TW201723068A - 一種環氧樹脂組合物以及含有其之預浸料、層壓板及印刷電路板 - Google Patents
一種環氧樹脂組合物以及含有其之預浸料、層壓板及印刷電路板 Download PDFInfo
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- TW201723068A TW201723068A TW105107816A TW105107816A TW201723068A TW 201723068 A TW201723068 A TW 201723068A TW 105107816 A TW105107816 A TW 105107816A TW 105107816 A TW105107816 A TW 105107816A TW 201723068 A TW201723068 A TW 201723068A
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- Prior art keywords
- epoxy resin
- resin composition
- weight
- parts
- composition according
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 103
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 89
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 89
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 31
- 150000002148 esters Chemical class 0.000 claims abstract description 26
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical group C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000003063 flame retardant Substances 0.000 claims description 21
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 17
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 17
- 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 claims description 15
- 239000000945 filler Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- -1 carboxylic acid aromatic compound Chemical class 0.000 claims description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 8
- 229910002113 barium titanate Inorganic materials 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000012779 reinforcing material Substances 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 239000012766 organic filler Substances 0.000 claims description 4
- 150000002989 phenols Chemical group 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000011152 fibreglass Substances 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- YYRHIWOOLJRQOA-UHFFFAOYSA-N (2,6-dimethylphenyl)-[3-(2,6-dimethylphenyl)phosphanylphenyl]phosphane Chemical compound CC1=CC=CC(C)=C1PC1=CC=CC(PC=2C(=CC=CC=2C)C)=C1 YYRHIWOOLJRQOA-UHFFFAOYSA-N 0.000 claims description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical group C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 2
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 claims description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- RERMPCBBVZEPBS-UHFFFAOYSA-N tris(2,6-dimethylphenyl)phosphane Chemical group CC1=CC=CC(C)=C1P(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C RERMPCBBVZEPBS-UHFFFAOYSA-N 0.000 claims description 2
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- GXIPHHIBYMWSMN-UHFFFAOYSA-N 6-phenylbenzo[c][2,1]benzoxaphosphinine 6-oxide Chemical compound O1C2=CC=CC=C2C2=CC=CC=C2P1(=O)C1=CC=CC=C1 GXIPHHIBYMWSMN-UHFFFAOYSA-N 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- 239000000378 calcium silicate Substances 0.000 claims 1
- 229910052918 calcium silicate Inorganic materials 0.000 claims 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 229910003468 tantalcarbide Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 26
- 238000010521 absorption reaction Methods 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 30
- 230000009477 glass transition Effects 0.000 description 19
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical group C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000004643 cyanate ester Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 3
- 239000001354 calcium citrate Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 235000013337 tricalcium citrate Nutrition 0.000 description 3
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000013022 formulation composition Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent 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
- 230000009172 bursting Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- WXANAQMHYPHTGY-UHFFFAOYSA-N cerium;ethyne Chemical compound [Ce].[C-]#[C] WXANAQMHYPHTGY-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- ZKEYULQFFYBZBG-UHFFFAOYSA-N lanthanum carbide Chemical compound [La].[C-]#[C] ZKEYULQFFYBZBG-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- 230000000930 thermomechanical effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 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
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4284—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with other curing agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
-
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Abstract
本發明提供一種環氧樹脂組合物以及含有其之預浸料、層壓板及印刷電路板。前述環氧樹脂組合物,其包括以下組分:(A)含有DCPD結構的環氧樹脂:38~54重量份;(B)活性酯固化劑:30~36重量份;(C)氰酸酯樹脂:16~32重量份。本發明利用上述特定含量的三種必要組分之間的相互配合以及相互協同促進作用,得到前述之環氧樹脂組合物。採用該環氧樹脂組合物製成的預浸料、層壓板以及印刷電路板,在同時具有高的耐濕熱性和高的耐熱性的前提下,還具有低熱膨脹係數、低吸水率和優異的介電性能。
Description
本發明屬於覆銅板技術領域,具體係關於一種環氧樹脂組合物以及含有其之預浸料、層壓板及印刷電路板。
近年來,隨著資訊通訊設備高性能化、高功能化以及網路化的發展,為了高速傳輸及處理大容量資訊,操作訊號趨向於高頻化,同時,為了滿足各類電子產品的發展趨勢要求,電路板向著高多層、高佈線密度的方向發展,這就要求基板材料不僅具有良好的介電常數和介質損耗因子來滿足訊號高頻傳輸的需要,而且要求其具有良好的耐熱性來滿足多層印刷電路板可靠性的需求。
氰酸酯具有良好黏結性和加工性,同時具有高的玻璃轉化溫度、較低的介電常數及低的介電損耗值。但易吸水而導致耐濕熱性不足,在PCB多層板運用中,容易出現分層爆板。
CN101967264A、CN101967265A和CN102504201A公開了採用氰酸酯和活性酯作為複合固化劑固化聯苯型酚醛環氧樹脂、亞芳烷基環氧樹脂、萘酚環氧樹脂,從而達到優化耐熱性和耐濕熱的目的。
CN 103304963A已解決上述發明中大量添加反應型含磷阻
燃劑和添加型阻燃劑後所導致的板材耐熱性或介電性能下降的問題。
但以上述現有技術中,並未提及如何解決耐熱性和耐濕熱的矛盾,並如何在其中找到平衡點,這成為技術難題之一。
針對已有技術的問題,本發明之目的在於提供一種環氧樹脂組合物。使用該環氧樹脂組合物製備之預浸料、層壓板及印刷電路板同時具有高耐濕熱性及高耐熱性。此外,前述預浸料、層壓板及印刷電路板還具有低熱膨脹係數、低吸水率和優異的介電性能。
為了實現上述目的,本發明採用了如下技術手段:一種環氧樹脂組合物,其特徵係其包括如下組分:(A)含有DCPD結構的環氧樹脂:38~54重量份;(B)活性酯固化劑:30~36重量份;(C)氰酸酯樹脂:16~32重量份。
本發明人為實現上述目的進行反復深入的研究,結果發現:特定含量的含有DCPD結構的環氧樹脂、活性酯固化劑和氰酸酯樹脂,及其他可選地組分適當混合得到的環氧樹脂組合物,可實現上述目的。
本發明採用特定含量的含有DCPD(雙環戊二烯)結構的環氧樹脂,其重均分子量為200~4000,且<400的重均分子量分佈所占比例<30%wt,可以提升環氧樹脂組合物的玻璃轉化溫度、耐濕熱性和降低其吸水率;特定含量的活性酯固化劑可以改善環氧樹脂組合物的介電性能和吸
水性能;特定含量的氰酸酯樹脂能很好地提高環氧樹脂組合物的玻璃轉化溫度和降低其熱膨脹係數。本發明利用上述特定含量的三種必要組分之間的相互配合以及相互協同促進作用,得到前述之環氧樹脂組合物。採用該環氧樹脂組合物製成之預浸料、層壓板以及印刷電路板,在同時具有高的耐濕熱性和高的耐熱性的前提下,還具有低熱膨脹係數、低吸水率和優異的介電性能。
在本發明中,前述組分(A)含有DCPD結構的環氧樹脂,可以提升環氧樹脂組合物的玻璃轉化溫度和降低其吸水率。前述組分(A)含有DCPD結構的環氧樹脂的添加量為38~54重量份,例如38重量份、40重量份、42重量份、43重量份、44重量份、46重量份、48重量份、49重量份、50重量份、51重量份、53重量份或54重量份,理想為45~54重量份。
理想地,前述組分(A)含有DCPD結構的環氧樹脂為具有式(1)結構的環氧樹脂:
式(1)中,R1、R2和R3相同或不同,均獨立地為氫原子、取代或未取代的C1~C8(例如C2、C3、C4、C5、C6或C7)的直鏈烷基或支鏈烷基,n表示重複單元,為大於等於1的整數,例如1、3、5、8、10或13,其重均分子量為200~4000,且<400的重均分子量分佈所占比例<30%wt。在本發明中,含DCPD結構的環氧樹脂滿足其重均分子量分佈為:200~4000,且<400
的重均分子量分佈所占比例<30%wt,有利於改善環氧樹脂組合物的耐濕熱性。
在本發明中,前述組分(B)活性酯固化劑,可以改善環氧樹脂組合物的介電性能和吸水性能。前述組分(B)活性酯固化劑的添加量為30~36重量份,例如30重量份、31重量份、32重量份、33重量份、34重量份、35重量份或36重量份,理想為30~33重量份。
理想地,前述組分(B)活性酯固化劑由一種透過脂肪環烴結構連接的酚類化合物、二官能度羧酸芳香族化合物或酸性鹵代物及一種單羥基化合物反應而得。
理想地,前述二官能羧酸芳香族化合物或酸性鹵化物用量為1mol,透過脂肪環烴結構連接的酚類化合物用量為0.05~0.75mol,單羥基化合物用量為0.25~0.95mol。
理想地,前述組分(B)活性酯固化劑包括具有式(2)結構的活性酯:
X為苯基或者萘基,j為0或1,k為0或1,n1表示重複單元為0.25~1.25。
由於該活性酯的特殊結構,其中的苯基、萘基和環戊二烯等剛性結構賦予該活性酯高的耐熱性,同時由於其結構的規整性及與環氧樹脂反應過程中無二次羥基產生,賦予其良好的介電性能和低吸水率。
在本發明中,前述組分(C)氰酸酯樹脂,可很好地提高環氧樹脂組合物的玻璃轉化溫度和降低其熱膨脹係數。前述組分(C)氰酸酯
樹脂的添加量為16~32重量份,例如16重量份、18重量份、20重量份、22重量份、24重量份、25重量份、26重量份、28重量份、30重量份或32重量份,理想為16~25重量份。
理想地,前述組分(C)氰酸酯樹脂為雙酚A型氰酸酯樹脂、雙酚F型氰酸酯樹脂、雙環戊二烯型氰酸酯樹脂或苯酚酚醛型氰酸酯樹脂所成群中任意一種或至少兩種之混合物。
理想地,一種環氧樹脂組合物,其包括如下組分:(A)含有DCPD結構的環氧樹脂:45~54重量份;(B)活性酯固化劑:30~33重量份;(C)氰酸酯樹脂:16~25重量份。
理想地,前述環氧樹脂組合物還可進一步包括固化促進劑,其使樹脂固化並加快樹脂固化速度。以組分(A)、組分(B)和組分(C)添加量之和為100重量份計,前述固化促進劑的添加量為0.05~1重量份,例如0.08重量份、0.1重量份、0.15重量份、0.2重量份、0.25重量份、0.3重量份、0.35重量份、0.4重量份、0.45重量份、0.5重量份、0.55重量、0.60重量份、0.65重量份、0.7重量份、0.75重量份、0.8重量份、0.85重量份、0.9重量份或0.95重量份。
理想地,前述固化促進劑為異辛酸鋅、4-二甲氨基吡啶、2-甲基咪唑、2-乙基4-甲基咪唑或2-苯基咪唑所成群中任意一種或至少兩種之混合物。
理想地,如有需要,前述環氧樹脂組合物進一步包括阻燃劑,使環氧樹脂樹脂組合物具有阻燃特性,符合UL94V-0要求,對視需要而添加的阻燃劑並無特別限定,理想地,該阻燃劑為含溴阻燃劑或/和無鹵阻燃劑。
阻燃劑的添加量根據固化產物達到UL 94V-0級別要求而定,並無特別的限定,理想地,以組分(A)、組分(B)和組分(C)添加量之和為100重量份計,前述阻燃劑的添加量為5~50重量份,例如5重量份、10重量份、15重量份、25重量份、30重量份、35重量份、40重量份或45重量份。
理想地,前述含溴阻燃劑選自十溴二苯乙烷、溴化聚苯乙烯、乙撐雙四溴鄰苯二甲醯亞胺或含溴環氧樹脂所成群中任意一種或至少兩種之混合物。
理想地,前述無鹵阻燃劑為三(2,6-二甲基苯基)膦、10-(2,5-二羥基苯基)-9,10-二氫-9-氧雜-10-膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯、10-苯基-9,10-二氫-9-氧雜-10-膦菲-10-氧化物、苯氧基膦腈化合物、硼酸鋅、氮磷系膨脹型、有機聚合物無鹵阻燃劑或含磷酚醛樹脂所成群中任意一種或至少兩種之混合物。
理想地,如有需要,前述環氧樹脂組合物進一步包含填料,前述填料為有機填料或/及無機填料,其主要用來調整環氧樹脂組合物的一些物性效果,如降低熱膨脹係數(CTE)、降低吸水率和提高熱導率等。
填料的添加量並無特別限定,理想地,以組分(A)、組分(B)和組分(C)的添加量之和為100重量份計,前述填料的添加量為0~100重量份且不包括0,理想為0~50重量份且不包括0。前述填料的添加量例如為0.5重量份、1重量份、5重量份、10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份、50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份、90重
量份或95重量份。
理想地,前述無機填料選自熔融二氧化矽、結晶型二氧化矽、球型二氧化矽、空心二氧化矽、氫氧化鋁、氧化鋁、滑石粉、氮化鋁、氮化硼、碳化矽、硫酸鋇、鈦酸鋇、鈦酸鍶、碳酸鈣、矽酸鈣、雲母或玻璃纖維粉所成群中任意一種或至少兩種之混合物。前述混合物例如熔融二氧化矽和結晶型二氧化矽的混合物,球型二氧化矽和空心二氧化矽的混合物,氫氧化鋁和氧化鋁的混合物,滑石粉和氮化鋁的混合物,氮化硼和碳化矽的混合物,硫酸鋇和鈦酸鋇的混合物,鈦酸鍶和碳酸鈣的混合物,矽酸鈣、雲母和玻璃纖維粉的混合物,熔融二氧化矽、結晶型二氧化矽和球型二氧化矽的混合物,空心二氧化矽、氫氧化鋁和氧化鋁的混合物,滑石粉、氮化鋁和氮化硼的混合物,碳化矽、硫酸鋇和鈦酸鋇的混合物,鈦酸鍶、碳酸鈣、矽酸鈣、雲母和玻璃纖維粉的混合物。
理想地,前述有機填料選自聚四氟乙烯粉末、聚苯硫醚或聚醚碸粉末所成群中任意一種或至少兩種之混合物。前述混合物例如聚四氟乙烯粉末和聚苯硫醚的混合物,聚醚碸粉末和聚四氟乙烯粉末的混合物,聚苯硫醚和聚醚碸粉末的混合物,聚四氟乙烯粉末、聚苯硫醚和聚醚碸粉末的混合物。
理想地,前述填料為二氧化矽,填料的粒徑中間值為1~15μm,理想填料的粒徑中間值為1~10μm。
本發明前述的“包括”,意指其除前述組份外,還可以包括其他組份,這些其他組分賦予前述環氧樹脂組合物不同的特性。除此之外,本發明前述的“包括”,還可以替換為封閉式的“為”或“由......組成”。
例如,前述環氧樹脂組合物還可以含有各種添加劑,作為具體例,可以舉出抗氧劑、熱穩定劑、抗靜電劑、紫外線吸收劑、顏料、著色劑或潤滑劑等。這些各種添加劑可以單獨使用,也可以兩種或者兩種以上混合使用。
本發明的環氧樹脂組合物膠液的常規製作方法:取一容器,先將固體組分放入,然後加入溶劑,攪拌直至完全溶解後,再加入液體樹脂、填料、阻燃劑和固化促進劑,繼續攪拌均勻即可,最後用溶劑調整液體固含量至60%~80%而製成膠液。
本發明之目的之二在於提供一種預浸料,其包括增強材料及通過含浸乾燥後附著其上的如上前述的環氧樹脂組合物。
示例性的增強材料如無紡織物或/和其他織物,例如天然纖維、有機合成纖維以及無機纖維。
使用該膠液含浸增強材料如玻璃布等織物或有機織物,將含浸好的增強材料在155℃的烘箱中加熱乾燥5~10分鐘即可得到預浸料。
本發明之目的之三在於提供一種層壓板,其包括至少一張如前述的預浸料。
本發明之目的之四在於提供一種印刷電路板,其包括至少一張如前述的預浸料。
與現有技術相比,本發明具有以下功效:
(1)本發明通過採用特定含量的含有DCPD(雙環戊二烯)結構的環氧樹脂,可以提升環氧樹脂組合物的玻璃轉化溫度和降低其吸水率;特定
含量的活性酯固化劑可以改善環氧樹脂組合物的介電性能和吸水性能;特定含量的氰酸酯樹脂能很好地提高環氧樹脂組合物的玻璃轉化溫度和降低其熱膨脹係數。本發明利用上述特定含量的三種必要組分之間的相互配合以及相互協同促進作用,得到了如上的環氧樹脂組合物。採用該環氧樹脂組合物製成的預浸料、層壓板以及印刷電路板,在同時具有高的耐濕熱性和高的耐熱性的前提下,還具有低熱膨脹係數、低吸水率和優異的介電性能,實現了A+B和A+C意想不到的技術效果,且有利於進一步改善組合物的PCT特性。
(2)本發明的環氧樹脂組合物中,含DCPD結構的環氧樹脂滿足其重均分子量分佈為:200~4000,且<400的重均分子量分佈所占比例<30%,有利於改善環氧樹脂組合的耐濕熱性。
以下透過具體實施方式來進一步說明本發明的技術手段。
根據上述所製成的一種環氧樹脂組合物覆金屬箔層壓板,測試其玻璃轉化溫度、熱膨脹係數、介電損耗因數、PCT及PCT吸水率,如下述實施例加於詳細說明與描述,其中有機樹脂的重量份按有機固形物重量份計。
實施例1
取一容器,加入54重量份的KES-7695,加入適量的MEK攪拌至完全溶解,隨後加入30重量份的活性酯固化劑HPC-8000-65T、16重量份的氰酸酯樹脂CE01PS、提前溶解好的固化促進劑DMAP和異辛酸鋅,繼續攪拌均
勻,最後用溶劑調整液體固含量至60%~80%,從而製成膠液。用玻璃纖維布浸漬前述膠液,並控制至適當厚度,然後烘乾除去溶劑得到預浸料。使用數張所製得的預浸料相互疊合,在其兩側分別壓覆一張銅箔,放進熱壓機中固化製成前述的環氧樹脂覆銅箔層壓板。物性數據如表1所示。
實施例2~4
製作工藝和實施例1相同,配方組成及其物性指標如表1所示。
比較例1~13
製作工藝與實施例1相同,配方組成及其物性指標如表2和表3所示。
表1~表3列舉的材料具體如下:KES-7695:含有DCPD結構的環氧樹脂(KOLON商品名),且<400的重均分子量分佈所占比例<30%wt。
7200-H:含有DCPD結構的環氧樹脂(日本DIC商品名),且<400的重均分子量分佈所占比例>30%wt。
NC-3000H:聯苯型酚醛環氧樹脂(日本化藥商品名)。
HPC-8000-65T:活性酯交聯劑(日本DIC商品名)。
CE01PS:雙酚A型氰酸酯樹脂(揚州天啟商品名)。
DMAP:固化促進劑,4-二甲氨基吡啶(廣榮化學商品名)。
異辛酸鋅:阿法埃莎的固化促進劑。
以上特性的測試方法如下:玻璃轉化溫度(Tg):根據差示掃描量熱法(DSC),按照IPC-TM-6502.4.25所規定的DSC方法進行測定。
熱膨脹係數(CTE):根據熱機械分析儀(TMA),按照IPC-TM-650 2.4.24.6所規定的TMA方法進行測定。
介電損耗因數:按照IPC-TM-6502.5.5.13的方法進行測試,測試頻率為10GHz。
PCT後耐浸焊性評價:將覆銅板表面的銅箔蝕刻後,評價基板;將基板放置壓力鍋中,在120℃、105KPa條件下處理2h;後浸漬在288℃的錫爐
中,當基板分層爆板時記錄相應時間;當基板在錫爐中超過5min還沒出現氣泡或分層時即可結束評價。3塊中如有0,1,2,3塊出現氣泡或分層現象記為0/3,1/3,2/3,3/3。
PCT吸水率:將覆銅板表面的銅箔蝕刻後,稱重並記錄為m1,將基板放置壓力鍋中,在120℃、105KPa條件下處理2h後取出,用乾布擦乾試樣後立即稱重,記錄為m2。則PCT吸水率%=(m2-m1)/m1*100%。
物性分析:
(1)實施例1和實施例4相比可知,實施例1的玻璃轉化溫度比實施例4的要高、實施例1的熱膨脹係數比實施例4要低,但其介質損耗因數和吸水率比實施例3的要高,說明隨著活性酯固化劑加入量增加,能很好地降低組合物的介質損耗因數和吸水率,但其帶來了玻璃轉化溫度的下降和熱膨脹係數的升高。
(2)實施例2、實施例3和實施例1相比可知,實施例2、實施例3的玻璃轉化溫度比實施例1的要高、實施例2和實施例3的熱膨脹係數、介質損耗因數比實施例1的更低,但其吸水率比實施例1的要高,說明隨著氰酸酯樹脂加入量增加,其能很好地提高組合物的玻璃轉化溫度、降低組合物的熱膨脹係數和介質損耗因數,但會帶來吸水率的升高。
(3)將實施例1與比較例1相比可知,實施例1的玻璃轉化溫度比比較例1的要高、實施例1的熱膨脹係數比比較例1要低,同時其介質損耗因數和吸水率與比較例1基本一致,但比較例1的PCT無法滿足要求,說明控制含DCPD結構的環氧樹脂中<400的重均分子量分佈所占比例<30%wt,有利於改善樹脂組合的耐濕熱性。
(4)將實施例1、實施例2、實施例3與比較例2相比可知,比較例2的玻璃轉化溫度比實施例1、實施例2、實施例3的要高、比較例2的熱膨脹係數比實施例1、實施例2、實施例3要低,但其介質損耗因數和吸水率比實施例1、實施例2、實施例3要高,且比較例2的PCT無法滿足要求,說明隨著活性酯加入量增加,有利於改善樹脂組合的耐濕熱性,且當活性酯加入量達到一定值時,即使氰酸酯的加入量不斷地在增加,組合物的耐濕熱性依然滿足要求。
(5)將實施例1與比較例3、比較例4、比較例5相比可知,實施例1的介質損耗因數較比較例3、比較例4、比較例5的要低,但比較例5的介質損耗因數較比較例3高,卻較比較例4低,另外比較例4和比較例5的PCT性能無法滿足要求,說明通過對組合物樹脂比例的控制,使組合物的介質損耗因數低於單獨A+B和A+C意想不到的技術效果,且有利於進一步改善組合物的PCT特性。
(6)將實施例1、實施例2、實施例3、實施例4與比較例6相比可知,雖然比較例6的PCT特性能滿足要求,且其吸水率比實施例1、實施例2、實施例3、實施例4的要低,但其玻璃轉化溫度比實施例1、實施例2、實施例3、實施例4要低,並且其熱膨脹係數、介質損耗因數較實施例1、實施例2、實施例3、實施例4的要高。說明通過增加活性酯的加入量和減少氰酸酯的加入量,有利於改善組合物的PCT特性和降低其吸水率,但帶來了玻璃轉化溫度的下降和熱膨脹係數和介質損耗因數的上升。
(7)比較例7、比較例8和比較例9相比可知,比較例9的介質損耗因數比比較例7高,但較比較例8的介質損耗因數高,說明不同結構
的環氧樹脂對組合物的介質損耗因數的影響是不同的。
(8)此外,通過實施例1~4與比較例2、5、6、10~13可以看出,只要採用特定含量的含DCPD結構的環氧樹脂、活性酯固化劑和氰酸酯樹脂才可以實現高玻璃轉化溫度、低熱膨脹係數、高耐濕熱性、低吸水率、低介質損耗因數。
因此,與一般的層壓板相比,本發明的環氧電路基板具有高玻璃轉化溫度、低熱膨脹係數、高耐濕熱性、低吸水率、低介質損耗因數。
申請人聲明,本發明透過上述實施例說明本發明的詳細方法,但本發明並不侷限於上述詳細方法,即不意味著本發明必須依賴上述詳細方法才能實施。所屬技術領域之通常知識者應該明瞭,對本發明的任何改進,對本發明產品各原料的等效替換及輔助成分的添加、具體方式的選擇等,均落在本發明的保護範圍和公開範圍之內。
Claims (24)
- 一種環氧樹脂組合物,其特徵係其包括如下組分:(A)含有DCPD結構的環氧樹脂:38~54重量份;(B)活性酯固化劑:30~36重量份;(C)氰酸酯樹脂:16~32重量份。
- 如申請專利範圍第1項所記載之環氧樹脂組合物,其中,前述組分(A)含有DCPD結構的環氧樹脂的添加量為45~54重量份。
- 如申請專利範圍第1項所記載之環氧樹脂組合物,其中,前述組分(A)含有DCPD結構的環氧樹脂為具有式(1)結構的環氧樹脂:
- 如申請專利範圍第1或2項所記載之環氧樹脂組合物,其中,前述組分(B)活性酯固化劑的添加量為30~33重量份。
- 如申請專利範圍第1項所記載之環氧樹脂組合物,其中,前述組分(B)活性酯固化劑由一種透過脂肪環烴結構連接的酚類化合物、二官能度羧酸芳香族化合物或酸性鹵代物及一種單羥基化合物反應而得。
- 如申請專利範圍第5項所記載之環氧樹脂組合物,其中,前述二官能羧酸芳香族化合物或酸性鹵化物用量為1mol,透過脂肪環烴結構連接的酚類化合物用量為0.05~0.75mol,單羥基化合物用量為0.25~0.95mol。
- 如申請專利範圍第1項所記載之環氧樹脂組合物,其中,前述組分(B)活性酯固化劑包括具有式(2)結構的活性酯:
- 如申請專利範圍第1項所記載之環氧樹脂組合物,其中,前述組分(C)氰酸酯樹脂的添加量為16~25重量份。
- 如申請專利範圍第1項所記載之環氧樹脂組合物,其中,前述組分(C)氰酸酯樹脂為雙酚A型氰酸酯樹脂、雙酚F型氰酸酯樹脂、雙環戊二烯型氰酸酯樹脂或苯酚酚醛型氰酸酯樹脂所成群中任意一種或至少兩種之混合物。
- 如申請專利範圍第1項所記載之環氧樹脂組合物,其中,前述環氧樹脂組合物進一步包括固化促進劑,以組分(A)、組分(B)和組分(C)添加量之和為100重量份計,前述固化促進劑的添加量為0.05~1重量份。
- 如申請專利範圍第10項所記載之環氧樹脂組合物,其中,前述固化促進劑為異辛酸鋅、4-二甲氨基吡啶、2-甲基咪唑、2-乙基4-甲基咪唑或2-苯基咪唑所成群中任意一種或至少兩種之混合物。
- 如申請專利範圍第1項所記載之環氧樹脂組合物,其中,前述環氧樹脂組合物進一步包括阻燃劑。
- 如申請專利範圍第12項所記載之環氧樹脂組合物,其中,該阻燃劑為含溴阻燃劑或/及無鹵阻燃劑。
- 如申請專利範圍第12項所記載之環氧樹脂組合物,其中,以組分(A)、組分(B)和組分(C)添加量之和為100重量份計,前述阻燃劑的添加量為5~50重量份。
- 如申請專利範圍第13項所記載之環氧樹脂組合物,其中,前述含溴阻燃劑選自十溴二苯乙烷、溴化聚苯乙烯、乙撐雙四溴鄰苯二甲醯亞胺或含溴環氧樹脂所成群中任意一種或至少兩種之混合物。
- 如申請專利範圍第13項所記載之環氧樹脂組合物,其中,前述無鹵阻燃劑為三(2,6-二甲基苯基)膦、10-(2,5-二羥基苯基)-9,10-二氫-9-氧雜-10-膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯、10-苯基-9,10-二氫-9-氧雜-10-膦菲-10-氧化物、苯氧基膦腈化合物、硼酸鋅、氮磷系膨脹型、有機聚合物無鹵阻燃劑或含磷酚醛樹脂所成群中的任意一種或至少兩種之混合物。
- 如申請專利範圍第1項所記載之環氧樹脂組合物,其中,前述環氧樹脂組合物進一步包含填料;前述填料為有機填料或/及無機填料。
- 如申請專利範圍第17項所記載之環氧樹脂組合物,其中,以組分(A)、組分(B)和組分(C)的添加量之和為100重量份計,前述填料的添加量為0~100重量份且不包括0。
- 如申請專利範圍第17項所記載之環氧樹脂組合物,其中,前述無機填料選自熔融二氧化矽、結晶型二氧化矽、球型二氧化矽、空心二氧化矽、氫氧化鋁、氧化鋁、滑石粉、氮化鋁、氮化硼、碳化矽、硫酸鋇、鈦酸鋇、鈦酸鍶、碳酸鈣、矽酸鈣、雲母或玻璃纖維粉所成群中的任意一種或至少兩種的混合物。
- 如申請專利範圍第17項所記載之環氧樹脂組合物,其中,前述有機填料選自聚四氟乙烯粉末、聚苯硫醚或聚醚碸粉末所成群中的任意一種或至少兩種的混合物。
- 如申請專利範圍第17項所記載之環氧樹脂組合物,其中,前述填料為二氧化矽,填料的粒徑中度值為1~15μm。
- 一種預浸料,其特徵係其包括增強材料及透過含浸乾燥後附著其上之如申請專利範圍第1至21項中任一項所記載之環氧樹脂組合物。
- 一種層壓板,其特徵係其包括至少一張如申請專利範圍第22項所記載之預浸料。
- 一種印刷電路板,其特徵係其包括至少一張如申請專利範圍第22項所記載之預浸料。
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CN111825951A (zh) * | 2020-07-28 | 2020-10-27 | 惠柏新材料科技(上海)股份有限公司 | 一种具有增韧性质的环氧树脂组合物及合成方法 |
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KR102054093B1 (ko) | 2019-12-09 |
EP3392286A4 (en) | 2019-06-26 |
EP3392286A1 (en) | 2018-10-24 |
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