CN114196189B - 一种适用于高耐热氧化性低介电无卤覆铜箔板的组合物及其应用 - Google Patents
一种适用于高耐热氧化性低介电无卤覆铜箔板的组合物及其应用 Download PDFInfo
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- CN114196189B CN114196189B CN202111459843.4A CN202111459843A CN114196189B CN 114196189 B CN114196189 B CN 114196189B CN 202111459843 A CN202111459843 A CN 202111459843A CN 114196189 B CN114196189 B CN 114196189B
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- Prior art keywords
- copper foil
- halogen
- free
- composition suitable
- fluorine
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000011889 copper foil Substances 0.000 title claims abstract description 30
- 239000000203 mixture Substances 0.000 title claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 239000011737 fluorine Substances 0.000 claims abstract description 16
- 239000010949 copper Substances 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 239000004005 microsphere Substances 0.000 claims description 6
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
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- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 5
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 3
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- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 claims description 2
- ZXLAFQNTMMFLSA-UHFFFAOYSA-N 1-ethenyl-4-[2-(4-ethenylphenyl)ethyl]benzene Chemical compound C1=CC(C=C)=CC=C1CCC1=CC=C(C=C)C=C1 ZXLAFQNTMMFLSA-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
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- 238000000576 coating method Methods 0.000 claims description 2
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- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical class 0.000 claims 2
- 239000000853 adhesive Substances 0.000 claims 1
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
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- 150000003254 radicals Chemical class 0.000 description 4
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- 230000004913 activation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-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
- 239000005062 Polybutadiene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-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
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910017083 AlN Inorganic materials 0.000 description 1
- 102100034112 Alkyldihydroxyacetonephosphate synthase, peroxisomal Human genes 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- WKJZWMMSPLYASX-UHFFFAOYSA-N CC1=CC=CC(C)=C1C1=PC(C2=C(C)C=CC=C2C)=CC=C1 Chemical compound CC1=CC=CC(C)=C1C1=PC(C2=C(C)C=CC=C2C)=CC=C1 WKJZWMMSPLYASX-UHFFFAOYSA-N 0.000 description 1
- 101000799143 Homo sapiens Alkyldihydroxyacetonephosphate synthase, peroxisomal Proteins 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- JAVAKQKVPGZTPU-UHFFFAOYSA-N Oc1ccc(O)c(c1)-c1cccc2-c3ccccc3OP(=O)c12 Chemical compound Oc1ccc(O)c(c1)-c1cccc2-c3ccccc3OP(=O)c12 JAVAKQKVPGZTPU-UHFFFAOYSA-N 0.000 description 1
- 241000153282 Theope Species 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 238000000848 angular dependent Auger electron spectroscopy Methods 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
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- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910002026 crystalline silica Inorganic materials 0.000 description 1
- SVRNLRHPTVJUBJ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ylidene-(2,6-dimethylphenyl)-oxidophosphanium Chemical compound CC1=C(C(=CC=C1)C)P(=O)=C1CC=CC=C1 SVRNLRHPTVJUBJ-UHFFFAOYSA-N 0.000 description 1
- RECMXUUCYFGBEZ-UHFFFAOYSA-N cyclohexyl cyclohexyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC1CCCCC1 RECMXUUCYFGBEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000550 effect on aging Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RERMPCBBVZEPBS-UHFFFAOYSA-N tris(2,6-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(C)=C1P(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C RERMPCBBVZEPBS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/036—Multilayers with layers of different types
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明公开了一种适用于高耐热氧化性低介电无卤覆铜箔板的组合物。还公开了将所述的组合物对玻璃纤维布进行涂覆，制得半固化片后，在半固化片两侧复合Hoz厚度的含氟RCC铜箔后固化制成覆铜箔板的应用。本发明所制备的覆铜箔板可完全满足毫米波雷达对于低插损、高稳定性的需求。
Description
技术领域
本发明涉及5G材料制备领域，具体涉及一种适用于高耐热氧化性低介电无卤覆铜箔板的组合物及其应用。
背景技术
伴随着5G商业化以及相关设施的全面建设，众多有着较高通信数据需求的产业得到了迅猛发展，而其中自动驾驶已成为当下热点。
高级驾驶辅助系统(Advanced Driver Assistant System，ADAS)，是利用安装在车上的雷达传感器，在汽车行驶过程中随时来感应周围的环境，从而预先让驾驶者察觉到可能发生的危险，有效的增加了汽车驾驶的舒适性和安全。汽车雷达系统主要频段分布在24GHz(短距毫米波雷达)和77GHz长距毫米波雷达，然而由于毫米波的相关特性，此类雷达基板需适应较高的数据传输条件，主要是集中在对高频率，宽温度和湿度范围的要求。
随着工作频率的升高，电路的导体损耗以及介质损耗都会急剧增加，当频率不断升高时，对于极性较强的树脂来讲，树脂内电荷产生的电流和树脂的极化无法赶上频率的变化，损耗越严重，因此其Df相对较高且随频率增大而增大；极性越弱Df越低，频率对其的影响越小。
目前主流77GHZ雷达基板Df均低于0.002(@10GHz)，同时根据汽车内部环境，要求材料电性能具有长期的高温稳定性。
在毫米波雷达装置中，需要采用高频电路基板。目前，这种高频基板的基材，一般采用的是聚四氟乙烯类(PTFE)覆铜板。由它和相关的增强材料可制得介电常数2.16～13.5、tanδ0.0009～0.004(10GHz)等一系列微波覆铜板。它所制得PTFE/E-玻璃纤维布基覆铜板(CCL),其介电常数的典型值为2.56，远比其它树脂覆铜板的介电常数低很多。
由于氟原子具有极高的电负性，使得C-F键变得很短，键能很强，加之氟原子体积大，使高分子链成螺旋状紧密排列，因而具有优异的耐化学药品性、耐酸碱性、耐湿热等特性。但这种基材现今仍存在着价格偏高、PCB加工较难的问题，因此用此类基材设计、制造的高频基板，其主流是单双面板。如在表面电路层部分采用PTFE类覆铜板的基材，而内层部分则采用FR-4型覆铜板等非PTFE树脂基材，这种基板的设计，不仅可降低基板的制作成本，而且电路层构成上还实现了四层等多层化，为实现基板的紧凑、高密度化电路设计做出贡献。
发明内容
为了克服现有技术的上述缺陷，本发明的目的在于提供一种适用于高耐热氧化性低介电无卤覆铜箔板的组合物及其应用。以满足毫米波雷达对于低插损、高稳定性(主要体现在宽温度和湿度范围的要求)的需求。
为了实现本发明的目的，所采用的技术方案是：
一种适用于高耐热氧化性低介电无卤覆铜箔板的组合物，按重量百分比计算，包括如下组分：
在本发明的一个优选实施例中，所述含不饱和键的聚苯醚树脂为数均分子量在1200-2200的乙烯苄基聚苯醚树脂(如OPE-2st 1200、2200，可购自三菱瓦斯化学公司)、数均分子量在1900-2300的甲基丙烯酸酯聚苯醚树脂(如SA-9000，可购自Sabic公司)、数均分子量在2400-2800的乙烯苄基改性双酚A聚苯醚树脂或数均分子量在2200-3000的乙烯基扩链聚苯醚树脂。
在本发明的一个优选实施例中，所述交联剂为分子链上具有碳-碳不饱和双键，能发生自由基聚合反应而形成交联物的化合物。
优选三烯丙基异氰脲酸酯、三聚氰酸三烯丙酯、苯乙烯、二乙烯基苯、双马来酰亚胺或三羟甲基丙烷三甲基丙烯酸酯中的任意一种或多种。
在本发明的一个优选实施例中，所述乙烯基热固性树脂为聚丁二烯、聚丁二烯共聚物、苯乙烯-二乙烯基苯低聚物、p,p’-二乙烯基-1,2-二苯基乙烷、乙烯-苯乙烯共聚物中的任意一种或多种。
在本发明的一个优选实施例中，所述无卤阻燃剂为含磷无卤阻燃剂。优选三(2,6-二甲基苯基)磷、10(2,5-二羟基苯基)-9,10-二氢-9-氧杂-10-磷菲-10-氧化物、2,6-二(2,6-二甲基苯基)磷基苯或10-苯基-9,10-二氢-9-氧杂-10-磷菲-10-氧化物中的任意一种或多种。
在本发明的一个优选实施例中，所述无机填料为粒径在0.01-24μm，纯度不低于99.9％的无机填料。
优选氮化铝、硼酸铝、氧化镁、碳酸镁、立方氮化硼、结晶二氧化硅、合成二氧化硅、中空二氧化硅、球形二氧化硅、熔融二氧化硅、滑石粉、氧化铝、硫酸钡、钛酸钡、钛酸锶、碳酸钙或二氧化钛中的任意一种或多种。
在本发明的一个优选实施例中，所述高温引发剂为促进碳-碳不饱和双键发生自由基聚合反应的有机过氧化物。优选2，5-二甲基-2，5-双(叔丁基过氧基)己烷、2，3-二甲基-2，3-二苯基丁烷、1，1-双(叔己基过氧化)-3，3，5-三甲基环己烷、过氧化苯甲酰、过氧化月桂酰、过氧化二叔丁基、过氧化二异丙苯、双叔丁基过氧化二异丙苯、过氧化苯甲酸叔丁酯、叔丁基过氧化特戊酸酯、过氧化甲乙酮、过氧化环己酮、过氧化二碳酸二异丙酯或过氧化碳酸二环己酯中的任意一种或多种。
一种适用于高耐热氧化性低介电无卤覆铜箔板的组合物的应用，所述应用为将其制得半固化片后，在半固化片两侧复合Hoz厚度的含氟RCC铜箔后固化制成覆铜箔板。
所述含氟RCC铜箔的含氟树脂层为全氟丙基全氟乙烯基醚与聚四氟乙烯的共聚物(PFA)或氟化乙烯丙烯共聚物(FEP)中的任意一种或多种，二者相较聚四氟乙烯其结晶度波动性较小，电性能优良，在毫米波范围内具有信号损失减小的效果。
所述含氟RCC铜箔的铜箔层为带有背胶的压延铜、标准电解铜箔、反转铜箔、低轮廓铜箔或超低轮廓铜箔。
在本发明的一个优选实施例中，所述含氟树脂层的100μm～1.0mm。
本发明的有益效果在于：
(1)采用小分子及高度反应性(短链)树脂，提高耐老化性。
(2)引入含氟RCC可根据不同性能需求搭配任意种类铜箔，甚至粗糙度较低的HVLP铜箔(指的超低轮廓铜箔)也能获得较高的拉力水平。同时也降低了对原基板的性能要求，可平衡背胶铜箔本身的高成本。
(3)由于含氟RCC的引入，有优异的耐老化及低吸水性能，满足了毫米波雷达的耐候需求。
(4)采用本发明所制备的高耐热氧化性低介电型覆铜箔板有如下性能方面的优势：
Tg＞200℃(DMA)；Z轴CTE＜3.5％；
耐热性方面：TD≥360℃，T288＞120min；
电性能方面：介电常数(10GHz)≤3.10；
介电损耗(10GHz＜0.00150；
铜箔剥离强度(H OZ)＞0.5N/mm，并且阻燃达到UL94V-0级，可完全满足毫米波雷达对于低插损、高稳定性的需求。
具体实施方式
本发明所基于的工作原理在于：
有研究表明,高分子材料在光、热和氧共同作用下老化是一个自动催化过程,主要是按照游离基反应历程进行:
1)链的引发:
RH———R·
RH+O2———R·+HO2·
R·+O2———RO2·
2)链的增加和传递:
RO2+RH———ROOH+R·
ROOH———RO·+·OH
ROOH+RH———RO·+R·+H2O
RO·+RH———ROH+R·
3)链的终止:
R·+R·———R—R
R·+RO2·———ROOR
RO2·+RO2·———ROOR+O2。
许多研究工作表明,引发阶段的反应活化能高,是整个反应过程中较难进行的一步。链的增加阶段的反应活化能很低,极容易进行,而氢过氧化物分解反应活化能较高,反应较慢,所以高聚物的氧化速度由它来决定。
高聚物热氧化的引发难易程度,取决于材料的分子结构。由于氧引起的自由基在高分子链上各个位置都有可能产生,反应的主要产物是过氧化氢,在适当的条件下,过氧化氢分解为游离基。当高聚物分子被引发后会产生活性中心,氢过氧化物在分解时也会产生活性中心,且后者比前者所需要的能量要少得多,所以氧化过程具有自动催化的特点,这些游离基能进一步引发链的连锁反应。
化学介质对高分子材料的老化可以理解为聚合物材料在化学介质中发生的,并引起材料性能变化的化学与物理过程的总和。
一些学者研究了聚氨酯在有机酸中的降解,发现聚氨酯表面与材料内部的降解程度差距很大,只有当流动的介质渗透到固态的高分子材料内部去,它们之间的相互作用才能实现。
自由体积论认为聚合物中变动不定的局部密度会造成自由体积或空穴,当一个足够大的空穴在渗入分子附近时,分子即移入或跳入空穴之中来达到迁移。遵循此原理可在材料表面认为添加耐氧化层阻隔氧气分子的进入，或采用位阻效应强的分子结构来减少空穴，以此来降低材料因热氧化过程发生的老化现象。
本发明也是基于此进行的研发，下面结合实施例对本发明的工作原理做进一步地说明。
实施例1-3以及比较例1-3
实施例1-3以及比较例1-3的配方如表4所示：
其中PPO指的是甲基丙烯酸酯聚苯醚树脂SA9000。
OPE指的乙烯苄基聚苯醚树脂OPE-2st 2200。
BVPE指的p,p’-二乙烯基-1,2-二苯基乙烷。
SEBS指的是氢化苯乙烯-丁二烯嵌段共聚物。
SBS指的是苯乙烯-丁二烯-苯乙烯嵌段共聚物。
固化剂(交联剂)具体为三烯丙基异氰脲酸酯。
无机填料为球型二氧化硅。
高温引发剂为过氧化二异丙苯。
中空玻璃微球为硼硅酸盐玻璃微珠，D50粒径为20微米。
阻燃剂具体为2,6-二(2,6-二甲基苯基)磷基苯。
表4
实施例1-3的制备方法如下：
将含不饱和键的聚苯醚树脂、固化剂(交联剂)、乙烯基热固性树脂、阻燃剂、中空玻璃微球、无机填料和高温引发剂在甲苯溶剂中溶剂并分散均匀；
后采用1078NE玻璃纤维布浸渍在以上胶液，在140℃烤箱中烘干溶剂，制得半固化片。
比较例1-3也采用同样的方法，只是部分配方不同。
在半固化片两侧复合Hoz厚度的超低轮廓含氟RCC铜箔，在压机中真空固化2h，固化温度为220℃，温升1.5℃/min，制成覆铜层压板(即覆铜箔板)。
表5
从表5数据可知比较例1OPE虽耐高温性能更佳，但热氧化环境下电性能下降更多；
比较例2大分子SEBS多直链易被氧化，但因为氢化处理其老化介质损耗DF下降幅度比比较例3中含反应双键的SBS低，但明显高于本发明实施例1-3的数值。
实施例1-3中采用反应活性高且分子结构稳定的PPO及BVPE有着更加优秀的抗老化性能，且在拉力，电性能，力学性能等因素中达到理想的平衡。
实施例2增加填料后对老化性能有所改善，实施例3中固化剂含量对老化影响不大。
在比较无RCC和有RCC的各实施例和比较例4周153℃的老化情况后可观察出实施例1-4的含氟涂层(用于制备半固化片的组合物)极大减缓基板电性能老化幅度。
Claims (4)
1.一种适用于高耐热氧化性低介电无卤覆铜箔板的组合物，其特征在于，按重量百分比计算，为如下组分：
含不饱和键的聚苯醚树脂 20-50％；
交联剂 5-20％；
乙烯基热固性树脂 5-20％；
无卤阻燃剂 5-15％；
无机填料 5-40％；
中空玻璃微球 1-5％
高温引发剂 0.05-0.2％；
所述含不饱和键的聚苯醚树脂为数均分子量在1900-2300的甲基丙烯酸酯聚苯醚树脂；
所述交联剂为三烯丙基异氰脲酸酯；
所述乙烯基热固性树脂为p,p’-二乙烯基-1,2-二苯基乙烷；
所述无卤阻燃剂为含磷无卤阻燃剂；
所述无机填料为粒径在0.01-24μm，纯度不低于99.9％的球型二氧化硅；
所述高温引发剂为促进碳-碳不饱和双键发生自由基聚合反应的有机过氧化物；
所述中空玻璃微球为硼硅酸盐玻璃微珠。
2.一种适用于高耐热氧化性低介电无卤覆铜箔板的组合物的应用，所述应用为将如权利要求1所述的组合物对玻璃纤维布进行涂覆，制得半固化片后，在半固化片两侧复合Hoz厚度的含氟RCC铜箔后固化制成覆铜箔板。
3.如权利要求2所述的一种适用于高耐热氧化性低介电无卤覆铜箔板的组合物的应用，其特征在于，所述含氟RCC铜箔的含氟树脂层为全氟丙基全氟乙烯基醚与聚四氟乙烯的共聚物或氟化乙烯丙烯共聚物中的任意一种或多种。
4.如权利要求2所述的一种适用于高耐热氧化性低介电无卤覆铜箔板的组合物的应用，其特征在于，所述含氟RCC铜箔的铜箔层为带有背胶的压延铜、标准电解铜箔、反转铜箔、低轮廓铜箔或超低轮廓铜箔；所述含氟树脂层的100μm～1.0mm。
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| JP2008115280A (ja) * | 2006-11-06 | 2008-05-22 | Hitachi Ltd | 低誘電損失樹脂組成物、その硬化物およびそれを用いた電子部品 |
| JP2010111758A (ja) * | 2008-11-06 | 2010-05-20 | Hitachi Chem Co Ltd | 樹脂組成物、プリプレグ、積層板及びプリント基板 |
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| CN110615876A (zh) * | 2019-09-27 | 2019-12-27 | 苏州生益科技有限公司 | 无卤聚苯醚树脂组合物及使用其制作的半固化片和层压板 |
| CN112500667A (zh) * | 2020-11-30 | 2021-03-16 | 南亚新材料科技股份有限公司 | 一种电子产品组件用热固性树脂组合物及其应用 |
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| JP2010111758A (ja) * | 2008-11-06 | 2010-05-20 | Hitachi Chem Co Ltd | 樹脂組成物、プリプレグ、積層板及びプリント基板 |
| CN110181904A (zh) * | 2018-12-31 | 2019-08-30 | 曾瑾 | 一种高频无胶双面挠性覆铜板及其制备方法 |
| CN110615876A (zh) * | 2019-09-27 | 2019-12-27 | 苏州生益科技有限公司 | 无卤聚苯醚树脂组合物及使用其制作的半固化片和层压板 |
| CN112500667A (zh) * | 2020-11-30 | 2021-03-16 | 南亚新材料科技股份有限公司 | 一种电子产品组件用热固性树脂组合物及其应用 |
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