetitive A can be derived from choosing free P-hydroxybenzoic acid, m-hydroxybenzoic acid, 6-hydroxyl-2-
At least one in the group that naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid and 2-hydroxyl-1-naphthoic acid are formed
Compound；Repetitive B can be derived from choosing free 3-amino-phenol, PAP, 5-amino-1-naphthols, 8-amino-2-
At least one compound in the group that naphthols and 3-amino-beta naphthal are formed；Repetitive B' can derived from choosing freely 1,
In the group that 4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 2,3-diaminonaphthalene and 1,8-diaminonaphthalene are formed at least
A kind of compound；Repetitive D can be derived from selecting free PABA, 2-amino-naphthalene-6-carboxylic acid and 4-amino-connection
At least one compound in the group that benzene-4-carboxylic acid is formed；Repetitive E can be derived from selecting free M-phthalic acid and naphthalene
At least one compound in the group that dioctyl phthalate is formed；Repetitive BP can be derived from selected from bisphenol-A, bisphenol-ap, bis-phenol
AF, bisphenol b, bisphenol b P, bisphenol-c, bis-phenol E, Bisphenol F, bis-phenol G, bis-phenol M, bisphenol S, bis-phenol P, bis-phenol PH, bis-phenol TMC and double
At least one compound in the group that phenol Z is formed.
Aromatic hydroxy-carboxylic, there is the aromatic amine of phenolic hydroxyl group, aromatic diamine, aromatic diol, aromatic series amino
The one or more hydrogen atom of carboxylic acid and/or aromatic dicarboxylic acid can be replaced by other above-mentioned substituent groups.
It addition, the amount of repetitive B, repetitive B', repetitive C and repetitive E can meet following condition:
0≤[n(B)+n(B')+n(C)]/n(E)<1.0
Wherein, n (B), n (B'), n (C) and n (E) represent the repetition list in aromatic polyester amide copolymer resin respectively
Unit B, repetitive B', repetitive C and the molal quantity of repetitive E.
If { [n (B)+n (B')+n (C)]/n (E) } is in above-mentioned scope, the most described aromatic polyester amide copolymer
Comprise substantial amounts of amino end group and/or hydroxyl end groups, and the curing reaction related between epoxy resin has to be formed
The thermosetting resin of high crosslink density.
Be contained in aromatic polyester amide copolymer resin repetitive DOPO-HQ (n (DOPO-HQ)) molal quantity and
The molal quantity of repetitive BP (n (BP)) can meet following condition:
0.2≤n(DOPO-HQ)/[n(DOPO-HQ)+n(BP)]≤0.7
Owing to the molal quantity of repetitive DOPO-HQ (n (DOPO-HQ)) and the molal quantity of repetitive BP (n (BP)) are full
The above-mentioned condition of foot, so described aromatic polyester amide copolymer resin can have high hot expansibility (i.e. low-thermal-expansion
Coefficient) and high-dissolvability in a solvent.The term " thermal coefficient of expansion " being used herein refers to thermal linear expansion coefficient.
Aromatic polyester amide copolymer resin-soluble solution prepared as described above in a solvent, and can be thermic liquid
Brilliant polyester-amide copolymer resin, it formed below can have optically anisotropic melt at 400 DEG C.Such as, described virtue
The melt temperature of fragrant adoption esteramide copolymers resin can be in the range of 250-400 DEG C, and number-average molecular weight is at 1000-
In the range of 20000.
Aromatic polyester amide copolymer resin can be prepared by following method: i.e. this aromatic polyester amide copolymer resin
Melt polymerization can be used to prepare, and it includes would correspond to the aromatic hydroxy-carboxylic of repetitive A, corresponding to repeating with anhydride
The aromatic amine with phenolic hydroxyl group of unit B and/or corresponding to the aromatic diamine of repetitive B', corresponding to repetitive C
Aromatic diol and the hydroxyl of aromatic amine yl carboxylic acid and/or amino corresponding to repetitive D carry out acylated to obtain acyl
Change product；And carry out ester exchange and/or amide groups between acylate and the aromatic dicarboxylic acid corresponding to repetitive E
Exchange.In this respect, by regulating the consumption of anhydride suitably, make aromatic polyester amide copolymer resin can have amino
End group and/or hydroxyl end groups and there is no carboxyl end groups, and make it can have the predetermined degree of polymerization.Such as, if increasing anhydride
Amount, the quantity of amino end group in the aromatic polyester amide copolymer resin of preparation and/or hydroxyl end groups reduces, and carboxyl
The quantity of end group and the degree of polymerization increase.On the other hand, if reducing the consumption of anhydride, then prepared aromatic polyester amide is altogether
In copolymer resin, the quantity of amino end group and/or hydroxyl end groups increases, and the quantity of carboxyl end groups and the degree of polymerization reduce.
In acylation reaction, integral molar quantity based on the hydroxyl and amino that are contained in all monomers is 1 part, the consumption of anhydride
Can be 1.0-1.2 molar part, all monomers be for example, corresponding to the aromatic hydroxy-carboxylic of repeated monomer A, corresponding to repeating
The aromatic amine with phenolic hydroxyl group of unit B, the aromatic diamine corresponding to repetitive B ', the virtue corresponding to repetitive C
Fragrant race's glycol and the aromatic amine yl carboxylic acid corresponding to repetitive D.If the amount of anhydride is in above-mentioned scope, then prepared
Aromatic polyester amide polymer resin there is amino end group and/or hydroxyl end groups, but not there is carboxyl end groups, and reduce
The coloring of aromatic polyester amide copolymer resin, and the monomer used will not be from the aromatic polyester amide copolymer of preparation
Resin distils, and reduces the amount generating phenol gas.Acylation reaction can carry out 30 points within the temperature range of 130-170 DEG C
Clock to 8 hours, such as, is carried out 1-3 hour within the temperature range of 140-160 DEG C.
Anhydride for acylation reaction can include acetic anhydride, propionic andydride, isobutyric anhydride, valeric anhydride, neopentanoic acid acid anhydride, butyryl oxide.
Deng, but it is not limited to this.Described anhydride can use the combination of at least two.
Ester exchange and amide groups exchange can be carried out within the temperature range of 130-400 DEG C, and heating rate is 0.1-2 DEG C/
Min, such as, at a temperature of 140-350 DEG C, heating rate is 0.3-1 DEG C/min.
When to by with aromatic dicarboxylic acid be acylated obtained acid esters carry out ester exchange and amide groups exchange time, in order to
Balanced by mobile response and increase reaction rate, can be using the sour and unreacted anhydride obtained as by-product by evaporating
Or distillation removes from reaction system.
It addition, acylation reaction, ester exchange and amide groups exchange can be carried out in the presence of a catalyst.This catalyst can be
It is commonly used for preparing any catalyst of polyester resin, such as magnesium acetate, tin acetate (II), butyl titanate, lead acetate, acetic acid
Sodium, potassium acetate, antimony trioxide, N, N-dimethyl aminopyridine and N-Methylimidazole..Generally, described catalyst can be same with monomer
Time join reaction system, carry out in the presence of a catalyst acylation reaction, ester exchange and amide groups exchange.
The polycondensation of ester exchange and amide groups exchange can be carried out by melt polymerization.Due to the aromatic polyester acyl manufactured
Amine copolymer resin after a while with cross linking of epoxy resin, i.e. solidify, so can prepare, there is high polymerization degree and high mechanical properties
Cured article, so solid phase is not necessarily.
The polyplant that melt polymerization uses can be typically used for heavy viscous material reaction any equipped with agitator
Reactor.In this respect, the reactor for melt polymerization can be identical or different with the reactor for being acylated.
According to current embodiment, aromatic polyester amide copolymer contains amino end group and/or hydroxyl end groups, but not
There is carboxylic end group.Thus, aromatic polyester amide copolymer resin can with the epoxy height that will describe after a while hand over
Connection.
It addition, described virtue phase adoption esteramide copolymers resin can have the single direction thermal expansion of 3ppm/K or following
Coefficient.
Epoxy resin that described epoxy resin can include selecting free bifunctionality and three-or the asphalt mixtures modified by epoxy resin of higher functionality
At least one in the group that fat is formed.The epoxy resin of described bifunctionality can be such as bisphenol A type epoxy resin, hydrogenation
Bisphenol A type epoxy resin, the bisphenol A type epoxy resin of bromination, bisphenol f type epoxy resin, bisphenol-s epoxy resin, double two
Toluene phenol-type epoxy resin or bisphenol-type epoxy resin.It addition, the epoxy resin of three-or higher degrees of functionality can be such as phenol
Novolac type epoxy resin, phenol aldehyde type epoxy resin, bis-xylene phenol-type epoxy resin, cresol novolac (cresol novolac)
Type epoxy resin, N-glycidyl (N-glycidyl) type epoxy resin, the phenol aldehyde type epoxy resin of bisphenol-A, bis-phenol phenolic aldehyde
Type epoxy resin, chelate type epoxy resin, Biformyl type epoxy resin, containing amino-type epoxy resin, rubber modified epoxy tree
Fat, bicyclopentadiene phenol (dicyclopentadiene phenolic) type epoxy resin, four phenol ethane
(tetrakisphenolethane) type epoxy resin, diglycidyl phthalate
(diglycidylphthalate) resin, heterocyclic epoxy resin, four glycidyl group xylenols ethane (tetra-
Glycidyl-xylenoylethane) epoxy resin that resin, the epoxy resin of Si modification or 6-caprolactone are modified.
According to current embodiment, the described compositions for preparing thermosetting resin can pass through aromatic polyester acyl
Amine copolymer resin, epoxy resin and at random BMI and known firming agent and/or known curing catalysts
At a predetermined ratio prepared by mixing.
Meanwhile, by using solvent casting method, thermosetting resin film can use the combination for preparing thermosetting resin
Prepared by thing.
It addition, the described compositions solubilized for preparing thermosetting resin is in a solvent.Therefore, prepreg can pass through
For preparing the compositions of thermosetting resin to be impregnated or coated with base material, then it is dried and heat cure (semi-solid preparation) is impregnated or coated with
After base material prepare.In this respect, the composition of the compositions for preparing thermosetting resin of prepreg it is included in by heat
It is cross-linked with each other to form crosslinked resin to cured portion.That is, for preparing a kind of composition (i.e. virtue of the compositions of thermosetting resin
Fragrant adoption esteramide copolymers) amino end group and/or hydroxyl end groups partly with another kind of composition (the i.e. epoxy of said composition
Resin) partial cross-linked to form crosslinked resin (i.e. cured article).Owing to described cured article has and aromatic polyester amide
The physical property that copolymer resin is same, therefore has low thermal coefficient of expansion, low-k and the low-dielectric loss factor.
Terminology used herein " semi-solid preparation " refer to wherein for prepare the solidification process of the compositions of resin be part enter
The state of row.Will not be melted when heating by the resin manufactured by semi-solid preparation compositions but can soften, in a solvent will not be molten
Solve but understand swelling.Generally, the resin obtained by semi-solid preparation compositions is referred to as B-stage resin.Further, it is used herein
Term " is fully cured " and represents that the solidification process of wherein said compositions is the state carried out completely.By being fully cured compositions
Manufactured resin will not soften when heating, and will not dissolve in a solvent.Generally, obtain by being fully cured compositions
The resin obtained is referred to as C-stage resin.
Can apply in the various modes in addition to the preparation of prepreg for preparing the compositions of thermosetting resin.
Such as, prepreg can be prepared in the following way: with by being used for preparing the compositions of thermosetting resin
It is dissolved in the composition solution prepared in solvent and impregnates organic or inorganic fabric base material, or should with the coating of said composition solution
Fabric and/or non-woven base material；And be dried and semi-solid preparation impregnate after or coating after product.In this respect, described prepreg
Solution impregnation or varnish impregnation can be used to prepare.
The compositionss for preparing thermosetting resin based on 100 weight portions, prepare thermosetting resin for dissolving
The amount of the solvent of compositions can be 100-100,000 weight portion.When solvent amount within the above range time, be used for preparing thermosetting
The compositions of property resin can be substantially dissolved in solvent, and can increase the product of compositions for preparing thermosetting resin
Rate.
Dissolving the solvent for preparing thermosetting resin can be with right and wrong halogen radical solvent.But, the invention is not restricted to this.Institute
Stating solvent can be aprotic, polar compound, halogenated phenols, o-dichlorobenzene, chloroform, dichloromethane, sym-tetrachloroethane etc., and it is permissible
It is used alone or uses the combination of at least two.
Same, it is dissolved in non-halogen based solvent, so need not owing to being used for preparing the compositions of thermosetting resin
Halogen-containing solvent.Thus it is possible to prevention in advance is produced when halogen-containing solvent is used for preparing the solidification comprising described compositions
The corrosion of metal forming caused when the metal-coating lamination material of product or printed circuit board (PCB).
Described base material can include aromatic polyester fiber, aromatic polyester nylon, glass fibre, carbon fiber, paper or
Comprise fabric and/or the non-woven of at least a part of which two kinds.
If using dipping process in the preparation of prepreg, then can use described composition solution that base material is impregnated 0.001
Minute-1 hour.When dip time within the above range time, this base material is uniformly impregnated with by described composition solution, and can increase
Add the productivity of prepreg.
Furthermore it is possible to impregnate described base material at a temperature of 20-200 DEG C with described composition solution.
It addition, the amount of the compositions for preparing thermosetting resin impregnated on unit are base material can be at 0.1-
1000g/m2In the range of.When for prepare thermosetting resin compositions pickup within the above range time, can improve pre-
The productivity of leaching material, and easily carry out its processing.Therefore, in the prepreg after semi-solid preparation process, it is used for preparing thermosetting
The amount base material based on unit are of the compositions of property resin and the cured article of said composition can be about 0.1g/m2-about
1000g/m2。
In order to control dielectric constant and thermal coefficient of expansion, can add in composition solution inorganic filler such as silicon dioxide,
Aluminium hydroxide or calcium carbonate；And/or organic filler as solidification after epoxy resin or crosslinking after acryl material
(crosslinked acryl).Inorganic filler can be titanate such as Barium metatitanate. or strontium titanates, or with other metal part generation
For the titanium in Barium metatitanate. or the compound of barium.Inorganic filler can include that at least two has the inorganic filler of variable grain size
(such as silicon dioxide).It addition, inorganic filler can be dispersed in the slurry in organic solvent.The granular size of inorganic filler can be
In 0.1 μm-10.0 μ m.Based on being 100 weight portions (that is, the groups of 100 weight portions for preparing the compositions of thermosetting resin
Compound does not has inorganic filler and organic filler), the amount being contained in the inorganic filler of composition solution and/or organic filler can be
In the range of 5 weight portion-200 weight portions.If the amount of inorganic filler and/or organic filler is in above-mentioned scope, prepreg
Thermal coefficient of expansion reduces, and the compositions and cured article thereof for preparing thermosetting resin has work after semi-solid preparation process
Enough degrees of functionality for binding agent.Therefore, after semi-solid preparation process, based on 100 weight portions being used for prepares thermosetting resin
Compositions and the total amount of cured article of compositions, the inorganic filler contained in prepreg and/or the amount of organic filler are permissible
It is 5 weight portion-200 weight portions.
Produce owing to comprising the solidification of the compositions for preparing thermosetting resin according to the prepreg of embodiment of the present invention
Product, it has fire resistance, low thermal coefficient of expansion, agent of low hygroscopicity energy and the low-dielectric energy of excellence, and described organic or nothing
Woven fabric and/or organic or inorganic non-woven have high mechanical properties, so prepreg has high dimensional stability, Bu Huire
Deformation and be firm.Therefore, this prepreg is suitable to through hole boring process and lamination treatment.
In the dipping for preparing prepreg, after being impregnated or coated with base material with composition solution, can be by evaporation
Remove solvent, but the method removing solvent is not limited to this.Such as, evaporation can pass through heating, be evaporated in vacuo or ventilate evaporation
Carry out.Described solvent can also pass through the prepreg of dry composition solution dipping 1 minute at a temperature of 20-190 DEG C
Removed to 2 hours.
Then, the prepreg being dried heats 1-8 hour at a temperature of 120-320 DEG C, is contained in prepreg with semi-solid preparation
For preparing the compositions of thermosetting resin.
Thickness according to the prepreg prepared by current embodiment can be within about 5 μm-about 200 μ m,
E.g., from about 30 μm-about 150 μm.
After cured article (that is, semi-solid preparation resin=B-stage resin) in being contained in prepreg is fully cured, measured
The single direction thermal coefficient of expansion of prepreg can be below 10ppm/K.If the one-directional thermal expansion coefficient of prepreg is upper
In the range of stating, then the metal-coating lamination material comprising prepreg will not be peeled off.
After cured article in being contained in prepreg is fully cured, the dielectric of the prepreg measured under 1GHz frequency is normal
Number and dielectric loss factor can be respectively less than less than 4.0 and 0.01.The term " dielectric loss factor " being used herein represents
The energy of the dissipation of heat and the energy putting on dielectric material is passed through from dielectric material when applying AC field on the dielectric material
Ratio.If dielectric constant and dielectric loss factor are respectively in above-mentioned scope, then the prepreg comprising cured article is fitted
For the insulating substrate in high frequency field.
It addition, the glass transition temperature of cured article can be in the range of 200-270 DEG C.If the vitrification of cured article
Transition temperature is in above-mentioned scope, and cured article has high-fire resistance, and warpage will not occur in cured article.
The glass transition temperature of the thermal coefficient of expansion of prepreg and dielectric constant and cured product generally can use down
Method of stating is measured.That is: metal forming is laminated on two surfaces of prepreg, by semi-solid preparation impregnated in base material for heat
The compositions of thermosetting resin prepares metal forming；And to this laminated material heating and pressurization to prepare metal-coating lamination material,
Then metal forming is removed from metal-coating lamination material.Then, the fire resistance of prepreg, heat can be measured by analysis prepreg
The coefficient of expansion and dielectric properties and be contained in the glass transition temperature of cured article of prepreg.When heating and pressurization, institute
State semi-solid preparation resin to be cured completely.
Meanwhile, then this laminated material can be added by prepreg laminate by being laminated the prepreg of predetermined number
Prepared by heat and pressurization.When heating and pressurization, this semi-solid preparation resin is fully cured to be largely converted into crosslinked resin.
Metal-coating lamination material also can be by configuring if the metal forming of Copper Foil, native silver or aluminium foil is to prepreg or prepreg
On one surface of pressure material or two surfaces, then heat and be prepared by this laminated material that pressurizes.If semi-solid preparation resin,
Then when heating and pressurization, this semi-solid preparation resin is cured to be largely converted into crosslinked resin completely.
The thermal coefficient of expansion (β m) of the single direction of the metal forming of metal-coating lamination material and the single direction of prepreg
Difference between thermal coefficient of expansion (β p) is below 7ppm/K.If the difference of the thermal coefficient of expansion of single direction (β m-β p) exists
In above-mentioned scope, then the metal forming of metal-coating lamination material will not be peeled off.Further, the thermal expansion of the single direction of metal forming
Coefficient can be in the range of 10-17ppm/K.
The thickness of the metal forming of described prepreg or prepreg laminate materials and metal-coating lamination material respectively can be
In the range of 0.1-300 μm.If the thickness of prepreg or prepreg laminate materials is within the above range, then in winding process
Will not rupture, and the multilayer laminated material with restriction thickness can be obtained.If the thickness of metal forming is at above-mentioned model
In enclosing, then it is suitable for manufacturing thin, weight amount, little product and being applicable to form pattern.
Put on prepare metal-coating lamination material heating and pressurization processing condition it may be that such as 150-250 DEG C and
10-50MPa.But, according to the performance of prepreg, for preparing the reactivity of compositions of thermosetting resin, processing unit (plant)
Ability, the thickness of desired metal-coating lamination material, can unrestrictedly change this condition.
Metal-coating lamination material according to current embodiment can further include and is in prepreg laminate and metal
Adhesive phase between paper tinsel, to strengthen bonding force therebetween.Thermoplastic resin or thermosetting resin can be used for bonding
The preparation of oxidant layer.It addition, the thickness of adhesive phase can be in the range of 0.1-100 μm.If the thickness of adhesive phase is upper
In the range of stating, then bonding force increases, and adhesive phase has suitable thickness.
Printed circuit board (PCB) can be by the etching metal forming of metal-coating lamination material and be formed on circuit and prepare.Printing
Circuit board can also be prepared by type metal circuit pattern at least one surface of thermosetting resin film.If needed
, printed circuit board (PCB) also can have through hole.
Multilayer board according to embodiment can be prepared in the following way, such as, according to be formed
The thickness of insulating barrier, is arranged in as between inner substrate or the composition of metal forming by the prepreg of predetermined number, the most right
This laminated material heats and pressurizes.In this respect, heat and the condition pressurizeed can with prepare those of metal-coating lamination material
Condition is identical.Can use it addition, be used as the prepreg laminate of electrically insulating material, metal-coating lamination material or printed circuit board (PCB)
Make inner substrate, or the combination of at least two in them can also be used.
Hereinafter, one or more embodiments of the present invention will be described in detail by below embodiment.But, this
A little embodiments are not meant to that the scope of the one or more embodiments to the present invention limits.
Embodiment
<preparation example 1-22: the preparation of aromatic polyester amide copolymer resin>
By 6-Hydroxy-2-naphthoic acid (HNA), PAP (AP), formula 1 compound (DOPO-HQ) represented, bis-phenol
A(BPA), PABA (ABA), letter phthalic acid (IPA) and acetic anhydride (Ac2O) according to the ratio shown in table 1 below
Join equipped with in the 20L reactor of agitator, torquemeter, nitrogen inlet, thermometer and reflux condenser.Then, reactor
Inside nitrogen fully purges, and then in 30 minutes, temperature is increased to 150 DEG C in nitrogen atmosphere.Keep 150 DEG C
Temperature, by reactor reflux 3 hours.
Subsequently, while the acetic acid being removed by distillation outflow and unreacted acetic anhydride, by the temperature liter of reactor
High to 320 DEG C are incubated 180 minutes.The time point that torque starts to increase is considered as reaction end, then releases in reactor
Content.The pressed powder obtained being cooled to room temperature (25 DEG C), and wears into powdery with flour mill, result is not carrying out any list
Aromatic polyester amide copolymer powder is obtained in the case of only solid phase.
Table 1
* 1: based on [(HNA mole)+(AP mole)+(DOPO-HQ mole)+(BPA mole)+(ABA mole
Amount)+(IPA mole)] total amount meter 100 molar part, the molar part of each repetitive.
* 2: based on [(HNA mole)+(AP mole)+2*(DOPO-HQ mole)+2*(BPA mole)+(ABA rubs
You amount)] total amount meter 100 molar part, acetic anhydride Ac2The molar part of O.
<embodiment 1-12 and comparative example 1-12: the preparation of copper-clad laminate>
First step: for preparing the preparation of the composition solution of thermosetting resin
By (prosperous to each aromatic polyester amide copolymer toner prepared in preparation example 1-22 and epoxy resin
Si Mai (Huntsman), MY-721) join in dimethyl acetylamide (DMAc) and stir 3 hours.Then, it is added thereto to
Silica dispersions (include the different silica solid composition of 70wt% two kinds, its be respectively provided with 0.5 μm and 5.0 μm
Grain size and be dispersed in DMAc) and dispersant (BYK, BYK-2009) stir 5 hours.Subsequently, add the most further
Enter firming agent (Samchun Chemical company, DICY) and curing catalysts (four countries (Shikoku) company, 2E4MZ).So
After, this mixture is stirred 4 hours at 25 DEG C the solution obtaining the compositions for preparing thermosetting resin.For implementing
Aromatic polyester amide copolymer powder in each embodiment of example 1-12 and comparative example 1-12, epoxy resin, DMAc, solidification
The amount of agent and curing catalysts is shown in Table 2.
Table 2
Second step: the preparation of prepreg
At room temperature, glass woven fabric (IPC1078) is at room temperature entered with composition solution prepared in first step
Row dipping, is then passed to double roller and removes the composition solution of excess to obtain uniform thickness.Then, the glass that will obtain
Glass product of weaving cotton cloth is put in hot air dryer, to remove solvents at 180 DEG C, thus obtains prepreg.But, in comparative example 11
In due to without solidification phenomenon and do not prepare prepreg.Further, do not prepare due to adhesion in comparative example 12 pre-
Leaching material.
Third step: the preparation of copper-clad laminate
The electrolytic copper foil (having the single direction thermal coefficient of expansion of 14ppk/m) that thickness is 18 μm is arranged in second step
To obtain laminated material on two surfaces of each prepreg prepared by, then use hot plate forcing press by this laminated material
Heat under 200 DEG C and 30MPa and pressurize 3 hours with prepared metal-coating lamination material.But, do not have in comparative example 11 and 12
Prepare metal-coating lamination material.
Evaluate embodiment
Remove 2 Copper Foils from each copper-clad laminate prepared embodiment 1-12 and comparative example 1-6, then lead to
Cross and analyze partial prepreg measurement and be contained in the crosslink density of resin of prepreg and glass transition temperature and prepreg
Fire resistance, thermal coefficient of expansion, dielectric properties.Measurement result represents in table 3 below.
Table 3
In table 3, crosslink density is by using differential scanning calorimetry (DSC) (DSC, TA instrument, DSC2910) to analyze heat release
Peak value and measure, this exothermic peak obtains by being increased to 300 DEG C from room temperature with the heating rate of 20 DEG C/min；Vitrification turns
Temperature is by using DSC(TA instrument, DSC2910) with the speed of 20 DEG C/min from the increase of the temperature of room temperature to 300 DEG C
Measure；Fire resistance is by using UL94(Underwriters Laboratories company, the U.S.) measure；Heat is swollen
Swollen coefficient is to use TMA(TMA Q400) measure at a temperature of 50-200 DEG C；With dielectric constant and dielectric loss factor it is
Impedometer (Agilent (Agilent) company, E4991A) is at room temperature used to measure.
Reference table 3, the copper-clad laminate not comprising Copper Foil (i.e. prepreg part) of preparation in embodiment 1-12
Part has the fire resistance (V-0) of excellence；Low thermal coefficient of expansion (below 10ppm/K)；Low-k (less than 4) and low Jie
The electrical loss factor (less than 0.01)；With the resin being contained in prepreg, there is high glass transition temperature (more than 247 DEG C).?
The each copper-clad laminate prepared in comparative example 1,2,4 and 6-9 all properties in addition to fire resistance reduces.?
Each copper-clad laminate prepared in comparative example 3 and 10 has the lower glass transition temperatures of described resin；Covering copper
The low adhesion of the Copper Foil in laminated material；High single direction thermal coefficient of expansion.Copper Foil lamination prepared in comparative example 5
The all properties of material all reduces (including fire resistance).
According to reference, the Copper Foil laminated material with V-1 fire resistance is unsuitable for the halogen-free flameproof copper foil layer of state-of-the-art technology
Pressure material.It addition, in comparative example 11 and 12, owing to the amount of aromatic polyester amide copolymer or epoxy resin is the highest, do not have
Prepare Copper Foil laminated material.Particularly, in comparative example 12, owing to the amount of epoxy resin is the highest, then there occurs serious
Adhesion, therefore curing reaction can not be carried out to B-stage.
As it has been described above, according to the one or more above-mentioned embodiment of the present invention, it is provided that for preparing thermosetting resin
Compositions, described compositions includes aromatic polyester amide copolymer resin and epoxy resin, and described aromatic polyester amide is altogether
Copolymer resin includes at least one in amino end group and hydroxyl end groups and has the hot expansibility of excellence, wherein said composition
May be dissolved in non-halogen based solvent.
One or more above-mentioned embodiment according to the present invention, it is provided that thermosetting resin film and prepreg, it is by bag
Include the cured article of compositions for preparing thermosetting resin, thus there is excellent fire-retardancy, low-k, low dielectric
Fissipation factor and agent of low hygroscopicity energy.It addition, this cured article has high glass transition temperature (i.e. excellent thermostability).
One or more above-mentioned embodiment according to the present invention, it is provided that include the metal-coating lamination material of described prepreg
And printed circuit board (PCB).
Although the most specifically have shown and described the present invention with reference to the exemplary of the present invention, but this area
Skilled artisan understands that, in the case of without departing substantially from the spirit and scope of the present invention defined by the following claims,
Can be to carry out the various changes in form and details.
Claims (13)
1., for preparing the compositions of thermosetting resin, described compositions comprises: 100 weight portions have amino end group and
The aromatic polyester amide copolymer of at least one in hydroxyl end groups, described aromatic polyester amide copolymer comprises: 10-35
The repetitive A derived from aromatic hydroxy-carboxylic of molar part；5-20 molar part derived from the aromatic series with phenolic hydroxyl group
The repetitive B of amine and at least one of repetitive B' derived from aromatic diamine；10-25 molar part derived from fragrance
The repetitive C of race's glycol；The repetitive D derived from aromatic amine yl carboxylic acid of 5-15 molar part；With 20-40 molar part
Repetitive E derived from aromatic dicarboxylic acid；And the epoxy resin of 10-300 weight portion, wherein, derived from aromatic series two
The repetitive C of alcohol comprises the repetitive DOPO-HQ of the compound derived from following formula 1 expression and derived from bis-phenol based compound
Repetitive BP:
Formula I
The amount of described repetitive DOPO-HQ and repetitive BP meets following condition: 0.2≤n (DOPO-HQ)/[n (DOPO-
HQ)+n(BP)]≤0.7。
Compositions for preparing thermosetting resin the most according to claim 1, wherein, described repetitive A derived from
Selected from P-hydroxybenzoic acid, m-hydroxybenzoic acid, 6-Hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid
At least one compound in the group formed with 2-hydroxyl-1-naphthoic acid；Described repetitive B is derived from selected from 3-aminobenzene
In the group that phenol, PAP, 5-amino-1-naphthols, 8-amino-beta naphthal and 3-amino-beta naphthal are formed at least one
Plant compound；Described repetitive B' is derived from selected from 1,4-phenylenediamine, 1,3-phenylenediamine, 1,5-diaminonaphthalene, 2,3-diamino
At least one compound in the group that base naphthalene and 1,8-diaminonaphthalene are formed；Described repetitive D is derived from selected from 4-amino
At least one compound in the group that benzoic acid, 2-amino-naphthalene-6-carboxylic acid and 4-Amino-biphenyl-4-carboxylic acid are formed；Institute
State repetitive E derived from least one compound in the group that M-phthalic acid and naphthalenedicarboxylic acid are formed；And institute
State repetitive BP derived from selected from bisphenol-A, bisphenol-ap, bisphenol AF, bisphenol b, bisphenol b P, bisphenol-c, bis-phenol E, Bisphenol F, bis-phenol
At least one compound in the group that G, bis-phenol M, bisphenol S, bis-phenol P, bis-phenol PH, bis-phenol TMC and bisphenol Z are formed.
Compositions for preparing thermosetting resin the most according to claim 1, wherein, based on being used for preparing thermosetting tree
The compositions of fat is 100 weight portions, and described compositions comprises in organic filler and the inorganic filler of 5-200 weight portion further
At least one.
4. a thermosetting resin film, comprise according to according to any one of claim 1-3 for preparing thermosetting resin
The cured article of compositions.
5. a prepreg, comprises: base material；Be contained in described base material according to according to any one of claim 1-3
For preparing the cured article of the compositions of thermosetting resin.
Prepreg the most according to claim 5, wherein, the base material of per unit area comprised for preparing thermosetting tree
The amount of the compositions of fat and the cured article of said composition is at 0.1-1000g/m2In the range of.
Prepreg the most according to claim 5, wherein, described base material includes selected from aromatic polyester fiber, fragrance adoption
At least one in the group that esteramides fiber, glass fibre, carbon fiber and paper are formed.
Prepreg the most according to claim 5, wherein, the cured article being included in described prepreg is fully cured rear institute
Dielectric constant and the dielectric loss factor of the described prepreg measured are less than less than 4.0 and 0.01 respectively.
Prepreg the most according to claim 5, wherein, described cured article has the glass in the range of 200-270 DEG C
Change transition temperature.
10. a metal-coating lamination material, comprises: the prepreg described in claim 5；Be arranged in described prepreg at least
At least one of which metal forming on one surface.
11. metal-coating lamination materials according to claim 10, wherein, the single direction thermal coefficient of expansion of described metal forming
Difference (β m-β p) between single direction thermal coefficient of expansion (β p) of (β m) and described prepreg is below 7ppm/K.
12. 1 kinds of printed circuit board (PCB)s, it is prepared by the metal forming of the metal-coating lamination material described in etching claim 11.
13. 1 kinds of printed circuit board (PCB)s, it is by printing at least one surface of the thermosetting resin film described in claim 4
Prepared by metal circuit pattern.
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| Application Number | Priority Date | Filing Date | Title |
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| KR10-2012-0023624 | 2012-03-07 | ||
| KR1020120023624A KR101767690B1 (en) | 2012-03-07 | 2012-03-07 | Composition for preparing thermosetting resin, cured product of the composition, prepreg having the cured product, and metal clad laminate and printed circuit board having the prepreg |
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| JP (1) | JP6047426B2 (en) |
| KR (1) | KR101767690B1 (en) |
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| CN106750226B (en) | 2014-11-11 | 2019-01-08 | 江苏雅克科技股份有限公司 | The preparation method of phosphorous-containing polyester compound composition and phosphorus-containing flame-retardant epoxy resin solidfied material |
| GB2533776B (en) * | 2014-12-23 | 2020-11-04 | Hexcel Composites Ltd | Resin Composition |
| JP6896591B2 (en) * | 2017-11-14 | 2021-06-30 | Ｅｎｅｏｓ株式会社 | Prepregs, fiber reinforced composites and moldings |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS63146927A (en) * | 1986-07-22 | 1988-06-18 | Nippon Ester Co Ltd | Aromatic copolyesteramide |
| JPH01319534A (en) * | 1988-06-21 | 1989-12-25 | Mitsubishi Kasei Corp | Aromatic polyester amide and production thereof |
| CN100362037C (en) * | 2005-10-14 | 2008-01-16 | 四川大学 | Liquid crystal atactic polyester containing phosphor and its preparing method |
| KR100929383B1 (en) * | 2007-05-23 | 2009-12-02 | 삼성정밀화학 주식회사 | Aromatic liquid crystal polyester amide copolymer, prepreg employing the above-mentioned aromatic liquid crystal polyester amide copolymer, laminate and printed wiring board employing the prepreg |
| KR101111644B1 (en) * | 2009-06-17 | 2012-02-14 | 삼성정밀화학 주식회사 | Aromatic polyester amide copolymer, prepreg or prepreg laminates having the copolymer, and metal clad laminates and print wiring board having the prepreg or the prepreg laminates |
| CN101585912B (en) * | 2009-07-10 | 2011-08-31 | 四川大学 | Thermotropic liquid crystal random copolyester containing phosphor and kinking groups and preparation thereof |
| KR101659081B1 (en) * | 2010-03-26 | 2016-09-23 | 삼성전기주식회사 | Liquid crystalline thermoset oligomer or polymer and thermosetting composition and subratrate inclduing same |
| KR101728547B1 (en) * | 2010-07-05 | 2017-05-02 | 심천 워트 어드밴스드 머티리얼즈 주식회사 | Composition for preparing thermosetting resin, cured product of the composition, prepreg and prepreg laminate having the cured product, and metal clad laminate and printed circuit board having the prepreg or the prepreg laminate |
| CN102140164B (en) * | 2010-12-23 | 2012-10-31 | 大连工业大学 | Novel phosphorus and nitrogen containing flame-retardant thermotropic liquid crystal copolyester with low melting point and synthesis method thereof |
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| TWI563035B (en) | 2016-12-21 |
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| KR20130102413A (en) | 2013-09-17 |
| JP2013185156A (en) | 2013-09-19 |
| TW201343785A (en) | 2013-11-01 |
| KR101767690B1 (en) | 2017-08-11 |
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