CN116638836A - Preparation method of liquid crystal fiber cloth reinforced laminated board - Google Patents
Preparation method of liquid crystal fiber cloth reinforced laminated board Download PDFInfo
- Publication number
- CN116638836A CN116638836A CN202211727456.9A CN202211727456A CN116638836A CN 116638836 A CN116638836 A CN 116638836A CN 202211727456 A CN202211727456 A CN 202211727456A CN 116638836 A CN116638836 A CN 116638836A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- fiber cloth
- crystal fiber
- producing
- laminate according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000000835 fiber Substances 0.000 title claims abstract description 108
- 239000004744 fabric Substances 0.000 title claims abstract description 102
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000011342 resin composition Substances 0.000 claims abstract description 15
- 239000000853 adhesive Substances 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000003292 glue Substances 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000009832 plasma treatment Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims description 59
- 239000011347 resin Substances 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 42
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical class O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 9
- 229920013638 modified polyphenyl ether Polymers 0.000 claims description 9
- 239000013032 Hydrocarbon resin Substances 0.000 claims description 8
- 229920006270 hydrocarbon resin Polymers 0.000 claims description 8
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 8
- 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 7
- 239000003063 flame retardant Substances 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- -1 vinyl bismaleimide Chemical compound 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 3
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 2
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000378 calcium silicate Substances 0.000 claims description 2
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 2
- 235000012241 calcium silicate Nutrition 0.000 claims description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000391 magnesium silicate Substances 0.000 claims description 2
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 2
- 235000019792 magnesium silicate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-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
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000003365 glass fiber Substances 0.000 abstract description 7
- 229920000728 polyester Polymers 0.000 description 11
- 238000009987 spinning Methods 0.000 description 9
- 229920001225 polyester resin Polymers 0.000 description 7
- 239000004645 polyester resin Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000009941 weaving Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- LPSOCVUXCQFHPD-UHFFFAOYSA-N [P]Oc1ccccc1 Chemical compound [P]Oc1ccccc1 LPSOCVUXCQFHPD-UHFFFAOYSA-N 0.000 description 2
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- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
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- 238000004140 cleaning Methods 0.000 description 2
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- 238000000576 coating method Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012768 molten material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000008054 signal transmission Effects 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- B32B5/024—Woven fabric
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- 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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/08—Impregnating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- 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
- B32B5/26—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 another layer next to it also being fibrous or filamentary
- B32B5/262—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 another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a woven fabric layer
- B32B5/263—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 another layer next to it also being fibrous or filamentary characterised by one fibrous or filamentary layer being a woven fabric layer next to one or more woven fabric layers
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- 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
- C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
- D06M10/10—Macromolecular compounds
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0276—Polyester fibres
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- B32—LAYERED PRODUCTS
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- 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
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- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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Abstract
The invention discloses a preparation method of a liquid crystal fiber cloth reinforced laminated board, which is characterized by comprising the following preparation steps: (1) Preparing liquid crystal fiber cloth, performing plasma treatment on the liquid crystal fiber cloth, immersing the liquid crystal fiber cloth in a mixed solution of polydiene, an adhesive and a solvent, and performing surface modification on the liquid crystal fiber cloth; (2) Preparing a thermosetting resin composition glue solution, and immersing the polydiene surface-treated liquid crystal fiber cloth into the thermosetting resin composition; (3) drying and curing in an oven to prepare a prepreg; the multi-layer prepreg is then hot pressed to form a laminate. Compared with the traditional inorganic glass fiber cloth, the laminated board reinforced by the liquid crystal fiber cloth has the advantages of lower dielectric constant and dielectric loss, good peel strength, high heat resistance and the like, and can be applied to the high-frequency and high-speed field.
Description
Technical Field
The invention belongs to the technical field of laminated board preparation, and relates to a preparation method of a liquid crystal fiber cloth reinforced laminated board.
Background
With the development of 5G communication, the communication frequency is higher and higher, so that the signal transmission speed is required to be as high as possible, and the signal transmission loss is required to be as low as possible, so that the copper-clad plate substrate is required to have extremely low dielectric constant and dielectric loss at high frequency. The prepreg of the copper-clad plate substrate comprises two parts of thermosetting resin and reinforcing material, and people always improve the two parts. Thermosetting resins have been studied by those skilled in the art for a long time for thermosetting polybutadiene or copolymer resins of polybutadiene and styrene having excellent dielectric properties because hydrocarbon resins have good dielectric properties. Patent CN 101544841B and patent CN104845363 use hydrocarbon resin as thermosetting resin to prepare a copper-clad plate, but have a problem of low heat resistance after curing and insufficient high frequency characteristics. In the aspect of reinforcing materials, the electronic-grade glass fiber cloth is upgraded by common glass fiber cloth, however, the dielectric loss is still not low enough.
As an organic polymer, the liquid crystal polyester fiber has a dielectric constant and dielectric loss which are much lower than those of inorganic glass fiber cloth, can meet the use requirement of 5G high frequency, and has good application prospect in copper-clad plates. In 2013, patent CN 203994944U used liquid crystal polyester non-woven fabric as a reinforcing material to replace inorganic glass fiber cloth, and a copper-clad plate was prepared. However, the copper-clad plate has no relation to whether the copper-clad plate can meet the high-frequency application, and has no relation to the binding force problem between the liquid crystal fiber cloth and the thermosetting resin. In fact, the common liquid crystal fiber has a large number of benzene rings in the structure, and only has hydroxyl and carboxyl at two ends of a molecular chain, so that the surface of the fiber is chemically inert, the fiber is difficult to chemically react with thermosetting resin, the interface bonding force of two phases is weak, and the prepared copper-clad plate is easy to fail in subsequent use.
Disclosure of Invention
In order to solve the problems, the invention prepares the laminated board by using the polydiene surface treated liquid crystal fiber cloth and the low dielectric loss thermosetting resin composition, solves the problem of weak bonding force between the common liquid crystal fiber cloth and the thermosetting resin, and simultaneously maintains excellent high-frequency dielectric property, thereby completing the invention.
The aim of the invention is achieved by the following technical scheme.
A preparation method of a liquid crystal fiber cloth reinforced laminated board is characterized in that:
(1) Preparing liquid crystal fiber cloth, performing plasma treatment on the liquid crystal fiber cloth, immersing the liquid crystal fiber cloth in a mixed solution of polydiene, an adhesive and a solvent, and performing surface modification on the liquid crystal fiber cloth;
(2) Preparing a thermosetting resin composition glue solution, and immersing the polydiene surface-treated liquid crystal fiber cloth into the thermosetting resin composition;
(3) Drying and curing in an oven to prepare a prepreg; the multi-layer prepreg is then hot pressed to form a laminate.
In the above-mentioned method for producing a laminate,
the polydiene surface treated liquid crystal fiber cloth is prepared by immersing liquid crystal fiber cloth in a polydiene and adhesive mixed solution after plasma treatment, and then curing in an oven to form a layer of film containing double bonds on the surface of the liquid crystal fiber cloth, and the film and thermosetting resin form good interfacial bonding force in the curing process. The crystalline melting temperature (Tm) of the liquid crystal fiber cloth should be higher than 310 degrees, preferably higher than 330 degrees, more preferably higher than 350 degrees. The fiber cloth has excellent dielectric properties, and particularly has a dielectric constant Dk of 3.0-3.6 at a frequency of 10GHz, and a dielectric loss Df of less than 0.002, preferably less than 0.0015. The thickness of the fiber cloth should be less than 100 microns.
The polydiene is one or more of butadiene or isoprene with a number average molecular weight of more than 1000 and less than 50000, and unreacted double bonds remain in the molecular chain. The polydiene molecule contains polar functional groups which can react with the adhesive and can be one or more of hydroxyl, carboxyl, amino, epoxy and isocyanato.
The adhesive is a thermosetting resin or a mixture containing one or more functional groups of acid ester groups, epoxy groups, isocyanate groups and vinyl groups.
The adhesion amount of the binder to the polydiene is 0.1% by mass or more and 1% by mass or less relative to the liquid crystal fiber cloth.
The thermosetting resin composition comprises the following components in parts by weight: 30-70 parts of hydrocarbon resin, 10-30 parts of modified bismaleimide resin, 30-90 parts of modified polyphenyl ether resin, 0.01-5 parts of initiator, 20-60 parts of inorganic filler, 10-30 parts of flame retardant and 50-120 parts of solvent.
In the thermosetting resin composition, the resin composition,
the hydrocarbon resin refers to unsaturated resin containing polymerizable carbon-carbon double bonds; the unsaturated resin containing polymerizable carbon-carbon double bonds is one or a mixture of at least two of styrene-butadiene copolymer, polybutadiene, styrene-butadiene-divinylbenzene copolymer and styrene-isoprene-styrene copolymer.
The bismaleimide resin is bismaleimide resin with double bonds at the molecular chain terminal, preferably methacrylic acid end-capped bismaleimide resin or vinyl bismaleimide resin.
The modified polyphenyl ether resin is a modified polyphenyl ether resin with double bonds at molecular chain terminals, and is preferably methacrylic acid end capped polyphenyl ether resin or vinyl ether polyphenyl ether resin.
The initiator is selected from one or more of the following substances: dicumyl peroxide, di-t-butylperoxycumene, dibenzoyl peroxide or t-butylhydroperoxide.
The inorganic filler is selected from one or a combination of several of the following substances: hollow glass beads, spherical silica micropowder, silicon carbide nanoparticles, titanium dioxide, mica powder, calcium silicate, magnesium silicate, talcum powder, aluminum oxide, aluminum nitride, beryllium oxide and boron nitride, preferably silicon dioxide;
the flame retardant is selected from one or more of the following substances: tricresyl phosphate, phenoxyphosphazene compound, tributyloxyethyl phosphate, triphenyl phosphate, zinc borate and antimonous oxide.
The solvent is selected from one or more of the following substances: acetone, butanone, methanol, methyl ether, ethylene glycol methyl ether, benzene, toluene, xylene.
The preparation method of the glue solution comprises the following steps: dissolving resin solid powder in a thermosetting resin composition in a solvent, uniformly mixing the mixture according to a proportion, then sequentially adding an inorganic filler, a flame retardant, an initiator and the rest solvent, and uniformly stirring the mixture to form a glue solution.
The preparation method of the laminated board comprises the following steps: the composition glue solution is coated on the surface of the polydiene surface-treated liquid crystal fiber cloth in a dipping way, and the prepreg is obtained by drying. The multi-layer prepreg is formed by overlapping and hot-pressing the multi-layer prepreg.
The present invention is described in detail below:
the liquid crystal fiber cloth is a cloth sample prepared by using liquid crystal polyester resin through a spinning and weaving process. Specifically, after the liquid crystal polyester resin particles or powder are dried, the liquid crystal polyester resin particles or powder are subjected to steps of melting by a screw of a spinning machine, a melt metering pump, forced filtration, a spinning component, cooling and crystallization of silk, winding and doffing, and the like to obtain primary silk, and then the primary silk is subjected to heat treatment under high-temperature nitrogen after being unwound, so that the liquid crystal polyester fiber is obtained. And (3) coating the surface with the sizing agent, weaving, and cleaning the sizing agent after finishing to obtain the liquid crystal fiber cloth with the thickness of less than 100 micrometers and clean surface.
The liquid-crystalline polyester resin exhibits liquid crystallinity in a molten state. The liquid crystal polyester may be liquid crystal polyester amide, liquid crystal polyester ether, liquid crystal polyester carbonate or liquid crystal polyester imide. The liquid crystal polyester is preferably a wholly aromatic liquid crystal polyester using only an aromatic compound as a raw material monomer. The wholly aromatic liquid crystalline polyester of the present invention is composed of aromatic hydroxycarboxylic acid repeating units, aromatic dioxy repeating units, and aromatic dicarbonyl repeating units.
The method for preparing the liquid crystal polyester resin of the present invention is not limited, and any method known in the art may be employed. For example, such as melt acidolysis. In this method, the raw material monomers corresponding to the repeating units constituting the raw material monomers are heated to react in a molten state, and the torque of the reactant is detected, and the reaction is stopped at a desired temperature and torque. Then discharging and cooling from the reaction vessel to obtain the liquid crystal polyester resin.
The liquid crystalline polyester resins herein should have a suitable melting point and molecular weight for use, and should have a melting temperature (Tm) of 280 to 350 degrees and a viscosity (viscosity in direct proportion to the molecular weight of the resin) of 20 to 50pa.s at tm+20 degrees. When the melting point of the resin is lower than 280 ℃, the melting point of the fiber cloth prepared by the resin after heat treatment is also lower, and the fiber cloth is easy to melt and cannot be used when the copper-clad plate is soldered. When the melting point of the resin is higher than 350 degrees, it is not recommended to make spinning difficult. After the fiber is obtained by the resin spinning, the mechanical strength is improved by the heat post-treatment process, and the melting temperature of the fiber is synchronously improved to improve the heat resistance. The melting temperature (Tm) of the liquid crystal fiber cloth after the heat treatment should be higher than 310 degrees, preferably higher than 330 degrees, more preferably higher than 350 degrees. When the crystallization melting temperature of the fiber cloth is lower than 310 ℃, the fiber cloth is low in heat resistance, easy to melt and cannot be used. When the viscosity of the resin is lower than 20Pa.s, the molecular weight is low, and the yarn is easy to break during spinning. When the resin viscosity is higher than 50pa.s, the resin flowability is poor, and it is difficult to prepare fine fibers, resulting in a thickness exceeding 100 μm after weaving, which is not suitable. The fiber cloth has excellent dielectric properties, and particularly has a dielectric constant Dk of 3.0-3.6 at a frequency of 10GHz, and a dielectric loss Df of less than 0.002, preferably less than 0.0015. The thickness of the fiber cloth should be less than 100 microns.
The bonding solution described herein is formed by mixing a binder, a polydiene, and a solvent.
The adhesive is a thermosetting resin or a mixture containing one or more functional groups of acid ester groups, epoxy groups, isocyanate groups and vinyl groups. Firstly, carrying out plasma treatment on the cleaned liquid crystal fiber cloth, thereby generating a large number of polar groups on the surface. The functional groups in the adhesive react with the polar groups in polydiene molecules and the polar groups of the liquid crystal fiber cloth after plasma treatment simultaneously to form covalent bonds, so that strong cohesive force is generated. After drying in an oven, a layer of adhesive film is formed on the surface of the liquid crystal fiber cloth, double bonds in polydiene molecules remain on the outer surface of the film, the adhesive film can be crosslinked with the double bonds of the thermosetting resin composition when the laminated board is prepared, and good interface bonding force is formed in the curing process.
The polydiene means that the polydiene unit is contained in the molecule, unreacted double bonds remain in the molecule, and the side chain or the terminal of the molecular chain contains polar functional groups which can react with the adhesive and can be one or more of hydroxyl, carboxyl, amino, epoxy and isocyanato.
Examples of the diene monomer include butadiene, 2-methyl-1, 3-butadiene (also referred to as isoprene), 2, 3-dimethylbutadiene, 2-phenylbutadiene, and 1, 3-pentadiene. These diene monomers may be used alone or in combination. Butadiene and isoprene monomers are preferred, with butadiene monomers being more preferred.
The polydiene has a number average molecular weight of more than 1000 and less than 50000, and is liquid at normal temperature, i.e. has a melt viscosity measured at 38deg.CMore preferably +.>Further preferably +.>
As the solvent, there may be mentioned: n-butane, n-pentane, isopentane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, methylcyclopentane, benzene, toluene, xylene, and the like.
Mixing a proper amount of polydiene, an adhesive and a solvent, fully stirring, putting the liquid crystal fiber cloth subjected to plasma treatment into a soaking tank, fishing out the liquid crystal fiber cloth after a few minutes, and curing the liquid crystal fiber cloth in an oven to obtain the polydiene surface-treated liquid crystal fiber cloth. The adhesion amount of the binder and polydiene is 0.1% by mass or more and 1% by mass or less relative to the liquid crystal fiber cloth, and when the adhesion amount is less than 0.1% by mass or less, the bonding effect is poor, and the laminate is liable to be broken when soldering; when the amount of the adhesion is more than 1% by mass, there is a risk of deterioration in dielectric properties.
Compared with the prior art, the invention has the following advantages:
the invention is characterized in that polydiene surface treated liquid crystal fiber cloth is used for replacing the traditional inorganic glass fiber cloth in the laminated board. The liquid crystal fiber cloth is obtained by spinning, heat treatment and weaving the liquid crystal resin particles. After the liquid crystal fiber cloth is treated by plasma, the liquid crystal fiber cloth is immersed into a polydiene and adhesive mixed solution, and then is cured in an oven, so that a layer of film containing double bonds is formed on the surface of the liquid crystal fiber cloth, and good interface bonding force can be formed in the curing process of thermosetting resin.
Meanwhile, the flexible hydrocarbon resin provides excellent dielectric property and toughness for the system, and the allyl modified polyphenyl ether resin with excellent electrical property is added into the system, so that the rigid benzene ring is introduced, and the heat resistance of the matrix is improved while the dielectric property is ensured. The addition of the modified bismaleimide resin effectively improves the glass transition temperature, heat resistance and peel strength of the plate.
The laminated board prepared by the invention has the advantages of lower dielectric constant and dielectric loss, good peel strength, high heat resistance and the like, and can be applied to the high-frequency and high-speed field.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
Crystallization melting temperature (Tm): using a differential scanning calorimeter DSC 8000 (PeckinElmec Inc, UDA), the LCP sample to be tested was heated from room temperature at a rate of 20 ℃/min and the endothermic peak (Tm l) was recorded. The sample was then kept at a temperature of Tm l 20 ℃ for 5 minutes. The sample was then cooled to room temperature at a rate of 10deg.C/min and again heated at a rate of 10deg.C/min. The endothermic peak obtained in the final step is recorded as the crystalline melting temperature (Tm) of the sample LCP.
Melt viscosity: melt viscosity rheometer Capillacy Cheometec Rh2000 (Malvecn) was used. By using a capillary of 0.5mm, at a shear rate of 1000s ―1 The melt viscosity of the LCP sample tm+20 ℃ was measured under the conditions of temperature.
Resin dielectric constant (Dk) and dielectric loss (Df): dielectric loss tangent of the LCP resin at 10GHz was measured by the split dielectric resonator method (SPDR method) using a network analyzer N5232A or the like from Keysight Technology. Unless otherwise specified, the dielectric loss tangent was measured at 23℃under normal atmospheric pressure and a humidity of 60%.
Modification example 1
676.79g of parahydroxybenzoic acid (4.9 mol), 395.18g of dihydroxyhexanaphthoic acid (2.1 mol), 165.17g of hydroquinone (1.5 mol) and 249.20g of terephthalic acid (1.5 mol) were fed into a reaction vessel equipped with a stirring device with a torquemeter and a condenser so that the total amount of monomers was 10 mol. Then 1.03 times the molar amount of acetic anhydride (moles) of the total amount of monomer hydroxyl groups was added to the vessel. The mixture was heated from room temperature to 150 ℃ over 1 hour under nitrogen atmosphere and maintained at 150 ℃ for 30 minutes, followed by 7 hours to 320 ℃ while evaporating the by-product acetic acid. And then starting vacuumizing, stopping vacuumizing after the torque of the motor reaches a preset value, and introducing nitrogen to discharge and cut particles. The crystalline melting temperature thereof was 290℃as measured using a differential scanning calorimeter, and the melt viscosity thereof was 45pa.s as measured using a capillary rheometer. Resin pellets were injection molded into 0.5mm thick, 80 x 80mm square pieces and tested for dielectric properties at 10GHz by SPDR method, showing a Dk of 3.4 and a df of 0.0014.
After the pellets were dried in an oven at 150 ℃ for 4 hours, the molten material was discharged from the spinneret orifices through a filter using a spinning apparatus, and melt-spun at tm+10 ℃ to obtain a nascent fiber having a monofilament linear density of 5 d. The fiber was unwound using an unwinder and then maintained at 280 ℃ (melting point-10) for 10 hours to give a heat treated fiber, which was tested for a melting point of 310 ℃.
Coating starch slurry on the surface of the liquid crystal polyester fiber, weaving by using a rapier loom, and cleaning the slurry after weaving to obtain the liquid crystal polyester fiber cloth with the thickness of less than 100 micrometers and clean surface.
And (3) placing the liquid crystal fiber cloth with the clean surface into vacuum plasma equipment, and treating for 4min under an oxygen atmosphere for standby.
3G of hydroxyl-terminated polybutadiene (Japanese Caocato, G3000) and 2G of caprolactam blocked isocyanate (Hengzhou clinical chemistry) solution are mixed, added into 95G of xylene, fully stirred for 1-2h, and then the liquid crystal fiber cloth is placed into a baking oven at 150 ℃ for curing for 2min, and repeated for 3 times, so as to obtain the polydiene surface treated liquid crystal fiber cloth A1. The weight of the liquid crystal fiber cloth was 0.2% by weight.
Modification example 2
607.73g of p-hydroxybenzoic acid (4.4 mol), 376.36g of dihydroxyhexanaphthoic acid (2.0 mol), 198.20g of hydroquinone (1.8 mol) and 299.03g of terephthalic acid (1.8 mol) were fed into a reaction vessel equipped with a stirring device with a torquemeter and a condenser so that the total amount of monomers was 10 mol. Then 1.03 times the molar amount of acetic anhydride (moles) of the total amount of monomer hydroxyl groups was added to the vessel. The mixture was heated from room temperature to 150 ℃ over 1 hour under nitrogen atmosphere and maintained at 150 ℃ for 30 minutes, followed by 7 hours to 330 ℃ while evaporating off the by-product acetic acid. The pressure was then reduced to 5 mmhg over 80 minutes, after which time the vacuum was stopped and nitrogen was vented to pellet the torque. The crystalline melting temperature thereof was determined using a differential scanning calorimeter and was 310 ℃. The viscosity was measured using a capillary rheometer and was 45pa.s. Resin pellets were injection molded into 0.5mm thick, 80 x 80mm square pieces and tested for dielectric properties at 10GHz using the SPDR method, which showed a Dk of 3.4 and a Df of 0.0016.
After the pellets were dried in an oven at 150 ℃ for 4 hours, the molten material was discharged from the spinneret orifices through a filter using a spinning apparatus, and melt-spun at tm+10 ℃ to obtain a nascent fiber having a monofilament linear density of 5 d. The fiber was unwound using an unwinder and then maintained at 290 ℃ (melting point-20) for 10 hours to give a heat-treated fiber. The melting point was measured to be 330 ℃.
The liquid crystal fiber cloth A2 is obtained by adopting the same method of modification 1 to weave and polydiene surface treatment. The weight of the liquid crystal fiber cloth was 0.22% by mass.
The specific components of the thermosetting resin composition are as follows:
b: hydrocarbon resin: styrene-butadiene resin (manufacturer, sartomer, trade name: riconl 04H)
C: allyl modified bismaleimide resin (manufacturer, japanese pill good chemical, trade name: BANI-M)
D: allyl modified polyphenyl ether resin (manufacturer, sabber basic innovative plastic, trade name: SA-9000)
E: and (3) an initiator: dicumyl peroxide (manufacturer, shanghai Gao Qiao)
F: and (3) filling: spherical silica micropowder (manufacturer, electric chemical industry Co., ltd., trade name: SFP-30M)
G: flame retardant: phenoxy phosphorus wax compound (trade name of Japan Otsuka chemical Co., ltd., trade name: SPB-100)
H: solvent, xylene
The parts thereof are parts by weight unless otherwise specified hereinafter.
Example 1
15 parts of allyl modified bismaleimide resin BANI-M powder solid is fully dissolved by dimethylbenzene, 50 parts of styrene-butadiene resin Riconl04H is added to react for 4 hours at 160 ℃, 70 parts of double bond modified polyphenyl ether resin SA9000 is added to continue to react for 2 hours, the mixture is cooled to room temperature, and finally 30 parts of spherical silica micropowder SFP-30M serving as a filler, 12 parts of phenoxy phosphorus wax compound serving as a flame retardant, 0.5 part of dicumyl peroxide serving as an initiator and 100 parts of dimethylbenzene serving as a solvent are sequentially added to uniformly stir to form a glue solution.
The liquid crystal fiber cloth A1 is immersed in the resin composition glue solution, and is placed in an oven at 125 ℃ for baking for 10min, and the solvent is removed, so that the prepreg is prepared. The resin content of the prepreg is 65%, and the resin gel time is 180s.
Laminating 2 prepregs together, and placing the prepregs in a vacuum hot press for pressing to obtain a laminated board, wherein the hot pressing process comprises the following steps: maintaining at 150deg.C and 3.0Mpa for 60min, and then maintaining at 210deg.C and 3.0Mpa for 120min.
Example 2 the same procedure as in example 1 was followed except that the liquid crystal fiber cloth was changed to A2. Comparative example 1 was prepared in the same manner as in example 1 except that the liquid crystal fiber cloth was replaced with a 1080 inorganic glass fiber cloth A3 (treated with a coupling agent to a thickness of 0.056mm, dielectric constant at 1MHz frequency of 4.6, loss factor of 0.0007). The composition formulation of the comparative example and the copper clad laminate for printed circuit board prepared by the method have the physical property data of dielectric constant, dielectric loss factor, flame retardance and the like shown in Table 1.
Table 1. Formulation compositions (all based on the weight of solid component) for each example and comparative example.
In comparative examples 1 and 2 and comparative example 1, the polydiene surface-treated liquid crystal fiber cloth was used in examples 1 and 2, while in comparative example 1, the low-loss inorganic glass cloth was used, and in examples 1 and 2, the overall dielectric constant and dielectric loss were greatly reduced and the dielectric properties were more excellent while ensuring that the other properties of the copper-clad laminate were not significantly changed. Because the surface of the liquid fiber cloth contains double bonds, the liquid fiber cloth reacts with the double bonds of other component substances during curing, has excellent binding force, and does not cause the reliability degradation of the copper-clad plate.
In conclusion, the copper clad laminate prepared by the method has excellent performance, low dielectric constant and electromechanical loss, high glass transition temperature, excellent heat resistance, flame retardance reaching UL-94V-0 level, and excellent PCB processing performance, and is suitable for high-speed printed circuits.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
The test method of the laminated board is as follows:
glass transition temperature (Tg): the measurement was performed according to the DSC method defined in IPC-TM-6502.4.25D by Differential Scanning Calorimetry (DSC).
Peel Strength (PS): the peel strength of the metal cap layer was tested according to the "post thermal stress" experimental conditions in the IPC-TM-650.2.4.8 method.
Combustibility: measured according to the UL94 vertical burn method.
Thermal stratification time T-288 was determined according to the IPC-TM-6502.4.24.1 method.
5% thermal decomposition temperature Td: the measurement was performed according to the IPC-TM-6502.4.26 method. Raising the temperature from room temperature to 550 ℃ at a heating rate of 10 ℃/min, and taking the temperature at which the weight is lost by 5%;
dielectric constant (Dk) and dielectric loss (Df) dielectric properties at 10GHz were measured according to IPC-TM-6502.5.5.5 using a bar-line resonance method.
Claims (21)
1. A method for preparing a liquid crystal fiber cloth reinforced laminate, comprising the following steps:
(1) Preparing liquid crystal fiber cloth, performing plasma treatment on the liquid crystal fiber cloth, immersing the liquid crystal fiber cloth in a mixed solution of polydiene, an adhesive and a solvent, and performing surface modification on the liquid crystal fiber cloth;
(2) Preparing a thermosetting resin composition glue solution, and immersing the polydiene surface-treated liquid crystal fiber cloth into the thermosetting resin composition;
(3) Drying and curing in an oven to prepare a prepreg; the multi-layer prepreg is then hot pressed to form a laminate.
2. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 1, wherein: the crystallization melting temperature of the liquid crystal fiber cloth is higher than 310 ℃; the dielectric constant Dk of the liquid crystal fiber cloth is between 3.0 and 3.6 at the frequency of 10GHz, and is less than 0.002, and the thickness of the fiber cloth is less than 100 micrometers.
3. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 2, wherein: the crystallization melting temperature of the liquid crystal fiber cloth is higher than 330 ℃, and the dielectric loss Df is smaller than 0.0015.
4. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 1, wherein: the polydiene means that the polydiene unit is contained in the molecule, unreacted double bonds remain in the molecular chain, the number average molecular weight is more than 1000 and less than 50000, and the repeating unit is one or more than one of butadiene or isoprene; the polydiene molecule contains polar functional groups which can react with the adhesive and are selected from one or more of hydroxyl, carboxyl, amino, epoxy and isocyanato.
5. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 4, wherein: the diene monomer is selected from one or a combination of more of butadiene, 2-methyl-1, 3-butadiene, 2, 3-dimethylbutadiene, 2-phenylbutadiene and 1, 3-pentadiene.
6. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 5, wherein: the diene monomer is selected from butadiene and isoprene monomers.
7. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 6, wherein: the diene monomer is selected from butadiene monomers.
8. A method of producing a liquid crystal fiber cloth reinforced laminate according to claims 4-7, characterized in that: the polydiene has a number average molecular weight of more than 1000 and less than 50000, and is liquid at normal temperature, i.e. has a melt viscosity measured at 38deg.C
9. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 1, wherein: the adhesive is a thermosetting resin or a mixture containing one or more functional groups of acid ester groups, epoxy groups, isocyanate groups and vinyl groups.
10. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 1, wherein: the adhesion amount of the binder to the polydiene is 0.1% by mass or more and 1% by mass or less relative to the liquid crystal fiber cloth.
11. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 1, wherein: the solvent is selected from n-butane, n-pentane, isopentane, n-hexane, n-heptane, n-octane, cyclopentane, cyclohexane, methylcyclopentane, benzene, toluene, xylene.
12. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 1, wherein: the thermosetting resin composition comprises the following components in parts by weight: 30-70 parts of hydrocarbon resin, 10-30 parts of modified bismaleimide resin, 30-90 parts of modified polyphenyl ether resin, 0.01-5 parts of initiator, 20-60 parts of inorganic filler, 10-30 parts of flame retardant and 50-120 parts of solvent.
13. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 12, wherein: the hydrocarbon resin refers to unsaturated resin containing polymerizable carbon-carbon double bonds; the unsaturated resin containing polymerizable carbon-carbon double bonds is one or a mixture of at least two of styrene-butadiene copolymer, polybutadiene, styrene-butadiene-divinylbenzene copolymer and styrene-isoprene-styrene copolymer.
14. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 12, wherein: the bismaleimide resin is bismaleimide resin with double bonds at the molecular chain terminals.
15. A method of making a liquid crystal fiber cloth reinforced laminate in accordance with claim 14, wherein: selected from methacrylic acid-terminated bismaleimide resins or vinyl bismaleimide resins.
16. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 12, wherein: the modified polyphenyl ether resin is a modified polyphenyl ether resin with double bonds at molecular chain terminals, and is preferably methacrylic acid end capped polyphenyl ether resin or vinyl ether polyphenyl ether resin.
17. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 12, wherein: the initiator is selected from one or more of the following substances: dicumyl peroxide, di-t-butylperoxycumene, dibenzoyl peroxide or t-butylhydroperoxide.
18. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 12, wherein: the inorganic filler is selected from one or a combination of several of the following substances: hollow glass beads, spherical silicon micropowder, silicon carbide nanoparticles, titanium dioxide, mica powder, calcium silicate, magnesium silicate, talcum powder, aluminum oxide, aluminum nitride, beryllium oxide and boron nitride.
19. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 12, wherein: the inorganic filler is selected from silica.
20. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 12, wherein: the flame retardant is selected from one or more of the following substances: tricresyl phosphate, phenoxyphosphazene compound, tributyloxyethyl phosphate, triphenyl phosphate, zinc borate and antimonous oxide.
21. A method of producing a liquid crystal fiber cloth reinforced laminate according to claim 12, wherein: the solvent is selected from one or more of the following substances: acetone, butanone, methanol, methyl ether, ethylene glycol methyl ether, benzene, toluene, xylene.
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| WO2024021897A1 (en) * | 2022-07-27 | 2024-02-01 | 华为技术有限公司 | Prepreg, substrate, printed circuit board and related preparation method |
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